Note: Descriptions are shown in the official language in which they were submitted.
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COMPOSITIONS CONTAINING SORBITAN MONOESTERS
FIELD OF THE INVENTION
The present invention relates to emulsifier compositions containing relatively
high levels
of sorbitan monoesters. These sorbitan monoester-containing compositions are
useful for a
variety of applications.
BACKGROUND OF THE INVENTION
Current sorbitan esters are used as emulsifiers in a wide range of
applications including
but not limited to cosmetics, hard surface cleaners, shampoos and other
personal cleaning
products, industrial manufacturing, and the like. Sorbitan esters also have a
variety of food and
beverage applications including ice cream, whip cream, whipped toppings,
confectionaries,
frostings, breads, baked goods, sauces, salad dressings, and the like.
The preparation of sorbitan esters results in a number of materials, including
sorbitan
mono-, di- tri-, and tetraesters, isosorbide mono- and diesters, unesterified
sorbitan and
isosorbide, and sorbitol and esters thereof. While such combinations have
utility in the
aforementioned applications, Applicants have now discovered that sorbitan-
containing
compositions comprising relatively high levels of soxbitan monoesters are
particularly useful
emulsifier systems having numerous applications. Commercially available
sorbitan ester
compositions are commonly referred to by the industry as "sorbitan
monoesters." However, these
compositions typically contain only from 25 to 35% sorbitan monoester. As
discussed below,
Applicants' use of the term "sorbitan monoester" refers to compositions
containing sorbitan
monoesters at levels greater than those described in the prior art.
The sorbitan monoesters that constitute a significant portion of the
compositions
described herein remain highly functional at temperatures above about
70°C, whereas the
prevalent current emulsifiers, such as monoglyceride, typically lose their
functionality.
Applications where these properties are particularly important include baking
of cakes, cookies,
breads and other sweet goods; high temperature emulsion stability such as
sauces and
confectionaries; and highly expanded or extruded products such as cereals,
rice cakes, etc. In
addition to having relatively high levels of the highly functional sorbitan
monoesters, the
compositions of the present invention also preferably contain relatively low
levels of the
deleterious isosorbide esters (which are (3-tending).
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Another application where the properties of the compositions described herein
are
paxticularly beneficial relate to the preparation of dehydrated starch
ingredients. The improved
emulsifier system of the present invention can be used to reduce the level of
emulsifier needed in
the dehydration process, in particular, the amount of emulsifier needed as a
processing aid in the
drum drying operation. This reduces the cost of raw materials, as well as the
potential for
formation of off flavors due to oxidation. For fat-free snacks such as those
fried in olestra, the
Ievel of emulsifier in the dehydrated starch ingredients may be decreased.
This allows the
formulator to increase the level of other sources of txiglycerides and still
provide the reduced
level of fat in the finished product necessary in most territories to make the
fat-free claim.
Of course, the compositions of the present invention are useful in any
application where
an emulsifier is employed. These include, by way of example only, cosmetics,
hard surface
cleaners, shampoos and other personal cleaning products, lotions, fabric
softeners, and
pharmaceuticals.
SUMMARY OF THE INVENTION
In one aspect, the present invention is directed to emulsifier compositions
comprising a
sorbitan component containing relatively high levels of sorbitan monoesters
and relatively low
levels of isosorbide esters. In particular, the compositions comprise a
sorbitan component,
wherein the sorbitan component comprises at least about 50%, by weight,
sorbitan monoesters
and no more than about 10%, by weight, isosorbide esters. As used herein,
unless otherwise
indicated, reference to the weight percent of a given sorbitan entity (e.g.,
sorbitan monoester,
sorbitan diester, isosorbide) is with respect to the total weight of the
sorbitan component (which
is defined below) of the composition, not the total weight of the composition
itself.
In another aspect, the present invention is directed to compositions
comprising a sorbitan
component, wherein the sorbitan component comprises at Ieast about 50%, by
weight, of sorbitan
monoesters and wherein not more than about 50% of the sorbitan positional
isomers is the 1,4
positional isomer.
In another aspect, the present invention is directed to an improved emulsifier
system for
making various food products including, but not limited to, dehydrated starch
ingredients,
wherein the emulsifier system comprises a sorbitan component, wherein the
sorbitan component
comprises at least about 50%, by weight, of sorbitan monoesters. Other
applications include
baked goods, confectionaries, sauces, cereals, etc.
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In another aspect, the present invention is directed to a process for making
dehydrated
starch ingredients. In one particular embodiment, the process is directed to
the production of
dehydrated potato ingredients. The process comprises the steps of:
(a) cooking potato pieces;
(b) foaming the cooked potato pieces into a potato mash;
(c) drying the potato mash to provide dehydrated potato ingredients;
(d) optionally comminuting the dehydrated mash; and
(e) adding an emulsifier system anytime prior to formation of the dehydrated
potato
ingredients in step (c); wherein the emulsifier system comprises a sorbitan
monoester or a mixture of sorbitan monoesters.
In yet another aspect, the invention relates to dehydrated potato ingredients
comprising a
sorbitan monoester or a mixture of sorbitan monoesters.
In still another aspect, the invention relates to a dough composition
comprising:
(a) from about 35% to about 85% of a starch-based flour comprising a
dehydrated
starch ingredient comprising a sorbitan monoester or a mixture of sorbitan
monoesters;
(b) from about 15% to about 50% added water; and
(c) optionally a dough emulsifier.
In still another aspect, the invention relates to a food product comprising
these
dehydrated starch ingredients.
In still another aspect, the invention relates to a composition comprising an
emulsifier
system comprising a sorbitan component, wherein the sorbitan component
comprises at least
about 50%, by weight, sorbitan monoesters and no more than about 10%, by
weight, isosorbide
esters.
DETAILED DESCRIPTION OF THE INVENTION
I. Definitions
As used herein, the term "added water" refers to water that has been added to
the
composition being discussed. Thus, for example, water that is inherently
present in the dry
dough ingredients, such as in the case of the sources of flour and starches,
is not included in the
term added water.
The term "alpha-stable" or "a-stable" means a material such as an emulsifier
having the
ability to remain in the a crystalline polymorph. It is common for emulsifiers
to transition from a
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to (3' and subsequently to the (3 crystalline polymorph. Alpha-stable
emulsifiers are desirable
herein because of their higher emulsification functionality.
The term "comprising" means various components and processing steps can be
conjointly
employed in practicing the present invention. Accordingly, the term
"comprising" encompasses
the more restrictive terms "consisting essentially of" and "consisting o~"
The abbreviation "cp" means centipoise.
The term "'dehydrated starch ingredient" refers to dehydrated potato products,
dehydrated
wheat product, dehydrated rice products, dehydrated corn products, and
dehydrated tapioca
products. These ingredients may be in the form of flakes, flanules, granules,
slivers, nubbins,
powder, flour, particles, or other pieces.
The terms "diacetylated tartaric acid esters of monoglycerides" and "DATEM"
each refer
to the mixture of products resulting from the reaction of diacetylated
tartaric acid anhydride with
monoglycerides. ' This reaction forms a complex mixture of various components,
the most
prevalent being diacetyl tartaric acid esters of monoglycerides (DATEM I), di-
(diacetyl tartaric
acid) esters of monoglycerides (DATEM II), diacetyl tartaric acid esters of
diglycerides (DATEM
III) and monoacetyl mono (diacetyl tartaric acid) esters of monoglycerides
(DATEM IV). See
Danisco Ingredients Technical Paper TP2-1e, available from Danisco Cultor (New
Century, KS).
The term "diglycerol monoesters" and "DGME" each refers to a preferred type of
polyglycerol monoester that may be used in the present invention. DGMEs are
polymers of two
glycerol units having one fatty acid esterified on the diglycerol backbone.
Particularly preferred
diglycerols are those esterified with palmitic, oleic, or stearic fatty acids,
or a mixture of
intermediate melting fatty acids.
The term "dispersion" refers to an emulsifier system that exists as a
colloidal system in
water. These systems include dilute lamellar liquid crystal, hexagonal,
crystalline and mixed
crystalline phases. The term "stable dispersion" refers to a dispersion that
exists for at least 5
minutes at the temperature in question. The method for determining whether an
emulsifier
system exists as a stable dispersion is described in the Analytical Methods
section of co-pending
U.S. Application Serial No. 09/965,113, filed September 26, 2001 by P. Lin et
al.
The term "dough emulsifier" means an emulsifier or emulsifiers that are added
during the
dough making process in addition to the emulsifiers) present in the dehydrated
starch ingredients
utilized.
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The term "flour blend" refers to a mixture of all dough ingredients, excluding
the water.
The "flour blend" includes all dry ingredients, as well as any other
ingredients such as liquid
emulsifier.
The term "free polyol" refers to the portion of unesterified soxbitol,
sorbitan and
isosorbide in a given composition.
The terms "intermediate melting" and "IM" each mean esters formed from a
mixture of
fatty acids that are liquid and fatty acids that are solid at room
temperature. Examples of fatty
acid mixtures include, for example, mixtures of palmitic, oleic, linoleic,
linolenic, stearic and
other Cl$ traps fatty acids. Partial hydrogenation is one way to produce IM
fatty acid esters.
The term "lecithin" includes conventional acetylated lecithins, hydroxylated
lecithins,
hydrogenated and partially hydrogenated lecithins and other suitable lecithin
or lecithin-like
compounds such as de-oiled lecithin, Iysolecithins, egg lecithins, egg yolk
powder, phosphotidyl
choline enriched lecithin, phosphatidic acid and its salts, lysophosphatidic
acid and its salts, and '
phospholated monoglycerides and any mixture thereof. Also suitable are
lecithins blended with
other emulsifiers, e.g., CentroMix~E from Central Soya, Ft. Wayne, IN, which
is a blend of
lecithin and Tween.
The term "moisture" means the total amount of water present in the material
being
discussed. With respect to doughs, "moisture" includes the water inherently
present as well as
any water that is added to the dough ingredients.
The term "monoglyceride" refers to a mixture of glycerides (mono-, di-, and
triglycerides) where at least ~0% of the glycerol backbones are esterified
with one fatty acid.
Monoglyceride can be made by the reaction of glycerin with triglyceride (i.e.,
glycerolysis) to
produce mono-, di- and triglycerides. The desired monoglyceride content is
typically achieved by
molecular distillation of the above described reaction mixture. Alternatively,
monoglyceride can
be made by an enzymatic process.
The term "mono-diglyceride" refers to a mixture of glycerides where from about
30% to
about 60% of the glycerol backbones are esterified with one fatty acid. Mono-
diglyceride can be
made by the reaction of glycerine with triglyceride (i.e., glycerolysis) to
produce mono-, di- and
triglycerides.
The terms "polyglycerol ester" and "PGE" are used interchangeably and each
mean a
polyglycerol ester having a polyglycerol backbone comprising from 2 to about
10 glycerol units,
wherein not more than about 40% of the hydroxyl groups of the polyglycerol
ester are esterified
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with fatty acids. For the sake of brevity, Applicants will use the following
shorthand
nomenclature to refer to PGEs:
No. of glycerol units- No, of esterified groups-Abbr. of the fatty acid ester
group
Fox example, use of the shorthand "2-1-P" refers to diglycerol rnonopalmitate;
use of the short
hand "6-2-O" refers to hexaglycerol dioleate; use of "2,3-1-S" refers to di-
triglycerol
monostearate. With respect to this nomenclature, the following definitions
apply to the fatty acid
aspect of the polyglycerol ester: O = oleic acid; P = palmitic acid; S =
stearic acid; and lM =
intermediate melting fatty acids.
The term "psig" means pounds per square inch gauge.
The term "sheetable dough" means a dough capable of being placed on a smooth
surface
and rolled to the desired final thickness without tearing or forming holes.
The term "sorbitan" refers to the various positional isomers of etherified
sorbitol having
one ring. There are several sorbitan positional isomers, including the most
commonly occurring
isomers 1,4-anhydro-D-glucitol, 1,5-anhydro-D-glucitol, 2,5-anhydro-D-
mannitol, 2,5-anhydro-
D-iditol, and 3,6-anhydro-D-glucitol.
The term "sorbitan component," fox purposes of the present disclosure, refers
collectively
to sorbitol and esters thereof (mono-, di-, tri-, tetra-, penta- and
hexaesters), sorbitan and esters
thereof (mono-, di-, tri-, and tetraesters) and isosorbide and esters thereof
(mono- and diesters).
A method for determining the sorbitan component of a sample is described in
the Analytical
Methods section below.
The term "sorbitan monoester" refers collectively to any sorbitan positional
isomer with
one fatty acid esterified to one free hydroxyl group. It is understood that
there are numerous ester
isomers for a given sorbitan positional isomer (dictated by which free
hydroxyl group is
esterified). A method for determining the sorbitan monoester content of a
sorbitan component is
described in the Analytical Methods section below.
The terms "starch" and "modified starch" have the meanings set forth in co-
pending U.S.
Application Serial No. 09/965,113, filed September 26, 2001 by P. Lin et al.
All amounts, parts, ratios and percentages used herein are by weight unless
otherwise
specified.
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II Compositions Containing Sorbitan Monoesters
It is readily understood by those of skill in the art that sorbitan monoesters
are typically
not obtainable in pure form (i.e., axe not a single sorbitan ester), and are
usually mixtures of
different esters. This results from the manner in which the sorbitan
monoesters are prepared. For
that reason, when types of molecules axe mentioned herein, it is meant that
the material referred
to is "predominantly" that material. For instance, an emulsifier referred to
as sorbitan
monooleate will include that material as a significant component, but will
often also include other
sorbitan esters with higher degrees of esterification (e.g., di- to tetra
esters), esters with other
fatty acid residues (e.g., steaxate), as well as unesterified sorbitan.
Further, there will be
unreacted sorbitol (CHZOH)-(CHOH)4CHZOH, the linear precursor to sorbitan),
isosorbide
(bicyclic side product) and esters thereof, and other "impurities" as well, as
will be understood
and appreciated by one of skill in the art.
The compositions of the present invention will comprise a sorbitan component
wherein at
least about 50%, by total weight of the sorbitan component, is sorbitan
monoester(s). As
indicated above, this level of sorbitan monoester is greater than the levels
in current sorbitan
compositions. The compositions of the present invention can be made by either
further purifying
commercial sorbitan compositions, or by controlling the synthesis of the
sorbitan starting with
sorbitol. In another aspect, the composition will comprise a sorbitan
component wherein at least
about 60%, by total weight, of the component is sorbitan monoester(s). In
another aspect, the
composition will comprise a sorbitan component wherein at least about 70%, by
weight, of the
component is sorbitan monoester(s). Typically, the composition will comprise a
sorbitan
component comprising from about 50% to about 98%, by total weight, sorbitan
monoester(s). In
this aspect, the composition's sorbitan component will comprise not more than
about 10%, by
weight, isosorbide esters. Typically, the sorbitan component will comprise not
more than about
7%, still more typically not more than about 4%, isosorbide esters.
For purposes of the present invention, to achieve the greatest functionality,
it is preferred
that the sorbitan component contains a mixture of the monoesters of the
various sorbitan
positional isomers. Without wishing to be bound by any particular theory, it
is believed that
monoesters of a mixture of sorbitan positional isomers leads to polymorphic
behavior that is
alpha-tending and perhaps alpha-stable. Alpha-tendency and alpha-stability
result in more highly
functional emulsifiers, particularly at relatively high temperatures.
Accordingly, it is preferred in
one aspect that the sorbitan component will comprise not more than about 50%,
by total weight,
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of a particular sorbitan positional isomer (e.g., the 1,4 positional isomer).
In another aspect, the
sorbitan component will comprise not more than about 40%, by total weight, of
a particular
sorbitan positional isomer.
The compositions useful herein will typically comprise relatively low levels
of free
polyol. In this regard, the free polyol component (e.g., sorbitol, sorbitan
and isosorbide) will
constitute not more than about 20%, more typically not more than about 15%,
still more typically
not more than about 10%, by total weight of the sorbitan component.
The sorbitan component of the present compositions will typically comprise not
more
than about 20%, more typically not more than about 12%, by weight, sorbitol
esters.
The sorbitan component of the composition will typically contain not more than
about
30% sorbitan diesters. In another aspect, the sorbitan component will contain
not more than
about 20% sorbitan diesters. In yet another aspect, the sorbitan component
will contain not more
than about 10% sorbitan diesters. In another aspect, the sorbitan component
will contain not
more than about 30% sorbitan tri- and tetraesters. In another aspect, the
sorbitan component will
contain not more than about 20% sorbitan tri- and tetraesters. In yet another
aspect, the sorbitan
component will comprise not more than about 10% sorbitan tri- and tetraesters.
The nature of the fatty acid moieties esterified to a hydroxyl group of a
given sorbitan
will depend in part on the end use of the composition. For example, where the
sorbitan
monoester containing composition will be utilized in making dehydrated
ingredients, the sorbitan
monoester will typically be esterified with at least about 80%, more typically
at least about 90%,
and most typically at least about 95%, saturated fatty acids. Further, the
sorbitan monoester will
typically comprise less than about 20%, more, typically less than about 10%,
and most typically
less than about 5%, by weight, unsaturated cis and traps fatty acids.
Preferred fatty acids include
Ciz~ Cia~ Ci6~ Cis~ Czo~ and Czz fatty acids. It is preferred that the
sorbitan monoesters used herein
be esterified with fatty acids chosen from oleic, palmitic and stearic acids;
however, fatty acids
may range from CIZ-CZ2~ and may be saturated or unsaturated. In general, in
order to avoid any
oxidation issues, in certain applications it may be desirable to minimize the
level of unsaturated
fatty acid esters.
Whore the sorbitan monoester containing composition is used in a dough making
application, preferred fatty acids include Clo~ Ciz~ Cia~ Cm~ Cis~ Czo~ and
Czz fatty acids. It is
preferred that the sorbitan monoesters used herein be esterified with fatty
acids chosen from
oleic, palmitic and stearic acids; however, fatty acids may range from Clo-
Czz~ and may be
saturated or unsaturated.
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In general, the following is a non-limiting list of particularly preferred
sorbitan
monoesters for use in the emulsifier system described herein: sorbitan
monopalmitate, sorbitan
monostearate, sorbitan monooleate, sorbitan monomyristate, sorbitan
monolaurate, and sorbitan
monocaprylate.
In another aspect, the present invention is directed to an improved emulsifier
system for
making various food products including but not limited to dehydrated starch
ingredients, wherein
the emulsifier system comprises at least about 50%, by weight, of sorbitan
monoesters. Other
applications include baked goods, confectionaries, sauces, cereals, etc.
While the compositions of the present invention can include sorbitan
monoesters as the
key emulsifier component, the compositions can include other known, functional
emulsifiers.
Fox example, another emulsifier that can be used in the emulsifier system of
the present
invention, along with the sorbitan monoester component, is diacetyl tartaric
acid ester
monoglyceride (DATEM). As discussed in the Definitions section, supra, DATEM
is a
monoglyceride (having an esterified fatty acid ranging from 12 to about 22
carbon atoms) that is
esterified with diacetyl tartaric acid.
The compositions can also include polyglycerol esters such as those described
in U.S.
Serial No. 09/965,113, filed September 26, 2001; lactic acid esters of mono
and diglycerides,
(e.g., Grinsted~ Lactam, available from Danisco (Kansas City, KS)); acetic
acid esters of mono
and diglycerides (e.g., Grinsted~ Lactam, available from Danisco); or
ethoxylated esters of mono
and diglycerides. Of course, the compositions can comprise mixtures of one or
more of these
materials together with the sorbitan monoester.
While the emulsifier system of the present invention may include only one or a
combination of sorbitan monoesters, it is possible to xeplace some portion of
those emulsifiers
with one or more other emulsifiers (including those having relatively lower
functionality) and
still provide an overall system that exhibits the desired functionality under
relevant conditions.
This is important because certain emulsifiers are relatively expensive.
Accordingly, it may be
desirable to have a portion of the emulsifier system comprised of other
emulsifiers, so long as the
desired functionality of the emulsifier system is maintained.
The ability to use other emulsifiers with the sorbitan monoester(s) and the
relative
amount of that use will be dictated by several factors, including the
functionality of the other
emulsifiers) used. For example, where a 'highly functional' sorbitan monoester
is used (e.g. a
sorbitan monopalmitate), it may be possible to include higher levels of other
emulsifiers while
maintaining the desired functionality of the entire emulsifier system.
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In one such system, the sorbitan monoester(s) can be blended with
monoglyceride or
mono-diglyceride that is currently used (at relatively high levels) in the
dehydration process.
Preferably, the monoglyceride is derived from, for example, hydrogenated or
partially
hydrogenated soybean oil, rapeseed oil, cottonseed oil, sunflower seed oil,
palm oil, palm olefin,
safflower oil, corn oil, peanut oil, palm stearin, tallow, lard and mixtures
thereof. The use of
hydrogenated or partially hydrogenated monoglycerides ensures oxidative
stability. For these
systems, preferred emulsifier systems comprise from about 40% to about 99%
sorbitan
monoester(s) and from about 60% to about 1% monoglyceride; typically, such a
blend will
comprise from about 40% to about 60% sorbitan monoester(s) and from about 60%
to about 40%
monoglyceride.
Tn another aspect, the sorbitan monoester(s) can be blended with a lecithin to
provide an
emulsifier system useful herein. In this regard, a preferred emulsifier system
comprises not more
than about 75%, and most preferably from about 1% to about 25%, of a lecithin,
and at Ieast
about 25%, most preferably from about 75% to about 99%, of the sorbtian ester
component.
In another aspect, the sorbitan monoester(s) can be blended with a polysorbate
(polyoxyethylene sorbitan esters) to provide an emulsifier system useful
herein. In this regard, a
preferred emulsifier system comprises not more than about 75%, and most
preferably from about
1 % to about 25 %, of a polysorbate, and at Ieast about 25 %, most preferably
from about 75 % to
about 99%, of the sorbitan component.
In another aspect, the invention relates to an improved emulsifier system
useful in
making dehydrated starch ingredients, wherein the emulsifier system exists as
a stable dispersion
at a temperature of at Ieast about 80°C. As discussed, because most
processing in the starch
dehydration process occurs under high temperature and high moisture
conditions, it is believed
that emulsifier systems exhibiting the above dispersibility properties are
able to function robustly
under such typical dehydration conditions. In contrast to emulsifier systems
that exist as a stable
dispersion at a temperature of at least about 80°C, under the high
temperature and high moisture
dehydration conditions generally utilized, saturated monoglycerides exist
predominantly in the
cubic plus water phase, which is a relatively low functional phase. In other
words, conventional
emulsifier systems do not exist as a stable dispersion at temperatures of
about 80°C or higher.
Applicants have identified emulsifier systems that provide the desired
dispersibility
under dehydration conditions (i.e., exist as a stable dispersion at a
temperature of at least about
80°C). These emulsifier systems will typically contain at least one
emulsifier that itself exists as
a stable dispersion. While a given emulsifier system may contain only an
emulsifier (or
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combination of emulsifiers) having those physical properties, it is possible
to combine one or
more such emulsifiers with other emulsifiers that themselves do not exhibit
the desired dispersed
phase at a temperature of about 80°C. In general, based on Applicants'
discovery and the present
disclosure, one can readily select useful emulsifiers based on their ability
to form the desired
dispersion (as measured according to the Analytical Method section of co-
pending U.S.
Application Serial No. 09/965,113, filed September 26, 2001 by P. Lin et al.)
under the
processing conditions indicated herein.
s
III. Preparation of Sorbitan Component with High Levels of Sorbitan Monoesters
Sorbitan ester (commercial quality) is typically obtained by simultaneous
anhydration
(also referred to as etherification) and esterification of sorbitol directly
with fatty acids. By
simultaneously etherifying and esterifying, it is possible to avoid
undesirably high concentrations
of the 1,4 positional isomer. Such a method of sorbitan ester preparation is
described more fully
in MacDonald, "Emulsifiers: Processing and Quality Control", Journal of the
American Oil
Chemists' Society, Volume 45, October, 1968. As discussed below, to achieve,
the high sorbitan
monoester content, the commercial sorbitan ester prepared by the above process
is molecular
distilled to enrich the sorbitan monoester content.
To reduce the level of isosorbide esters, it is preferred that the process of
esterification
and anhydration be monitored to determine when the sorbitol has been converted
to sorbitan such
that the reaction can be terminated (neutralization of the catalyst) prior to
formation of the
bicyclic isosorbide. Additionally, isosorbide ester levels can be further
reduced by steam
stripping under reduced pressure or molecular distillation
A. Purification/Enrichment
Sorbitan monoesters according to this invention can be prepared using
Glycomul~-S, a
commercial sorbitan monoester obtained from Lonza Group, Fairlawn, N.J. (this
emulsifier
comprises 25% sorbitan monoester and less than 15% isosorbide esters; Less
than 40% 1,4
sorbitan isomers), as a starting material.
In a first step, the predominant portion of the isosorbide esters, along with
the free fatty
acids, are removed by steam stripping using conventional shortening/oil
deodorization
equipment. .
The following conditions are suitable for sorbitan esters containing palmitic,
stearic and oleic
fatty acids:
Minutes 100-120 minutes
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Temperature 360-400°F (182-204°C)
Absolute Pressure 5-10 nun Hg
At the end of the deodorization step, the level of free fatty acid is
typically less than 0.5%
and the isosorbide ester content is typically less than 3%.
In the second step, the deodorized sorbitan ester (reduced isosorbide content)
can be
fractionally distilled, fox example using a CMS -15A centrifugal molecular
still (CVC Products,
Inc., Rochester, NY) using multiple passes. The following conditions are
suitable for sorbitan
esters containing palmitic, stearic and oleic fatty acids:
Feed rate 15 lbs/hr
Rotor feed Gradually increased from 130 - 190°C during
the consecutive passes
Rotor Residue temperature 140-220°C
Cooling Water temperature 30-37°C
' Bell Jar pressure 6-12 micron
Distillation cuts for each pass 10-15%
The distillate fractions are collected on the surface of the bell ~ jar that
is heated to
facilitate removal. Distillate and residue are continuously removed by
transfer pumps. The
fractionation process is monitored by differential scanning calorimetry (DSC),
HPLC, and
refractive index determinations.
B. Sorbitan Component Synthesis
Alternatively, sorbitan components having high levels of sorbitan monoester
can be
synthesized from sorbitol and fatty acids using esterification followed by
etherification. This
synthesis results in low levels of isosorbide and their esters and low levels
of 1,4 sorbitan
positional isomers.
This process is conducted in a stainless steel reactor equipped with a
mechanical agitator,
heating and cooling coils, a condenser, and an electric heating jacket. The
reactor is charged with
sorbitol (e.g., 70%), oleic acid (e.g., Panmolyn 100, Hercules), and NaOH
(e.g., 50%) as the
esterification catalyst. Mechanical agitation and nitrogen sparging is
applied. The temperature is
increased to 220°C. The reaction is allowed to proceed for 2-3 hours
with the reactor at slightly
below atmospheric pressure. Esterification is complete when the free fatty
acid is less than 1.5%.
The pressure is gradually reduced to 10-15 mm Hg.
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13
The temperature is reduced to 170°C and phosphoric acid (e.g., 70%) is
added to the
reactor to initiate the etherification process. A slight amount of water is
used to wash all
phosphoric acid into the reactor. The temperature is gradually increased to
220°C for the
etherification process. Etherification is conducted until most of the sorbitol
esters are converted
to sorbitan esters and no significant level of isosorbide esters are formed.
The free fatty acid level in the reaction mixture is determined by titration
with base. The
etherification endpoint is determined by HPLC according to the Test Methods
section below.
After the esterification and etherification processes, the reaction mixture is
molecular
distilled (according to Section BIA, above) to produce a sorbitan component
with greater than
50% sorbitan monoesters. Because deodorization has already been carried out
during synthesis,
distillation can be carried out without additional deodorization.
C. Solvent Crystal Fractionation to Enrich Sorbitan Monoester Content
Alternatively or in addition to the procedures described in sections A and B
above,
sorbitan monoester enrichment may be accomplished using solvent crystal
fractionation
procedures on crude mixtures. A crude mixture containing sorbitan, sorbitol
and isosorbide
mixed esters of fatty acids is added to polar solvents, such as methanol or
ethanol, at a
temperature above the final melting point of the mixture. The mixture is
cooled (e.g., to 0-10°C)
and filtered. The filtrate will contain relatively higher concentrations of
sorbitan monoester. The
crystals or filter cake will contain higher levels of isosorbide esters,
sorbitan diesters, and
sorbitan triesters. This process can be repeated to further enhance the
concentration of sorbitan
monoester.
1V. Dehydrated Starch Ingredients and Processing of those Ingredients
As discussed above, Applicants have discovered that sorbitan monoesters are
highly
functional and therefore compositions containing relatively high levels of
these monoesters are
useful in emulsifier systems for various purposes. The present invention is
directed in one
respect to a process for making dehydrated starch ingredients. The process is
particularly
suitable for making dehydrated potato ingredients. In the context of
dehydration processes,
saturated monoglycerides are currently used exclusively in the starch
dehydration industry.
Under the high temperature (typically between 80 and 95°C) and high
moisture (greater than 50%
moisture) dehydration conditions generally utilized, saturated monoglycerides
exist
predominantly in the cubic plus water phase, which is a relatively low
functional phase. To
compensate for their relatively low functionality under typical dehydration
conditions, saturated
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monoglycerides are typically used at levels of approximately 0.3 to 0.5%, by
weight of the
resulting dehydrated starch ingredients normalized to 0% moisture content.
Applicants have surprisingly found that compositions containing relatively
high levels of
the sorbitan monoesters described herein are sufficiently functional in the
range of from about
0.005 to about 0.2%, by weight of the resulting dehydrated starch ingredients
normalized to 0%
moisture content, in the dehydration process. Accordingly, a benefit of
utilizing emulsifiers
having relatively high levels of sorbitan monoesters is the ability of a
formulator of raw materials
to reduce the level of the emulsifier needed as a processing aid in the drum
drying operation.
This reduces the cost of raw materials and also reduces the potential for the
formation of off-
flavors due to oxidation. By reducing the level of emulsifier in the
dehydrated starch ingredients,
in fat-free foods such as snacks fried in non-digestible fats like Olean~
(sold by the Procter &
Gamble Company, Cincinnati, OH), the end producer can use other sources of
triglycerides while
still providing a low-fat food and while meeting the regulatory requirements
in many geographies
to Iabe1 the food as ":fat free."
The process of the present invention will be described emphasizing the
preparation of
dehydrated potato flakes. This is by way of illustration and not limitation.
In its broadest aspect,
the process of the present invention is generally applicable to the
preparation of dehydrated
vegetables (e.g., potatoes, sweet potatoes, beets, spinach, onion, carrots,
celery, pumpkin,
tomatoes, zucchini, broccoli, mushrooms, peas); grains such as corn products
(e.g., masa), barley,
oats, rye, wheat, rice, amaranth, sago and cassava; and the like. The present
invention is also
applicable in producing flakes that can be used in baby foods. The process of
the present
invention can also be applied for other starch containing materials such as
glues and
pharmaceutical materials.
Any commercially available potatoes used to prepare conventional potato
ingredients
such as flakes, flanules or granules can be used to prepare the dehydrated
potato ingredients of
the present invention. Preferably, the dehydrated ingredients are prepared
from potatoes such as,
but not limited to, Norchip, Norgold, Russet Burbank, Lady Russeta, Norkota,
Sebago, Bentgie,
Aurora, Saturna, Kinnebec, Idaho Russet, and Mentor. Any of a variety of
potato pieces (as used
herein, "potato pieces" includes potato by-products, e.g. slivers, slices
nubbins, or slabs) can be
used in the practice of the present invention.
In one embodiment the potato pieces are pre-conditioned. As used herein "pre-
conditioned" refers to treatments such as blanching and cooling, which causes
the potato cells to
toughen.
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Co-pending U.S. Application Serial No. 09/965,113, filed September 26, 2001 by
P. Lin
et aL, describes the production of dehydrated potato ingredients using
polyglycerol esters. The
conditions described therein (see in particular page 13, line 5 to page 17,
line 8) are also useful in
preparing dehydrated potato ingredients in accordance with the present
invention. As indicated
in the U.S.S.N. 09/965,113 application, the emulsifier system of the present
invention can be
added during or between the cooking, mashing and drying steps, or any
combination thereof. To
aid in processing, most preferred is where the emulsifier system is combined
with the cooked
potatoes just prior to or during the mashing step. Additionally, the potato
ingredient will exhibit
the other properties set forth in U.S.S.N. 09/965,113 (see page 17, lines 9-
30), other than their
possessing sorbitan monoesters as a result of their preparation.
V. Fabricated Farinaceous Products and Baked Goods
Although the disclosure of final products derived from the dehydrated starch
ingredients
described above relates primarily to the formation of fabricated chips, it
will be readily apparent
to one skilled in the art that the dehydrated ingredients can be used in the
production of any
suitable food product. For instance, the dehydrated potato products can be
rehydrated and used
to produce food products such as mashed potatoes, potato patties, potato
pancakes, potato soup,
and other potato snacks such as extruded French fries and potato sticks. For
mashed potatoes,
potato flakes may be coarsely ground to about 0.1-1 cm2. Optionally,
seasonings such as salt,
pepper, onion powder, garlic powder, MSG, butter flavors, or cheese powder,
may be added to
the ground flakes before packaging. Additionally, various stabilizers may be
added, for example
BHT and citric acid. The consumer prepares the mashed potatoes by adding the
potato flakes to
hot water containing salt, margarine and milk. The product is mixed and is
ready for
consumption in a few minutes.
Alternatively, dehydrated starch ingredients can be used to produce extruded
French fried
potato products such as those described in U.S. Patent No. 3,085,020, issued
April 9, 1963 to
Backinger et al., and U.S. Patent No. 3,987,210, issued October 18, 1976 to
Cremer. The
dehydrated potato products can also be used in breads, gravies, sauces, or any
other suitable food
product.
As indicated, an especially preferred use of the dehydrated potato ingredients
is in the
production of fabricated chips made from a dough. Examples of such fabricated
chips include
those described in U.S. Patent No. 3,998,975 issued December 21, 1976 to
Liepa, U.S. Patent No.
5,464,642 issued November 7, 1995 to Villagran et al., U.S. Patent No.
5,464,643 issued
November 7, 1995 to Lodge, PCT Application No. PCT/LTS95/07610 published
January 25, 1996
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16
as WO 96101572 by Dawes et al., and U.S. Patent No. 5,928,700 issued July 27,
1999 to
Zimmerman et al.
U.S.S.N. 09/965,113 describes the preparation of farinaceous products from a
dough. In
particular, the application describes the dough compositions themselves, the
preparation of the
dough, sheeting of the dough, preparation of dough pieces and frying of the
dough pieces to
provide the end product. The skilled artisan can refer to the teachings of the
'113 application,
including relevant materials and ranges of incorporation, in using the
dehydrated starch
ingredients of the present invention.
VI. Ana~tical Methods
1. Sorbitan Ester Positional Isomer Determination
This is representative of a method that allows the determination of sorbitan
positional
isomers from a sorbitan component sample, using a two-step procedure. In the
first step, the
sorbitan component is converted to sorbitan by saponification. In the second
step, the sorbitan is
analyzed for its sorbitan isomer distribution using gas chromatography with a
flame ionization
deflector.
1A. Converting Sorbitan Esters to Sorbitan
Eauipment
Analytical balanceAccurate to 0.1 mg
Heating stir plateCMS #267-914, capable of 160C, or equivalent
Water jacketed Tls 24-40 Ground glass joint, CMS #067-470
condenser
Magnetic stirringCMS #271-825
bars
Extraction flask T/s 24-40 Ground glass joint, 250 mL capacity,
CMS #095-943
Erlenmeyer flask Wide mouth, 250 mL, CMS #098-228
Beaker 150 mL, CMS #029-546
Stirring plate Unheated, CMS #267-955
Reagents
Methanol ACS Reagent Grade
Hexane Bulk
Sodium methoxide Aldrich Catalog # 156256-25ML (25 wt % methanol)
Sodium methoxide solution Dilute 2 mL sodium methoxide to 100 mL with methanol
Exchange resin Amberlite Monobed, Rohm & Hass, IRN 150 Technical Grade
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Procedures
1. Place approximately lg of sample in a 250 mL extraction flask.
2. Add 100 mL sodium methoxide solution and a stirring bar.
3. Attach the flask to a condenser and place on a heated stir plate, preheated
to
approximately 160°C.
4. Reflux the sample while stirring rapidly for 30 minutes.
5. Pour 25 mL air-dried exchange resin into a 250 mL wide mouth Erlenmeyer
flask.
6. Rinse resin twice with methanol, using approximately 150 mL of solvent for
each
rinse.
7. Qualitatively transfer the hot methylating solution and stirring bar to the
Erlenmeyer
containing the resin.
Stir the solution and resin on an unheated stir plate for one hour.
9. Filter the solution through two sheets of Whatman #41 filter paper into a
150 mL
beaker.
10. Evaporate it to near dryness on a steam bath under a stream of nitrogen.
11. Deep the sample beaker on the steam bath without nitrogen and add about 5-
10 mL
methanol to dissolve the residue in the beaker.
12. Add about 50 mL hexane to the beaker, swirl the contents and return to
heat until
most of the methanol layer has boiled away.
13. Decant the hexane layer into a waste solvent container.
14. Repeat Steps 11 through 13 as many times as is necessary to obtain a clear
residue.
Normally this is three times.
15. Return the residue to the steam bath and evaporate it to dryness under
nitrogen.
16. This residue may then be treated as a sorbitan sample and prepared for GC
analysis
in the same manner.
1B. Sorbitan Positional Isomer Determination by Gas Chromatogra~hy
Approximately 3 mg of sorbitan is reacted with 0.5 mL of a suitable agent for
silylation
of sorbitan hydroxyl groups [typically Tri Sil Z (Pierce), heat for 5-10 min.
at about 105°C].
Sample is injected (1 ~L, split injection, 30-35 mL split vent flow,
300°C injector temperature)
onto a I5 M x 0.25 mm DB-5 column (J&W) with 0.25 ~m film thickness. Helium
carrier gas
flow rate is about 1 mL/min. The initial column temperature is 100°C (1
min. hold) and it is
programmed at 10°C/min. to 325°C. Detection is by flame
ionization detector (FID; temperature
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18
= 335°C). Applicants have identified, by gas chromatography/mass
spectrometry (GC/MS), 11
peaks with a molecular weight of 452 (chemical ionization m/z 453), that
corresponds to the
molecular weight of fully silylated sorbitan. The Fm areas of these peaks are
integrated and the
results axe normalized to the total area of the 11 peaks. Table 1 below shows
retention times and
normalized area % for a composition of the present invention. (This sample
contains less than
50% 1,4-anhydro-D-glucitol.) NMR data are used along with MS data to identify
1,4-anhydro-D-
glucitol, a peak of primary interest. Two other peaks (2,5-anhydro-D-mannitol
and 1,5-anhydro-
D-glucitol) are confirmed with commercially available standards from the
electron ionization (EI)
fragmentation patterns and GC retention times. Two other peaks (3,6-anhydro-D-
glucitol and
2,5-anhydro-L-iditol) are tentatively identified from their EI mass spectra
and from MS/MS
spectra of protonated sorbitans. The remaining relevant peaks are not
typically identified. (It
will be recognized that there will be additional, non-sorbitan peaks in the
chromatogram that are
not relevant to this analysis.)
Table 1
Retention Time (min.)Peak Identity Normalized Area
%
9.60 #1 0.31
9.80 #2 2.43
10.11 #3 27.62
10.26 #4 10.17
10.34 #5 16.96
10.38 #6 5.84
10.46 #7 (1,4-anhydro-D-glucitol)12.66
10.49 #8 6.97
10.54 #9 7.41
10.78 #10 2.83
11.30 #11 6.80
2.' Sorbitan Ester Profilins by Reverse-Phase HPLC
Free polyol and fatty acid esters of sorbitol, sorbitan and isosorbide are
separated by
gradient elution (water:acetone:methylene chloride) on two Beckman ODS
columns. An
evaporative light scattering detector is used for eluent detection. Elution
order is first by class
with unesterified polyols eluting first followed by sorbitol rnonoesters,
sorbitan monoesters and
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19
isosorbide monoesters. Analytes with a higher degree of esterification elute
after the monoesters
and in the same backbone order. Within classes, analytes elute in order of
increasing carbon
number (acyl chain length).
The detector response for unesterified polyols is lower than the detector
response for
sorbitan esters. Therefore, to compensate for these differences, percent free
polyol per sample is
determined using an external sorbitol calibration curve.
Rea ents
Methylene Chloride Burdick & Jackson
Acetone Burdick ~ Jackson
HPLC Grade Water VWR, #JT3140-5
Equipment
Volumetric Flask 25 mL
LC System HP-1090L with PV5 pumps,
variable volume injector
equipped
with 25 ~,L syringe and
a
temperature controlled
auto-
sampler, or equivalent
LC Column 2 Beckman ODS columns,
4.6 mm
X 25 cm, 5 ~,m.
Laboratory Automation SystemHewlett-Packard #3357
(LAS)
Evaporative Light ScatteringApplied Chromatography
Detector Systems
#750/14
Autosampler Vials 2 mL, VWR, #66020963
Autosampler Vial Caps 11 mm, VWR #66020-963
Disposable Pasteur Pipets Glass, VWR, #14672-200
Column Inlet Filter Rheodyne #7335; Alltech
Assoc.
#7335RV
Replacement Filter Discs 0.5 ~m x 3 mm, Alltech
Assoc.
#7335-010
Drierite Fisher #07-578-4A, or
equivalent
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Sample Preparation
1. Weigh approximately 0.50 g of sample into a 100 mL volumetric flask and add
approximately 50 mL of acetone. Warm sample gently to dissolve. Early reaction
samples
may contain unesterified polyol and appear cloudy in the acetone. As needed,
add several
drops of water with warming to the sample to clear the solution. Allow
solution to cool to
room temperature and dilute to volume with acetone.
2. Transfer a portion of each sample to an autosampler vial and cap.
Pr~aration of Sorbitol Standards fox External Calibration Curve
1. Prepare a 1% sorbitol stock solution by first weighing approximately 1 g of
sorbitol in a 100
mL volumetric flask.
2. Add 10 mL HPLC grade water and swirl to dissolve the sorbitol completely.
3. Slowly fill volumetric flask to volume with acetone. Solution may become
cloudy upon
addition. Mix thoroughly.
4. Prepare a 1:50 dilution of sorbitol stock by transferring 1 mL of stock
solution into a 50 mL
volumetric flask. Fill to volume with acetone.
5. Repeat step 4 to prepare a 3:50, 5:50, 7:50, and 9:50 dilution of sorbitol
stock.
6. Transfer a portion of each sample to an autosampler vial and cap.
LC Operation (with above specified equ~ment)
1. Turn on power for the HP-1090.
2. Filter all solvents with the filtration apparatus.
3. Fill reservoirs with filtered solvent. Reservoir A contains water,
reservoir B contains
methylene chloride and reservoir C contains acetone.
4. Open helium toggle on back of HP-1090 module and spurge solvent for at
least 5-10 minutes.
Close helium toggle.
5. Turn on power to the evaporative light scattering detector by depressing
the green power
button. Allow instrument to warm up for 30 minutes before analysis. Set other
detector
conditions as follows.
Attenuation 2 Evaporator Setting 60
Photomultiplier 2 Nitrogen 15 psi
Time Constant 5
6. Set up mobile phase program and instrument parameters on the HP-1090 as
shown below.
Refer to HP-1090 Operators' Handbook for programming directions.
Method 0
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Sorbitan
SDS Config A=1 B=1 C=1
Flow = 1
%B=0 %C=50
Max Press = 400
Min Press = 0
Oven Temp = 40
Inj Vol = 20
Slowdown = 5
Stop Time = 25
Post Time = 10
Column SW = 1
E1=1, E2=0, E3=0, E4=0
At 0 %B=0 %C=50
0 E4=1
0.1 E4=0
%B=0 %C=80
%B=0 %C=100
%B=0 %C=100
%B=100 %C=0
22 %B=0 %C=100
%B=0 %C=100
Calculation of Results
External Sorbitol Calibration Curve: the sorbitol peak is integrated to
provide the total sorbitol
peak area. Peak areas (dependent variable) are then plotted against the total
amounts of sorbitol
injected in grams (independent variable) to create the external sorbitol
calibration curve.
Percent free polyol: free polyol peaks are integrated and summed to provide
the total free
polyol peak area. The total free polyol peak area is then used to determine
the total amount of
free polyol injected based on the external sorbitol calibration curve.
The total amount of sample injected is calculated by multiplying the
concentration of the
sample solution (in g/100mL) by the injection volume (in mL).
Percent free polyol (% free polyol) is then determined by dividing the amount
of free
polyol injected by the total amount of sample injected, and multiplying the
quotient by 100.
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Percent sorbitan monoesters: all sorbitol ester, sorbitan ester and isosorbide
ester component
peaks in the resulting LC chromatogram are integrated and summed to provide
the total ester
component peak area. (Ester component peaks are identified by LC/MS or by LC
retention time
of standards.) Sorbitan monoester peaks are integrated and summed to provide
the total sorbitan
monoester peak area. Percent sorbitan monoester (%SME) is determined by
dividing the total
sorbitan monoester peak area by the total ester component peak area and
multiplying by the
difference between 100 and the percent free polyol. See equation below:
Areasi,,~
%SME= x (100 - %free polyol)
AreasME+ AreasDa+ Areas~+ AreaSTes+ Area~+ AreamE + Areass
AreasME = total sorbitan monoester peak area, AreasnP = total sorbitan diester
peak area, Areas
= total sorbitan triester peak area, AreasT~E= total sorbitan tetraester peak
area, AreaB,,~ = total
isosorbide monoester peak area, AreamE = total isosorbide diester peak area,
and AreaSE= total
sorbitol mono-, di-, txi-, tetra-, penta-, and hexaester peak area.
Percent isosorbide esters: isosorbide ester peaks are integrated and summed to
provide the total
isosorbide ester peak area. Percent isosorbide esters (%ISE) is determined by
dividing the total
isosorbide ester peak area by the total ester component peak area and
multiplying by the
difference between 100 and the Percent free polyol. See equation below.
Area~+ AreamE
%ISE= x (100 - %free polyol)
AreasME+ AreaSDE+ Areas.~+ AreaSTeE+ AreaB,,ø+ AreamE + Areasa
Aqueous dispersion characterization is performed in accordance with the method
described in Section V-Analytical Methods of co-pending U.S. Application
Serial No.
09/965,113, filed September 26, 2001 by P. Lin et al.
VII. Examples
The following examples i illustrate the improved emulsifier systems,
dehydrated
ingredients and various food of the present invention. The examples are given
solely for the
purpose of illustration, and are not to be construed as limitations of the
present invention since
many variations thereof are possible without departing from its spirit and
scope.
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A. Composition and Dehydration Examples
Example 1
An improved emulsifier containing a sorbitan component having a high level of
sorbitan
monoester (hereafter referred to as "Emulsifier-1") has the following
composition:
Ester Composition
82% Sorbitan Monoester
2% Sorbitan diester
14% Sorbitan
1% Isosorbide monoester
Fatty Acid Composition
88% Palmitic Acid
11% Stearic Acid
1 % Other fatty acids
The material is prepared by taking Glycomul~-P and applying the following two
enrichment steps. The predominant portion of the isosorbide esters, along with
the free fatty
acids, are removed by steam stripping using conventional shorteningloil
deodorization equipment
and the following conditions:
Minutes 110 minutes
Temperature 385°F (196°C)
Absolute Pressure 8-10 mm Hg
At the end of the deodoxization step, the level of free fatty acid is less
than 0.3% and the
isosorbide ester content is less than 1%.
In the second step, the deodorized sorbitan ester is fractionally distilled
using a CMS -15A
centrifugal molecular still (CVC Products, Inc., Rochester, N.Y.) using 5
passes. The following
conditions are used:
Feed rate 15 lb/hr,
Rotor feed Gradually increased from 130-190°C during the
consecutive passes
Rotor Residue temperature 140-220°C
Cooling Water temperature 30-37°C
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Bell Jar pressure 6-12 micron
Distillation cuts for each pass 10-15%
The distillate fractions are collected on the surface of the bell jar that is
heated to
facilitate removal. Distillate and residue are continuously removed by
transfer pumps. The
fractionation process is monitored by differential scanning calorimetry (DSC),
HPLC, and
refractive index determinations.
Example 2
An improved emulsifier containing a sorbitan component having a high level of
sorbitan
monoester (hereafter referred to as "Emulsifier-2") has the following
composition:
Ester Com osition
70% Sorbitan Monoester
9% Sorbitan diester
1% Sorbitan triester
15% Sorbitan
5% Isosorbide monoester
Fatty Acid Composition
86% Palmitic Acid
13% Stearic Acid
1 % Other fatty acids
The material is prepared according to the enrichment procedure described in
Example 1.
Example 3
An improved emulsifier containing a sorbitan component having a high level of
sorbitan
monoester (hereafter referred to as "Emulsifier-3") has the following
composition: '
Ester Composition
60% Sorbitan monoester
15% Sorbitan diester
17% Free polyol (2% Isosorbide)
Fatty Acid Composition
90% Palmitic Acid
8% Stearic Acid
2% Other fatty acids
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The material is prepared according to the enrichment procedure described in
Example 1.
Example 4
An improved emulsifier containing a sorbitan component having a high level of
sorbitan
monoester (hereafter referred to as "Emulsifier-4") has the following
composition:
Ester
Composition
75% Sorbitan monoester
15% Sorbitan diester
7% Free polyol (3%
Isosorbide)
Fatty Acid Composition
15 % Palmitic Acid
5% Stearic Acid
55% Oleic Acid
20% Linoleic Acid
5 % Other fatty acids
This composition is prepared in a stainless steel reactor equipped with a
mechanical
agitator, heating and cooling coils, a condenser, and an electric heating
jacket. The reactor is
charged with 20 kg of sorbitol (70%), 25 kg oleic acid, and 85g NaOH (50%) as
esterification
catalyst. Mechanical agitation and nitrogen sparging is applied. The
temperature is increased to
220°C. The reaction is allowed to proceed for 2-3 hours with the
reactor at slightly below
atmospheric pressure. Esterification is complete when the free fatty acid is
less than 1.5%. The
pressure is gradually reduced to 10-15 mm Hg.
The temperature is reduced to 170°C and 70g of phosphoric acid (70%) is
added to the
reactor to initiate the etherification process. A slight amount of water is
used to wash all
phosphoric acid into the reactor. The temperature is gradually increased to
220°C for the
etherification process. Etherification is conducted until most of the sorbitol
esters are converted
to sorbitan esters and no significant level of isosorbide esters are formed.
The free fatty acid level in the reaction mixture is determined by titration
with base. The
etherification endpoint is determined by HPLC according to the Test Methods
section.
After the esterification and etherification processes, the reaction mixture is
molecular
distilled (according to Section aIA) to produce sorbitan component with
greater than 50%
sorbitan monoesters. Because deodorization has already been carried out during
synthesis,
distillation can occur without additional deodorization.
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Examples 5-7
A mixture of 66% Russet Burbank and 34% Norkota potatoes having an overall
solids
level of about 20% and reducing sugars of about 1.6% are washed in room
temperature water to
remove dirt and any foreign materials. The potatoes are then steam-peeled and
cut into 0.625 in.
(1.59 cm) thick slices. The slices are then cooked for 30 nunutes at a steam
pressure of 38-40
psig. The cooked potato slices are then shredded and mashed as they are forced
through a die
plate. Emulsifier is added to the potato mash in the form of a 5% aqueous
dispersion as outlined
in the table below. The potato mash is mixed with the dispersion as it is fed
through an augur
and distributed to two single drum dryers. The potato mash is spread onto the
drying drum with
four applicator rolls, forming a thin sheet Iayer of 0.005-0.008 in. (0.013 to
0.020 cm). The drum
is rotated at approximately 14-16 s/rev. This results in a dehydrated potato
sheet having a
moisture content of 7-8%, which is removed from the drum by a doctor knife.
Properties Example Example Example
5 6 7
Emulsifier added Emulsifier-1Emulsifier-2Emulsifier-3
Emulsifier concentration0.1 0.1 0.1
(% in finished dehydrated
flakes)
Examples 8-14
The following emulsifier systems are used to produce dehydrated potato
ingredients in
the manner described in Examples 5 through 7:
Example No. 8 9 10 11 12 13 14
Emulsifier-150% 0% 0% 0% 0% 0% 80%
Emulsifier-20% 75% 50% 90% 50% 95% 0%
DATEM 0% 0% 50% 0% 0% 0% 15%
Monoglyceride50% 25% 0% 0% 40% 0% 0%
Lecithin 0% 0% 0% 10% 10% 5% 5%
DATEM: PanodanT"' 205, a commercially available DATEM made by Danisco Cultor
(New
Century, IBS). It has the following fatty acid composition:
11 % Palmitic acid
87% Stearic acid
1 % Oleic acid
1% Other fatty acid
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Monoglyceride: Dimodan~ PVP, a commercial distilled monoglyceride available
from Danisco
Cultor, New Century, KS.
Lecithin: UltraLecOF is a deoiled, ultrafiltered soybean lecithin available
from ADM, Decatur,
IL.
B. Dough and Finished Product Examples
Exanxple A
A dough composition is prepared that comprises 35% water, 3% dough
emulsifier*, and
62% of the following mixture of ingredients:
Ingredient Wt. % in mixt.
Potato flakes (made according to Example 60
5)
Potato flanules (XL-Potato Granules from 13
Basic American Foods,
Plover, WI)
Corn Meal (PCPF400T"~ Lauhoff Corn Milling 12
Co., St. Louis,
MO)
Wheat starch (Aytex PT"", ADM, Decatur, 8
IL)
Maltodextrin (DE 18 from Grain Processing, 7
IA)
'The dough emulsifier used in the preparation of the dough is Aldo~ DO, which
is
available from Lonza Group, Fairlawn, NJ. Aldo~ DO comprises monoglycerides,
diglycerides,
and triglycerides with the following composition:
Fattyacid com ositionEster
composition
44% Oleic acid 37% Monoglyceride
10% Linoleic acid 48% Diglyceride
39% Palmitic acid 12% Triglyceride
4% Stearic acid 3% Other species
3% Other fatty acid
The potato flakes, potato flanules, corn meal, wheat starch, and maltodextrin
are mixed
together in a blender. (Alternatively, the maltodextrin may be dissolved in
the water before being
added to the dough.) The emulsifier is heated to produce a homogeneous liquid.
Using a dough
mixer the emulsifier is added to the dry mixture followed by water (or water
plus maltodextrin) to
form a loose, dry dough. The dough is sheeted by continuously feeding it
through a pair of
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sheeting rolls, forming an elastic continuous sheet without pinholes. Sheet
thickness is controlled
to about 0.02 in. (0.051 cm). The dough sheet is then cut into oval shaped
pieces and fried in a
constrained frying mold at 375°F (191°C) for about 6 seconds to
make a finished product. The
frying oil is NuSunT"' oil. NuSunT"~ oil is a mid-oleic sunflower oil that is
commercially available
from ADM (Decatur,1L).
Example B
A dough composition is prepared as in Example A, wherein the dough emulsifier
is a di-
triglycerol monoester. This dough PGE, referred to as 2,3-1-O, is a
developmental sample from
Lonza Group (Fairlawn, NJ). This PGE (2,3-1-O) has the following composition:
Fatty acid composition Ester Composition
90% Oleic acid 53% Diglycerol monoester
6% Linoleic acid 4% Triglycerol monoester
3% Stearic acid 10% Diglycerol diesters
1% Palmitic acid 3% Triglycerol diesters
23% Unesterified polyglycerol
7% Other esters
Examples C-J
A dough composition is prepared as in Example A, where the flakes and dough
emulsifier blend are specified in the following table:
Example No. C D E F G H I J
Potato flakesEx. Ex. Ex. Ex. Ex. Ex. Ex. Ex.
5 5 6 7 6 6 5 7
Aldo~ DO 70% 70% 50% 40% 40% 50% 50% 50%
PGE (2,3-1-O)0% 0% 50% 20% 20% 0% 0% 0%
Emulsifier-4 0% 0% 0% 0% 0% 50% 30% 45%
NuSunT"" oil 30% 25% 0% 40% 35% 0% 20% 0%
UltraLec~ 0% 5% 0% 0% 5% 0% 0% 5%
F
NuSunT"' oil is a mid-oleic sunflower oil that is commercially available from
ADM (Decatur, IL).
UltraLec~ F is a deoiled, ultrafiltered soybean lecithin that is commercially
available from ADM
(Decatur, IL).
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Examples K-R
A dough composition is prepared as in Example A, where the flakes and dough
emulsifier blend are specified in the following table:
Example No. K L M N O P Q R
Potato flakesEx. Ex. Ex. Ex. Ex. Ex. Ex. Ex.
6 5 5 7 5 6 5 5
Aldo~ DO 0% 0% 0% 0% 0% 50% 50% 65%
PGE (2.3-1-O)0% 0% 0% 0% 0% 20% 20% 0%
Emulsifier-470% 70% 90% 80% 40% 30% 0% 0%
Span 80TM 0% 0% 0% 0% 60% 0% 30% 35%
PanodanT~~ 0% 0% 0% 20% 0% 0% 0% 0%
SD
NuSunTM oil 30% 25% 0% 0% 0% 0% 0% 0%
UltraLec~ 0% 5% 10% 0% 0% 0% 0% 0%
F
Span 80TM is a commercial sorbitan ester available from Uniqema (Wilmington,
DE).
PanodanTM SD is a DATEM available from Danisco Cultor, New Century, KS and has
the
following composition:
Fatty acid composition
64% linoleic acid
20% oleic acid
7% stearic acid
7% palmitic acid
2% other fatty acid
Examples S-Z
A dough composition is prepared as in Example A, where the flakes and dough
emulsifier blend are specified in the following table:
Example No. S T U V W X Y Z
Potato flakesEx. Ex. Ex. Ex. Ex. Ex. Ex. Ex.
6 7 5 5 6 5 5 7
PGE (2.3-1-O)60% 70% 30% 0% 0% 0% 0% 60%
Emulsifier-40% 0% 50010 0% 0% 0% 0% 0%
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Sorbitan 0% 0% 0% 75% 70% 90% 80% 40%
ester*
PanodanT"~ 0% 0% 20% 0% 0% 0% 20% 0%
SD
NuSunTM oil 40% 25% 0% 25% 25% 0% 0% 0%
LTltraLec~ 0% 5% 0% 0% 5% 10% 0% 0%
F
Examples AA and AB
The following dough emulsifier blends are used to prepare fat-free fabricated
chips.
Ingredient* Example AA Example AB
PGE (2,3-1,2-IM)17.5% 35%
Lecithin (LTltraLec~17.5% 0%
P)
Olean~ 65% 65%
*Olean~ is available from the Procter and Gamble Company, Cincinnati, Ohio.
The
Lecithin component is a commercial lecithin, LTltraLec~ P, available from ADM,
Decatur, IL.
The PGE, a mixture of di- and triglycerol mono- and diesters of IM fatty
acids, is a
developmental sample from Lonza Group, Fairlawn, NJ. This PGE has the
following
composition:
Fattyacid composition Ester
Composition
73%oleic acid 26% diglycerol monoester
14%palinitic acid 23% diglycerol diester
8% stearic acid 12% triglycerol monoester
5% linoleic acid 7% triglycerol diester
6% tetraglycerol
monoester
6% tetraglycerol
diester
7% unesterified polyglycerols
13% other PGEs
Dough compositions are prepared using the potato flakes prepared in Example 5.
Each
dough composition comprises 35% water, 3% dough emulsifier, and 62% of the
following
mixture of ingredients:
Ingredient Wt. % in mixture
Potato flakes 74
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Potato flanules (XL-granules Basic 10
American Foods,
Plover, WI)
Precooked Waxy Corn Starch (Ultrasperse~-A)8
from
National Starch ~ Chemical Corp., Bridgewater,
NJ)
Substituted Waxy Maize (N-CreamerTM46 1
from National
Starch & Chemical Corp.)
Maltodextrin (DE 18 from Grain Processing,7
IA)
The potato flakes, potato flanules, modified starches, and maltodextrin are
mixed
together in a blender. (Alternatively, the maltodextrin may be dissolved in
the water before being
added to the dough.) The emulsifier is heated to produce a homogeneous liquid.
Using a dough
mixer the emulsifier is added to the dry mixture followed by water (or water
plus maltodextrin) to
form a loose, dry dough. The dough is sheeted by continuously feeding it
through a pair of
sheeting rolls, forming an elastic continuous sheet without pinholes. Sheet
thickness is controlled
to about 0.02 in. (0.051 cm). The dough sheet is then cut into oval shaped
pieces and fried in a
constrained frying mold in Olean~ at 375°F (191°C) for about 6
seconds to make a finished
product.
Example AC
A dough composition is prepared as in Example A, wherein the dough emulsifier
is a
50:50 mixture of triglyceride oil (NuSunT"" oil, described above) and 2-1-O, a
DGME available
from Danisco Cultor (New Century, KS) having the following composition:
Fattyacid compositionEster Composition
90%Oleic acid 79% Diglycerol monoester
6% Linoleic acid 2% Triglycerol monoester
3% Stearic acid 3% Diglycerol diesters
1 Palmitic acid 1 % Triglycerol diesters
%
14% Unesterified polyglycerols
1% Other esters
Example AD
A dough composition is prepared that comprises 35% water, 3% dough
emulsifier*, and
62% of the following mixture of ingredients:
Ingredient I Wt. % in mixt.
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Potato flakes (Winnemucca Farms, Winnemucca, 60
NV)
Potato flanules (XL-Potato Granules from 13
Basic American Foods,
Plover, WI)
Corn Meal (PCPF400T"" Lauhoff Corn Milling 12
Co., St. Louis,
MO)
Wheat starch (Aytex PTM, ADM, Decatur, II,) 8
Maltodextrin (DE 18 from Grain Processing, 7
IA)
*The dough emulsifier used in the preparation of the dough comprises
Emulsifier 4.
The potato flakes, potato flanules, corn meal, wheat starch, and maltodextrin
are mixed
together in a blender. (Alternatively, the maltodextrin may be dissolved in
the water before being
added to the dough.) The emulsifier is heated to produce a homogeneous liquid.
Using a dough
mixer the emulsifier is added to the dry mixture followed by water (or water
plus maltodextrin) to
form a loose, dry dough. The dough is sheeted by continuously feeding it
through a pair of
sheeting rolls, forming an elastic continuous sheet without pinholes. Sheet
thickness is controlled
to about 0.02 in. (0.051 cm). The dough sheet is then cut into oval shaped
pieces and fried' in a
constrained frying mold at 375°F (191°C) fox about 6 seconds to
make a finished product. The
frying oil is NuSunT"~ oil. NuSunT"' oil is a mid-oleic sunflower oil that is
commercially available
from ADM (Decatur, IL).
Example AE
A mashed potato is made with the following composition:
45 g Flakes made according to Example 5
169 g Water
12 g Margarine (60% fat)
1 g Salt
77g Milk (Whole)
Water, margarine & salt are heated to boiling. Milk and flakes are then added
and the
combination is mixed well. The finished mashed potato is comparable to current
commercial
mashed potato products.
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Example AF
A decorative frosting for cakes and pastries is made with the following
ingredients.
Ingredient Wt. % in mixture
Sucrose 14
Corn syrup solids (24 DE) 2
Salt 0.1
Sodium carboxymethyl cellulose0.1
Sodium citrate 0.05
Methyl ethyl cellulose 10-12
(5% solution)
Fat 30
Tween 60 0.2
Sorbitan monoester (of 0.4
Example 1)
Water q.s. to 100%
To make the frosting, the dry ingredients (sucrose, corn syrup solids, salt,
sodium
carboxymethyl cellulose, and sodium citrate) are mixed and added to a solution
of methyl ethyl
cellulose and water. The temperature is raised to 50°C. The fat and the
emulsifier system
(Tween 60 plus sorbitan monoester) are melted together and the homogeneous
mixture is blended
with the aqueous mixture with stirring. The final composition is pasteurized,
homogenized at a
total of 1,500 psi and frozen.
Example AG
A microwave cake mix is prepared as follows. An emulsifier-shortening blend is
prepared by warming soybean oil to a temperature of about 79°C. An
emulsifier blend
(monoglyceride, propylene glycol monoesters of palm oil, lactic acid esters of
monoglyceride and
soxbitan ester) is added to the heated oil.
Ingredient Percent
Monoglyceride (Myverol 17
1804)
Propylene glycol monoesters18
of
hydrogentated palm oil
Lactic acid esters of monoglyceride5.6
Sorbitan Ester (SME-1) 4.4
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Soybean oil (I-107) 55
A cake mix is pxepared by combining the following ingredients.
Ingredient Percent
Sugar 41
Flour 31
Emulsifier-shortening blend10.3
Monocalcium phosphate 0.7
Sodium aluminum phosphate 0.15
Soda 1.7
Dicalcium phosphate 0.3
Guar and Xanthan Gums 0.2
Salt ~ 0.6
Starch 5.2
Cocoa 8.3
Flavors Remainder
The sugar and flour are co-milled as described in U.S. Patent No. 3,694,230,
to Cooke.
The co-milled sugar and flour are then added with the shortening and the
remaining ingredients in
a ribbon blender. '
The dry mix (460 g) is then mixed with 144 g eggs, 55 g oil, and 320 g water
to make a
batter. The mixing time is for 2 minutes at 850 rpm with a portable mixer. The
batter has a
density of 0.85 g/cc and a viscosity of 5800 cp (at 21°C). The batter
is then baked in a
microwave oven (preferably with a carousel) in a Pyrex bowl for 11.5 minutes
using 500 watts
power.
A cake having a good grain and texture is prepared.
Example All
30 g of triglycerol monostearate (Paniplus 504 from the Paniplus Company) and
28 g of
sorbitan monoester (SME-1) is melted with 0.87 g of sodium oleate by heating
to a temperature
of 104°C. This melt is then placed in a stainless steel beaker with
767.4 g of high fructose corn
syrup (Isomerose 100 from the Clinton Corn Processing Company) having a
temperature of 60°C
and subjected to high shear. The sheared mix is cooled to 32°C. Then
813.8 g of a triglyceride
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oil (Crisco Oil from the J.M. Smucker Co.) at a temperature of 32°C is
blended into the
emulsifier-water dispersion and subjected to additional high shear. The
resulting product is a
homogeneous emulsion suitable for use, when mixed with additional water or
milk, nonfat milk
solids and saccharides, to make frozen desserts having good eating quality
characteristics,
texture, appearance and flavor.
109.4 g of the emulsion is blended in a home mixer running at high speed with
278.7 g of
ice water, 93.9 g nonfat milk solids, and 105.0 g of sucxose for about 2
minutes. The resulting
aerated mixture has an overrun of about 75%. The aerated mixture is then
placed in a freezing
compartment at a temperature of about -18°C for about 5 hours. The
resulting product is a frozen
dessert that has a density of about 0.62 g/cc and had good texture and
appearance.
Example AI
A cake mix is prepared as follows:
In edient Percent
Shortening 9.14
Sugar 48.69
Flour 32.27
Salt - 0.75
Leavening 1.78
Gums 0.33
Starches 2.17
Enrichments, flavors, colors4.00
,
The shortening composition
is:
Sorbitan component of Example6.9
1
Propylene glycol monoesters18.9
soybean oil (IV-107) 66.95
soybean oil (IV-8) 3.35
The sugar and flour are
co-milled together using
the method described in
U.S. Pat. No.
3,694,230. The shortening
is prepared by mixing
the propylene glycol monoestex
and the sorbitan
component at a temperature71 C. This mixture is then added
of about to the remaining
ingredients in the shortening.is allowed to settle out and is
The polyol separated.
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The shortening and co-milled sugar/flour are mixed together. To this mix is
then added
the remaining ingredients. Cake batters are prepared by using the following
formulation:
Dry mix 524 g
Egg 144 g
Water 300 g
Oil 73 g
Batter weight per layer 510 g
Batters are prepared by mixing the above ingredients for two minutes using a
standard
home mixer at a medium speed. The batter is weighed into two 20 cm round pans.
The layers are
baked to doneness; about 37 minutes at 177°C.
A moist, light tasting cake is produced.
INCORPORATION BY REFERENCE
All of the disclosure of the aforementioned patents, patent applications,
publications, and
other references are herein incorporated by reference.
