WO1998019565A1

WO1998019565A1 - Edible preservative and acidulant composition

Info

Publication number: WO1998019565A1
Application number: PCT/US1997/020216
Authority: WO
Inventors: Joan K. Glascock; Barbara B. Heidolph; Louis A. Highfill
Original assignee: Solutia Inc.
Priority date: 1996-11-08
Filing date: 1997-11-07
Publication date: 1998-05-14
Also published as: BR9713332A; AR015798A1; AU5170098A; EP0938268A1; CA2270432A1

Abstract

An acidulant composition comprising hemipotassium phosphate; food products, consumable non-food products and processes for preparing or modifying these products which incorporate the acidulant composition.

Description

TITLE

EDIBLE PRESERVATIVE AND ACIDULANT COMPOSITION

BACKGROUND OF THE INVENTION

Field of the Invention

This invention relates to a novel food acidulant composition and to systems employing such composition. More particularly, the invention relates to hemipotassium phosphate exhibiting advantageous functions as a food acidulant.

Description of the Related Art

Various salts of the acids of phosphoric acid, usually orthophosphoric acid or pyrophosphoric acid are commonly employed as the acidulant in manufactured food compositions. While 100% phosphoric acid and pyrophosphoric acid are solids at room temperature, these acids have serious disadvantages in the practical applications in the manufacture of foodstuff. One hundred percent phosphoric acid is very hygroscopic and is therefore very difficult to maintain in the dry state. Pyrophosphoric derivatives are usually not acceptable due to their affect on flavor. Aside from the use of pyrophosphoric acid salts as the acid factor in leavening systems, little use is found for such compounds in the manufacture of foodstuffs. The use of sodium acid pyrophosphate as an acid factor in bakery leavening is known but an undesirable flavor has been observed.

Typically, the generally employed acids in foodstuff for the general purposes of an acidulant are organic acids such as succinic, acetic, citric, tartaric, fumaric, adipic, lactic, malic and gluconolactone . These acids are normally solid at room temperature providing ease in handling, measuring and general safe keeping in the food industry without special precautions. While orthophosphoric acid is used routinely in beverages such as soft drinks, its use in solid foodstuff manufacture is not convenient. Orthophosphoric acid is a liquid typically available in 75%, 80% and 85% concentrations. There has not been available in generally commercial quantities a solid form of phosphoric acid salt which would be acceptable as a food acidulant to replace the more expensive organic acids .

Codepending provisional application U.S. Serial No.

60/003,479, filed September 8, 1995 discloses a process for preparing hemipotassium phosphate. Co-pending application U.S. Serial No. 08/603,201, filed February 20, 1996, discloses a leavening composition comprising hemipotassium phosphate. The disclosures of these applications are hereby incorporated in their entirety into this specification.

SUMMARY OF THE INVENTION

In accordance with this invention there is provided hemipotassium phosphate which is solid at room temperature and which provides a convenient acidulant function in a wide variety of food products and consumable non-food products.

DETAILED DESCRIPTION OF THE INVENTION

This invention generally provides an acidulant composition comprising hemipotassium phosphate ("HKP"). Hemipotassium phosphate can be prepared in commercial quantities by combining mono potassium orthophosphate with phosphoric acid in equal molar amounts and heating to a temperature above 100 °C. The hot mixture is then placed in a vessel and agitated vigorously whereby the free water is removed as the mixture crystallizes. Hemipotassium phosphate crystallizes driving off any free water to produce a granular, free flowing, fast dissolving, dry material having less than about 0.3% free water.

The reaction may be represented as follows:

KH₂P0₄ + H₃PO₄ > KH₅(P0₄)₂

Hemipotassium phosphate in the form produced by the above described process is highly useful as an acidulant in manufactured foods.

The hemipotassium phosphate can be initially prepared by combining a potassium source other than the orthophosphate salt such as the hydroxide or other suitable potassium base. The convenience in providing the potassium by means of the orthophosphate salt is the reduction in the amount of free water introduced into the mixture. It has been found that the most efficient process employs the least amount of free water. There is usually free water present in the initial mixture from the phosphoric acid, which is typically only 85%, the remaining weight being water. The hemiphosphate is heated by any typical means such as a jacketed vessel or oven to a temperature in the range of from about 100°C to about 195°C. Higher temperatures may be employed, however, the hemiphosphate becomes highly corrosive at higher temperatures making the process expensive and cumbersome. Usually, the initial mixture, typically of mono potassium orthophosphate and phosphoric acid, is heated to a temperature in the range of from about 105 °C to about 120°C. The mixture is usually heated for a period of from 1.5 to about 2 hours. After undergoing the heating step, the hemiphosphate still contains free water and is relatively fluid.

The hot liquid is then placed into a suitable mixing device which is capable of providing vigorous agitation and also preferably containing cooling means. As the liquid cools, crystals of potassium hemiphosphate form, first at the sides of the vessel and then throughout the mixture. Continued agitation and cooling provides an increasingly viscous slurry of crystals and with continuous, vigorous stirring the entire contents of the vessel becomes crystalline, driving off substantially all of the free water. As the contents of the mixing vessel cools to a range of from about

25 °C to about 40°C the material becomes a free flowing powder. Immediately after cooling and crystallization, the powder can be placed in containers and shipped as substantially dry powder. Surprisingly, the free water contained in the initial mixture, after heating, is removed at ambient room conditions (25°C, standard pressure) during the crystallization step without special devices or removal steps. Thus, although the crystallized potassium hemiphosphate is found to contain very little free water, no special devices or process steps are required to achieve this result. The hemipotassium phosphate is usually sized by conventional means to comminute the material as desired, depending upon the end use.

The hemipotassium phosphate of this invention has been found to be somewhat hygroscopic at higher temperatures during extended exposure to humid air. For example, after 24 hrs . of exposure at 30°C and 74.9% relative humidity, weight gain was in the range of from 2.5% to 2.8% while exposure extending for 70 hrs. provided a weight gain of from 10.6% to 11.6%.

Clear aqueous solutions of hemipostassium phosphate can be prepared to the following concentrations at the following temperatures:

25°C 39.4%

32°C 45.7%

50°C 51.9%

60°C 63.6%

The rate of dissolution of hemipotassium phosphate at

25°C is as follows: lOg/lOOml H₂0 17.35 sec

15g/100ml H₂0 49.36 sec

25g/100ml H₂0 54.41 sec

This invention also provides a wide variety of food products and consumable non-food products comprising the dried, sized hemipotassium phosphate acidulant of this invention. "Foods" as used herein includes substances normally referred to as a food, i.e., material consisting essentially of protein, carbohydrate and fat used in the body of an organism to sustain growth, repair and vital processes and to furnish energy. "Foods" also includes substances which provide the nutritional value of food but in a form different from their natural state. Such substances include, but are not limited to, vitamins, minerals, nutritional supplements and condiments. "Consumable non-food product (s) " as used herein refers to any substance which is edible by humans and animals yet provides little or no nutritional value that "foods" would be expected to provide .

Table 1 lists examples of foods and consumable non-food products in which the preferred use level of solid hemipotassium phosphate has been determined. The use levels are given as percent by weight of the food product. In general, the levels of hemipotassium phosphate incorporated into the food products and consumable non-food products is between about 0.001% and about 10.0% by weight. In practice, any limitation to the amount of hemipotassium phosphate that can be incorporated into foods will not be a physical limitation but a regulatory limitation. Those skilled in the art recognize that levels of acidulants used in foods are regulated in most countries and allowable levels vary according to country. Although the levels listed in Table 1 have been determined to provide the desired characteristics for a food acidulant described throughout this specification, it should be understood that the levels presented for certain items may be outside the regulated amounts for those items in certain countries.

TABLE 1

The products listed in Table 1 are representative only and not intended to limit the invention in any way. Additional preferred embodiments of food products in which the acidulant of the invention can be incorporated include, but are not limited to, soy bean curd, sausage, creamed cottage cheese, dry- cured cottage cheese, buttermilk cultures, flavoring extracts, evaporated milk and nonfat dry milk, margarine, fruit butters, canned vegetables, canned juices, canned figs, fried potatoes, relishes, picante sauce, fish fillets, onion powder, seaweed based foods, molasses, fondants, bread dough, soy sauce, canned and dry mix gravies, yeast foods, and pickled, freeze dried or cured meats .

Additional preferred embodiments of consumable non-food products in which the acidulant of the invention can be incorporated include, but are not limited to, gargles & mouth wash, ice cream, sherbet, hard candy, caramels, divinity, marshmallows , honey, spices and blends, chewing gum, medicines and medicinal syrups such as cough syrup, frostings, maraschino cherries and effervescent tablets.

The invention also provides a preservative composition for food products and consumable non-food products comprising hemipotassium phosphate as well as food products and consumable non-food products comprising this food preservative composition. The preservative composition can be used, for example, in canning, packing, curing and/or freeze drying any of the food products listed above. The preservative composition can be used alone or in combination with typical food preservatives including, but not limited to, propionates, sorbates and benzoates. Thus, the invention also provides a process for preserving a food products and consumable non-food products which comprises incorporating the preservative composition comprising hemipotassium phosphate in the product. The term "incorporating" in its various grammatical forms includes all modes of preparing a food or consumable non-food product including, but not limited to, adding, combining, admixing, solvating, and salting. In a preferred embodiment of the process, the incorporated hemipotassium phosphate comprises between about 0.001% and about 10.0% by weight of the food product.

The invention also provides processes for modifying the pH of a food product or consumable non-food product which comprises incorporating an acidulant composition comprising hemipotassium phosphate in the food product. Modification of pH is useful for inhibiting the growth of microorganisms in both food products and consumable non-food products which contain moisture and for stabilizing texture, color and flavor of food and consumable non-food products.

The invention provides processes for preparing food products and consumable non-food products which comprises incorporating an acidulant composition comprising hemipotassium phosphate in the food product. In a preferred embodiment of the processes, the incorporated hemipotassium phosphate comprises between about 0.001% and about 10.0% by weight of the final food product or final consumable non-food product. Examples of such processes in which this invention would be useful include, but are not limited to, fermentation processes and brewing, frozen fruit processing, yeast stimulation, fruit peeling processing, clarifying and acidifying collagen in the production of gelatin, purification of vegetable oils, sugar refining to reduce molasses loss, egg processing, agent for preventing inversion of sucrose in candy, and for neutralizing lye in peeling operations. In general, the level of hemipotassium phosphate used in a formulation can be determined by substitution for a food's current acid based on the neutralizing value (NV) . The NV of hemipotassium phosphate is 140. For example:

Level of HKP =

(level of current acid x NV of current acid) NV of HKP

The "level" of acid in a food or non-food product can be measured as weight percent or concentration of acid in the product. Certain applications require achieving a desired pH of the final product, for example when trying to achieve a certain flavor, color or texture or for microbiological control. In these applications, HKP is added in a concentration such that the final product pH is at the target pH. This can be determined through addition and pH measurement. In general, when replacing acetic, citric or malic acids, approximately half the current acid level is required to achieve the desired effect with HKP. To replace fumaric or adipic acids, approximately 1.4 times the current acid is required. In applications where a specific flavor such as tartness or sweetness is desired, the level of HKP is added until a suitable level of flavor is achieved. These determinations are within the level of skill of those of ordinary skill in the art.

Because hemipotassium phosphate is readily soluble in water, it can be easily and quickly incorporated into foods using water based materials. Dry mixtures are prepared by incorporating the dry crystals of hemipotassium phosphate into a dry mix.

The acidulant composition of this invention can also comprise hemipotassium phosphate in admixture with other previously known acidulants which include, without limitation, organic acids such as acetic, succinic, citric, tartaric, fumaric, adipic, lactic, malic and glucono-delta-lactone, and inorganic acids such as phosphoric acid.

Typical acidulant functions of hemipotassium phosphate are microbial inhibition, flavor enhancement, texture modification, foam stabilization and phase change inducement. Although such functions are typical of food acidulants, it has been found that hemipotassium phosphate provides advantages over prior art organic acidulants. In some instances, particularly in fruit flavored beverages, the effect of hemipotassium phosphate is the same as with organic acids with respect to pH but the inorganic acid of this invention has been found to exhibit less tartness and therefore the fruit flavor is more pronounced. It has been found that in most applications the hemipotassium phosphate of this invention achieves a pH in the food product at levels of from about 20% to about 80% less than conventional organic acid acidulant. The hemipotassium phosphate of this invention has been found to provide less tartness at similar use levels than prior art organic acids to achieve the same physical characteristics. However in most applications the hemipotassium phosphate can be interchanged with prior art organic acidulants on the same weight basis, making conversion in existing recipes easy.

The following examples illustrate the preparation of compositions useful in the process of this invention. In these examples percent is expressed as percent by weight unless otherwise noted. The examples are not intended, and should not be interpreted, to limit the scope of the invention defined in the claims which follow. DESCRIPTION OF THE PREFERRED EMBODIMENTS

EXAMPLE 1

Into a suitable container were placed 581 g of mono potassium phosphate and 493 g of concentrated phosphoric acid (85%) . The mixture was agitated by means of a power mixer for a period of 5-10 minutes resulting in a viscous liquid. The liquid was then placed in an oven heated to a temperature in the range of 190°C to about 200°C. After heating the liquid in the oven for a time in the range of from 1.5 to 2 hrs., the temperature of the liquid reached 120 °C at which temperature it was removed from the oven. The liquid was again subjected to vigorous agitation by means of a power mixer whereupon crystals formed as the liquid cooled by air convection. No external cooling was applied. Crystals continued to form during cooling and when reaching a temperature in the range of from about 25°C to about 40°C the material became a free flowing powder.

The powder was analyzed (ASTM D-2761) and found to have the following analysis as percent by weight:

TABLE 2

Trimetaphosphate 0 . 10 Tripolyphosphate 0 . 08 Pyrophosphate 2 . 20 Potassium Orthophosphate 97 . 62 Recovery 99 .21 P₂0₅ 60.67

An aqueous solution (1%) of the above described composition indicated a pH of 2.24 and loss on drying at 110°C was 0.07% EXAMPLE 2 Use of HKP as an Acidulant in Jelly

An apple pectin jelly was prepared. The formula used for production of a synthetic jelly can be found in Griswold, "The Experimental Study of Foods" 1962, substituting various acids for tartaric acid. Percent sag and gel strength (using a texture analyzer) were measured. Acid solution - 4.88 gm of test acid + 10 ml water, dissolve acid in water.

Jelly - 450 gm water + 5.2 gm Apple Pectin + 775 gm sucrose

Pectin and water were mixed in a large sauce pan and brought rapidly to a hard boil, stirring constantly.

Sugar was added all at once. The solution was brought to a full rolling boil, then boiled hard for 1 minute, stirring constantly. The solution was then poured into four 250 ml beakers, each of which had 2.0 ml of the appropriate acid in it.

TABLE 3

Tartaric Citric HKP No Acid

% Sag 15.6 14.1 14.1 62.8

Reading 1 6.4 6.4 6.4 7.0

Reading 2 5.4 5.5 5.5 2.6

Texture

Analysis: 460 483 475 NA pH 2.56 2.64 2.45 3.35

Pectin was difficult to get into solution, not all was equally dispersed. The sample with no acid was more liquid than solid, there was some gel formation. 50 grams of gel and 50 ml water were blended together for pH measure. The pH of the water used in manufacturing the gels of this Example was measured at 5.60. For the percent sag measurement, the gels were formed in beakers and allowed to sit for 24 hours before measurements are taken. Percent sag is determined by inserting a skewer into the gel approximately 2 cm from the edge of the gel . The skewer was inserted making sure it remained vertically straight. The height of the gel is determined by measuring how far the skewer penetrates the gel . The gel is removed from the beaker by inverting the beaker. Immediately the height of the gel is measured with the skewer. Two measurements or "readings" are taken, "reading 1" is the height of gel in beaker and "reading 2" is the height of gel inverted and removed from beaker analyzer. The difference of the two heights expressed as a percentage of the original height is percent sag.

Percent sag =

[(reading 1 - reading 2) ÷ reading 1] x 100

Gel strength was measured using a Texture Analyzer TA- XT2 (Texture Technologies, Scarsdale, N.Y.). The instrument is set up with a 1.0 inch round lucite probe moving with a compression force of 212g at a speed of 1.5mm/sec. at a height of 6.0 cm above the testing surface. Gel strength is reported as the distance the probe travels to reach a 212g opposite force.

EXAMPLE 3 Citrus Pectin Gels

1. Pectin paste: 5.2 g CITRUS Pectin + 25 g sucrose +

75 ml H₂0

2. Acid solution: 4.88 gm of test acid + 10 ml H₂0. Dissolve acid in water.

3. Jelly: 350 gm H₂0 + pectin paste + 750 gm sucrose. Pectin paste and water were mixed in a large sauce pan and brought rapidly to a hard boil, stirring constantly. Sugar was added all at once. The solution was brought to a full rolling boil, then boiled hard for 1 minute, stirring constantly. The solution was then poured into four 250 ml beakers, each of which had the appropriate acid in it.

TABLE 4

2.0 ml 2.0 ml 1.5 ml 1.0 ml

Citric Acid HKP HKP HKP

% Sag 13.2 13.0 9.0 13.0

Reading 1 5.3 5.4 5.0 5.4

Reading 2 4.6 4.7 4.6 4.7

Texture Analysis 4.22 4.29 4.12 4.15 pH 2.49 2.34 2.42 2.51

The citrus pectin dissolved adequately when first making a paste out of the pectin sugar mixture. The gels were allowed to set 24 hrs before measurements were taken. Percent sag and gel strength were measured as described in Example 2. pH is determined by blending 50 grams of jelly and 50 grams of milling water, the pH of this mixture is taken after the electrode has set in the mixture for 1 minute.

The gel made with 1.5 ml HKP was the strongest gel based on % sag and gel strength measurements. The citric acid gel and 1.0 HKP gel had similar sag and gel strength values.

EXAMPLE 4 Apple Pectin Gels

1. Pectin paste: 5.2 g Apple Pectin + 25 g sucrose + 75 ml H₂0 2. Acid solution: 4.88 gm of test acid + 10 ml H20 Dissolve acid in water.

3. Jelly: 350 gm H20 + pectin paste + 750 gm sucrose.

Pectin paste and water were mixed in a large sauce pan and brought rapidly to a hard boil, stirring constantly. Sugar was added all at once. The solution was brought to a full rolling boil, then boiled hard for 1 minute, stirring constantly. The solution was then poured into four 250 ml beakers, each of which had the appropriate acid in it.

TABLE 5

2.0 ml 2.0 ml 1.5 ml 1.0 ml

Citric Ac:id HKP HKP HKP

% Sag 5.9 3.9 9.0 11.1

Reading 1 5.1 5.1 5.5 5.4

Reading 2 4.8 4.9 5.0 4.8

Gel Strength 4.03 3.89 3.97 4.09 pH 2.47 2.30 2.38 2.50

The apple pectin went into solution relatively easy after being made into a sugar, pectin, water paste. The physical separation of the pectin by the sugar was effective. The gels were aged 24 hours before measurements were taken. The gel made with 2.0 ml HKP was the strongest gel based on percent sag and texture analysis values. The citric acid gel values were closest to the 1.5 ml HKP gel.

EXAMPLE 5

Apple and Grape Jelly - HKP as Acidulant

Recipes for jellies made with Sure- Jell^® (Kraft General Foods, Whiteplains, NY) were examined to determine the proper ratio of pectin to sugar to be used with bottled apple juice and bottled grape juice such as Motts Apple Juice, no additives, and Welch's Grape Juice, ascorbic acid added. Sure-Jell^® is a combination of dextrose (corn sugar) fumaric acid and fruit pectin. Bottled or frozen juices usually need added pectin because the process does not extract enough pectin (Griswold, "The Experimental Study of Foods" (1962)). Some pectin will naturally be found in the bottled juices. The recipe for peach jelly was used as the basis for formulating the apple and grape jelly made with bottled juices and lab pectin. Since peach is low in acid and pectin (the synthetic jelly had all its pectin and acid added) , the amount of pectin used in the Sure Jell is believed responsible for the gel formation of peach jelly with little contribution from the juice. The recipe for peach jelly requires 3 . cup of juice for each package of Sure Jell which is twice an amount of liquid as the synthetic jelly. To make half batches of jelly either package Sure Jell (25 g) or 5.2 g pectin would be needed. The Sure Jell recipes were cut in half and 5.2 grams of pectin substituted for the Sure Jell.

Basic Recipes A B

Apple - 3 % cup juice 3 K cup juice 4 cup sugar 4 % cup sugar

25 gm Sure 5.2 gm apple pectin

Jell 2 ml acid per jar

Grape - 2 ^ cup juice 2 cup juice

3 % cup sugar 3 % cup sugar

25 gm Sure 5.2 gm apple pectin

Jell 2 ml acid per jar A . APPLE JELLY

1. Pectin paste: 5.2 g APPLE Pectin + 25 g sucrose + 75 ml juice. Dry ingredients were mixed together, juice was added and blended until achieving a paste consistency.

2. Acid solution: 4.88 gm of test acid + 10 ml H₂0 Acid was dissolved in water.

3. Jelly: 790 gm juice + pectin paste + 875 gm sucrose

Pectin paste and juice were mixed in a large sauce pan and brought rapidly to a hard boil, stirring constantly. Sugar was added all at once. The solution was then brought to a full rolling boil, then boiled hard for 1 minute, stirring constantly. The solution was then poured into four 8 ounce jars each of which had the appropriate acid in it. TABLE 6

Acid Texture pH Analysis

2.0 ml Citric 2.67 3.09

2.0 ml HKP 2.38 2.93

1.5 ml HKP 2.44 3.05

1.0 ml HKP 2.33 3.09

No Acid No gel -

Jelly made as describe above and tested eleven days later. The jars used were slightly necked in therefore the jelly could not be turned out to measure percent sag. The texture analyzer was used on the product still in the jar.

The jelly made with HKP had a strong gel based on texture analyzer results. The jelly acidified with 1.0 ml HKP had the same pH as 2.0 ml citric acid jelly.

The pH was determined by blending 50 grams of jelly and 50 grams of milling water, the pH of this mixture is taken after the electrode has set in the mixture for 1 minute .

Sensory Evaluation of Apple Jelly

Eight panelists were asked to evaluate the apple jelly using a scorecard provided to them. The panelists were presented the samples in the following order:

TABLE 7 1st 2nd 3rd 4th Panelist 1 2 3 4 GB

2 3 4 1 CR 269 = 2.0 ml citric

3 4 1 2 DG

4 1 2 3 JG 631 2.0 ml HKP

4 3 2 1 SS

3 2 1 4 SV 3) 592 - 1.5 ml HKP

2 1 4 3 KL

1 4 3 2 DM 4) 867 - 1.0 ml HKP The panelists were asked to make a hash mark across a line for each flavor parameter as a measure for that flavor. The distance from the left edge of the parameter line to where the hash mark crossed the line, was measured in centimeters. The resulting "score" for each sample is listed below in Table 8.

TABLE 8

Sample Attribute Averaqe GB CR DG JG SS SV KL DM

269 flavor 5.89 8.40 8.85 5.80 3.50 5.30 5.30 1.60 8.40 sweetness 5.86 7.10 8.70 6.00 3.60 6.40 4.80 1.80 8.50 sourness 3.30 0.10 0.70 4.50 6.85 7.80 3.85 1.80 0.80

631 flavor 6.52 4.50 8.30 5.10 3.75 3.80 7.20 10.00 9.50 sweetness 6.17 4.60 8.40 5.70 5.75 3.40 6.85 5.80 8.90 sourness 2.96 0.20 0.50 4.00 5.40 6.50 2.45 3.70 0.90

592 flavor 5.51 9.10 8.70 7.70 3.20 3.00 5.90 0.0 6.50 sweetness 5.50 4.75 8.30 6.80 6.20 3.30 5.05 0.0 9.60 sourness 2.02 0.10 0.80 4.70 3.20 4.60 1.75 0.0 1.05

867 flavor 6.18 9.05 7.50 6.00 4.95 3.15 9.40 0.0 9.35 sweetness 6.91 9.10 8.70 6.50 6.65 7.20 9.05 0.0 8.10 sourness 2.32 0.15 0.70 4.40 4.30 1.10 6.90 0.0 1.00

20

B . GRAPE JELLY

1. Pectin paste: 5.2 g Apple Pectin + 25 g sucrose + 75 ml juice. The dry ingredients were mixed together, juice was added and blended in Warring blender until achieving a paste consistency.

2. Acid solution: 4.88 gm of test acid + 10 ml H20 Acid was dissolved in water.

3. Jelly: 540 gm juice + pectin paste + 625 gm sucrose.

Pectin paste and juice were mixed in a large sauce pan and brought rapidly to a hard boil, stirring constantly. Sugar was added all at once. The solution was then brought to a full rolling boil, then boiled hard for 1 minute, stirring constantly. The solution was then poured into four 8 ounce jars, each of which had the appropriate acid in it. TABLE 9

Acid Texture pH Analysis

2.0 ml Citric 2.01 3.10

2.0 ml HKP 1.78 2.99

1.5 ml HKP 1.92 3.07

1.0 ml HKP 1.95 3.21

No Acid 2.45 3.40

Jelly was made as described above and tested eleven days later. The jars used were slightly necked in so the jelly cold not be turned out to measure percent sag. The jelly was analyzed on the texture analyzer while it was still in the jar.

The jelly made with HKP had a slightly stronger gel than the citric acid jelly, when comparing texture analyzer results. The jelly made with 1.5 ml HKP had the pH most similar to the pH of the citric acid jelly.

The pH was determined by blending 50 grams of jelly and 50 grams of milling water, the pH of the mixture was taken after the electrode sat in the mixture for 1 minute .

Sensory Evaluation of Grape Jelly

Seven panelist were asked to evaluate the grape jelly. The panelists were asked to evaluate each of the four samples for overall flavor, sweetness, and sourness using a score card. The panelists were presented the samples in random order.

Sample #1 - 1.0 ml HKP

Sample #2 - 1.5 ml HKP

Sample #3 - 2.0 ml HKP Sample #4 - 2.0 ml citric

The panelists were asked to make a hash mark across a line for each flavor parameter as a measure for that flavor. The distance from the left edge of the parameter line to where the hash mark crossed the line, was measured in centimeters. The resulting "score" for each sample is listed below in Table 10

TABLE 10

Sample Attribute Average CR JS DG JG GB SS LK

1 flavor 5.14 7.70 5.60 8.10 5.45 4.45 2.70 2.00 sweetness 6.33 7.75 7.40 5.00 2.55 4.70 7.60 9.30 sourness 2.95 0.45 5.60 4.95 7.50 0.30 1.60 0.25

2 flavor 5.13 8.40 3.60 5.80 4.95 7.80 3.30 1.60 sweetness 6.88 7.65 5.80 6.90 6.80 6.90 4.85 9.25

10 sourness 2.04 0.55 3.20 5.10 2.30 0.45 1.60 1.10

3 flavor 5.84 7.70 3.90 6.05 6.75 4.95 6.80 4.75 l I sweetness 6.24 7.90 4.05 6.40 5.15 4.85 6.70 8.60 sourness 3.61 2.20 6.45 3.70 5.15 0.55 3.00 4.20

15

4 flavor 6.01 6.95 5.70 5.80 3.95 9.05 4.70 5.90 sweetness 7.61 8.60 5.60 5.90 6.45 9.10 6.20 8.40 sourness 3.37 0.35 4.95 3.40 4.25 0.80 6.60 3.25

EXAMPLE 6 Use of HKP in Sweet and Sour Tablets

Sweet and sour tablets are traditionally made with either citric acid or malic acid. This example shows a formulation using HKP as the acid. A test mixture was initially prepared to test the "tablet-ability" of the mold made for the Carver Press.

A. Formulation.

Dextrose 87 gm

Maltodextrin 10 gm

Citric acid 1.82 mg Magnesium

Stearate 1.0 gm

Flavoring 0.12 gm (H&R Grape 230125; Harman and

Reimer)

Dextrose and maltodextrin were blended together and then the other dry ingredients were blended in. Blending was done using a mortar and pestle to crush any large crystal .

B. Tablet formation.

The following results are shown for various amounts of dry mixture and pounds of pressure examined to determine the amount needed for an acceptable tablet.

1.5 gm dry mix, 4000 psi - tablet too thick and crumbled easy.

1.0 gm dry mix, 4000 psi - tablet appropriate thickness, crumbled easy.

1.0 gm dry mix, 6000 psi 30 sec - edge of tablet crumbled off, tablet broke easy. 1.0 gm dry mix, 8000 psi/30 sec - slight crumbly edge, force needed to break.

1.0 gm dry mix, 8000 psi/60 sec - good edge, force needed to break tablet.

1.0 gm dry mix, 6000 psi/60 sec - good edge, force needed to break tablet.

Based on the above testing, one gram at 6000 psi of pressure for 60 sec was selected for tablet parameters. Repeated use of the mold of 8000 psi resulted in slight distortion of the mold plunger.

C. Sweet and Sour Tablets.

Three formulations were made differing only in the acid used:

TABLE 11

A B c

Dextrose 87 gm 87 gm 87 gm

Maltodextrin 10 gm 10 gm 10 gm

Citric Acid 1.82 gm -

Malic Acid - 1.82 gm

HKP - - 2. .57 gm

Magnesium Stearate 1.0 gm 1.0 gm 1. .0 gm

Flavoring 0.12 gm 0.12 gm 0. .12 gm pH 3.11 3.39 2.86

Dextrose and maltodextrin were blended together and the other dry ingredients were then blended in. 10 gm of the mixture was set aside for pH testing. The remainder was pressed into tablets, pouring 1 gram into mold and applying 6000 psi of pressure for one minute.

The pH was determined using 1 gram dry mix and 2.5 ml milling water, mixed until dry mix dissolved. The pH reading was taken after the electrode sat in solution for one minute. A small amount of each dry mix was tasted and evaluated for sourness :

- Citric: tart acid bite, overwhelms sweet and flavor. - Malic: mild tart, mild sweet, mild flavor.

- HKP: mild tart, sweet, mild flavor.

EXAMPLE 7 GELATIN DESSERT

Three batches of a dessert gelatin were made according to the following formulation. Percent sag, pH and gel strength were measured for each as described above.

TABLE 12

A B C

Sucrose 130 gm 130 gm 130 gm

Gelatin 12.6 gm 12.6 gm 12.6 gm

Sodium Citrate 0.7 gm 0.7 gm 0.7 gm

Sodium Chloride 0.7 gm 0.7 gm 0.7 gm

Flavor 0.18 gm 0.18 gm 0.18 gm

Color 0.02 gm 0.02 gm 0.02 gm

Fumaric Acid 3.3 gm - -

HKP - 3.3 gm 1.7 gm pH 2.81 3.13 4.48

% sag 17.1 14.3 13.6 reading #1 4.1 4.2 4.05 reading #2 3.4 3.6 3.5 gel strength 8.32 8.86 8.51

The dry ingredients were blended together. 85 gm of the dry mix was dissolved in 475 ml boiling water. The solution was mixed thoroughly until all the gelatin was dissolved. Approximately 125 ml of the solution was poured into each of four 200 ml beakers and allowed to cool to room temperature . The pH was measured for one of the samples . The other three samples were placed into a refrigerator and allowed to chill overnight before percent sag and gel strength were measured.

For each batch, the gelatin was allowed to cool slightly and then the top of each of the three beakers was covered with plastic wrap. After the gelatin had cooled to room temperature the covered beakers were placed in the refrigerator. The other beaker of gelatin was used to measure pH, without dilution, at room temperature.

The gelatin remaining after testing for gel strength was used for sensory evaluation. Three panelists evaluated the gelatin for overall flavor, sweetness and sourness. Score cards were not used, results were reported verbally.

A. 3.3 gm fumaric - very tart, sharp, good flavor

B. 3.3 gm HKP - some tartness and flavor

C. 1.7 gm HKP - sweet, lacking flavor

Our experience shows that commercial gelatin has a pH between 3.8 and 3.9, higher than the gelatin made with fumaric acid. Test gelatin (liquid) was tasted against commercial gelatin (liquid) and showed that fumaric acid gelatin was more tart than the commercial gelatin.

It was decided that the pH of the gelatins needed to be adjusted by increasing the amount of fumaric and decreasing the amount of HKP. The following dessert gelatin solutions of fumaric and HKP were checked for pH TABLE 13

HKP 1-100 2.17 pH fumaric 1-200 2.03 pH

1-150 2.23 pH 1-250 2.11 pH

1-175 2.25 pH 1-300 2.18 pH

1-200 2.27 pH 1-350 2.23 pH

1-250 2.31 pH 1-375 2.26 pH

1-300 2.34 pH 1-400 2.28 pH

The 1-200 solution is approximately the acid strength of the gelatin. The fumaric acid is a stronger acid in this pH range. The amounts of acid were adjusted by decreasing fumaric acid 20% and increasing HKP 20% to see if pH values would be closer to commercial gelatin.

Based on the experiments adjusting the pH, a second test dessert gelatin was made:

TABLE 14

A B

Sucrose 130 gm 130 gm

Gelatin 12.6 gm 12.6 gm

Sodium Citrate 0.7 gm 0.7 gm

Sodium Chloride 0.7 gm 0.7 gm

Flavor 0.18 gm 0.18 gm

Color 0.02 gm 0.02 gm

Fumaric Acid 2.6 gm -

HKP - 4.0 gm

PH 3.06 2.97

% sag 21.9 23.2 reading #1 4.1 4.3 reading #2 3.2 3.3 gel strength 8.32 8.37

The dry ingredients were blended together. 85 gm of dry mix were dissolved in 475 ml boiling water and mixed thoroughly until all the gelatin was dissolved. Approximately 125 ml of the solution was poured into each of four 200 ml beakers and allowed to cool to room temperature. The pH of one of the samples was measured. The remaining three samples were placed into a refrigerator and allowed to chill overnight before percent sag and gel strength were measured.

This formulation resulted in a less tart fumaric acid gelatin as compared to the previous formulation. Since commercial gelatins are a blend of acids such as fumaric and adipic acids, this formulation is slightly more acid than commercial gelation.

The HKP gelatin is acceptable in gel strength. The flavor characteristics of the gelatin are a rounded, smoother flavor when compared to the fumaric acid gelatin. The addition of adipic acid may add the "bite" to the flavor.

EXAMPLE 8 Mayonnaise

Two HKP solutions, 5% and 2.5%, were tested as substitutes for vinegar (acetic acid) in mayonnaise formulations. 5% HKP represents a 100% substitution of HKP for acetic acid in the basic recipie and 2.5% represents a 50% substitution of HKP. The 5% solution was formed by combining 20.7091g MilliQ^® water with 1.0351g HKP calculated as 4.998% HKP by weight. The 2.5% solution was formed by combining 20.1978g MilliQ^® water with 0.5119g HKP calculated as 2.53% HKP by weigh .

The test recipies were as follows:

TABLE 15

Basic 5% HKP 2.5% HKP

Sugar 2.5085g 2.5098g 2.5018g

Salt 2.0116g 2.0089g 2.0555g

Mustard 0.6027g 0.6057g 0.6019g

Egg Yolk 16.0481g 16.0673g 16.0654g

Vinegar 15ml - -

HKP - 15 ml 15 ml

Oil 110.0182g 110.2362g HO g

The mayonnaise test mixtures were blended as follows. Sugar, salt & mustard were mixed for 50 strokes with wire whip. Egg yolk and half of the vinegar or HKP solution was added, beating for 50 strokes. Two tablespoons oil (3 plastic pipettes) were added dropwise, beating the mixture 100 strokes per pipette. Six teaspoons of oil were added one at a time mixing each with 50 strokes. The remaining vinegar or HKP solution was added and mixed with 50 strokes. The remaining oil was added one tablespoon at a time beating 50 strokes after each addition. The emulsions were placed in a 250 ml glass beaker and covered with plastic wrap.

The height of the main body and peaks was measure as follows.

TABLE 16 Basic 5% 2.5%

3.50 pm 1 3/4" 4:25 1 3/4" 5:00 2" 4:25 pm 1 3/4" 5:00 1 3/4" 5:35 2" (peak)

7:45 am - 7:45 am - 5:35 1 15/16"

(main body)

7:45 1 15/16" (peak)

1 7/8" (main body)

The test mixtures were visually evaluated for color and texture. More color was observed for the 2.5% HKP emulsion. The 2.5% emulsion also appeared stiffer, forming more peaks that still remained after 24 hours.

The test emulsions were also organoleptically evaluated for taste and texture. All three recipies gave a smooth, thin textured product. The acetic recipie had a poor flavor tasting too much like vinegar. The 2.5% and 5% HKP both had good flavor showing low tartness. The texture of the 2.5% HKP appeared creamier.

The product was covered, put into the refrigerator, and allowed to set overnight. No breakdown of emulsion was noted after 24 hours. Samples of mayonnaise were removed from the refrigerator and allowed to warm up to room temperature, approximately 4 hours.

Each sample was evaluated for line spread using a two inch biscuit cutter which is 2 inches in diameter by 1 5/8 inches high. The biscuit cutter was placed in the center of a graph on which 13 concentric circles were drawn. The cutter covered the first circle which was 2 inches in diameter and the remaining 12 circles were spaced 1/4 inches apart, up to a final diameter of 5 inches .

After filling the cutter with the product to the rim and leveling, the cutter is removed from the circle graph with a straight upward movement. The product was then allowed to flow over the circle graph and sit for exactly two minutes. After two minutes, four readings are taken in four directions north, south, east and west. The diameter of the circle to which the product flowed in each direction is recorded and the four values were averaged. The line spread results and further observations were recorded.

The vinegar (acetic acid) recipe showed an average line spread of 2.625 inches. The product was thick and the peaks didn't spread out. The product was dense with small air bubbles and a rich yellow color. The 5% HKP emulsion showed and average line spread of 2.9125 inches. The product was slightly thinner, with peaks that spread out. The product had large air bubbles and a yellow color. The 2.5% HKP showed an average line spread of 2.75 inches, spreading out evenly in all directions. The product was thick, with peaks that didn't spread very much. The product was dense with small air bubbles and a rich yellow color.

Claims

WHAT IS CLAIMED IS:

1. An acidulant composition comprising hemipotassium phosphate.

2. The acidulant composition of claim 1 further comprising one or more acids chosen from the group consisting of organic and inorganic acids.

3. The acidulant composition of claim 2 wherein the organic acid is chosen from the group consisting of acetic, succinic, citric, tartaric, fumaric, adipic, lactic, malic and glucono-delta-lactone.

4. The acidulant composition of claim 2 wherein the inorganic acid is phosphoric acid.

5. A food product comprising the acidulant composition of claim 1.

6. The food product of claim 5 wherein hemipotassium phosphate is present in an amount between about 0.001% and about 10.0% by weight.

7. A consumable non-food product comprising the acidulant of claim 1.

8. The consumable non-food product of claim 7 chosen from the group consisting of candy, gum, lozenges, effervescent tablets, medicine, gargle and mouthwash.

9. A preservative composition comprising hemipotassium phosphate .

10. The preservative composition of claim 9 further comprising one or more additional preservatives chosen from the group consisting of proprionates, sorbates and benzoates .

11. A food product comprising the preservative composition of claim 9.

12. A consumable non-food product comprising the preservative composition of claim 9.

13. The preservative composition of claim 9 wherein the hemipotassium phosphate is present in an amount such that it will comprise between about 0.001% and about 10.0% by weight of a food product to which it is added.

14. The preservative composition of claim 9 wherein the hemipotassium phosphate is present in an amount such that it will comprise between about 0.001% and about 10.0% by weight of a consumable non-food product to which it is added.

15. A process for preserving a food product which comprises incorporating a preservative composition comprising hemipotassium phosphate in the food product.

16. The process of claim 15 wherein the food product comprises an ingredient chosen from the group consisting of meat, fish, milk, fruit or grain.

17. The process of claim 15 wherein the incorporated hemipotassium phosphate comprises between about 0.001% and about 10.0% by weight of the food product.

18. A process for modifying the pH of a food product which comprises incorporating an acidulant composition comprising hemipotassium phosphate in the food product.

19. The process of claim 18 wherein the incorporated hemipotassium phosphate comprises between about 0.001% and about 10.0% by weight of the food product.

20. The process of claim 18 wherein the food product is chosen from the group consisting of creamed cottage cheese, margarine, fruit butters, canned vegetables, canned juices, canned figs, relishes, molasses, fondants , bread dough and soy sauce .

21. A process for modifying the pH of a consumable non-food product which comprises incorporating an acidulant composition comprising hemipotassium phosphate in the food produc .

22. The process of claim 21 wherein the incorporated hemipotassium phosphate comprises between about 0.001% and about 10.0% by weight of the consumable non-food product.

23. The process of claim 21 wherein the consumable non-food product is chosen from the group consisting of candy, gum, lozenges, effervescent tablets, medicine, gargle and mouthwash.

24. A process for preparing a food product which comprises incorporating an acidulant composition comprising hemipotassium phosphate in the food product.

25. The process of claim 24 wherein the incorporated hemipotassium phosphate comprises between about 0.001% and about 10.0% by weight of the food product.

26. The process of claims 24 wherein the process further comprises one or more steps chosen from the group consisting of fermentation processes and brewing.

27. The process of claim 24 wherein the process comprises purification of vegetable oils.

28. The process of claim 24 wherein the process comprises sugar refining.

29. A process for preparing a consumable non-food product which comprises incorporating an acidulant composition comprising hemipotassium phosphate into the consumable non-food product.

30. The process of claim 29 wherein the incorporated hemipotassium phosphate comprises between about 0.001% and about 10.0% by weight of the consumable non-food product .

31. The process of claim 29 wherein the process comprises clarifying and acidifying collagen in the production of gelatin.

32. The process of claim 29 wherein the consumable non-food product is chosen from the group consisting of candy, gum, lozenges, effervescent tablets, medicine, gargle and mouthwash.