Note: Descriptions are shown in the official language in which they were submitted.
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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
Z5 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
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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.
SUL~M~tARY 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
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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 0.3s
free water.
The reaction may be represented as follows:
KHZP04 + H3P04 > KHS ( 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.
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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 a11 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
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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:
10g/100m1 Hz0 17.35 sec
15g/100m1 H20 49.36 sec
25g/100m1 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
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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.
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TABLE 1
Product Level Product Level Product Level
Jelly 0.01- Jam 0.01- Gelatin 0.1-
0.25 0.04 0.4
Pet Food 0.01- Candy 1-3 Salad 0.1-
0.5 Dressing 0.5
Mayonnaise 0.1- French 0.1- pasteurized- 0.008
0.6 Dressing 0.5 cheese -0.01
spreads and
foods
pasteurized 0.02- Preserves 0.01- hot pepper 0.1-
process 0.15 0.04 sauce 2.0
cheese
Instant 0.04- Cheese and 0.02- Cheese Cake 0.04-
Puddings 0.17 cheese 0.15 0.17
analogues
cold-pack 0.008 lozenges 0.1 butter 0.1 -
-
cheese -0.01 1.0 cultures 0.28
water ice 0.01- sauces 0.07- teriyaki 0.05-
0.2 0.7 0.4
structured 0.26- cheese sauce 0.1- milk gel 0.056
fruit 1.12 0.45 acidified -
0.238
dessert gel 0.001 candy jelly 0.2- chili sauce 0.12-
- 0.9 0.7
0.005
bar-b-que 0.1- seafood 0.08- tomato aspic 0.26-
sauce 0.3 sauce 0.5 1.12
sweet sour 1-3 fruit pie 0.09- salsa 0.1-
candy filling 0.5 0.4
pickles 0.24- catsup 0.1- tortillas, 0.01-
1.022 0.8 corn and 0.05
flour based
olives 0.24- algin gel 0.001 cheese 0.02-
1.022 desserts - 0.15
0.005
cheese 0.02- hot pepper 0.1-
analogs 0.15 sauce 2.0
*rB
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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
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comprising hemipotassium phosphate in the product. The
term "incorporating" in its various grammatical forms
includes a11 modes of preparing a food or consumable
non-food product including, but not limited to, adding,
combining, admixing, solvating, and salting. Tn 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.
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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)
*rB
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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 804 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.
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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
PZOS 6 0 . 6 7
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%
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EXAMPLE 2
Use of HKP as an Acidulant in Jellv
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 a11 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 Z4.1 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 a11 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.
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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 HzO.
2. Acid solution: 4.88 gm of test acid + 10 m1 H20.
Dissolve acid in water.
3. Jelly: 350 gm H20 + pectin paste + 750 gm sucrose.
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Pectin paste and water were mixed in a large sauce pan
and brought rapidly to a hard boil, stirring
constantly. Sugar was added a11 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 a 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
3 5 ml H20 .
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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 a11 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 Acid HKP HKP HKP
o 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 Gr~e 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
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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 ~ 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
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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 a11 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
grams of milling water, the pH of this mixture is
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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 1) 269 2.0 ml citric
-
3 4 1 2 DG
4 1 2 3 JG 2) 631 2.0 ml HKP
=
3 2 1 SS
4
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.
O
~o
TABLE 8 ~~
~o
Sample Attribute Average 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
N
N
O
1
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 0
sourness 2.02 0.10 0.80 4.70 3.20 4.60 1.75 0.0 1.05
0
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
n
H
~o
N
O
N
rr
CA 02270432 1999-04-30
WO 98I19565 PCT/US97/20216
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H. 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 a11 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
grams of milling water, the pH of the mixture was
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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 - ml citric
2.0
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 O
- ~o
00
~o
Sample Attribute Averacre 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
sourness 2.04 0.55 3.20 5.10 2.30 0.45 1.60 1.10
N
N
J
O
3 flavor 5.84 7.70 3.90 6.05 6.75 4.95 6.80 4.75 w
sweetness 6.24 7.90 4.05 6.40 5.15 4.85 6.70 8.60
sourness 3.61 2.20 6.4S 3.70 5.15 0.55 3.00 4.20
0
w
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
b
n
0
N
r.
CA 02270432 1999-04-30
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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.
b
n
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1.0 gm dry mix, 8000 psi/30 sec - slight crumbly edge,
force needed to break.
1.0 gm dry mix, S000 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.
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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 Chloride0.7 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 l4.3 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
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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 1200 2.03 pH
1l50 2.23 pH 1250 2.l1 pH
1175 2.25 pH 1300 2.1$ pH
1200 2.27 pH 1350 2.23 pH
1250 2.31 pH 1375 2.26 pH
1300 2.34 pH l-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
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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 a11 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
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gelatin. The addition of adipic acid may add the
"bite" to the flavor.
EXAMPLE 8
Mayonnai~
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
weight.
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 15m1 - -
HKP - 15 ml 15 ml
Oil 110.0182g 110.2362g Z10 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
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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. A11 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
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-31-
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 a11
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.
