PH27164A - Method of preparing fruit juice beverages and juice concentrates nutritionally supplemental with calcium - Google Patents

Description

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FRUIT JUICE BEVERAGES AND JUICE CONCENTRATES

RUTRITIONALLY SUPPLEMENTED WITH CALCIUM

This application is a divisional application of Fhilippine Appli- cation Serial Number 35223 filed on May 03, 1987. )

TECHNICAL FIELD so This application relates to fruit juice beverages and juice con-~ bo J centrates which are nutritionally supplemented with significant levels of caletum, this application further relates to a method for preparing these beverages and concentrates.

Dietary calcium inadequacy may be a contributing cause to osteo- porosis, at least for some populations. For example, a positive correlation between calcium intake and bone mass has been found across many ‘age groups. It has also been suggested that the level of calcium intake early in {ife directly influences the peak bone mass achieved at skeletal maturity.

During the period of late teenage to your adulthood, it has been found that a significant reduction in dietary calcium intake typl-

Ea 714 cally occurs, This 1s especially true of theifemale population where - reduced dietary calcium intake usually happens much earlier in life compared to their male counterparts, Accordingly, females, as a class, are especially susceptible to a prolonged calcium deficit over their life span, This calcium deficit may be one reason for the greater incidence of osteoporosis in postmenopausal women,

Calcium cen be obtained from a variety of dietsry sources. The pri- mary sources of cal¢ium are dairy products, in particular milk. Milk provides a very valuable source of dietary calcium. However, begin- ning in late teenage to young adulthood and continuing through later 1ife, milk is typically not consumed in sufficient quantities by the general population to obtain needed levels of caléiom, This may be caused by the unattractiveness of milk as a drink for "social occa- ; ' sions”. Indeed, it has been found that teenage girls, and especially young sdult women, ganerally find milk to be a socially unattractive drink, as well as too caloric and unappealing in taste, Additionally, a significant portion of the population becomes lactose intolerant as they reach maturity, resulting in gastrointestinal problems tf they comsume milk, 70 To achieve greater consumption of calcium, a more appealimg aslter- - native to milk is apparently needed. This alternative must be one which 1s consumbd in sufficient quantities to provide nutritionally beneficial amounts of caldium. Beverages which are consumed often by the general public at breakfast are fruit juice products, espe- cially orange juice, Like milk, orange juice has a wholesome, nutri- tional images Also, orange juice is generally considered to have an appealing taste. Accordingly, orange juice nutritionally supple- 4 mented with calcium could be viewed as an additional vehicle for achieving greater dietary calcium intake throughout life. ‘

Nutritional supplementation of orange juice, or other fruit Juices, with significant levels of calcium is not straight forward, Milk

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L716 contains, on average, about 0.12% calcium by weight, Inclusion of . such a high level of calcium in orange juice requires consideration of a number of issues,

One is making sure that the calcium-supplemented orange juice has desirable taste qualities. It has been found that direct addition of calcium sources, such as calcium carbonate or calcium hydroxide, to orange juice can generate undesirable cooked/browned off-flavors or cause desirable aroms and flavor compounds to be stripped from the juice, Addition of calclum salts such as calcium chloride at ’ high levels (e.g. above 0.117% calcium chloride) can impart undesi- rable brackishness to the juice. Calcium chloride addition has also been found to reduce the flavor intensity and quality, as well as the sweetness of orange juice, Accordingly, the calcium source needs to be added in a way which does not significantly affect the desi- rable taste and sweetness properties of orange juice, ‘Another potential issue is Insuring that the calcium is solubilized in the juice. Solubilization of calcium in juice concemtrates can be a very significant problem because of the high level of calcium present, However, solubilization of calcium in single-strength "0 juice products can also be difficult due to ithe acid systems and ; other components present in the juice. Orange juice naturally con- eo ae tains a mixture’ of citric acid and malic acid. The most thermody- nahically stable calcium citrate species which form when a calcium source is directly added to orange juice are also the most insoluble.

These insoluble calcium citrate species can precipitate out of the orange juice fairly rapidly. Accordingly, the calcium source also needs to be added in a way which insures solubilization of the cal- cium in both single-strength orange juice beverages and juice con- centrates.,

Another factor which must be considered is the absorbability and bioavailability of the calcium from the juice, As used herein,

oo 27164 “absorbability" refers to the amount of calcium which ends up in i» the blood serum. As used herein, "bioavailability" refers to the sbillty of the calctum to reach the site of bioactivity,” i.e. bone, MILK is likely to be the standard against which absorbabi- lity and bloavailability of calcium from a nom-milk beverage will be measured, Accordingly, to the extent possible, calcium-supplemen- ted orange juice should approach, or desirably exceed, milk in terms of absorbability and bioavailability of calcium,

BACKGROUND ART

U.S. Patent 2,325,360 to Ayres et al,, issued July 27, 1943, dis- closes a method for replacing gases removed during deaeration of fruit juices, such as orange juice, with carbon dioxide, In this method, dry calcium carbonate, or a mixture of calcium carbonate and citric acid, ls dropped into a can which is then filled with deaerated orange juice. (Other organic acids such as malic and tartaric acid can be used in place of citric actd.,) The reaction between the calcium carbonate and added citric acid, or citric acid in the Juice, generates the carbon dioxide,

U.S, Patent 3,657,424 to Akins et al, issued April 18, 1972, dis- 0 closes the fortification of citrus juices, including orange juice, with sodium,’ calctum and chloride ions in amounts beyond what is naturally present in the juice. Calcium salts which can be used in fortification include the chlorides, citrates or phosphates, although cale um chloride is preferred for providing the desired chloride Sonia The maximum amounts of calcium salts permitted in these fortified citrus juices is up to about 0.04%. (this calcu- lates to about 0.015% calcium in the juice {if calcium chloride is used.) The eltrus juices fortified can be single-strength, diluted or frozen concentrates, }

U.S. Patent 3,114,641 to Sperti et al,, issued December 17, 1963, discloses extended orange juice products obtained by diluting .

BE 2714 single-strength orange juice or concentrated orange jdice., To main- feo tain the flavor of the diluted orange juice product, materials such as caletun chloride, magnesium chloride, sodium or potassium citrates, tartaric and male acids (or thelr salts) are included in “very small amounts," These extended orange juice products are based on a dilu- tion factor of lil to li4 when single-strength juices sre used or 1112 to 1316 when concentrated juices are used, The one example given of an additive formula for use with these extended products contains calcium chloride (0,04%), citric acid (0.85%) and sodium citrate (0,06%)., This additive formula can be added directly to the single-strength Juice or concentrate, the water used to make the extended product, or to the extended product itself,

British Pstent Specification 2,095,530, published October 6, 1982, dis¢leses a process for obtaining an acld beverage enriched in pro-

LJ tein, particularly a fruit juice or fruit-flavored beverage, In this process, an aqueous suspension of soy protein is prepared using ‘water and/or fruit juice, Calcium in a concentration of from 5 to 50mM is added, after which the pH of the suspension is reduced ond the insoluble material separated to yield a protein solution, A fruit juice or fruit flavoring can then be added to this protein oo solution, The calcium can be added in the form of the chloride, acetate, tartrate, malate or lactate salt, although calcium chlo- : ride spears. to be preferred. ‘the beverage described in Example 11, which uses orange juice as the extraction medfum, has 30mM of calcium added,

European Patent Application 75,114, published March 30, 1983, dis- closes protefn-containing fruit juice drinks enriched with vitamins and minerals, These drinks contain 30-907 fruit juice (a mixture of 20-70% apple juice, 4-407% white grape juice, 1-10% passion fruit : 30 juice and 53-25% lemon juice), 2 to 20% whey protein concentrate, end mineral salt mixture of potassium, sodium, magnesium, calcium and phosphate, Calcium is present in these drinks at 0.01 to 0.3%,

preferably at 0.02 to 0.03%. these drinks can be prepared by com- bining a first solution of apple, passion fruit and grape juice con- - taining the whey concentrate with a second aqueous solution of lemon juice containing the mineral salt mixture. The calcium salts used {n this mineral salt mixture are not specified.

DISCLOSURE OF THE INVENTION

The present invention relates to single-strength fruit juice beverages, in particular eramnge juice beverages, which are nutritiomally supple- mented with significant levels of calcium, These beverages are subs- tantially free of added protein and comprises (a) from about 0.05 to about 0.26% by weight solubilized calciumg (b) from about 04% to about 4% by weight of an acid component comprising a mixture of citric acid and malic acid - in a weight ratio of from about 53195 to about 903104 15- (c) at least about 45% fruit juicey (d) a sugar content of from about 2 to about 16° Brix; and (e) no more than about 0.07% by weight chloride f{on.

The present invention also relates to calcium-supplemented fruit Juice concentrates, in particular orange juice concentrates. These juice 1 concentrates comprises (a) from ‘about 0.15 to about 1,307 by weight solubilized calciumg (b) from about 1.2 to about 20% by welght of an acid component comprising a mixture of citric acid and malic acid in a weight ratio of from about 5:95 to about 90:10 (¢) at least about 45% fruit juicey and (d) a sugar content of from about 6 to about 75° Brix.

The present invention further relates to a method for preparing these calcium-supplemented juice products. 1n this method, an at least meta-stable aqueous premix solution of solubilized calclum is formed from water, an acid component comprising from 0 to about 90% by weight citric acid and from about 10 to 100% by weight malic acid, snd a calcium source selected from calcium carbonate, calcium oxide,

and calcium hydroxide. This premix solution of solubilized calcium on, is then combined with fruit juice materials which comprise concentrated . 3 1 fruitjjulce having a sugar content of from about 20 to about 80° Brix, to provide a calcium-supplemented juice product having (1) at least about 0.05% solubilized calcium (2) at least about 453% fruit juicey and (3) a sugar content of from about 2 to alo ut 75° Brix.

The method of the present {nvention solves several significant prob- lems which can be cause by direct addition of calcium sourees to fruit juices or fruit juice concentrates. One is insuring solubilization of substantial levels of calcium fn the juice or-juice concentrate.

Another is avolding generation of cooked/brown off-flavors or the inclusion of undesirable species such as chloride fons. This method also permits the removal of carbon dioxide generated by the reaction . of calcium carbonate with the acids se that undesirable carbonation 5 of the juice does not occur. In addition, it has been surprisingly - found that the absorbability/bloavailability of calcium from the fruit juice products of the present invention is at least as good as that of calcium from milk, ‘ A, Brief Description of the Drawing

J the Figure represents a schematic diagram of a preferred method for preparing cadolum-supplemented fruit juice products accordimg to the present invention,

B., Definitions .

As used herein, the term "fruit juice product” refers te both fruit juice beverages and fruit juice concentrates which comprise at least about 45% fruit juice. ‘

As used herein, the term "fruit juice beverage" refers to a fruit juice product which is in a single-strength, ready-te-saxve, drinkable form. Fruit juice heverages of the present inventon can be of the "full-strength" type which typically comprise at least about 957 fruit juice.

Fruit juice bevercges within the scope of the present invention alse oa include extended juice products which are referred to as "mectars”, . ) i .

These extended juice products typically comprise from about 50 to about 90% fruit juice. Preferred extended juice products cemprise 5 from about 50 to abeut 70% fruit juice.

As used herein, the term “fruit juice concentrate” refers to a fruit

Juice product which, when diluted with the appropriate amount of water, forms drinkable fruit juice beverages, Fruit juice concentrates with- in the scope of the present invention are typically formulated to provide drinkable beverages when diluted with 3 to 5 parts by weight water,

As used herein, the term "concentrated fruit juice" refers to fruit juice from which a portion of the water has been removed. ’

As used herein, the term "fruit juice materials” réfers to concentra- ted fruit juice, plus other fruit juice materials such as fruit juice aroma and flavor volatiles, peel oils, and pulp or pomace,

As used herein, the term "fruit juice’ refers to citrus juices, non- citrus juices such as apple juice, grape juice, pear juice, cherry juice, berry juice, pineapple juice, peach juice, apricot Juice, plum juice, prune juice, and mixtures of these juices. : t Yad ’ ! ; . I © {

As used heréin, the term “cittus juice" refers to fruit juices sel- ected from orange juice, lemon juice, lime juice, grapefrult juice, tangerine juice and mixtures thereof.

As used heréin, the term "comprising" means various components can be conjointly employed in the fruit juice beverages and juice con- centrates of the present invention. Accordingly, the term “compris- ing" encompasses the more restrictive terms “consisting essentially of" and "consisting of",

All amounts of fruit juice referred to hereln are on a single- strength basis,

C. Calcium Supplemented Fruit Juice Beverages and Juice Concentrates

The key nuts tional component added to the fruit juice beverages and julce concentrates of the present invention is calcium, - Suitable sources of calcium include calcfum carbonate, calcium oxide, and cal- cium hydroxide. To be useful in the present {nvention, the calcium needs to be "solubilized", i.e., dissolved, fn the fruit juice beve- rage or juice concentrate, Accordingly, the amount of calcium included in the beverages and concentrates of the present invention will be referred to in terms of "solubilized calcium", i.e., the amount of calcium lon dissolved in the beverage or concentrate,

For fruit Juice beverages of the present invention, calcium is present in an amount of at least about 0.05% by weight. This minimum level } . of calcium (about half of milk level) provides significant nutritional . supplementation for the beverage. <The maximum level of calcium is up to about 0.26% by weight, As the level of calcium in the beverage is . increased auch beyond about 0.26% by weight, satisfactory taste and : stability properties become much more difficult to achieve, Prefer- ably, the level of calcium in such beverages is from about 0.10 to about 0.15% by weight which includes milk level, i.e., 0.12% by weight. ) With regard fo fruit juice concentrates of the present invention usdd to prepara, drinkable beverages, the amount of calcium present is from . ah Ss about 0,15 td about 1,307 by weight, 1ypically, drinkebla beverages are prepared from 3-fold (3X) to 5-fold (3X) Juice concentrates. Accor= dingly, the favel of calcium is preferably in the range of from about 0.3 to about 0.75% by weight for these concentrates when ‘they are used to prepare beverages having from sbeut 0.10 to abeut 0.15% by weight solubilized calcium. wo

A key component in the fruit juice beverages and juice concentrates of the present invention from the standpoint of solubilizing thé cal- cium and providing desirable taste properties ls the acid component. .

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This acid component comprises a mixture of citric acid and malic acid. ~ these acids can be present in theit undisassocliated form, but are typi- cally present as the respective citrate and malate species, If desired, other edible acids such as phosphoric acid, fumaric acid, and the like can also be included in the fruit juice beverages and juice concentrates of the present invention. Preferably, the acid component consists essen- tially of a mixture of citric and malice acids, rhe level at which the acid component (hereafter total acids) is present depends on the fruit juice product involved, the level of calcium in- cluded, as well as the taste properties desired. (For the purpcses of the present invention, "total acids" include those naturally present, plus any acids added.) For fruit juice beverages having from about 0.05 to about 0.26% by weight solubilized calcium, the level of total : acids can range from about 0.4 to about 47% by weight. (For juice con- centrates used to prepare such beverages, the level of total acids can range from about L.2 to about 20% by weight). For beverages hav- ing from about 0.10 to about 0.15% by weight solubilized calcium, the level of total acids preferably ranges from about 0.8 to about 1,8% by weight. (For juice concentrates used to prepare such beverages, the level of total acids preferably ranges from about 2.4 to about 9% by weight.)

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The weight ratios of citric acid to malic acid in the acid component can vary, especially depending upon the flavor and sourness effects desired, and the fruit juice used. Generally, the weight ratio of citric acid to malic acid can be from about 5195 to about 90310 over the entire range of fruit juices, For citrus juice products such as orange julce, this welght ratio 1s typically from about 20380 to about 90310, preferably from about 60340 to about 90310, For noncitrus juices such as apple juice, this weight ratio ls typically from about 5195 to about 80120, preferably from about 30170 to about 50850.

27 fegt

The fruit juice beverages and juice concentrates of the present fnven- tion also contain the sugars normally present in fruit juice products. - ‘These sugars include sucrose, fructose, high fructose SE — glu- cose, invert sugar, and mixtures thereof, the amount of sugar natu- rally present fn fruit juices is usually sufficient for the calcium- supplemented fruit juice beverages and juice concentrates of the pre- sent invention. However, in the case of extended juice products, sugar is typically added, usually in the form of sucrose or high fruc- tose corn syrup.

In addition to sugar, extended fruit juice beverages of the present invention can contain other sweeteners. Other suitable sweeteners include saccharin, cyclamates, acetosulfam, L-aspartyl-L-phenylala- nine lower alkyl ester sweeteners (e.g. aspartame), L-aspartyl-D-ala- ~ ’ nine amides disclosed in U.S, Patent 4,411,925 to brennan et al., issued October 23, 1983 (herein incorporated by reference), L-aspsr- tyl-D-serine amides disclosed in U.S, Patent 4,399,163 te Brennan et al,, Lasudd August 16, 1983 (herein {ntorporated by reference),

L-aspartyl-L-l-hydroxymethylalkaneanide sweeteners disclosed in U.S.

Patent 4,338,346 to Brand, issued December 21, 1982 (herein incorpo- rated by reference), L-aspartyl-l-hydroxyethylalkaneanmide sweeteners

Co disclosed in u.s. Patent 4,423,029 te Rizzi, {ssued December 27, 1983 (herein incorporated by reference), L-appartyl-D-phenylglyéine ester and amide sisateners disclosed in European Patent application 168,112 to J. M. Janusz, published January 15, 1986 (herein tncotporated by reference), ind the Like, A particularly preferred sweetener for use in such extended juice products is aspartame.

For single-strength fruit juice beverages, the sugar content can ; range from about 2 to abeut 16° Brix, typically, the suger content of such beverages depends upon the amount of fruit julce contained therein. For full-strength beverages containing at least sbeut 95% fruit Jutce, the sugar content is typically from about 5 to about 14°

Brix, For extended juice beverages which comprise from about 50 tro oo 22164 about 90% fruit juice, the sugar centent is typically from abeut 5 ~ te about 13° Brix (no other sweetener) or from about about 2 to sbeut 8° Brix (other sresiener containing).

For fruit juice concentrates according to the present invention, the sugar content can range from about 6 to about 75° Brix. Typically, the sugar content of these juice concentrates is from about 20 to a about 50° Brix. For orange juice concentrates, the sugar content is preferably from about 35° to about 50° Brix.

The fruit juice beverages and juice concentrates of the present i{nven- tion are substantially free of added protein. Examples of such pro- teins include soy protein, whey protein concentrate, and the like,

These proteins can react with frutt juice aromas and flavors and, if hydrolyzed, can form short chain peptides or amino acids which have undesirable bitter flavors. For fruit julce beverages of the present £5 fnvention, the amount of added protein is generally no more than about 0.1% by weight. Preferably, these heverages and concentrates contain no added protein, the fruit juice beverages and juice concentrates of the present inven- tion also contain minimized levels of chloride ion, Inclusion of too 0 high a level ‘of chloride ion can cause undesirable brackishness in a frult Juice, beverage. High levels of chloride fon have also been found to reduce the flavor and sweetness intensity of orange juice.

The level offchloride lon is generally no more than about 0.07% by weight of the fruit juice beverage, and is preferably such that unde- 25. sirable brackishness cannot be detected, i.e, no more thin about 0.03% by weight. (Fruit juice concentrates of the present invention are formulated such that they provide, when diluted with the appro- priate amount of water, drinkable beverages which have the specified maximum level of chloride. fon.)

Calcium-supplemented fruit juice products of the present {nvention can also comprise low levels of soluble phosphate. Addittion of sol-

uble phosphate, in particular phospheric acid, at up to 0.04% by n weight has been found te improve the upfront acidity of calcium- supplemented apple juice beverages, However, this benefit does mot occur when the soluble phosphate is added at much above abeut 0.04% by weight,

Other optional ingredients typically present fruit juice products can be included in the beverages and concentrates of the present in- vention. For example, preservatives, vitamins and other minerals can be included. Suitable vitamins include A, D, E, C (ascorbic acid),

Bs B,, Bes Ba niacin, folic acid, thiamine, bietin and riboflavin, 7

Other minerals besides calcium which can be included are iron, zine, potassium, magnesium, manganese and cepper. 1f desired , natural and synthetic flavorings and colorings can be included in these beverages and concentrates. :

A surprising property of the calcium-supplemented fruit juice products of the present invention ls the excellent abserbability/bloavailability of calcium therefrom, even compared to milk. This observation is based en data obtained In experiments where the whole body retention of radio- labeled calcium (““ca) from calcium-supplemented orange juice, calcium- ! 20 supplemented apple juice, and goats' milk dosed to rats was measured, (Measurements of whole body retention of radiolabled calcium are believed to accurately reflect combined absorbability and bioavailability of the calcium), Each of the beverages dosed contained 0.12% by weight calcium, Calcium retention for the goats’ milk.was about 26 (intrin- ' sically labelled “7 ca) to about 31% (extrinsically labelled 47¢a) based on the total amount of calcium in the milk, By comparison, cal- cium retention for the supplemented orange juice and apple juice prb- ducts was 541 and 47%, respectively, based on the total amount of calcium in the juice.

D. Method for Preparing Calcium Supplemented Fruit Juice Products - 13 - ‘ f

276d

The calcium-supplemented frutt juice products of the present invention are prepared by a unique method, This method is shown schematically in the Figute. The following discussion of this method will generally be with regard’ to formation of orange juice beverages and juice con- centrates, which are highly preferred fruit juice products according to the present fnvention, However, this method can also be used to prepare calcium-supplemented fruit juice products based on other citrus juices such as grapefruit juice, noncitrus juices such as apple julce, as well as mixtures of julces,

Referring to the Figure, an acld component comprising citric acid and malic acid (Acids) is typically dissolved ir the appropriate quantity of water. (If desired, fruit juice or concentrated fruit juice such as lemon juice can be used to supply a portion of the acids). Gene- } rally, this acid component comprises from 0 to about 90% by weight . } citric acid and from about 10 to 100% by weight malic acid, For orange juice, this acid component typically comprises from about 20 to about 90% by welght citric acid and from about 10 to about 80% by weight malic acid. Preferably, this acid component comprises from about 15 to about 60% by weight citric acid and from about 40 to about 85% by weight malic acid. (For noncitrus juices such as apple juice, this acid component typically comprises from about 5 to about 80% by weight citric acid end, from about 20 to about 95% by weight malic acid, and preferably comprises from about 20 to about 50% by wefght citric acid and from about 50 to about 807% by weight malic acid.) As a rule, the ratio of these acids is selected to provide optimum flavor character in the Juices a.

Once thesolution containing the dissolved acids is formed, a source ) of calcium is then added. Calcium carbonate (CaCo,) is a preferred calcium source. this calcium source leads to the greatest and wost rapid initial solubilization of calcium and causes tne least amount of off-flavor generation. Calcium hydroxide (Caton), 7 and calcium oxide (CaO) are also acceptable calcium sources, but can cause more - off-flavor generation than calcium carbonate, The weight ratio of total acids to calcium added in the solution is typicdlly from about 0.5 to about 12, Preferably, this weight ratio is from about 1 to about 6.

Addition of calcium carbonate, calcium oxide, or calcium hydroxide to the aqueous solution of acids provides a premix containing an at least meta-stable solution of solubilized calcium. This is due to the fact that highly soluble calcium citrate and malate species such as Cali- citrate, Ca(H, citrate),, and Celmalate are formed in the solution due to the reaction between the calcium source and the acids, Without added stabilizers, the highly soluble calcium citrate species are stable in the premix solution for periods up to. only about a_few hours. :

After tnis short period of time, the highly soluble citrate species tend to disproportionate to the corresponding acid and the more ther- modynamically stable, insoluble calcium citrate salts, such as Ca, citrate, :

To impréve the stability of the more soluble calcium malate and espe- cially citrate species in the premix solution, ft is preferred in the ) "0 method of the present invention to include a premix stabilizer. Mate- rials which can complex with calcium and/or act as crystallization inhibitors gre ubeful as premix stabilizers, These materials include sugars, such as sucrose, glucose, fructose, high fructose corn syrup, {nvert sugar, and polysaccharides /such as pectin, algins, hydrolyzed starches, xanthan gum, and other edible gums. Concentrated juices which naturally contain both sugars and polysaccharides are particu- larly suitable premix stabilizers. Preferred premix stabilizers are sucrose and high fructose corn syrup (especially for extended julce products) and concentrated orange juice having a sugar content of from about 33 to about 80° Brix whose source is described hereafter.

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The premix stabilizer can be sdded immediately after the calcium source - is added to the aqueous solution containing the acids. (When calcium : earbonate 1s the calcium source, carbon dioxide evolution: is prefer- ably alloved, to substantially cease before the premix stabilizer is added). However, ff desired, the premix stabilizer (especially in the case of sugars and concentrated juice) can be added to the aqueous sol- ution of the acids prior to addition of the calcium source. The amount of premix stabilizer included in the premix solution typically depends upon the stabilizer used. When sugars are used as the premix stabilizer, they arte typically added in an amount sufficient to provide a sugar content of from about Z to about 46° Brix. When polysaccharides are used, the amount can vary widely, but is typically frem about 0.01 to

Co about 0.5% on a welght/volume basis. When concentrated jutce is used . as the premix stabilizer, it is typically included in an amount suffi- ) cient to provide a sugar content of from about 2 to about 12° Brix (preferably from about 2 to about 6° Brix). :

The premix solution of solubilized calcium is typically prepared in a batch-type fashion, as in the description above, at rook temperature.

However, ent premix solution can also be prepared in @ continuous fashion. In this continuous method, the ingredients (water, acids, : calcium source and eptional premix stabilizer) are constantly metered together J the premix solution. ‘the level at which the ingre- dients are ‘matered is adjusted, as necessary, to Insure appropriate solubl lization of the calcium in the premix solution and ‘to provide the appropriate acidity. oo the premix solution containing the solubilized calcium is combined in a mix tank with chilled (e.g., belew about 40°F (6.4°C) concen=- trated orangs Juice (Conc, Juice) having a sugar content of from about 35 te about 80° Brix (preferably from about 60 te abeut 70°

Brix,), orange Juice aroma and flaver volatiles (Aroma/Flavor Concen- trate), plus other orange juice materials such as pulp and peel oils,

Lo 2 aed to provide calcium-supplemented orange juice products having: (1) at least about 0.05% solubilized calcium (2) at least abeut 45% orange Jutcdy ‘and (3) a sugar content of from about 2 to about 75°

Brix. the particular proportions of premix solution, concentrated juice, aroma and flavor volatiles, pulp and peel oils used will de- pend upon a number of different factors, including the degree of cal- cium supplementation desired and the type of orange juice product in- volved (single-strength juice beverage or juice concentrate). For example, calcium-supplemented (0,567 calcium) 42° Brix orange Juice lo concentrates can be prepared by combining 65 parts concentrated orange juice (65° Brix), 5 parts pulp, 15 parts of an aroma/flavor concen- trate, 0.4 parts peel oil and 14,6 parts of a premix solution obtalned by combining L.4 parts calcium carbonate, 2.2 parts of & mixture of citric and malic acid, 10 parts water and 1 part concentrated orange > juice (42° Brix). Similar single-strength juice beverages can be prepated by appropriate variation of the amounts of concentrated orange julce, pulp, iaroma/flavor concentrate, peel oil and premix solution, ss well as the inclusion of water, After the calcium-supplemented orange juice product {as obtained, it is then filled into cans, cartons, bottles or other appropriate packaging. In the case of calcium-supple- mented orange juice concentrates, these products are typically frozen

Co after being filled {nto cans, ' oh

The concentrated orange juice, orange juice aroma and flavor volatiles, pulp and peel oils used in the method of the present invention can be obtained frem standard orange julce processing. See Nagy et al., Cit-

Tus Science dnd technology, Volume 2, (AVl Publishing Co. 1977), pp 177-252 (hetdtn incorporated by reference) for standard processing of oranges, grapefruit and tangerines; (See also Nelson et al, Fruit &

Vegetable Juice Processing Technology (3rd Ed,, AVI Publishing 1980), pp. 180-505 (herein incorporated by reference) for standard process- ing of noncitrus Juices such as apple juice, grape juice, pineapple juice, etc, to provide sources of juice and juice materials for cal- cium-supplemented noncitrus juice products.) Fresh juice is extracted frem the oranges, principally of the Valencia type. (the peel of the oranges is initially rasped to provide peel oils which can be used = in the method of the present invention). Juices from different oranges am frequently blended to adjust the suger to acid ratio. A sugar to acid ratio of from about 83l to about 203l is considered scceptable,

However, preferred sugar to acid ratios are typically from about lls} to about 1531.

Juice is extracted from the oranges by using automatic juicing machines, or less often by hand squeezing of the oranges. The type of equipment used to extract the juice is not critical, the raw julce exiting from the squeezing device contains pulp, rag and seeds, the rag and seed are separated from the juice and pulp in a finisher. The Jutce is then typically separated inte 2 pulp portiur and a serum portion. (the pulp portion can be used as 2 source of pulp In the method of the pre- sent invention).

The serum portion can be concentrated by a variety of techniques which typically include evaporative concentration or freeze concentra- tion. In evaperative concentration, the serum portion of the Juice 1s passed through an evaporator (e.g. talling film or temperature accelerated short time evaporator (TASLE) type). Water vapor, as well as the aroma and flavor volatiles, are stripped from the juice, These stripped volatiles are then centrifuged to provide an upper layer (essence oils) and a lower layer (aqueous essence). (A pertion of these essence oils and aqueous essence are typically used as the source of orange Jutce aroma and flavor volatiles for the method of the pre- 15 sent invention). the remaining stripped juice is then concentratéd in the evaporator (by heat) to the appropriate amount of solids as mea- . sured by the sugar content of the concentrated juice. This concentra- ted juice can then be used in the method of present {nvention.

Most concentrated orange juices are obtained by evaporative concentra- tion. However, freeze concentration can also be used to obtain con- centrated orange juice useful in the method of the present invention.

Freeze concentration typically involves passing the serum portion ofjj " the juice through a scrapped wall heat exchanger to form substantially pure ice crystals which are then separated from the concentrated Juice.

A preferred freeze concentration method is disclosed in U.B, Patent 4, 374,865 to Strobel, issued February 22, 1963, which is incorporated by reference. Unlise evaporative concentration, concentrated orange juice obtained by freeze concentration typlcally contains the aroma and flavor volatiles as well,

Calcium-supplemented fruit juice beverages and juice concentrates of the present invention can be prepared by other méthods, Fer example, the acids and calcium carbonate can be directly added to a concentrated fruit juice stripped of aroma and flavor volatiles, this method re- quires that the acids and calcium carbonate be mixed well te -insure solubilization of the calcium. this can cause undesirable foaming and loss of volatile flavor compounds in the juice unless done carefully.

Care also has to be taken in this method to avoid the generation of cooked/browned off-flavors due to the reaction and/or interactions of flavor components in the local basic environment surrounding the dis- solved calcium carbonate or calcium hydroxide, Further, when calcium carbonate (alone or with citric acid) is directly added to the Juice, wt there is residual carbonation. This residual carbonation has been found to mpage an unpleasant spoiled fermented note, especially in orange Jutcdst For these reasons, the use of the premix solution of solubilized calcium is the preferred method for preparing calcium- supplemented fruit juice beverages and juice concentrates of the pre- sent tnvent fon.

Specific Illustrations of Methods for Preparing Calcium-Supplemented

Fruit Juice Concentrates

The following illustrate the preparation of calcium-supplemented fruit juice concentrates according to the present invention:

A. Orange Nectar Concentrate

A calciun-subplemented orange nectar concentrate was prepared from the following ingredients

Ingredient Amount (g.) 65° Brix Orange Juice Concentrate 2070

Aqueous Orange Essences 550

Orange Pulp 270

Orange Oils , 2

Orange Flavor Mix 14

Calcium Carbonate 58

Citric Acid 68 } Malic Acid 54

Sucrose 910

Water 1450

Total 5446

The premix solution was prepared by dissolving the sugar and then the acids (citric and malic) in the water, Calcium carbonate was adddd and the mixture agitated until foaming ceased. This premix solution had a total acids to calcium weight ratio of 5.3 and a citric acids- -.0 maldc acid welght ratio of 56344. ‘The premix solution was added, with stirring, to the 65° Brix orange juice concentrate, followed by the orange essences, orange pulp, orange oil, and orange flavor mix, the resulting calcium-supplemented orange concentrate nectar had a sugar content of 42° Brix, 0.44% by weight calcium, a total acids to calcium weight ratloiof 10, and a citric acidsmallc acid weight ratio of 67133, One part of this orange nectar concentrate, when diluted with three parts water, provides an orange nectar beverage contalning 60% orange julce and 0.11% by weight calcium,

B. Orange Juice Concentrate

A calcium-supplemented orange juice concentrate was prepared from the following ingredients

Ingredient Amount I) te 65° Brix grange Juice Concentrate 3472 on

Aqueous Orange Essences 549 oh

Orange Pulp 273 .

Orange oils 9

Calcium Carbonate 62 citric Acid 11 -

Malic Acid 14 .

Water lo40

Total 5460

The premix solution wns prepared by dissolving the acids In the water and then adding the calciun carbonate. To this mixture was immediately - 7 added portions of the 15° Brix orange Juice concentrate up to-about a third of the total to be used. This premix solution had a total ac lds

L5 to calcium weight ratio ofl 1 and a citric acidimalic acid weight ratio of 20180. the premix solution was added to the remaining 65° Br ix orange juice concentrate, followed by the aqueous orange essences, . orange pulp and orange oils, the resulting calcium-supplemented orange juice concentiate had a sugar content of -5° Brix, 0.4% by weight cal- cium, a total jacids to calcium weight ratio of Ll and a citréc acidse-

SE malic acid welght ratlo of 67333, One part of this orange juice: con- centrate, chen! d1 luted with three parts water, provides an orange

Juice beverage containing 987, orange juice and 0.1% by weight calcium,

Embodiment Ll -

A calcium-supplemented apple juice beverage was prepared from the following Ingredients n

Ingredient ! Amount (g.) 70° Brix Apple Juice Concentrate 243,22

Apple Aroma Concentrate 212,85 aN - 2 - BAD ORIGINAL 9 ar - continued - ~

Ingredient Amount (g.)

To —

Calcium Carbonate 4,26

Citric Acid 1.06

Malic Acid 2,98

Water 954,63

Total 1419.0

The premix solution was prepared by dissolving the acids in 400 g, of the water and then carefully adding the calcium carbonate with stirring, After foaming ceased (about 5 min,), the premix solution was added to the 70° Rrix apple juice concentrate, followed by the apple aroma concentrate and the remaining 554.63 g. of water. the mixture was stirred vigorously and then bottled to provide a galcium- supplemented apple juice beverage containing 0.12% by weight calcium,

Embodiment 2

A calcium-supplemented apple juice beverage vas prepared from the following ingredients;

Ingredient Amount (g.)} 70° Brix Apple Juice Concentrate 243.22 120 Apple Aroma Concentrate 212.85

Sucrose, 1a, 19 calcium Carbonate 4,26

Citric Acid 1,42

Malic Acid 3.97

Water 939.09 rotal 16419,0

The calcium-supplemented apple julce beverage was prepared according ! to the procedure of Embodiment 1, except that the sucrose (as a pre- mix stabilizer) was added during preparation of the premix solution,

Claims (18)

} 27164 + 7° 4 WHAT IS CLAIMED 1S3 LT -

1. A method for preparing a calcium-supplemented single strength fruit julce beverage which comprises the steps of a) forming an at least meta-stahle aqueous premix solution of solubilized calcium comprising: £) solubilized calcium in an amount from about 0,05 to about 0.26% by weight of said frult Juice beve- rage, wherein the source of said solubilized cal- cium is gelected from the group consisting of cal- cium carbonate, calcium oxide and calcium hydroxide; fi) acid cémponent in man amount from about 0.4 to about n,07 by weight of said fruit juice beverage, wherein said acld component consists essentially of citric acid and malic acld in a weight ratio of from about 5:95 to about 90:10; and 1ii) watery and b) combining said premix solution of solubilized caleium with fruit juice material comprising concentrated frait juice having a sugar content from about 20 to 80° Brix, to provide a finished, single-strength, calcium supplemented fruit juice product having: 1) at least about 43% fruit juices and 2) a sugar, gontent of from about 2 to about 16° Brix.

v

2. the method of claim 1 wherein the premix solution of solubilized calcium is formed by the steps ofs (1) forming an aqueous solution containing the acid componenty and (2) adding the calcium source to the acid compounent-containing solution,

3. the method of claim It wherein the premix solutfon of solubilized calcium further comprises an effective amount of a premix solution stabilizer, . 4, rhe method of claim 2 wherein the premix solution stabilizer com- prises sugar in an amount sufficient to provide a premix solution

2716Yy sugar content of from about 2 to 40° Brix. '

5. 7The methdd 6f claim 2 wherein the premix solution stabillizer com- prises from about 0,01 to about 0.5% by weight/premix solution volume basis of a polysaccharide selected from the group consisting of pec- tin, algins, hydrolyzed starches and xanthan gum,

6. The method of claim 2 wherein the premix solution stabilizer com- prises concentrated fruit julce In an amount sufficient to provide a premix solution sugar content of from about 2 to about 12° Brix,

7. the method of claim t wherein the fruit juice fs concentrated orange juice and wherein the acid component comprises from about L5 ’ to about 60% by weight citric acid and from about 40 ro about 85% ’ malic acid. .

8. The method of claim 7 wherein the calcium source is calcium car- bonate and wherein the weight ratio of acids to calcium in the premix solution is from about 1 tw about 6.

9, The method of claim 8 wherein the premix solution of solubilized calcium further comprises concentrated orange juice in an amount su- fficient to provide a sugar content in the premix solution of from - about 2 to about 12° Brix. oo | we

10. ‘the method of claim 7 wherein the premix solution of solubilized calcium further comprises sugar in an amount sufficient to provide a sugar content in the premix solution of from about 2 to about 40° Brix,

11, The method of claim 7 which provides a calcium supplemented orange juice beverage having from about 0.05 to about 0.26% by finished, single- strength fruit julce product weight basis, solubilized calcium and a sugar content of from about 5 to about 14° Brix.

12. A method for preparing a concentrated calcium-supplemented fruit juice product which crrprises the steps of a) forming an at least meta-stable aqueous premix solution of solubilized calcium comprisings if) from about 0.15 to about 1,30% by concentrated ton, Ca juice product weight, solubilized calcium, wherein n the source of said solubilized calcium is selected - Co from the group consisting of calcium carbonate, a calcium oxide and calcium hydroxidey it) from about 1,2 to about 20% by concentrated juice product weight, of an acid component consisting essentially of citric acid and malic acid In a weight ratio of from about 5895 to about 90110; and 111) wnterp and b) combining said premix solution of solubilized calcium with fruit juice material comprising concentrated fruit juice hav- ing a sugar content from about 20 te about 50° Brix, to pro- ‘ vide a concentrated calcium-supplemented fruit juice product Co having a sugar content of from about 6 to about 75° Brixg wherejn the concentrated calcium-supplemented fruit Juice product provides upon dilution a single-strength, calciim- supplemented fruit juice product having: 1) at least about 457% by weight fruit juices 2) a sugar content of from about 2° to about 16° Brixy and 3) a calcium content from about

0.05 to about 0,267 by welght,

13, The me thad;-of claim 12 wherein the premix solution of solubilized calcium bur hee comprises an effective amount of a premix stabilizer.

14, the method -of claim 12 wherein the premix solution of solubilized calcium is formed by the steps of} (1) forming an aqueous solution containing the acid componenty and (2) adding the calcium source to the acid containing aqueous solution.

15. the method of claim 14 wherein the concentrated fruit julce is concentrated orange juice .and wherein the acid component comprises from about 15 to about 60% by weight citric acid and from about 40 to about $57 by weight malic acid,

) Cong 16, the method of claim 12 which comprises the further step of freez- ing the calcium-supplemented orange juice concentrate,

17, The method of claim 13 wherein the premix solution stabilizer comprises sugar in an amount sufficient to provide a premix solution sugar content &f from about 2 to 40° Brix. oo

18. The method of claim L3 wherein the premix solution stabilizer coriprises from about 0.01 to about 0.5% by weight/premix solution volume basis of a polysaccharide selected from the group consisting of pectin, algins, hydrolyzed starches and xanthan gum, 19, the method of claim 13 wherein the premix solution stabilizer comprises concentrated fruit juice in an amount sufficient to provide A o a premix solution sugar content of from about 2 to about 12° Brix. : , * * w ».! ® * * % * # * * * * * * * *

Ch . Li David C. HECKERT : ; or Inventor oo ro Cl :

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