MXPA99005969A - Method of suspending insoluble calcium salts in protein compositon - Google Patents

Abstract

A method for forming a dry powder of insoluble calcium salts and protein from an aqueous composition. The process results in a dry powder that can be reconstituted in water with an unexpected extended and beneficial suspension of the insoluble calcium salts in the aqueous composition. The process includes blending the insoluble calcium salt with an agitated aqueous mixture of a protein source, either soluble or insoluble, followed by drying the resulting mixture. The resulting dry powder can be reconstituted in water or other media to produce a suspension of the insoluble calcium salts with the beneficial feature that the calcium salts do not sediment or separate.

Description

METHOD FOR THE SUSPENSION OF INSOLUBLE CALCIUM SALTS IN COMPOSITIONS PROTE I N I FIELD OF THE INVENTION This invention relates in general to the treatment of insoluble calcium salts in protein compositions to produce a dry powder which can be reconstituted in water or other medium to produce a suspension of the insoluble calcium salts with the beneficial characteristic that the calcium salts treated do not form a sediment or are otherwise separated from the prepared suspensions.

BACKGROUND OF THE INVENTION to. Calcium as Supplementary Food Calcium is a beneficial component of animal nutrition. In human nutrition, calcium should be a part of the diet from birth to death. From birth to up to young age Ref: 30648 Adult, calcium consumed as part of the diet is used for bone growth, bone density, tooth enamel, and a number of important cellular activities. For the years from adolescence to mature adults, calcium is used to maintain bone density and prevent osteoporosis. The maintenance of a routine, the daily consumption of bioavailable calcium also contributes to a low blood pressure and to reduce the incidence of kidney stones. All published nutritional guidelines recommend daily the consumption of foods that contain calcium. The recommendation varies according to the age, size, and sex of an individual with the average consumption for a recommended adult to be approximately 1,000 mg of calcium per day, see Code of Federal Regulations U.S. 101.9 (c) (8) (iv). In a recent review promoted by the state's National Institute of Health, "Calcium-rich foods such as daily products are the preferred source of calcium, calcium-fortified foods and calcium supplements are other means which can be reached an optimal calcium consumption in those who do not suggest this need through the ingestion of conventional foods ". See Nutrition (1995) pages 409-4117. Calcium supplements are, in general, calcium salts that are either soluble or insoluble in water. Soluble calcium salts (eg, calcium chloride, calcium lactate, calcium malate and, some extensions, calcium citrate) form relatively clear solutions when dissolved in water and have a high calcium activity. Due to the high calcium reactivity of soluble salts, they can cause undesirable effects in processed foods, such as coagulation and flocculation of proteinic somatics. Insoluble calcium salts, calcium carbonate and calcium phosphate, have low calcium reactivities and do not have undesirable reactions with other processed food components. However, the insoluble calcium salts have a greldosa or gritty texture and are completely separated from the food formulations instead of remaining homogeneously dispersed in the food. There are three general ways in which food processors and food ingredient developers treat insoluble calcium salts in order to use them as calcium supplements in foods and in order to use them in non-food applications such as pigments and covers or paper coatings. The three general forms are reduced to the particle size, to increase the viscosity or gel strength of the supplemented product, and use specialized forms of these insoluble calcium salts. These techniques are described in more detail in the following paragraphs. A method used in the preparation of insoluble calcium salts used in foods is to reduce the size of the particles. The U.S. US Pat. No. 5,205,493 describes a process for the production of a variety of grinding steps and particle selection procedures in order to produce a small, uniform particle size. , T, Bleeck and A.- E ..- H of (Chemical Processing, May 1967, page 149) describe a method for grinding and then using air classification techniques to separate and select small particles of the insoluble salt. Although small particle sizes can be obtained, it is d-i-f-íc-il to obtain high yields that are less than 1 micron. However, particles that are 1 micron in diameter still sstab_lecidañ outside Jj.quidos. Quickly, spjri because of the lack of interaction with other components and due to a relatively high particle density. The second way of suspending calcium salts insolubles in food preparations, especially in liquids, is by using gums and thickeners in order to increase the viscosity of the composition. This is exemplified by the U.S. 4,701, 329 which describes the addition of a calcium compound finely divided into mosses containing milk and guar gum. However, according to Stokes., Law., Finely divided calcium salts will still remain, but at a lower ratio than in less viscous preparations. The third way to keep calcium salts insoluble permanently or packed to the bottom of liquid suspensions is through special preparations that involve physical barriers and chemical reactions. Hirotsuka et al (J. Food Science, 1111-1112, 1127: 1984) describes the preparation of calcium-containing liposomes making use of soluble calcium salts coated with a soy lecithin membrane. This invention will be able to release reactive ions from the released protein if they are heated. The U.S. 5Y 317., 053 discloses a method for maintaining a stable, high solids suspension of calcium carbonate, using an acrylic acid copolymer and a sulfonated vinyl monomer. These compositions then do not rest or are left in the food. Rosenberg et al (Journal of Dispersion Sciences and Technology, 1989, 241-250) describes the use of an anionic polysaccharide as a dispersing agent for finely divided calcium carbonate.

Highly concentrated calcium carbonate suspensions can be maintained at a viable consistency using this invention, but, in foods, calcium supplements are not concentrated which limit the utility of the invention for food compositions. Li and Cho (US Pat. No. 4,642,238) describe a process for maintaining calcium phosphate from the placement of aqueous suspensions by the first elaboration of a hydrated gel (not particles) of calcitium phosphate, then adding soy protein. -a -to the hydrated gel, and finally dry the soy protein supplemented with calcium phosphate. The product dried by this process can then be reduced. í1 a liquid food with improved suspension of the calcium supplement. The process described by Li and Cho requires the careful preparation of a calcium phosphate gel, which was washed and centrifuged several times to remove excess reagents. Due to the high water content of the gel (05%) the soy protein blend and the hydrated gel are also high moisture content, so the subsequent drying of the mixture must be carried out under the same conditions. ideals of a high solids content. The soy protein that contains calcium phosphate has a calcium content that -v-ar-ia of 1.5% -5.0% -per weight of the protein. It should be desirable to use commercially available raw materials quickly, to prepare and wash the specialized calcium phosphate gel, and to extend the content of calcium or calcium to the proportion of protein at very high levels suitable for use as a supplement. in other foods. There are three significant differences between the teachings of Lin and Cho (4,642,238) and the invention described here. First, 4,642,238 reports that a hydrated calcium phosphate gel is required and a dry mineral supplement np provides the envenomic properties of the suspension. It has been found that mineral supplements, especially calcium carbonate and calcium phosphate, can be used in accordance with the process of our invention. Second, 4,642,238 reports that an eroded suspension is achieved before and after drying the composition. It is found that the desired benefits of the suspension are obtained only after the drying of the pomppsj.pj.pn .. le-jc jp 4,64,2,2 8 reports a calcium at a protein ratio of approximately 0.05 while, it is found that the calcium to protein ratios are as high as possible 3.16. "b. Proteins used in Foods A variety of proteins are used in the formulation and production of processed foods. Proteins are used for two main reasons. First, they are used to provide desirable sensory or functional characteristics, and these include; emulsion stability, texture, appearance, sensitivity to the mouth, taste and physical stability during production, storage and preparation for consumption. Second, proteins can be included in formulations for processed foods for nutritional purposes. That is, approximately 50 grams of high quality diet protein should be consumed daily as part of a diet. Foods that are high in protein are used by processing ingredients to prepare protein concentrates and isolated proteins. These proteins contain ingredients that can be from 25 to 95% protein, in a dry base, and can for example be in the form of: milk and dry milk, concentrates of milk proteins and concentrates xie dry milk, protein fractions of milk such as casein and whey, concentrated soy protein and soybean isolates, egg albumin, plasma and meat extracts for concentrates, protein and nut flavor concentrates derived from them, fish and fish protein concentrates, and a number of others. Apart from milk, most of these protein sources are not good sources of calcium. Some proteins can be isolated from food by the precipitation of proteins with an acid treatment. The preparation of soy protein isolates and the preparation of milk proteins, especially casein, typify this type of isolation technique. The proteins are precipitated at or near the isoelectric point of the protein, usually around pH 4.5. These acid precipitates are washed to remove oils, carbohydrates, and other soluble materials and are then either dried or can be neutralized with a variety of food grade alkaline agents to produce high functionality food ingredients. If the alkaline used is calcium hydroxide, Ca (0H) 2 then, for example, an isolation of a calcium caseinate or a calcium soybeans can occur. These calcium-containing, neutralized proteins are also good sources of bioavailable calcium, but there is a limit to the amount of calcium that can be provided per gram of protein, this limit dictated by acid treatment and the buffering capacity of the acidic protein is It produces as a precipitate. It may be highly desirable that ingredient manufacturers be able to provide proteins which retain their well-understood characteristics, but which also contain a high level of calcium adequate to provide supplemented calcium in the form of a stable and homogeneous suspension.

C. Calcium level in milk proteins The calcium in milk is provided by a natural colloidal suspension of calcium phosphate in a complex structure involving casein aggregates or caseinates. The ratio of calcium to protein in milk is approximately 35 mg of calcium per gram of protein or 3.5 grams of calcium per 100 grams of protein. This colloidal suspension is solubilized and removed during the preparation of the casein of the precipitated acid. When acid casein is reneutralized with silt, Ca (OH) 2, the maximum level of calcium that can be reached is approximately 1.4 to 1.5 grams of calcium per 100 grams of protein. It may be highly desirable to prepare casinates and other isolated proteins with higher levels of calcium, in order to equal or exceed the 0.035 ratio of calcium to protein found in milk. Calcium caseinates are less soluble than caseinates made by neutralizing acid casein with a monovalent base such as sodium hydroxide, NaOH, or potassium hydroxide, KOH. Due to the limited solubility of calcium caseinates, they do not have the same functional attributes of soluble sodium caseinate. That is, calcium caseinates do not have the body, mouth sensitivity, viscosity, adhesive or emulsion characteristics and foam stabilization properties of most soluble sodium caseinates. It may be highly desirable to prepare calcium caseinates which have a high calcium level and which also have the functional attributes of the more soluble sodium caseinates. Coprecipitated milk protein is an insoluble form of both, casein and whey proteins. Coprecipitate derives its name from the fact that usually insoluble whey proteins are collected as precipitates along with the casein under conditions in which they are coprecipitated. There are two days to elaborate the coprecipitated. In the first case, skimmed milk is heated to >90 ° C and then calcium chloride, CaCl2, added to the hot milk to cause both whey and casein proteins to precipitate together; the precipitate is then washed and dried as a co-precipitate. This technology and processing has been reviewed in two articles (Mulle, LL Hayes, JF, and Snow, N. Studies on coprecipitates of milk proteins, Part J. Manufacture with varying calcium contents, Aust. J. Dairy Technol., 22, 12 , 1967, and Buchanan, RA Snow, NS and Hayes JF The elaboration of "coprecipitated calcium" Aust J. Dairy Technol, 20, 139, 1965). The second way of preparing milk protein coprecipitates is described in U.S. Pat. 4,376,072 (March 8, 1983) which illustrates methods for hot treatment and pH adjustments necessary to precipitate whey proteins at the isoelectric point of casein, pH 4.5. This coprecipitated fruit set is washed, dried and can be neutralized with any type of food grade alkaline agent. The second method produces a product called Total Milk Protein, TMP, available from New Zealand Milk Products. For milk protein coprecipitates, prepared with CaCl2, the calcium to protein ratio can be as high as 0.05 and for neutralized Ca (OH) 2 / TPM, the ratio of calcium to maximum protein is about 0.015, or lower than the one of milk. It may be desirable to be able to produce milk protein coprecipitates and functional variations thereof with calcium to protein ratios exceeding those of milk and exceeding those left for current technology. Milk cream can be processed using filtration membranes to remove water and water soluble components, such as lactose and soluble minerals. The ultrafiltration process produces so-called Milk Protein Concentrates, which retain most of the natural casein, calcium and phosphate. In the preparation of food products, milk protein concentrates are used where non-fat milk is used and where lactose from non-fat milk is either undesirable or not required. Ultrafiltration, however, reduces the calcium to protein ratio. In spite of milk protein concentrates with high protein levels and very low levels of lactose, they can be produced by extensive ultrafiltration processing, these milk protein concentrates have a low calcium to protein ratio compared to milk. Table I below lists non-fat dry milk and some of the milk proteins, commercially available along with their calcium contents and the calcium to protein ratio.

TABLE. 1 Ingredient Calcium as% Protein as% Calcium / Protein Non-fat dry milk 0.123 3.5 0.035 Concentrate of Milk Protein 1.8 56 0.032 Milk protein concentrate 2.2 81 0.027 Calcium Caseinate 1.4 90 0.015 Co-precipitated milk protein 3.0 86.4 0.035 Isolated Soy Low 90 < 0.01 Calcium carbonate 40 0 Na Trisodium calcium phosphate 39 0 Na It may be very desirable to produce milk protein concentrates with high protein contents with a low level of lactose and with a higher level of calcium than current technology allows so that these ingredients can be used to provide high levels of calcium as well as a high quality protein A process for making ingredients high in calcium having all the desired attributes mentioned above has been found. The products of this invention contain higher levels of calcium than here obtained by any method. The calcium-containing proteins of this invention are calcium-containing proteins not similar to the described technique in that the new products have solubility, viscosity, and emulsion-like characteristics similar to the sodium forms of proteins, which still have opaque characteristics of the calcium forms of the protein. Quickly available food ingredients and standard processing equipment are used. Using ingredients high in calcium and formulations are not adversely affected by heat or retort processing, while milk proteins, milk protein concentrates, coprecipitates of milk protein, and soy isolate can used in the preparation of calcium supplements that do not sediment in processed foods, those skilled in the art will recognize that other proteins and combinations of proteins may also be used. Likewise, calcium carbonate and calcium phosphate have been used, and those skilled in the art will recognize that combinations and other anionic and cationic salts can be used beneficially.

BRIEF DESCRIPTION OF THE INVENTION A calcium and protein composition suitable for use in foods supplemented with calcium of any viscosity and suitable for use also in non-food applications has been developed. The compositions that use cheap ingredients are quickly available. The processing employs equipment currently used for the manufacture or manufacture of ingredients. It has been found that by drying a suspension of an insoluble calcium salt in the presence of a protein, the insoluble salt is converted, without dissolution and without apparent chemical conversion, "to a form especially employed as a calcium supplement in processed foods in where the calcium salts settle in general, or, create instability.In these foods, the modified calcium salt of this invention remains dispersed and suspended for a much longer time than the unmodified calcium salt. Calcium also has among its desirable attributes, which do not precipitate proteins, do not form a sediment layer, do not have an ash or dusty sensitivity in the mouth, providing opacity or a white appearance, and are stable to heat treatments. Calcium can be used for liquid food supplements, i-solids, and solids, and the techniques that can be used maintain pigme of insoluble calcium salts, suspended for consistency, even coatings in fish feed. The two components of this new invention are a protein and a calcium-containing salt. These are mixed together and the mixture is dried to produce a calcium-containing protein ingredient with the increased calcium suspension properties. The protein component can originate from numerous sources, including milk and soy proteins, as well as soluble or partially soluble proteins from other foods (grains, meats, fish, legumes, plasma, nuts, eggs and microbial sources) to produce the desired effect. The form of the protein can be in monomers, polymers, aggregates, or hydrolysates. Milk, cream, white egg, grain extracts, etc., can be used in their most convenient economic forms. The dried protein preparations are suspended or dissolved in water or other liquid media. Insoluble proteins such as acid or soy casein are changed at least partially soluble by the addition of alkali oxides or hydroxides. Na, K, Ca, Mg, as well as alkaline phosphates of ammonia, citrates or carbonates are some of the alkaline agents that can be used to adjust the previous pH to the isoelectric pH. Hot treatment, chelation and enzymatic or chemical modifications can also be applied to produce a suitable protein component. Reconstitution of a dry form of the protein ingredient is not required. Casein is the protein that is precipitated from the milk by adjusting the pH of the milk to the isolelectric point of the milk protein. The precipitated protein is typically washed to remove fat, soluble carbohydrates and minerals and proteins. The precipitated casein may be dried and stored for later use or the casein may be converted from the hydrous acid to another form by treatment with alkalis, heat, salts, enzymes or other processing aids. The casein of the precipitated acid is converted to a caseinate, a more soluble functional form, by treatment with alkaline agents. Typical alkalies include Na, K, Ca, Mg or other oxides or hydroxides. The alkali salts or ammonia phosphate, carbonate or citrate can also be used. The alkaline agents can be used either separately or in combination in accordance with methods practiced by those skilled in the art.

In general, the alkali is added to a casein suspension of water insoluble acid in an amount sufficient to reach the pH of the isoelectric point, pH 4.5, or between pH 6 and 8, and more generally around pH 7. When use calcium hydroxide as the alkaline agent alone, the amount of calcium that needs to be added is indicated by the desired pH change and the neutralizing properties of this protein. Typically, calcium caseinates can be made through standard processing techniques to contain a maximum of about 1.4 grams of calcium per 100 grams of protein. An insoluble or partially soluble calcium salt is added to the previous suspension or protein solution. Calcium carbonate, calcium phosphate (in any of its various forms), and calcium citrate are three such salts, but this does not suggest that they are inclusive, all listed. The insoluble salts should have a particle diameter in the range of 0.1 to 100 microns, and preferably less than about 20 microns. Smaller particle sizes are preferred, but calcium carbonate and calcium phosphate with average particle sizes between 1 and 15 microns are suitable. The insoluble calcium salt can be added directly to the preparation of the protein in a stirred vessel, the salt can be suspended in water or other medium as a suspension, which is added to the preparation of the protein, or the salt can be added to the preparation of proteins through in-line mixing or milling in any continuous or batch operation. The small reaction seems to take place between the insoluble calcium salt and the protein, and the insoluble calcium salt can be quickly placed outside the protein and the salt mixture and the mixture is not continued stirring. Other components should be added to the mixture of protein and calcium salt (for example, carbohydrates, gums, fats, emulsifiers, salts, and those so exposed), but these are not required to obtain the desired effect of producing a stable suspension of the insoluble calcium salt. The mixture is then dried. For food use, the mixture must be pasteurized by treatment or by other means to reduce the microbial content prior to drying. Spray dryers of various configurations are typically used for this operation, but friction dryers, ring dryers, band dryers or other pieces of equipment known to those skilled in the art should also be used. The dry composition can now be used in the same way that individual components can be used with the beneficial effect that the reconstitution and use of this dry composition provide a calcium supplement that does not settle or is separated from high, medium or low viscosity products. The advantageous suspension properties appear to be due to the interactions between the insoluble calcium salt and the protein during the drying process. During this process, the removal of water or the liquid medium can provide intimate contact between the components of the mixture in a form that can not be achieved by other means. In order to more clearly describe the nature of the present invention, specific examples of the practice of the invention will be given later. It should be understood, however, that this is done by way of example and it is thought that none delineates the scope of the invention without limiting the scope of the appended claims.

DESCRIPTION OF THE PREFERRED MODALITIES EXAMPLE 1 Eighteen point fourteen grams of acid casein (ALACID 741, New Zealand Milk Products) were added to 81.64 grams of water at 1110 ° C. The pH was adjusted to approximately pH 7 by the addition of 200 grams of NaOH pellets plus 218 grams of silt. The mixture was stirred at 110 ° F or alternatively pumped through a mill for a period of 30 minutes. Fourteen hundred and forty grams of calcium carbonate CaC03, with an average particle size of 1 micron, were added directly to the mixture. Note: CaCO3 may also be added by dispersing the salt in 6,000 grams of water, or added by injecting the water dispersion of the salt through a high-wing mill. The mixture is then pasteurized (heated to 71.5 ° C and maintained for 30 minutes) and spray dried. The product elevated in calcium caseinate, dry has a protein content of 86%, and an ash content of 8%, and a calcium content of 3.8%. The calcium to protein ratio is 0.043. The improvement for the separation of sediment from the insoluble calcium salt was evaluated in two ways. Five (5) grams of the high product in dry calcium caseinate, of Example 1, was suspended in 100 grams of water. Fifteen (15) milliliters were placed in a graduated tube and the suspension allowed to remain quiescent for up to 12 hours. During that time, the volume of the white sediment was measured and noted as shown in the table below. As a control, an equivalent composition of unprocessed sodium caseinate, mixed with 1 micron unprocessed CaCO3, was also prepared and observed. The two 15-milliliter suspensions contain 0.68 grams of protein and 0.07 grams of CaCÜ3.

TABLE II Volume of Sediment (ml) Ingredients of 10 minutes 2 hours 12 hours Caseinate plus CaCO3 test not 0. 02 0. 03 0. 07 processed High calcium caseinate 0. 00 < 0 01 0. 04 processed It is noted that the maximum amount of sediments is around 0.07 milliliters, and this is observed for the caseinate plus unprocessed CaCO3. For the high calcium caseinate, the accumulation of sediment was much lower. The high calcium caseinate was also compared to a mixture of standard caseinate and unprocessed calcium carbonate in a liquid nutritional formulation containing a balanced amount of protein, carbohydrates, fats and minerals. The ingredients used to prepare the control and test formulations are given below. The test formulations were made with high calcium caseinate replacing both the standard caseinate and the calcium carbonate. In both the control formulation and the test formulation, calcium carbonate with an average particle size of 1 micron was used.

TABLE III Ingredients Control Grams Assay Grams Water 1250 1250 Maltodextrin (DE 150 150 10) Sucrose 65 65 Safflower oil 50 50 Caseinate 60 - Calcium carbonate 5.5 - High caseinate - 65.5 Calcium Lecithin 5.0 5.0 Magnesium chloride 2.6 2.6 Potassium chloride 2.5 2.5 Potassium citrate 1.7 1.7 Sodium Phosphate 1.1 1.1 Potassium Phosphate 0.6 0.6 Sodium Citrate 0.6 1.8 Moss 0.5 0.5 Zinc Sulphate 0.08 0.08 Ferrous Sulfate 0.07 0.07 The test and control formulations were prepared in the same way, processed in the same equipment, and evaluated in the same way. The liquid formulations were homogenized at 2000 psi, packaged in 10 oz glass jars, and sterilized on a rotary replicator. The maximum temperature was 250 ° F for 5 minutes. After sterilization, the characteristics of the product were noted during six months of storage at room temperature. Observations during storage showed that the formulations made with the high calcium casein have a better appearance (less sandy or greldosa) immediately after the sterilization, and this formulation also does not sediment virtually after the long term of quiescent storage.

TABLE IV Formulation Properties Attributes Standard caseinate High calcium caseinate Time = 1 week Sediment Packaged with no sediment Appearance Fine grain Soft Time = 3 months Sediment Packaged with No sediment Appearance Very few particles A few large small particles Time = 6 months Sediment Packed with white sediment None Appearance Long particles A few curds. small particles Axis l 2 High calcium caseinate was prepared as described above (Example 1) using calcium carbonate of 1 micron particle size. At four point fifty-three (4.53) grams of acid casein, neutralized in the same manner as in Example 1, twelve point twenty-four (12.24) grams of 1 micron CaCO3 were added. The mixture was pasteurized and dried as in Example 1. The dried product has a protein content of 25% and an ash content of 43%, and a calcium content of 34%. The ratio of calcium to protein was 1.36 or about 40 times that in milk. The improvement in the separation of the sediment from the insoluble calcium salt was assessed by the suspension of five (5) grams of the high calcium caseinate processed in 100 milliliters of water and observing the sediment compared to that of a similar composition of sodium caseinate. not processed plus CaC? 3. The two 15-milliliter suspensions contain 0.13 grams of caseinate and 0.62 grams of CaCO3.

TABLE V Volume of sediment (ml) Ingr «3dientes de prueba 2 minutes 10 minutes 2 hours 12 hours Caseinate not processed plus 0.02 0.02 1.0 1.8 CaC03 Example 2, calcium caseinate 0.05 0.28 high Compared with the control of unprocessed caseinate and CaCO3, the high calcium caseinate of Example 2 produced less sediment over a long period of time. It is also unexpected that a small amount of a protein will be able to improve the suspension characteristics of a relatively large amount of insoluble CaCO3. Because the sediment was evident in the control mixture of unprocessed caseinate and calcium carbonate, the mere presence of caseinate was sufficient to produce the observed benefit.

Example 3 Elevated calcium caseinates were prepared as described in Example 1, but using either 1 micron, Example 3A; or 5 microns, Example 3B; or calcium carbonate with a particle size of 14 microns, Example 3C. The particle sizes provided here are the average particle diameters reported by the supplier, ECC America, Inc., a Division of ECC International. The spray dried products all have similar compositions: the protein was 85%, the ash was 8%, the calcium was 3.8% and the calcium to protein ratio was 0.043. The improvement in the sediment separation of the insoluble calcium salt was evaluated by suspending 0.75 grams of the dry product in 15 milliliters of water and observing and measuring the amount of sediment compared to a control suspension of mixed unprocessed sodium caseinate. with the calcium salt not processed at the same concentrations.

TABLE VI Test Ingredients Sediment Volume (mi; minutes 2 hours 12 hours Unprocessed caseinate Plus 1 0.02 0.03 0.07 micron CaC03 Example 3A Calcium Caseinate 0.00 < 0.01 0.04 Elevated Caseinate unprocessed plus 5 0.02 0.05 0.07 microns CaC03 Example 3B Calcium caseinate 0.01 0.03 0.06 high processed Calcium caseinate - not processed plus 0.04 0.07 0.08 14 microns CaC? 3 Example 3, Calcium Caseinate 0.03 0.06 0.08 High Processed Two of the three ingredients (3A and 3C) were used in the preparation of liquid formulations containing a balanced amount of protein, carbohydrates, fats and minerals. The ingredient levels in the formulations were similar to those shown in the table of ingredients in Example 1, except that the test products were made with the high calcium caseinates of Examples 3A and 3C. Observations were made during the storage of these formulations for up to six months.

TABLE VII Formulation properties after preparation and storage High calcium caseinate Attributes Caseinate standard 3A 3C Plus 1 micron (with 1 micron (with 14 micron CaCO3 CaCO3) CaCO3) After 1 week Sediment Packed, None None White sediment, Appearance Fine grain Soft Fine grain After 3 months Sediment Packing, white sediment, None none Appearance Many Particles Some few Large particles large small particles After 6 months Packed Sediment, None A few sediment white white particles Appearance Large particles, A few large particles, coagulated small coagulated particles Unexpectedly, formulations containing high calcium caseinates made with 1-micron (3A) and with 14 microns (3C) calcium carbonate of average particle size did not show any sediment even after six months of quiescent storage while the formulation containing 1-micron calcium carbonate, unprocessed, quickly accumulated an obvious white sediment that was difficult to resuspend. The overall appearance of the liquid was also improved when elevated, processed calcium caseinates were used in the formulations (Examples 3A and 3C). There are smaller grains immediately after sterilization, and homogeneous grains remaining for a very long time during storage than the control product which was made using unprocessed caseinate and calcium carbonate.

Example 4 The high calcium caseinate was prepared as described in Example 1, above, but with tricalcium phosphate (Fortitech, micronized at 15 microns) as the insoluble calcium salt. Calcium phosphate was selected because it is commonly used as a calcium supplement and because both calcium and phosphates are complementary parts of a balanced diet. The product of high calcium caseinate, dry, has a protein content of 86%, an ash content of 8% and a calcium content of 3.8%. The calcium to protein ratio was 0.043.

The characteristics of the high calcium caseinate sediment was compared to the characteristics of the sodium casein and non-processed calcium phosphate sediment and compared to the high calcium caseinate of Example 3C made with 14 microns of calcium carbonate.

TABLE VIII Volume of Sediment (ml) minutes 2 hours 12 hours Unprocessed caseinate Plus 15 microns of Ca Phosphate 0.06 0.10 0.14 Processed High Calcium Caseinate (Example 4) 0.00 0.02 Q.Q7 Processed High Calcium Caseinate (Example 3C) 0.03 0.06 0.08 The unprocessed 15-micron calcium phosphate quickly settles out of a standard, unprocessed sodium casein suspension. When the 15-micron calcium phosphate was dried in the presence of casein and then reconstituted in water, the processed insoluble calcium salt remained in suspension longer than the unprocessed calcium phosphate and longer than the insoluble calcium carbonate processed. of about the same particle size.

Example 5 Eleven point thirty-three kilograms (twenty-five pounds) of milk protein concentrate (ALAPRO 4560, New Zealand Milk Products), which is a powder product with a protein content of 56%, was added to 127 kg. (280 pounds) of water at 43 ° C (110 ° F). After 15 minutes and without the addition of alkali or acid, the pH of the product was about 6.7. To this was added 579 grams of CaCO3 (particles of 1 miera) suspended in 3,000 grams of water. Alternatively, the calcium carbonate suspension can be added to the reconstituted milk protein concentrate by circulating through a colloid mill. The mixture was pasteurized (heated to 72.2 ° C (162 ° F) and maintained for 30 minutes) and then spray dried. The dry, high calcium dairy product had a protein content of 535, an ash content of 9.9%, and my calcium content of 3.8%. The ratio of calcium to protein is 0.072, or twice the ratio found in milk.

The progress for sediment separation was tested by turning suspension 0.75 grams of the dried product into 15 milliliters of water and observing and measuring the amount of sediment compared to the control suspension of unprocessed milk protein concentrate mixed with calcium carbonate. not processed in the same concentrations.

TABLE IX Test Ingredients Sediment Volume (ml) 10 minutes 2 hours 12 hours MPC not processed More 1 miera of CaCQ3 0.02 0.03 0.08 MPC of High Calcium Processed, Example 5 0.00 0.00 O.Ol The unprocessed calcium carbonate quickly produces a sediment in a water suspension of milk protein concentrate (MPC), while the smaller sediment was observed with the high calcium milk protein concentrate using this technology. It is also expected that skimmed milk and pasteurized whole milk will help the character of the sediment in the same way as the milk protein concentrate.

Example 6 Eighteen point fourteen kilograms (forty pounds) of dry Total Milk Protein (TMP) powder (New Zealand Milk Products) were added to 81.64 kilograms (180 pounds) of water at 43 ° C (110 ° F). The pH was adjusted to approximately pH 7 by adding 200 grams of NaOH pellets plus 218 grams of quicklime. The mixture was stirred at 43 ° C (110 ° F) and pumped through a colloid mill for a period of 30 minutes. Fourteen hundred and forty grams of calcium carbonate, CaCO3, with an average particle size of 1 miera were dispersed in 6.000 grams of water and were added to the TMP through the colloid mill. The mixture was pasteurized. (heating to 71 ° C (160 ° F) and maintained for 30 minutes) and then spray-dried. The composition of the product was similar to that of the high calcium caseinates in Examples 1, 2 and 3. The powder was 86% protein, 8% ash or residues, and 3.8% calcium, and the ratio of calcium to proteins was 0.043, the same as for the casein examples. The separation of sediments from the processed calcium carbonate was tested by returning 0.75 grams of the dry powder of Example 6 in 15 milliliters of water and observing the amount of sediment.

TABLE X Sediment Volume (ml) Test Ingredient 10 min. 1 hr 2 hrs 12 hrs Total Milk Protein Processed with CaCO3 0.00 < 0.01 < 0.01 0.01 Primarily no sediment was observed for the reconstituted powder of Example 6, while the unconjugated CaC03 control mixtures in Examples 1, 2, and 3 showed three to ten times much sediment. Although the types of milk proteins (casein plus serum) are similar for the Milk Protein Concentrate (Example 5) and for this coprecipitation (TMP, Example 6), the interactions between whey and casein are different for the two ingredients of proteins. It is not known whether the presence of whey proteins, or whether the presence of soluble protein aggregates, or whether completely different main motifs can be used to explain the highly beneficial effects that this invention provides when the insoluble calcium salts are dried in the presence of a combination of casein and serum.

Example 7 Eleven point thirty-four kilograms (twenty-five pounds) of soy isolate protein (Supro 1500, Protein Technologies, International) were dispersed to 127 kilograms (280 pounds) of water at 43 ° C (110 ° F). After stirring for 15 minutes, the pH was measured to 6.8, more or less, and 1.080 grams of CaCO3 (particles of 1 miera ECC) mixed with 5,000 grams of water were added to the isolated soybean through the colloid mill. The mixture was stirred for 15 minutes, pasteurized (heated to 72.2 ° C (162 ° F) and maintained for 30 minutes), and spray dried. The composition of the product was 80% protein, 8% ash, and 3.7% calcium. The ratio of calcium to proteins was 0.046, which is higher than the ratio of calcium to protein in milk (0.035) and close to that of the high calcium caseinates of Examples 1, 2 and 3. The separation of the sediment from the Calcium salt was measured by suspending 5 grams of the product of Example 7 in 100 milliliters of water and observed the sediment that was collected when 15 milliliters of this preparation was allowed to stand or settle inactive for 12 hours.

TABLE XI Sediment volume (ml) 10 min, 1 hour 2 hours 12 hours Processed Isolated Soybean With 1 Miera of CaC03 0.00 0.0 0.0 < 0.01 None of the insoluble CaC03 settled out of the resuspended elevated calcium soybean isolate. The high calcium soy isolate was also formulated into a beverage similar to that described in Example 1. The formulation was packed in 10 oz glass jars and sterilized by the retort process or treatment boiler described in Example 1 During six months of storage, no sediment was observed. From these examples, it is clear that the various types of food proteins can be supplemented with the two main types of insoluble calcium salts, and it should be obvious that the proteins in addition to those of the milk or soy should also be suitable for prepare calcium supplements with the desired suspension characteristics. Other protein sources that could be used by those familiar with the technique include ingredients that contain protein, or protein concentrates, or protein extracts with or without fat, carbohydrate, and other minerals. The beneficial suspension characteristics of the Milk Protein Concentrates supplemented or supplemented with calcium (Examples 5 and 6) indicate that the same technique could be used to prepare powdered milk supplemented with calcium, either with or without fat, which then It is reconstituted or used in other processed foods. This can also be one of the main beneficial uses of this technology and invention. The elevated calcium proteins made by this invention retain desirable functional attributes while also providing a high level of calcium. The high-level or high-calcium caseinates of Examples 1 to 3, for example, they are really sodium caseinates with characteristics of solubility, viscosity and stabilization of the calcium casein emulsion, but they also form opaque dispersions similar to calcium casein and they contain more calcium than a typical calcium caseinate made by the technology of conventional processing. The product of Example 2 shows that the insoluble calcium salts can be modified to greatly improve their suspension characteristics by drying these salts in the presence of up to a small amount of protein. The product of Example 2 could be used not only as an ingredient to manufacture or produce processed foods, but also as a calcium supplement dispersible by addition to prepared foods, for consumption as a compressed tablet, for confections or supplementary gums, for bleaching or grout of coffee and tea, and as an anti-fragrancing ingredient of cake or powdery sediment on grated cheese. This high-level, low-calcium protein product can also be useful in the pigment, paper coating, paper filling industries, where an insoluble calcium salt of small particle size, easily dispersible, which does not settle quickly from the suspension and that contains a type of protein adhesive (casein or soy isolate) may provide unique benefits for processing or product quality in those particular industries. The numerous food products could benefit by having an easily dispersible calcium supplement which remains homogeneously distributed in the composition. Dairy and analogous products such as milk, milkshakes, yogurt, cheese and sour cream, can be supplemented homogeneously with more calcium that they are commonly released. Beverages and dry mixes for making or producing beverages can now be supplemented with bioavailable calcium that does not settle or is not very sandy or cretaceous. Processor foods, confections, bakery items that typically use a protein source from soy, eggs, milk or grains can now obtain the same attributes using a high calcium protein from the same source. The opacity feature of this invention can be used by those skilled in the art by providing visual appeal to low-fat foods or to produce a coffee bleach which also delivers calcium to a cup of coffee to be equivalent to drinking eight ounces of milk. While the foregoing provides a full and complete description of the preferred embodiments of the invention, various modifications, alternate constructions and equivalents may be employed, as desired. Therefore, the foregoing description and examples will not be construed as limiting the scope of the invention, which is defined by the appended claims.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which refers to the manufacture of the objects to which it refers. • Having described the invention as above, the content of the following is claimed as property.

Claims (20)

1. A process for improving the aqueous suspension characteristics of an insoluble calcium salt, characterized in that it comprises the steps of: mixing a protein source with water; adding a calcium salt generally insoluble to said mixture, wherein the protein solution or suspension is heated to a temperature in the range of about 110-195 ° F; and dry the mixture

2. A process according to claim 1, characterized in that the calcium salt, which is generally insoluble, is selected from at least one of calcium carbonate, calcium phosphate and calcium citrate.

3. A process according to claim 1, characterized in that the protein source is soluble or partially soluble or prepared from an insoluble protein by adjusting the pH above or below the isoelectric pH.

4. A method according to claim 3, characterized in that the source of protein is an acid casein, a milk protein coprecipitate, or an acid soy protein concentrate or isolate.

5. A method according to claim 3, characterized in that the protein source is selected from milk, milk protein concentrate, sodium caseinate, calcium caseinate, isolated milk protein, and soy protein concentrate or isolate.

6. A process according to claim 1, characterized in that the mixture containing the calcium salt is pasteurized by heating to about 160 ° F for about 30 minutes.

7. A process according to claim 2, characterized in that the calcium salt in general insoluble is calcium carbonate.

8. A process according to claim 2, characterized in that the calcium salt generally insoluble is tricalcium phosphate.

9. A process for obtaining a dry powder from an aqueous composition which can be reconstituted in water to produce a stable suspension of an insoluble calcium salt, characterized in that it comprises the steps of: mixing a protein source with water; mixing a calcium salt generally insoluble with said mixture, wherein the protein solution or suspension is heated to a temperature in the range of about 110-195 ° F; and drying the mixture, the resulting dry mixture is adapted for reconstitution in water with an increased time of a suspension of said insoluble calcium salt without producing visible sediment.

10. A process according to claim 9, characterized in that the insoluble calcium salt is selected from at least one of: calcium carbonate, calcium phosphate and calcium citrate.

11. A method according to claim 9 characterized in that the protein source is soluble, partially soluble, or prepared from an insoluble protein by adjusting the pH above or below the isoelectric pH.

12. A method according to claim 11, characterized in that the protein source is selected from at least one of: acid casein, milk protein coprecipitate and concentrate or acid soy protein isolate.

13. A method according to claim 11, characterized in that the source of protein is selected from one or more of milk, milk protein concentrate, sodium caseinate, calcium caseinate. Isolated milk protein, and concentrate or soy protein isolate.

14. A process according to claim 10, characterized in that the calcium salt in general insoluble is calcium carbonate.

15. A process according to claim 10, characterized in that the calcium salt in general insoluble is tricalcium phosphate.

16. A process for obtaining a dry powder from an aqueous composition which can be "reconstituted in water to produce a stable suspension of an insoluble calcium salt, characterized in that it comprises the steps of: mixing about 40 pounds of an acid casein with about 180 pounds of water at a temperature in the range of 110 ° F; adjust the pH of said mixture to about 7.0 by the addition of approximately 200 grams of sodium hydroxide and 218 grams of silt; stirring said mixture for approximately 30 minutes; combining 1440 grams of calcium carbonate with said stirred mixture while maintaining the temperature at 110 ° F for approximately 30 minutes and heating said stirred mixture containing calcium at a temperature in the range of 160 ° F for about 30 minutes; and drying the resulting hot mixture,

17. A product produced in accordance with the process of claim 1.

18. A product produced in accordance with the method of claim 9.

19. A product in accordance with the method of claim 16.

20. A process for increasing the aqueous suspension characteristics of an insoluble calcium salt, characterized in that it comprises the steps of: mix at least one partially soluble protein source with water; mixing a generally insoluble calcium salt selected from at least one of calcium carbonate, calcium phosphate, and calcium citrate to said mixture; heating the resulting mixture to a temperature in the range of about 110 to 195 ° F; and drying the resulting mixture at a temperature higher than 195 ° F.