METHOD FOR MAKING CHEESE USING CARRAGEENAN

Abstract: An improved method for making cheese wherein curd formation is effected in the presence of carageenan, preferably iota carrageenan having molecular weight in the range of from about 80,000 to about 250,000, and having a dominant cation selected from the group consisting of Na<+>, Ca<++>, and K<+>.

Description: METHOD FOR MAKING CHEESE USING CARRAGEENAN The present invention is concerned with an improvement to conventional cheese making methods which provides for cheese having a desirable texture and contains at least as much, if not more, of the nutrients, and particularly proteins, that are in the original milk or cream source, than cheese made by conventional methods. More specifically, this inven¬ tion is directed to an improved method for curd formation in which carrageenan, and preferably the iota fraction or type carrageenan, is employed in enhancing the harvest of at least some of the proteins, without resorting to high temperature, which would otherwise be sacrificed as part of the whey in conventional cheese making methods. Carrageenan is defined as that group of galactan polysaccharides extracted from red algae (Rhodophyceae class) of the Gigartinaceae, Solieriaceae, Hypneaceae, and Phyllophoraceae families, and that have an ester content of 20% or more and are alternately α 1-3, . 1-4 glycosidically linked. While carrageenan is a complex mixture of several polysaccharides, it consists essentially of three main fractions, kappa, lambda, and iota, the relative proportions of which vary with the seaweed source. In general, the kappa carrageenan fraction contains over 34% of 3,6-anhydro-D-galactose (3,6-AG) and 25% ester sulfate, by weight. A 1.5% by weight concentration thereof in water at 75°C exhibits a viscosity of about 50 mPa. Upon cooling, such water solution will gel at a temperature of from about 45 to 65°C, with the gelling temperature and gel firmness being dependent upon the quantity and types of metallic ionsj such as K+,• NH,+, and Ca++, in the solution. The lambda carrageenan fraction generally contains about 35% ester sulfate, by weight, and no 3,6-AG. While the lambda fraction forms free-flowing pseudoplastic solutions in water, its rheology is essentially independent of specific inorganic ion effects and thus it is non-gelling. The lambda carra¬ geenan fractions produce the highest water viscosities of the carrageenan family, for example , a 2.0%, by weight, concentration thereof in water can produce viscosities upwards of 600 mPa. The iota carrageenan fraction contains approximately 30% 3,6-AG and 32% ester sulfate, by weight, and upon cooling from a temperature, say 75°C, and in the presence of gel-inducing cations, ' such as Ca ++ , Mg++ and K+, the iota carrageenan fraction forms, elastic, syneresis-free, thermally-reversible gels at concentrations as 'low as 0.3%,. by weight. For the sake of brevity and as understood in the art, the carrageenan fractions described above are hereafter each referred to as carrageenan , it being understood that reference, for example, ' to iota carrageenan, does not preclude the presence of the kappa and lambda fraction, as well as precursors of all fractions, any and all of which would be present in minor amounts relative to the iota fraction or other fraction to which specific reference is made. Also reference made hereinafter to "water viscosity" shall be taken to mean the viscosity of a water solution at 75°C containing a 1.5%, by weight, concentration of carrageenan. As set forth in the Food Chemicals Codex, Second Edition (F.C.C.II), 1972, National Academy of Sciences, Washington, D. C, and the third supplement to F.C.C. II, dated 1978, for use in food applications, carrageenans must have water viscosities (1.5%, by - - weight, concentration in water at 75°C) which are not less than 5 centipoises (5 mPa). Referring now to the making of cheese (as described in F. Kosikowski's "Cheese and Fermented Milk Foods", Edwards Brothers Inc., Ann Arbor, Michigan 1966), one step that is common to many cheese varieties is the selective concentration of the insoluble components of milk. This selective concentration or curd formation or "setting" is noriiially carried out while the milk is in a heated condition and may be achieved, for example, by the controlled fermentation, as initiated by streptococci or lactobacilli bacteria of the milk lactose to lactic acid which, in tur j forms an isoelectric casein curd in the milk at a pH of 4.6. Alternatively, by the action of the clotting enzyme, rennin, the insoluble milk components may be coagulated as ' a calcium paracasein curd at a higher pH. If desired, both a bacteria starter 1 and rennin may be employed to provide a curd formation. A still further alternative is the direct addition of food grade acids, such as, lactic acid, or salts, to pasteurized cream, whole milk, milk of reduced fat content or skim milk. This last-mentioned manner of setting or curd formation is often referred to in the art, and is referred to hereinafter, as the "direct set" method. The resulting curd is composed of water, proteins, chiefly casein, fat, milk sugar, and salts, such as, calcium phosphate^ while the remaining serum or watery portion, whey, may contain perhaps 45% of the nutrients of the cream or milk from which the cheese is made, including perhaps 25% of the available proteins, such as, albumin and globulin. The formed curd is then subjected to "cutting" or breaking to increase the curd surface area and thus enhance whey expulsion and facilitate a more uniform distribution of heat throughout the curd during a following "cooking" stage if, indeed, such cooking stage is employed. In addition to establishing moisture control, the cooking stage serves to develop the curd texture. In the direct set method of curd formation, a cooking stage is generally not necessary. Subsequently, the curd is permanently separated from the whey during a "draining stage, " afterwhich the recovered curd is transformed, as by hooping, pressing and "curd knitting," and other well known techniques, . into the desired texture and other characteristics of the particular cheese which is being made. The present invention is primarily concerned with the basic step in the cheese making method^ curd formation, and provides for the capture; during such curd formation, of milk proteins and other nutrients which would otherwise be part of the whey. It is well known that simply increasing the temperature of the cream or milk during this basic step of curd formation will provide for a corresponding increase in the amount of protein contained in the resulting curd. It is also well recognized with such increasing temperatures the curd retains not only more protein but also more moisture and has an undesirably soft texture. Significantly, the desired protein retention by the curd which is achieved by the improved method of this invention does not entail a sacrifice in curd texture for its success is not dependent upon temperatures which are higher than those conventionally employed. Actually, in conventional methods, such as that used in making of Queso Blanco cheese, which purposely rely upon high temperatures during curd formation for high protein retention, albeit at a sacrifice in curd texture, the improved method of the present invention facilitates the use of lower temperatures, and thus a curd of improved texture, yet without sacrifice in the amount of protein captured within the curd. For the sake of simplicity and ease of descrip¬ tion, the present invention is hereafter described using milk and particularly in connection with the making of cottage cheese by the conventional direct set method; that is, by the direct acidification of skim milk, and employing temperatures less than milk pasteurization temperatures (161°F/72°C) and preferably not greater than about 120 β F (49°C). Reference will also be made- to the manufacture of Queso Blanco, or Latin-American white cheese , which " is formed without any starter and simply by adding an organic acid, such as, diluted glacial acetic acid, phosphoric, citric, or lactic acid, to whole milk, " or milk containing 2-3% fat, which is at a temperature no greater than about 180°F (82 °C). The milk insolubles precipitate instan¬ taneously, after which the whey is quickly removed and the curd is then salted and pressed. Specific reference to the direct set cottage cheese and Queso Blanco cheese making methods is deemed most appropriate for the use of the improvement .provided by this invention in such methods will illustrate, on the one hand, the manner of providing a cottage cheese curd having higher protein content without resorting to high temperatures and, on the other hand, the making of Queso Blanco cheese having a protein content generally as high as that made by the conventional high temperature (180 β F) method, but a more desirable texture. Further, such cottage cheese and Queso Blanco cheese making methods can be readily controlled, provide rapid results, and will make apparent to those skilled in the art the applicability of the teachings of the present invention to methods of making other varieties of cheese. Moreoveri in view of the large volumes of cottage cheese and Queso Blanco cheese which are produced, and the correspondingly large volumes of whey which result, the method of the present invention is particularly significant as it provides for the harvest of valuable proteins which would otherwise be lost in the whey. The presence of proteins in whey is a waste for whey, and particularly the acid whey which results from the direct set methods of curd formation, finds very limited uses, notwithstanding its high nutrient value. Relatively small amounts of whey find use in animal and. poultry feeds and the disposal of the remainder of such whey is an ecological problem. The discharge of whey into streams is closely regulated as its organic content greatly influences the biological oxygen demand (BOD) and too often results in loss of marine life. The problems of capturing the nutrients of whey and its suitable disposal have received considerable attention but satisfactory solutions to such problems are still lacking. One approach that, on its face, appeared to have merit, is described in Cultured Dairy Products Journal of November 1983, Volume 18, Number 4, published by The American Cultured Dairy Products Institute. In this particular issue, described by Gerald W. Smith is "Innovative Cottage Cheese Manufacturing Processes," referred by the author as the "Sir-Jay process," which involves pasteurization of skim milk, containing a stabilizer, at 195-200°F (90-93 β C), cooling the pasteurized milk to a setting temperature and adding a mineral solution, coagulator, and culture (mucor pusillus lindt), cutting the cheese curd while at a pH of 4.95-5.0, heating it for 30 minutes and cooking out the cheese curd at a temperature above 125°F (52°C). The "Sir-Jay process" is predicated upon the - /- theory that by denaturing the milk proteins at the high pasteurization temperature employed, the stabilizer, a blend of sodium caseinate and carrageenan, interconnects chains of the proteins. Thus, upon cooling of the pasteurized milk, there would no longer be casein and/or whey proteins, but a protein that was a commingled product that would have its own reaction to pH and heat. As this publication mentions known high-temperature processes for harvesting whey proteins, it is not clear whether the stabilizer, in fact, contributes to the described success of the high temperature "Sir-Jay process." Moreover, as the optimum pasteurization temperature is 161.6°F (72°C) for 16 seconds (Kosikowski), the over-pasteurization that occurs at 195-200°F (90-93°C) results in too soft a curd, as is well known) one that normally exhibits increased moisture retention. Further, the description of the "Sir-Jay process" makes no mention as to the reasons for selecting the blend of sodium caseinate and carrageenan as a stabilizer, or the proportions of the constituents of such blend and it also offers no suggestion as to the carrageenan fraction employed or its characteristics. A primary objective of this invention, which indeed distinguishes the present invention from the "Sir-Jay process," and other known similar processes, is the provision of an improved method for making cheese wherein the harvest of whey proteins is enhanced without resorting to extra ordinary high temperatures; that is, temperatures above those employed in conventional cheese making methods. Another object of this invention is the provision of an improved method for making cheese having a desirable texture and high nutrient value using iota carrageenans as a preferred carrageenan for capturing milk proteins during curd formation. Still another object is to provide an improvement - to conventional cheese making methods wherein carrageenan, and preferably essentially the iota fraction of carrageenan, is utilized in precipitating casein along with proteins which, in conventional cheese making methods, are contained within the whey that results during curd formation. A further object of this invention is to provide an improved method for making cheese having a high nutrient content, yet is soft, but not weak or mushy, and fluffy in texture and palatable. A still further and more specific object of this invention is an improvement to conventional, direct set cheese making methods wherein carrageenan, and preferably the iota fraction of carrageenan, is utilized in capturing, as part of the curd, nutrients, and particularly proteins, which are normally sacrificed with the whey that results. A still further object of this invention is an improved method for making Queso Blanco cheese at lower temperatures than conventionally employed, yet result in a cheese which possesses a more desirable texture with little, if any, sacrifice in protein content. These and other objects of the present invention are achieved by an improved method, and more particularly to an improvement to conventional methods for making cheese, wherein the setting of whole milk, milk of reduced fat content or skim milk, all of which is hereinafter ref rred to as "milk, " is achieved in the presence of an effective amount of the iota faction of carrageenan having a molecular weight (Mn) in the range of from about 80,000 to about 250,000. Present also with the iota carrageenan is a cation selected from the group consisting of sodium (Na ) , calcium -y- (Ca ), and potassium (K ), such cation being a constituent of the milk or additive incorporated and, preferably by providing such iota carrageenan in the form of one or more salts having as a cation Na +,• Ca++, or K . In another embodiment of the present invention for manufacturing cheese, the improvement involves setting milk in the presence of carrageenan to form cheese curd and whey, the milk having a solubilized calcium, i.e., ionic calcium (Ca ), content of from about 40 to 110 ppm and the carrageenan being present in an amount effective to bind to the curd at least some of the protein which would otherwise be lost with the whey. The solubilized calcium ion content of the milk, at the time the carrageenan is introduced, is critical so the solubilized calcium ion content is preferably adjusted to be within the desired range, when necessary, prior to the addition of the carrageenan. A solubilized calcium ion content of from 50 to 100 ppm Ca is preferred. Another aspect of the invention involves use of a sequestrant to adjust, or control, the concentration of solubilized calcium ion, as necessary. The sequestrant is introduced in amounts as needed to reduce the level of solubilized calcium; typically not more than 250 ppm is required. Normally the sequestrant, when required, is introduced in an amount of 50 to 200 ppm. Especially preferred as sequestrants are the polyphosphates and metaphosphates, with sodium hexametaphosphate being most preferred. The specified levels of calcium ion, present in solubilized form in the milk that is being set, are one factor that greatly influences the effectiveness of carrageenans in capturing or binding protein that would otherwise be lost with the whey. Unduly low levels of solubilized calcium in the milk can interfere with formation of casein resulting in lowered overall curd yields. Controlled addition of calcium chloride, in measured amounts as necessary, can correct a solubilized calcium ion deficiency. Excessively high levels of solubilized calcium, on the other hand, may cause co plexing with the carrageenan in a manner that results in excessive moisture retention in the curds, an undesirable result. Another factor that influences the effectiveness of carrageenan in this invention is the pH of the milk at the time the carrageenan is introduced. Fresh milk typically has a pH in the range of 6.5-6.7. For purposes of this invention, it is desirable to ensure that the milk pH is less than 6.7, preferably in the range of 6.0-6.5, at the time the carrageenan is introduced. Reactivity of the carrageenan with whey protein is enhanced at the lower pH values, so milk whose pH is above 6.7 is desirably acidulated prior to introduction of the carrageenan. This can be accomplished by simply introducing the carrageenan after the (acidic) culture has been added to the milk. Suitable acidulants include commercial culture media, as well as dilute lactic, phosphoric and acetic acids and other food grade acids. While iota-carrageenan is most preferred for use in the present invention, kappa and lambda carrageenans are also suitable. Carrageenan performance in this invention is enhanced by the carrageenan 1 s protein reactivity characteristics and is adversely affected by its water-binding or gel-forming characteristics, so the choice of a specific carrageenan must balance these two factors. As employed herein "an effective amount" of carrageenan is such as to provide for the harvest of at - - least some of the nutrients, and especially proteins, which would otherwise be included with, or lost, as part of the whey. Thus, the addition of carrageenan in an amount as low as 10 parts per million (ppm) to a source milk will provide, during the setting step, for the precipitation of at least some of the protein which would otherwise be contained in the whey and is, therefore, "an effective amount." Desiredly, amounts of carrageenan of at least 50 ppm, but not greater than about 1000 ppm, and more preferably not greater than 500 ppm and most preferably not more than 200 ppm, are employed to provide for cheeses which contain as much, if not more, of the nutrients from the source milk than is achieved by conventional cheese making methods, yet are pleasing palatable and exhibit desirable texture and other physical characteristics. In many cases, an amount of carrageenan of from 50 to 100 ppm provides satisfactory results. It should be noted that the amount of carrageenan required to effect an improved curd yield is often reduced when sequestrants are used to control the solubilized calcium ion content. Of particular significance is that of the kappa, lambda, ' and iota carrageenan fractions, the iota carrageenan is most reactive with the nutrients which, if not denatured and precipitated under high temperatures, would otherwise collect within the whey formed by conventional cheese making methods, and has been found to be particularly effective in causing the coprecipitation of whey proteins with casein in the curd while maintaining desirable textural properties. As carrageenans in the presence of a cation selected from the group consisting of Na , Ca , and K have water viscosities of not less than 5 mPa) their use in food products is permitted, and carrageenans having i water viscosities within the range of from 5 to about 25 mPa have served well in accordance with the present invention. The water viscosities of the carrageenans employed in the present invention will vary with the molecular weight thereof, within the range of from about 80,000 to about 250)000 and the cation which is present, with the latter having a greater influence than the molecular weight. In general, however) carrageenans of increasing molecular weight will exhibit progressively higher water viscosities in the presence of the same cation, Na +, Ca++, or K+,- or, stated differently, carrageenans of essentially the same molecular weight will exhibit progressively lower water viscosities in + ■ ++ ■ the presence of the respective cations K , Ca , and Na . Thus, and as illustrated by Examples hereinafter set forth) with sodium salts of the preferred iota carrageenan having molecular weights of about 80,000, 163,000, and 250,000, water viscosities of 5, 10, and 25 mPa) respectively, were obtained. The evidence is such that a reaction does indeed occur between the defined carrageenans and the proteins that, in the absence of protein precipitating temperatures, would otherwise be present in the whey which results during curd formation by known cheese making methods. While the nature of this reaction is still lacking, an explanation thereof is not necessary for one skilled in the art to reap the benefits which are derived by the use of carrageenans in accordance with this invention. The carrageenans used in this invention, in the form of a salt containing a cation selected from the +■ ++• + group consisting of Na , Ca , and K , are preferably solubilized) as for example) in water) before addition to the milk or within the milk prior to heating the same in preparation for the setting step. Such presolubilization provides for increased harvest of proteins, especially as curd formation is almost instantaneous during the direct set cottage method and the Queso Blanco method described. While the sodium salt form of the preferred iota carrageenan is cold water soluble, it is preferably presolubilized in water heated to perhaps 100-150°F, as is necessary for the calcium and potassium salt forms, to insure rapid and complete solubilization thereof. Most preferably, one or more of salts of iota carrageenan are added to the milk before the pasteurization thereof. As heretofore noted, the water viscosities will vary with the molecular weight of the carrageenan employed and. the dominant cation, Na +, Ca++, and K+, which is present. In general, carrageenans of high water viscosities appear to be less reactive with milk- proteins than carrageenans of lower water viscosities when present in relatively low concentrations, and more reactive with such proteins than the lower viscosity carrageenans when present in high concentrations. However, while the higher concentrations of the high water viscosity carrageenans are capable of harvesting more of the milk proteins, the resulting cheese exhibits less desirable characteristics. For example, cottage cheese prepared by the direct-set method in the presence of 500 ppm of iota carrageenan having a water viscosity of 10 mPa is soft and sweet and contains less protein than a cottage cheese containing 750 ppm of iota carrageenan having a water viscosity of 25 mPa which is of desired consistency but acid in taste. With reference to cheeses made from low fat or skim milk, the preferred iota carrageenan exhibits better reactivity; that is, a greater harvest of milk proteins, when fresh pasteurized milk is employed as compared reconstituted non-fat dry milk (NFDM). With further reference to the production of Queso Blanco cheese) in lieu of resorting to high temperatures ranging up to 180°F (82 β C) as are conventionally employed to provide for the precipitation of milk proteins but at the expense of curd texture, the use of the preferred iota carrageenan heretofore described facilitates the production of such cheese at lower temperatures) and thus with an improved texture, with little, if any, sacrifice in protein content. Preferably, but not necessarily, rennet extract is employed in combination with the iota carrageenans to take advantage of its well-known properties of contributing to the formation of a smooth curd, providing for desirable curd contract during cooking and is tolerant to changes in heat and pH. Rennet, the enzymatic extract from the fourth stomach of a butchered) 2-week-old) milk-fed calf, is described as being dominant among coagulators for cheese making. Its use in making Queso Blanco cheese in accordance with the present invention may be in amounts as used in conventional methods where 0.9 ml. per 1000 pounds of milk is common, although the concentration may vary within a wide range without adversely affecting the flavor of the resulting cheese. Thus, rather than employing conventional high temperatures of up to 180°F (82°C) in the making of Queso Blanco cheese, the preferred iota carrageenans, in the presence of a cation selected from the group consisting of Na +, Ca++, and K+,- as heretofore described, facilitate the use of signi icantly lower temperatures of from about 88 to 125°F (31 - 53°C) and provide Queso Blanco cheese having a good protein yield and good textural properties. Moreover, when rennet extract is employed with such iota carrageenans, it contributes to the formation of a hard curd. To further illustrate the merits of the present invention, reference is made to the following Examples which illustrate the improvement to conventional cheese making methods, and particularly the setting or curd forming step of such methods. EXAMPLE I - COTTAGE CHEESE PROCEDURE 1. Five hundred pounds water and fifty pounds spray process non-fat dried milk (NFDM) were put through a dry blender system to reconstitute the powder to 9% concentration of solids. 2. Thirty pounds of reconstituted milk was used for each batch of 14 batches. 3. pH and temperature were checked at the beginning of heating. 4. Sodium salts of iota carrageenan having molecular weights of about 80,000; 163,000; and 250,000, and water viscosities of 5 mPa (1/5); 10 mPa (1/10), and 25 mPa (1/25), respectively) were added to separate 50 ml quantities of milk, whipped in a blender for 30 seconds, and then added to the batches in amounts to provide concentrations of 250, 500, 750, and 1000 ppm. 5. Three runs were made of controls and each batch containing the different concentrations of the iota carrageenans having water viscosities of 5, 10, and 25 mPa, as set forth in the respective Tables I, II, and III, under conditions as described in steps which follow. 6. The milk was heated to 100°F (38 β C) (in a Groen jacketed kettle)) and then 65 ml of 88% lactic acid) diluted with water to 1:10, was added into the milk. 7. Coagulation of milk appeared instantaneously. 8. The contents were gently agitated for five minutes. 9. Then the whey was checked for pH. 10. The contents of the kettle were put through a strainer) where they remained for 20 minutes for draining of whey. 11. After that, the curds were checked for moisture and pH. 12. Also the weight was taken at this point. 13. Then the body and the taste of the curds was evaluated. The results achieved by following the above procedure are set forth in Tables I-V) with the results given in Table V being depicted graphically in the single figure of the drawing. From such results, the conclusions were as follows: 1. The yield of cottage cheese, made with direct acidification was increased by 10% and 17%, when 250 ppm and 500 ppm of iota carrageenan was added to the milk respectively. 2. The body and taste of the curds at 250 ppm and 500 ppm concentrations of carrageenan were desirable. At a 750 ppm concentration) the curds were criticized for being soft and acid) yet suitable for blending as with sweet fruits. Concentration of carrageenan in excess of 750 ppm were not satisfactory. 3. From the three iota carrageenans tested) that which had a water viscosity of 10 mPa (1/10) gave consistent yields at the range of 500 -17- ppm to 1000 ppm concentration. The iota carrageenan having a water viscosity of 5 mPa (1/5) decreased the yield at a higher level, while that having a water viscosity of 25 mPa 5 (1/25) increased the yield at a higher level. 4. Cottage cheese made with the same amount of acid without iota carrageenan (Control) was criticized for being too firm and acid in taste. 10 EXAMPLE II - COTTAGE CHEESE PROCEDURE 1. In 90 pounds of water, 10 pounds of one-year-old Non-Fat Dry Milk (NFDM) was added. 15 2. In another series of experiments, Fresh Skim Milk was used. 3. pH and temperatures were taken at the beginning, and at the end of heating. 4. Sodium iota carrageenan having a molecular 20 weight of about 163,000, and a water viscosity of 10 mPa (1/10), was added into a blender with 1)000 ml water, blended for one minute, and then added into the milk at a concentration of 500 ppm. 25 5. The milk was heated to 120°F (49 β C). Then, 65ml of 88% lactic acid) diluted with water to 1:10, was added into the milk. When Fresh Skim Milk was used, the amount of acid was increased to 75 ml. 30 6. Coagulation of milk appeared instantaneously. 7. The curds and whey were stirred gently for five minutes. 8. Then the whey was removed through a fine strainer which held the fine particles of the 35 curd. 9. The fines were incorporated into the curd. 10. The curds were drained for 15 minutes. 11. At the end of draining, pH was taken on the curds and the whey. 12. Weight and moisture were taken on the curd. 13. Then the body and the taste of the curd were evaluated. 14. No salt or flavorings were added to curd. 15. No pressure was applied on the curd. Table VI sets forth a comparison of the yields and other characteristics of cottage cheese which resulted when using fresh skim milk and reconstituted non-fat dry milk; the results shown in Table VII illustrate the improved yields of cottage cheese provided by solubilization of the sodium iota carrageenan prior to the addition to the milk. The conclusions arrived at from the results set forth in Table VI and VII are as follows: 1. On the basis of same milk solids (9.0%), the yield of cottage cheese made with fresh skim milk was 21% higher than the yield of the reconstituted non-fat dry milk (Table VI). 2. The quality of cottage cheese made with fresh skim milk was superior to the quality of cottage cheese made with NFDM. The texture of fresh skim milk was fluffy, while the powder produced a drier product (Table VI). 3. Presolubilization of the iota carrageenan in 150°F (66°C) water, which insured rapid and complete solubilization thereof) increased the yield of cottage cheese by 10% (Table VII) . 4. Table VII also shows that cottage cheese made with sodium iota carrageenan unsolublized provided a 12% higher yield while that which was solubilized had 23% higher yield than the one made without such carrageenan. EXAMPLE III - DIRECT SET CHEESE Curd formation was achieved by the direct set method (with aqueous HC1) using samples of pasteurized skim milk without additional heating, heated to 80°C for 30 minutes (double heated), and heated and supplied with different levels of sodium iota carrageenan- having a molecular weight of about 80,000, and a water viscosity of 5 mPa, in accordance with the procedure, as follows: 1. Dispense the sodium iota carrageenan into 100 ml aliquots of milk. 2. Heat samples to 80°C and hold for 30 min. 3. Cool to 4°C and adjust pH to 4.6 ( 1.0 ml 6N HC1). 4. Set beaker in 35°C water bath to raise temperature of curd to 30"C and hold for 30 min. 5. Cut curd with spatula and hold curd in bath for 30 min. 6. Decant whey and measure volume of whey, total solids in whey, protein by "Lowery" method and visual and tactile examination of the curd, the "Lowery" method being described by 0. H. Lowery) et al., "Protein Measurements with Folin Phenol Reagents," Jour. Biochem. 193, 265-275 (1951). The results achieved and conclusions are set forth in Tables VIII-XI. EXAMPLE IV - QUESO BLANCO CHEESE Queso Blanco cheese was prepared using reconstituted non-fat dry milk (NFDM) with and without the addition of sodium iota carrageenan having a molecular weight of about 163,000, and a water -2ϋ- viscosity of 10 mPa (l/lO)) in accordance with the procedure, as follows: 1. In 90 pounds of water 10 pounds of one-year-old commercially available non-fat dried milk (NFDM) was incorporated. 2. For each batch one-third of the reconstituted NFDM was used. 3. pH and temperatures were taken at the beginning and at the end of heating. 4. The sodium iota carrageenan, of a molecular weight of about 163,000 was added into a blender with 1,000 ml hot water at 150°F (66 β C)) blended for one minute to provide for rapid and complete solubilization thereof, and then added to the milk. 5. The milk was heated to 120 β F (49 β C) in a Groen jacketed kettle) and 65 ml of 88% lactic acid) diluted with water to 1:10, was added into the milk. 6. Coagulation of milk appeared instantaneously. 7. ' The curds and whey were stirred gently for five minutes. 8. Then the whey was removed through a fine strainer which held the fine particles of the curd. 9. The fines were incorporated into the curd. 10. The curds were drained for 15 minutes. 11. At the end of draining) pH was taken on the curds and the whey. 12. Weight and moisture were taken on the curd. 13. Then the body and the taste of the curd were evaluated. 14. No salt or flavorings were added to curd. 15. No pressure was applied on the curd. The results achieved are set forth in Tables XII and XIII and the conclusions are as follows: 1. The yield of "Queso Blanco" cheese made with sodium iota carrageenan gum was increased by 13.4%, notwithstanding the lower (120°F) than conventional (180°F) temperature employed. 2. No difference was noticed in the taste and the body of "Queso Blanco" cheese made with and without the iota carrageenan. 3. The increased yield was attributed to the precipitation of whey proteins which is facilitated by the presence of the iota carrageenan. Terms and abbreviations employed in the Examples and accompanying Tables are defined as follows: 1/5, 1/10 and l/25 refer to the sodium iota carrageenans having molecular weights of about 80,000, 163,000 and 250)000 and water viscosities of 5, 10, and 25 mPa respectively. Yield at 80% H^O is the yield of curd containing 80% water which is the accepted standard for uncreamed cottage cheese. Curd texture and taste are described in terms generally used by cheese makers and consumers as follows: Very Desirable Desirable Satisfactory Undesirable Right Soft Slightly Acid Very Soft Sweet Fluffy Sweet/Acid Acid Firm Acid/Tart Soft/Mushy TABLE I EVALUATION OF IOTA CARRAGEENAN IN THE MANUFACTURE OF COTTAGE CHEESE IOTA CARRAGEENAN WHEY CURD Yield at Water H 2 0 Yield 80$ H O Viscosity Concentration ϋ*L US. (%) (Grams) (Grams) Texture Taste CONTROL 4-42 4.76 62 1,205 1,554 Firm Acid 5 mPa .250 ppm 4-53 4.93 63 1,375 1,774 Right Sweet (1/5) 500 ppm 4-52 4.61 67 1,543 1,959 Right S eet 750 ppm 4.65 4.65 70 1,535 1,754 Soft Acid • 1000 ppm 4-93 4.41 70 1,230 1,405 Very Soft Acid/Tart 250 ppm 4-48 4.68 65 1,365 1,680 Soft Sweet 10 mPa 500 ppm 4-85 4-76 69 1,542 1,787 Soft Sweet (i/io) 750 ppm 4-80 4-78 68 1,535 1,805 Soft Acid/Slight 1000 ppm 4-71 4.82 77 1,645 1,709 Very Soft Acid/Slight 250 ppm 4-57 4.74 65 1,505 1,852 Soft Sweet 25 mPa 500 ppm 4-48 4-78 65 1,678 1,696 Soft Sweet (1/25) 750 ppm 4.57 4.92 62 1,515 1,954 Right Acid/Sl 1000 ppm 4-61 4-84 68 1,672 1,967 Soft Sweet/Acid CONTROL 4-38 4.67 67 1,232 1,471 Firm Acid TA13LE II EVALUATION OF IOTA CARRAGEENAN IN THE MANUFACTURE " OF COTTAGE CHEESE IOTA CARRAGEENAN WHEY CURD Yield at Water H 2 0 Yield 80# H O Viscosity Concentration pH pH (. ) (Grams) (Grams) Texture Taste CONTROL 4.50 4-72 64 1,350 1,687 Firm Acid 250 ppm 4-55 4-83 63 1,420 1,803 Right Sweet 5 mPa 500 ppm 4.58 4-65 66 1,600 1,939 Right Sweet (1/5) 750 ppm 4-65 4.66 68 1,650 1,940 Soft Acid 1000 ppm 4-95 4-40 70 1,320 1,508 Soft Acid 250 ppm •4-42 4-65 66 1,420 1,721 Soft Sweet 10 mPa 500 ppm 4.80 4-75 69 1,650 1,912 Soft Sweet (1/10) 750 ppm 4-85 4-75 68 1,585 1,864 Soft Acid 1000 ppm 4-72 4.82 70 1,800 2,056 Very Soft Acid 250 ppm 4-50 4-72 65 1,520 1,870 Soft Sweet 25 mPa 500 ppm 4.50 4-75 66 1,482 1,796 Soft Sweet (1/25) 750 ppm 4-58 4-92 63 1,620 2,056 Firm Acid 1000 ppm 4-60 4-85 68 1,750 2,058 Soft Acid CONTROL 4-40 4-75 66 1,330 1,615 Firm Acid TABLE III EVALUATION OF IOTA CARRAGEENAN IN THE MANUFACTURE OF COTTAGE CHEESE IOTA CARRAGEENAN WHEY CURD Yield at Water H 2 0 Yield 80.: ] * 2 o Viscosity Concentration PH (. ) (Grams) (Grams) Texture Taste CONTROL 4-44 4-75 63 1,300 1,650 Firm Acid 250 ppm 4.55 4-90 64 1,390 1,736 Right Sweet 5 mPa 500 ppm 4-55 4-62 66 1,550 1,878 Right Sweet (1/5) 750 ppm 4-63 4-67 69 1,600 1,855 Soft Acid 1000 ppm 4-90 4.40 71 1,300 1,464 Very Soft Acid - Tart 250 ppm 4-45 4.66 66 1,400 1,696 Soft Sweet 10 mPa 500 ppm 4-82 4.74 70 1,620 1,851 Soft Sweet (1/10) 750 ppm 4-82 4.77 69 1,620 1,878 Soft & Weak Slight Acid 1000 ppm 4-70 4.80 78 1,720 1,764 Very Soft Acid 250 ppm 4-56 4-75 65 " 1,495 1,840 Soft Sweet 25 mPa 500 ppm 4-46 4.75 65 1,425 1,753 Soft Sweet (1/25) 750 ppm 4.55 4-90 63 1,585 2,012 Right Slight Acid 1000 ppm 4-62 4-84 68 1,720 2,023 Soft & Mushy Acid Control 4.48 4-72 63 1,320 1,676 Firm Acid TABLE IV SUMMARY OF 42 RUNS EVALUATION OF IOTA CARRAGEENAN IN THE MANUFACTURE OF COTTAGE CHEESE IOTA CARRAGEENAN WHEY CURD Yield at % Yield Water H 2 0 Yield 80$ H O at 80# Viscosity Concentration PH PH ill (Grams) (Grams) H 2 0 Texture Taste CONTROL 4-5 4.74 63 1,285 1,564 11.43 Firm Acid 5 mPa 250 ppm 4-54 4.89 63 1,395 1,771 13.00 Fluffy Sweet (1/5) 500 ppm 4-55 4-63 66 1,584 1,924 14.13 Fluffy Sweet 750 ppm 4-64 4-66 69 1,595 1,849 13.57 Soft Acid 1000 ppm 4-92 4.40 70 1,283 1,492 10.95 Very Soft Acid/Tart 250 ppm 4-45 4.66 66 1,395 1,699 12.55 Soft Sweet 10 mPa 500 ppm 4-82 4-75 69 1,604 1,786 13-85 Soft Sweet (i/io) 750 ppm 4.82 4-76 68 1,580 1,846 13.55 Soft-Weak Slight Acid 1000 ppm 4-71 4.81 75 1,721 1,843 13.53 Very Soft Acid 250 ppm 4-54 4-74 65 1,507 1,854 13.61 Soft Sweet 25 mPa 500 ppm 4.48 4-76 65 1,528 1,748 12.83 Soft Sweet (1/25) 750 ppm 4-57 4-91 63 1,570 2,044 15-00 Fluffy Slight Acid 1000 ppm 4.61 4-84 68 1,714 2,019 15-56 Soft & Mushy Acid CONTROL 4-42 4.71 65 1,294 1,588 11.66 Firm Acid ■ TAI3LE V EFFECT OF IOTA CARRAGEENAN ON THE YIELD, BODY AND TASTE OF COTTAGE CHEESE YIELD IN % AT 80% " MOISTURE IOTA Carrageenan Concentration Water Viscosity - (mPa) Curd 1/5 1/10 1/25 Texture Taste Comments 250 ppm 13.00 12.55 13.61 Desirable Desirable Fluffy & Sweet 500 ppm 14.13 13-85 12.83 Desirable Desirable Fluffy & Sweet 750 ppm 13.57 13-55 15.00 Undesirable Undesirable Very Soft & Acid 1000 ppm 10.95 13-55 15.56 Undesirable Undesirable Very Soft & Acid CONTROL 11.55 11-55 11.55 Firm Acid TABLE VI EFFECT OF IOTA CARRAGEENAN ON THE YIELD OF COTTAGE CHEESE Fresh skim milk vs Reconsitituted Non-Fat Dry Milk (NFDM) Curd Yield Total Moisture at 80$ Solids Yield Content H 2 0 Milk . (Grams) (Grams) Texture Taste Non-Fat 1,478 72 1,641 Firm Sweet Dry Milk 9. 1,405 65 1,728 Firm Sweet (NFDM) 1,520 74 1,640 Firm Sweet Fresh 1,612 60 2,144 Fluffy Sweet Skim 9-22 1,655 64 2,064 Fluffy Sweet Milk 1,570 63 1,992 Fluffy Sweet TABLE VII EFFECT OF IOTA CARRAGEENAN ON THE YIELD OF COTTAGE CHEESE Presolubilized vs Non-Solubilized Curd Treatment Yield of Milk Moisture at 80$ Carrageenan Sample Yield Content H 2 0 (500 ppm-l/10) lbs. (Grams) (. ) (Grams) Texture Taste Not Being 35 lbs. Solubilized Fresh 1,500 61 1,960 Fluffy Sweet Skim Milk Presolubilized 35 lbs. at 150° F. Fresh 1,612 60 2,148 Fluffy Sweet Skim Milk No Carrageenan 35 lbs. Added Freeh 1,400 64 1,74 Soft Sweet Control Skim Milk TiIBLE VIII . Whey Volume Protein Total Solids Sample (ml) (mg/ml) Total (mg) (%) Past. Skim Milk 70 7.72 540.7 6.84 Past. Heated Skim Control 36 6.66 239.6 7.11 100 ppm Carrageenan 32 4.89 156.4 7.26 200 ppm Carrageenan 30 4.11 123-2 6.80 300 ppm Carrageenan . 30 5.43 162.8 6.58 400 ppm Carrageenan 28 6.46 180.9 7.62 500 ppm Carrageenan 26 3-96 103-0 6.64 Conclusions: 1. Heating pasturized milk for 30 minutes at 80 C results in 48.6% reduction in whey volume and 55 - 1% reduction in protein content in whey. 2. Adding carrageenan at any concentration reduces the whey volume, and protein content of the heated, pasteurized skim milk. TABLE IX % Whey Volume Reduction % Protein Reduction Controls Cont:rols Using Past. Using Double Using Past, <. Using Double Sample Skim Heated Milk Skim Heiated Milk 100 ppm Carrageenan 54.3 11.1 71.0 34-7 200 ppm Carrageenan 57.1 16.7 77.2 48.6 300 ppm Carrageenan 57.1 16.7 69-9 32.1 400 ppm Carrageenan 60.0 22.2 66.5 24-5 500 ppm Carrageenan 62.9 27.8 81.0 57.0 3 TABLE X Total Total Whey Vol. Solids Solids Sample (ml) (. ) (g) Past. Skim Milk 70 6.84 4-79 Past. Heated Skim Milk 36 7.11 2.56 100 ppm Carrageenan 32 7.26 2.32 200 ppm Carrageenan 30 6.80 2.04 300 ppm Carrageenan 30 6.58 1.97 400 ppm Carrageenan 28 7.62 2.13 500 ppm Carrageenan 26 6.64 1.73 Conclusion: Not only did the whey decrease, the solids content of the whey also decrease. TABL E XI Reduction in Total Solids % Over % Over Past. Sample Past. Milk Heated Skim Milk 100 ppm Carrageenan 51.7 9-4 200 ppm Carrageenan 57-4 20.3 300 ppm Carrageenan 58.9 23.0 400 ppm Carrageenan 55.5 16.8 500 ppm Carrageenan 63-9 32.4 TABLE XII EFFECT OF IOTA CARRAGEENAN ON THE YIELD OF "QUESO BLANCO" CHEESE Curd Yield at Iota PH Mois¬ Yield 10% H 2 0 Carrageenan Milk Whey Curd ture (. ) Grams (Grams) Texture Taste No Addition 6.65 4.80 4-65 66 1,340 1,421 Soft Sweet of 6.65 4-85 4.60 64 1,310 1,432 Soft Sweet (Control) 6.65 4.80 4.65 65 1,330 1,428 Soft Sweet Addition of 6.70 4.80 4-65 70 1,625 1,625 Soft Sweet 500 ppm of 6.70 4.85 4-65 69 1,650 1,673 Soft Sweet 1/10 6.70 4.80 4.65 68 1,550 1,589 Soft Sweet TABLE XIII YIELD OF "QUESO BLANCO" CHEESE MADE WITH AND WITHOUT IOTA CARRAGEENAN (Average of 3 Runs) Yield at 70$ Yield IOTA Rate of Moisture Increase Carrageenan - NFDM Reconsititution (Grams) . With 500 ppm of 1/10 10 lbs. 10. 4,887 13-4 Without 10 lbs. 10.; 4,281

Claims: CLAIMS: 1. A method for making cheese including at least the steps of setting mill., to form a curd and whey, cutting the curd, separating the curd from such whey and transforming the curd into the texture and other characteristics of the cheese desired, characterized by achieving the setting step in the presence of an effective amount of carrageena essentially of the iota 10 fraction thereof to provide for capture of at least some of the protein which would otherwise comprise part of the whey, said iota carrageenan fraction, having a molecular weight in the range of from 80,000 to 250,000. ic 2. A method as defined in claim 1 characterized in that said iota carrageenan has a water viscosity of not less than 5 mPa at a 1.5% concentration, by weight, in a water solution at 75°C. 3. A method as defined in claim 1 characterized 2 in that said setting step is effectuated in the presence of said iota carrageenan and a dominant cation selected from the group consisting of sodium, calcium, and potassium. 4. A method as defined in claim 3 characterized r, -. in that said iota carrageenan. is present during the setting step in an amount not exceeding 1000 ppm. 5. A method as defined in claim 3 characterized in that said iota carrageenan is present during the setting step in an amount ranging from 50 to 750 ppm. 6. A method as defined in claim 3 characterized 30 in that the iota carrageenan is added to the milk in the form of a salt containing a dominant cation selected from the group consisting of Na +, Ca++, and K + . 7. A method as defined in claim 3 characterized 35 in that said milk is heated to a temperature less than 82 β C and to which is added during the setting stage an organic acid selected from the group consisting of glacial acetic, phosphoric, citric, and lactic, or salts thereof. 8. A method as defined in claim 7 characterized in that said milk is heated to a temperature not greater than 49 β C and to which lactic acid is added to provide for curd formation during the setting stage. 9. A method as defined in claim 7 characterized in that rennet is also added to said milk in an amount not less than 0.9 ml. per 454 kilograms of milk. 10. A method as defined in claim 7 characterized in that said milk is heated to a temperature of not less than 31 β C. 11. A method as defined in claim 7 characterized in that the iota carrageenan is added to the milk in the form of a salt containing a dominant cation selected from the group consisting of Na , Ca , and K + . 12. A method as defined in claim 11 characterized in that said salt of iota carrageenan is solubilized prior to the addition thereof to the milk. 13. A method as defined in claim 12 characterized in that said milk is pasteurized and characterized in that said solubilized salt of iota carrageenan is added to the milk subsequent to the pasteurization thereof. 14. A method as defined in claim 13 characterized in that said salt is the sodium salt of iota carrageenan. 15. A method as defined in claim 7 characterized in that said iota carrageenan is added to the milk as a salt having a dominant cation selected from the group + ++ + consisting of Na , Ca , and K , said carrageenan salt being solubilized in water heated to a temperature not greater than 66°C. 16. A method as defined in claim 7 characterized in that said iota carrageenan has a water viscosity of not less than 5 mPa at a 1.5% concentration, by weight, in a water solution at 75°C. 17. A method as defined in claim 16 characterized- in that said iota carrageenan is present in an amount of not less than 50 ppm. 18. A method as defined in claim 16 characterized in that said iota carrageenan is present in an amount not greater than 1000 ppm. 19. A method as defined in claim 14 characterized in that iota carrageenan is present. 20. A method as defined in claim 16 characterized in that said iota carrageenan is present in an amount ranging from 250 to 750 ppm. 21. A method as defined in claim 20 characterized in that said iota carrageenan is added to the milk in the form of a sodium salt. 22. A method for manufacturing cheese characterized by setting milk in the presence of carrageenan " to form cheese curd and whey, the milk having a solubilized calcium ion content of from 40 to 110 ppm and the carrageenan being present in an amount effective to bind to the curd at least some of the protein which would otherwise be lost with the whey. 23. A method for manufacturing cheese characterized by setting milk in the presence of carrageenan and a sequestrant to form cheese curd and whey, the amount of sequestrant being adjusted to provide a solubilized calcium ion content in the milk of from 40 to 110 ppm and, further, the amount of carrageenan being effective to bind to the curd at least some of the protein which would otherwise be lost with the whey. 24. The method of claim 22 or 23 characterized in that the solubilized calcium ion content of the milk is adjusted, prior to addition of the carrageenan, so as to be within the specified concentration range. 25. The method of claim 24 characterized in that the solubilized calcium ion concentration is adjusted to be . within the range of from 50 to 100 ppm. 26. The method of claim 22 or 23 characterized in that the milk is acidulated, prior to addition of the carrageenan, to enhance the reactivity of carrageenan with whey proteins . 27. The method of claim 26 characterized in that sufficient acidulant is employed, as necessary, to reduce the milk pH to a value less than 6.7. 28. The method of claim 26 characterized in that sufficient acidulant is employed, as necessary, to reduce the milk pH to a value within the range of 6.0-6.5. 29. The method of claim 22 or 23 characterized in that the carrageenan is present in an amount of not more than 500 ppm. 30. The method of claim -22 or 23 characterized in that the carrageenan is present in an amount of not more than 200 ppm. 31. The method of claim 22 or 23 characterized in that the carrageenan is present in an amount of at least 50 ppm. 32. The method of claim 22 or 23 characterized in that the carrageenan is present as a sodium, potassium or calcium salt. 33. The method of claim 22 or 23 characterized in that the carrageenan contains a substantial portion of iota-carrageenan. 34. The method of claim 22 or 23 characterized in that the carrageenan contains a substantial portion of kappa-carrageenan. 35. The method of claim 22 or 23 characterized in that the carrageenan contains a substantial proportion of lambda-σarrageenan. 36. The method of claim 22 or 23 characterized in that the carrageenan has an average molecular weight in the range of from 80,000 to 250,000. 37. The method of claim 36 characterized in that the carrageenan has a water viscosity of not less than 5 mPa at 1.5 wt. % concentration in a water solution at 75°C. 38. The method of claim 23 characterized in that the sequestrant is introduced, as required, in an amount not greater than 250 ppm. 39. The method of claim 23 characterized in that the sequestrant is introduced, as required, in an amount of 50 to 200 ppm. 40. The method of claim 23 characterized in that the sequestrant is selected from poly hosphates and metaphosphates. 41. The method of claim 40 characterized in that sodium hexametaphosphate is employed as a sequestrant.

Inventors: WITT HENRY JOSEPH, WITT, HENRY, JOSEPH
Applicants: FMC CORP, FMC CORPORATION
Application year: 1985
Main classification: A23C9
IPC codes: A23C19