FLAVORING AGENT CONTAINING ALL NATURAL COMPONENTS, AND METHOD FOR ITS MAKING

Abstract: The invention relates to a phosphoric acid hydrolyzed vegetable or animal substance that is suitable for use as a flavoring agent and does not contain undesirable chlorohydrins. The flavoring agent has a surprisingly light color and a taste that mimics the taste of flavors derived from other hydrolytic means.

Description: FLAVORING AGENT CONTAINING ALL NATURAL COMPONENTS, AND METHOD FOR ITS MAKING Background of the Invention This invention relates to a flavoring agent which contains all-natural components, and a method for its preparation by phosphoric acid hydrolysis of proteins. Recipes for the preparation of foodstuffs typically call for a combination of several ingredients to provide the appropriate, desired taste, texture and nutrient value. Such recipes also often call for the use of flavoring materials and enhancers. These may range from ingredients as simple as salt to complex materials produced by semi-synthetic methods, such as "reaction" beef flavor and chicken flavor, which are derived from the reaction products of protein hydrolysates, sugars, added amino acids, and the like. Generally, the more complex flavoring materials present in prepared foodstuffs are derived from a protein source such as soy flour. Beginning with vegetable or animal protein, which usually will be in natural admixture with complex carbohydrates such as starch, processes such as hydrolysis, enzymatic conversion, and/or reaction with a variety of natural reactants and optionally with heat, generally provide the flavor desired. Acid hydrolysis is a part of most of these processes, and it is usually accomplished commercially with hydrochloric acid. Recently, the consumer products community has become aware that the production of flavoring materials by hydrochloric acid treatment has several drawbacks. " ~ Irrespective of whether a vegetable or animal protein source is used, fats are almost always present. It is virtually impossible to effect complete removal of these fats. Consequently, hydrolysis of such fats followed by reaction between hydrochloric acid and the glycerol hydrolysis product usually results in the formation of chlorohydrins. Such chlorohydrins can also be formed by the direct reaction of the triglycerides with hydrochloric acid during the hydrolysis reaction. The chlorhydrins produced have been characterized as toxic materials, sterilants, and the like. See J. Valisik, et al. Lebensm - Wiss. Technol. , 12, 234 (1979). Several methods have been developed for the elimination of chlorohydrins from flavoring agents synthesized from protein hydrolysates. These methods either remove the fatty substances before hydrolysis or take advantage of the volatility of the chlorohydrins subsequent to hydrolysis. Nevertheless, residual chlorohydrins can remain in the hydrolyzed protein mixture and will raise questions concerning the drawbacks mentioned above. Therefore, it is an object of the invention to develop a method for the preparation of a hydrolyzed protein mixture that avoids the formation of chlorohydrins, yet may have the same or similar final concentrations of salt as generally similar products that are derived from the neutralization of a hydrochloric acid based hydrolysate. Another object of the invention is the production of a flavoring agent with controlled osmolality and inorganic salts content. Another object of the invention is the development of a flavoring agent that contains all-natural or nature- equivalent components. Yet another object is a flavoring agent containing components natural to biological systems. Summary of the Invention These and other objects are achieved by the present invention which is directed to a flavoring agent containing all natural components. The flavoring agent is a product of the phosphoric acid hydrolysis of a vegetable or animal substance. This product contains extensively hydrolyzed protein fragments and optional carbohydrate fragments that impart flavor to the product. Glycerol from the hydrolyzed fats present is, or may be, converted into the corresponding phosphate esters, which are natural components of biological systems. Consequently, the agent is : substantially free of physiologically undesirable derivatives of glycerol. Especially preferred flavoring agents include those prepared from vegetable protein, such as soy, rice, corn, wheat and potato, or their mixtures, as well as those prepared from animal protein, such as collagen and casein. The invention is further directed to a method for preparing a flavoring agent. This method includes the steps of treating a vegetable or animal substance with aqueous phosphoric acid under heated conditions to produce a hydrolyzed intermediate and neutralizing the phosphoric acid present with an alkaline earth compound such as calcium hydroxide, magnesium carbonate, calcium bicarbonate, and the like in the intermediate steps to produce the flavoring agent. Sodium chloride can then be added to mimic a flavor system comparable to that derived by hydrolysis with hydrochloric acid. This flavor system, however, will not contain the undesirable chlorohydrins. This invention is as well directed to a method whereby the phosphoric acid containing reaction mixture is neutralized with an alkali hydroxide, carbonate, or bicarbonate, such as sodium carbonate or sodium hydroxide followed by the precipitation of the inorganic phosphates with an alkaline earth chloride such as calcium chloride or magnesium chloride. The resulting mixture can be readily filtered to remove the phosphate salts and results in a solution of hydrolysate which is naturally light in color. Decoloration treatment,as is generally required when hydrolysis is accomplished by other known means, is not needed to develop this surprisingly light color according to the invention. The invention includes, in addition, a method for controlling the soluble inorganic salt content and osmolality of a flavoring agent, whereby alkaline earth bases are used to neutralize phophoric acid hydrolysates, thereby creating insoluble phosphate salts. The invention also includes a method for producing phosphoric acid hydrolysates containing soluble salts. Such agents are produced by neutralization using alkaline bases followed by addition of alkaline earth chlorides to form alkaline salts. The invention moreover includes a combination of the flavoring agent and ancillary ingredients, and a modified flavoring agent produced by heating this combination to cause reaction among ingredients and flavoring agent. The invention further includes a method for flavoring a foodstuff, which includes the step of combining the foodstuff and a flavoring agent as described above, and the flavored foodstuff produced thereby. Detailed Description of the Invention The flavoring agent of the invention meets prospective purity standards required for food ingredients made by acid hydrolysis. These standards are expected to require virtually complete elimination of chlorohydrins. The flavoring agent of the present invention meets this criterion because after processing it only contains glycerin components that are natural to biological systems. The flavoring agent according to the invention is an acid hydrolyzed protein and may include soluble carbohydrate fractions derived from the original vegetable flour, concentrate, or isolate which have survived hydrolysis. Depending on the processing modifications, and the other materials to be combined with the agent, the desired flavor notes such as beef, chicken, turkey, ham, fish, vegetable and the like can be produced. According to the method of the invention, the acid hydrolysis of the proteins of the starting material is both random and extensive. Because phosphoric acid is the hydrolysis catalyst, phosphoric esters of hydroxy- containing components in the starting material are produced. For example, the glycerol residue from fat hydrolysis could be converted by the process of the invention into the corresponding glycerol phosphate ester compound. The flavoring agent of the invention can be formulated as a solid or liquid solution. As a solid, it is prepared by spray-drying, vacuum-drying, or otherwise obtained in dry form from the preparation medium. As a liquid solution, it can be taken directly from the preparation medium, or can be reformulated as an aqueous solution from the solid formulation. Ancillary ingredients can also be added to the flavoring agent. These include wetting agents, dispersion agents, natural and semi-synthetic flavors, spices and accent agents, such as salt, sugars, monosodium glutamate, amino acids, sulfur containing a ino acids, nucleotides, nucleosides, organic acids, such as acetic acid, and the like. According to another aspect of the invention, the combination of the flavoring agent and ancillary ingredients can be heated at a temperature of no more than about 200°C to cause development of a modified flavoring agent with further flavor notes. The heating effects a reaction, such as the browning reaction, among the ingredients and agent in the combination and allows development of an aromatic, pungent taste and flavor. The heating may be accomplished neat or in aqueous solution and is conducted over a period of about 10 minutes to 6 hours or until the desired aroma is achieved. The solid or liquid forms of the flavoring agent may be combined with foodstuffs to develop the desired flavor therein. Typically, the flavoring agent can be added at any stage during the foodstuff preparation. It may be added in bulk, the foodstuff divided and packaged, or it may be combined into individual consumable portions of foodstuff as the consumer desires. Generally, an amount of from about 0.01 grams per kilogram of foodstuff to about 50 grams per kilogram of foodstuff will deliver the appropriate flavor. The amounts will adjusted according to the taste and consistency of the foodstuff. The flavoring agent of the invention is produced by treating a vegetable or animal substance with aqueous phosphoric acid. The vegetable or animal substance contains protein and optionally may contain carbohydrate. It may be derived from rice, potato, wheat, rye, corn, soy bean, cotton seed, coconut, and animal substances such as casein, collagen, fish protein, seaweed protein, and the like. Typically, in the method of making the flavoring agent according to the invention, a concentration of phosphoric acid of from about 10 percent to about 90 percent in water is combined with a vegetable or animal substance and maintained at a minimum temperature of about 40-150 β C, preferably at least about 100°C, for about at least 30 minutes to 16 hours, or until it is hydrolyzed to the desired degree. The weight ratio of aqueous phosphoric acid to vegetable or animal substance to will be in the range of from about 1:20 to about 20:1. This step produces a hydrolyzed intermediate. In the next step of the method, the free phosphoric acid and the amino acid salts thereof, which are present after the hydrolysis, are neutralized with portions of base. Several embodiments of this step include (a) neutralization with an alkaline earth base, (b) neutralization with an alkaline base optionally followed by addition of an alkaline earth salt, and (c) optional addition of alkaline salts to adjust the taste of the agent. This step produces an aqueous solution of the flavoring agent. As a further modification of this step of the method, the osmolality and inorganic salts content of the hydrolysate can be controlled through selection of the method used for its neutralization. For instance, the neutralization may be accomplished with a calcium or magnesium base. In this manner, the inorganic phosphate salts produced during neutralization will be precipitated as the calcium or magnesium salts and can be removed by filtration. This embodiment has the advantage that phosphates, which can be undesirable under some circumstances where calcium intake is to be regulated, are eliminated. In other instances, however, the presence of alkaline earth phosphates is desirable and can be accomplished according to the invention. Moreover, this process yields a calcium phosphate salt co-product in admixture with carbohydrate and protein derived fractions, which co-product is suitable for use either directly or after minor clean up, as animal or human nutrients. Alternatively, according to embodiment (b) described above, the neutralization can be performed using an alkaline base such as sodium hydroxide, followed by treatment with an alkaline earth salt such as magnesium or calcium chloride. The resultant alkaline salt thereby formed contributes to the flavor of the hydrolysate, while the alkaline earth salt can be removed . The taste and consistency of the aqueous solution of flavoring agent may be adjusted with the ancillary ingredients mentioned above such as especially sodium chloride. An especially preferred method according to the invention employs foregoing embodiment (b) wherein the alkaline earth salt is a chloride. In this preferred embodiment, the concentrations of phosphoric acid, alkaline base and alkaline earth chloride are maintained within a range of from about 10% to 30% by weight relative to total weight and about 2% to 10% by weight relative to total solids excluding alkaline earth phosphate. It has been found that these ranges cause development of a natural- flavor enhancer within the flavoring agent that augments the desired flavor obtained. It has been further found that these ranges largely contribute to production of a flavoring agent having a taste that mimics that of hydrochloric acid hydrolyzed vegetable or animal substance, but avoids production of chlorohydrins. The method of the invention produces a hydrolysate that is naturally light in color. This is surprising in view of the dark colors that are typically caused by other hydrolytic methods and the decolorization treatment that is typically needed therefor. It is believed that the combination of the phosphoric acid treatment, the concentrations of ingredients and reagents, and the neutralization provide this surprising property. This property permits the combination of the flavoring agent and foodstuff without creating discoloration or other undesirable visual characteristics within the resulting product. It significantly improves the yield of the flavoring agent and obviates the need for decolorization treatment. For embodiments of the invention in which the neutralization steps produce a flavor enhancer such as sodium chloride, there is the additional advantage of its in-situ formation. This preferred embodiment mimics flavor properties of finished flavors derived from the hydrochloric acid catalyzed hydrolysis of proteins followed by neutralization with sodium hydroxide, carbonate, or bicarbonate. Flavor enhancers such as sodium chloride are almost always present in significant concentrations in such hydrochloric acid derived hydrolysate flavored products. As obtained directly from the preparation medium, the flavoring agent is ready for use as a liquid solution. It can also be dried by conventional means such as those mentioned above to produce the solid formulation thereof. The flavoring agent according to the invention can be combined with such foodstuffs as canned tuna, prepared meats, such as sausage, frankfurters, bologna, cooked hams, prepared turkey, fish and shellfish products, soups, sauces, and the like. Following the steps for combination outlined above, the flavoring agent can be intimately mixed with any of these foodstuffs. The flavoring agent is stable, has a long term shelf life on the order of years, and does not degrade under vacuum or heat treatment of foodstuffs. Consequently, it is an appropriate ingredient for cooked and canned foodstuffs. The following examples further illustrate the invention. They are not, however, intended as limitations of the scope of the invention, which is fully outlined above. Example 1 Phosphoric Acid-Hydrolyzed Soy Flavoring Agent Into a reaction vessel were added 58.4 pounds of phosphoric acid, 19.8 pounds of water and 39.6 pounds of soy flour. The ingredients were heated to 270"F. at 60 psi for 4 hours. During this time the reaction mixture was stirred continuously. Thereafter, the reaction mixture was neutralized to pH 5.5 with calcium hydroxide. Upon neutralization, significant precipitate was produced which was filtered to yield a clear, light-colored solution. The solids content in the reaction medium (a) after cooking, (b) after pH adjustment, and (c) after filtration were respectively 53.5%, 41.3% and 12%. Example 2 Phosphoric Acid-Hydrolyzed Soy-Corn Gluten Flavoring Agent II To the reaction vessel were added 58.4 pounds of phosphoric acid, 19.8 pounds of water, 28.9 of soy flour, 10.7 pounds of corn gluten (not less than 60% protein). The ingredients were heated to 300"F at 50 to 60 psi for 16 hours. Thereafter, 29 pounds of the reaction mixture was neutralized to pH 5.84 with 7.6 pounds of sodium carbonate and filtered. This mixture was treated with calcium chloride and the pH readjusted to pH 5.5 with sodium hydroxide. Following filtration, the resulting liquid mixture of hydrolyzed protein was dried to yield a product which had a light, pleasant taste in solution. Example 3 Phosphoric Acid Hydrolyzed Soy-Corn Gluten Flavoring Agent III Alternatively, after the 16 hour treatment with phosphoric acid (as in Example 2) , 29 pounds of the reaction mixture was treated with 10 pounds of calcium hydroxide to result in a pH of 5.86. This treatment resulted in a exothermic reaction without the formation of excess foam. The mixture was filtered and sodium chloride was added to taste and the resulting product was spray-dried. Example 4 Phosphoric Acid Hydrolyzed Soy-Corn Gluten Flavoring Agent IV Alternatively, after the 16 hour treatment with phosphoric acid (as in Example 2) , 2500 mis. of 50% sodium hydroxide was very carefully added to 25 pounds of the reaction mixture. This procedure caused a violent exothermic reaction and the mixture was kept cool. After the pH stabilized at 5.75, the mixture was filtered. 2000 grams of this 54% solids filtrate was treated with 420 grams of calcium chloride resulting in the formation of calcium phosphate precipitate. The pH was further adjusted to 6.8 and the product was filtered and spray-dried. Example 5 Flavored Bologna To a ground mixture of 45 weight percent beef scraps, 35 weight percent pork scraps, 5 weight percent swollen cereal, and 5 weight percent of a mixture edible organic acid, spices, tumeric may be added about 10 weight percent of a liquid solution containing about 5 weight percent of the flavoring agent of Example 1. The mixture may be packed into natural casing and cooked at about 300°F under pressurized steam conditions for about 30 to 60 minutes to provide bologna sausage.

Claims: Claims : 1. A method for controlling the soluble inorganic salt content and osmolality of a flavoring agent, comprising: treating a vegetable or animal substance with aqueous phosphoric acid under heated conditions to produce a hydrolyzed intermediate mixture, neutralizing the phosphoric acid present in the intermediate mixture with an alkaline earth base thereby producing a flavoring agent that is substantially free of chlorohydrin derivatives of glycerol. 2. A method according to claim 1, wherein the vegetable or animal substance is a vegetable or animal protein with or without carbohydrate content. 3. A method according to claim 1 or 2, which further comprises removing a substantial portion of the inorganic phosphate from the intermediate mixture after completing the neutralization step. 4. A method according to claim 3, which further comprises combining the phosphate-depleted intermediate mixture with a flavor enhancer to produce the flavoring agent. 5. A method according to claim 1 or 2, wherein the concentration of aqueous phosphoric acid is from about 10% to about 90%, and the weight ratio of aqueous phosphoric acid to vegetable or animal substance is from about 20:1 to about 1:20. 6. A method for preparing a flavoring agent comprising treating a vegetable or animal substance with aqueous phosphoric acid under heated conditions to produce a hydrolyzed intermediate mixture, neutralizing the phosphoric acid present in the intermediate mixture with an alkaline base, and treating the mixture with an alkaline earth chloride to form an alkaline earth metal phosphate salt and an alkaline chloride, wherein the alkaline chloride enhances the flavor of the flavoring agent. 7. A method according to claim 6, wherein the alkaline base is a sodium base, the alkaline earth chloride is a calcium or magnesium chloride and the alkaline chloride is sodium chloride which is present at a concentration that enhances the flavor of the flavoring agent. 8. A flavoring agent produced according to the method of claim 1. 9. A flavoring agent according to claim 8, wherein the vegetable or animal substance is a protein. 10. A flavoring agent according to claim 9, wherein the components contained in the flavoring agent are all compounds that occur naturally in biological systems . 11. A flavoring agent according to claim 9, wherein the substance also contains carbohydrate. 12. A flavoring agent according to claim 8 which further comprises a natural flavor enhancer in combination with the hydrolyzed vegetable or animal substance. 13. A flavoring agent according to claim 12, wherein the flavor enhancer is sodium chloride that is produced during the preparation of the agent. 14. A flavoring agent according to claim 13, having a flavor that substantially mimics the flavor of a hydrolyzed protein flavor produced by hydrochloric acid treatment. 15. A flavoring agent according to claim 8, which is substantially free of inorganic phosphates. 16. A flavoring agent according to claim 8, which contains a substantial quantity of inorganic phosphates. 17. A flavoring agent according to claim 8, which mimics the taste of hydrochloric acid hydrolyzed vegetable or animal substance. 18. A flavoring agent according to claim 8, which is in solid form. 19. A flavoring agent according to claim 8, which is in liquid form. 20. A combination flavoring agent which comprises a mixture of the flavoring agent according to claim 8 and ancillary ingredients selected from one or more of the group consisting of salt, sugars, spices, emulsifiers, extenders, water, oil, monosodium gluta ate, amino acids, nucleotides, yeast autolysates and hydrolysates, nucleosides, gums, cream of tartar, vinegar, and acetic acid. 21. A modified flavoring agent comprising the reaction product produced by heating the combination flavoring agent of claim 20 at a temperature of no more than about 200 β C. 22. A flavoring agent produced according to the method of claim 6. 23. A flavoring agent according to claim 20, 21 or 22 which mimics the taste of a hydrochloric acid hydrolyzed vegetable or animal protein substance. 24. A method for flavoring a foodstuff comprising combining the foodstuff and a flavoring agent of claim 8. 25. A method according to claim 24, wherein the foodstuff is a prepared meat product, prepared fish product, a soup or a sauce. 26. A foodstuff flavored with a flavoring agent of claim 8, 20 or 22. 27. A method of producing a flavoring agent from a fat-containing animal or vegetable substance, wherein said agent is substantially free of chlorohydrin derivatives of glycerol, comprising treating said substance with phosphoric acid. 28. A flavoring agent produced according to the method of claim 27.

Inventors: CALLAHAN TIMOTHY Q, GRINDSTAFF DONALD, HERZ JACK L, CALLAHAN, TIMOTHY, Q., GRINDSTAFF, DONALD, HERZ, JACK, L.
Applicants: DELTOWN CHEMURGIC CORP, DELTOWN CHEMURGIC CORPORATION
Application year: 1989
Main classification: A23J1
IPC codes: A23J3, A23L1