U.S. patent application number 15/138933 was filed with the patent office on 2016-08-25 for food product containing table salt formulation.
The applicant listed for this patent is Frito-Lay Trading Company Gmbh. Invention is credited to Carlos Jose BARROSO, Eapen GEORGE, Samuel Claude HALIM, Wendelin Jan STARK.
Application Number | 20160242447 15/138933 |
Document ID | / |
Family ID | 39247207 |
Filed Date | 2016-08-25 |
United States Patent
Application |
20160242447 |
Kind Code |
A1 |
STARK; Wendelin Jan ; et
al. |
August 25, 2016 |
Food Product Containing Table Salt Formulation
Abstract
The present invention relates to food products which are dry and
which contain a table salt formulation characterized in that said
table salt formulation comprises a mixture of at least two types of
particles of one or more physiologically acceptable inorganic salts
and at least one of the type of said particles is composed of
primary particles of which at least 50 wt % are 5-5000 nanometer in
diameter; to manufacturing methods of such food products; further
it relates to specific table salt formulations, to manufacturing
methods and methods of use of such table salt formulations.
Inventors: |
STARK; Wendelin Jan;
(Zurich, CH) ; HALIM; Samuel Claude; (Zurich,
CH) ; GEORGE; Eapen; (Frisco, TX) ; BARROSO;
Carlos Jose; (Dallas, TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Frito-Lay Trading Company Gmbh |
Bern |
|
CH |
|
|
Family ID: |
39247207 |
Appl. No.: |
15/138933 |
Filed: |
April 26, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12866210 |
Aug 4, 2010 |
9352974 |
|
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PCT/CH2008/000042 |
Feb 4, 2008 |
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15138933 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A23L 27/40 20160801;
C01D 3/26 20130101; A23V 2002/00 20130101; C01D 3/04 20130101 |
International
Class: |
A23L 1/237 20060101
A23L001/237 |
Claims
1. A method of manufacturing a food product which is dry and which
comprises a table salt formulation wherein said table salt
formulation comprises aggregates of a mixture of at least two types
of primary particles of one or more inorganic salts suitable to
human nutrition, wherein each said aggregate comprises partially
sintered primary particles, and at least 50 wt % of said primary
particles are 5-5000 nanometer in diameter, the method comprising
the steps of manufacturing primary particles in a flame spray
process thereby providing an aerosol and directly contacting said
food product with said aerosol.
2. A food product obtained by a process of claim 1.
3. A method of manufacturing a table salt formulation comprising
the steps of: a) forming primary particles of physiologically
acceptable inorganic salts by means of a grinding process and/or a
flame synthesis process and/or precipitation process and/or spray
drying process b) isolating the particles obtained c) forming
aggregates by applying heat and/or pressure and/or exposure to
diluted steam to the obtained primary particles.
4. A table salt formulation obtained by the method of claim 3.
5. A method of manufacturing a table salt formulation comprising
the steps of: a) forming primary particles of one and only one
physiologically acceptable inorganic salt with diameters between 5
and 5000 nanometers, by means of a grinding process and/or a flame
synthesis process and/or precipitation process and/or spray drying
process; b) isolating said primary particles; c) forming aggregates
of said primary particles by applying heat and/or pressure and/or
exposure to diluted steam to the obtained primary particles.
6. The method of claim 5 further comprising crushing and separating
said aggregates into specific size fractions.
7. The method of claim 5 wherein said physiologically acceptable
inorganic salt is selected from group consisting of NaCl,
CaSO.sub.4, CaCl.sub.2, MgSO.sub.4, MgCl.sub.2, KCl.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a divisional patent application of U.S.
Ser. No. 12/866,210 entitled "Food Product Containing Table Salt
Formulation" filed on Aug. 4, 2010, which is a 371 National Phase
filing under Chapter II of International Application No.
PCT/CH2008/000042 entitled "Food Product Containing Table Salt
Formulation" filed on Feb. 4, 2008, the technical disclosures of
which are hereby incorporated herein by reference.
TECHNICAL FIELD
[0002] The present invention relates to food products containing
table salt formulations; to manufacturing methods of such food
products; further it relates to specific table salt formulations,
to manufacturing methods and methods of use of such table salt
formulations.
BACKGROUND ART
[0003] Table salt is used to augment and enrich flavor of food
products: it contains essential minerals for human life and is
considered as a cultural part of cooking. The widespread use of
table salt, however, also bears risks and disadvantages. High
sodium levels in blood are associated with severe diseases or
disorders, such as high blood pressure, kidney failure, heart
attacks. This results in large endemic costs to societies and is a
major contributing factor to rapidly growing health care cost in
western societies.
[0004] It is also known that the taste of certain sea salts, e.g.
fleur de sel, differ from the taste of standard table salt in a
beneficial way. Such salts are, however, difficult to obtain and/or
are not consistent in their quality. Such inconsistent quality and
availability do not make application of such salts amenable to
large scale industrial manufacturing. Hence, a reliable and
scalable process for substituting such advantageous natural salts
is required.
[0005] A number of documents disclose and claim the reduction of
sodium in table salts (WO85/00958, BE902690, EPO417062, WO98/53708,
US 2004/0224076) by the substitution of sodium chloride with
different other salts, e.g. KCl, or different magnesium salts. Said
compositions provide a salt flavor enhancing effect to food
products containing such compositions. The disclosed compositions
contain relatively high amounts of sodium and are not satisfactory
with regards to their taste.
[0006] The prior art relating to the field of salt perception and
salt delivery can be best separated into two subfields using a
distinction based on the food's characteristics:
[0007] A) A distinct group of applications of salt is made on wet
foodstuff, e.g. soups, sauces, mashed potatoes, beverages, or
bread. This group of food is characterized by the fact that the
salt is present in the form of aqueous ions broadly distributed
within the food material. During preparation of the food, the salt
is added in a process step where abundant liquid is present. As a
result, the salt dissolves and is homogeneously distributed within
the food material. A special case of products are "ready to use"
powder soups (so called instant soups where the ingredients are
present as a dry mixture but hot water added by the consumer also
results in dissolution of the salt); these products are added to
this group as the consumer makes the last processing step during
preparation of the soup.
[0008] B) A different distinct set of applications of salt concerns
dry foodstuff. This group contains dry snacks, dry, processed food
such as fried or baked chips (e.g. potato, rice, wheat chips),
scones, pastries, and others. During the preparation of this group
of materials, salt is added in a dry form within one or more
distinct processing steps. Insufficient liquid is present to
dissolve and redistribute the salt. As a result, distinct salt
grains are scattered on or within the food material. The consumer
eats the material without further processing in contrast to e.g.
instant soups (see group A).
[0009] As a direct consequence of above distinction, group A must
specify a salt according to composition as ions well distributed
throughout the material. No groups of cations and anions can be
assigned to one another. Salts are typically identified or
described as mixtures of specific mass content of specific
ingredient salts (e.g. 90 wt % NaCl, 8 wt % KCl, 2 wt %
CaCl2-6H2O). However, if looking at the food material, no distinct
remainders of the ingredients can be identified beyond the ions
that make up the salt.
[0010] While intuition may suggest that salt perception only
depends on the chemical composition as described in the prior art
(see above), the inventors of the present invention have
surprisingly found a significantly improved salt perception on dry
foodstuff if a specific structure and substructure of the salt
constituents is provided. In particular the fact that ingredients
for table salts (e.g. NaCl, KCl, Ca and Mg chlorides or sulfates,
others) can be combined in specific ways, as further described
below, will result in different and improved salt perception during
consumption of the dry food.
DISCLOSURE OF THE INVENTION
[0011] Hence, it is a general object of the invention to provide a
dry food product that overcomes one or more of the problems of the
known dry food products. In particular, the present invention aims
to provide dry food products that simultaneously delivery salty
perception to the consumer whilst reducing sodium uptake. Further,
the invention aims to provide cost effective and reproducible
preparation of large amounts of such food products and the
corresponding table salt formulations. The invention also aims to
provide a platform of designed salts that can both deliver improved
saltiness at reduced sodium consumption and that can be adapted to
a broad variety of dry food products.
[0012] These objectives are achieved by a food product as defined
in claim 1 and a table salt formulation as defined in claim 9.
Further aspects of the invention are disclosed in the specification
and independent claims, preferred embodiments are disclosed in the
specification and the dependent claims.
[0013] The present invention will be described in more detail
below. It is understood that the various embodiments, preferences
and ranges as provided / disclosed in this specification may be
combined at will. Further, depending of the specific embodiment,
selected definitions, embodiments or ranges may not apply.
[0014] Unless otherwise stated, the following definitions shall
apply in this specification:
[0015] The term "table salt" is known in the field. It particularly
denotes a composition traditionally mainly containing NaCl,
intended for human consumption, which may contain fluorine and/or
iodine sources as well as further components to improve handling.
The term implies certain purity of all components, defined by
national legislation. Since it has recently been found that some
other inorganic salts are also perceived as salty by the human
tongue, table salts can contain substantial amounts of these other
salts, namely potassium and magnesium salts. This directly reflects
the fact that neurologically, the salt perception is a combination
of anion and cation detection on the tongue. However, saltiness is
not unique to NaCl and therefore, other inorganic salts suitable to
human nutrition have been applied.
[0016] The term "food product" is known in the field. It
particularly denotes any solid product intended for human
alimentation. Particular relevant are in the context of the
invention are dry food products, especially snack food products
(e.g. potato chips, tortilla chips, crackers, popcorn and the
like); cereals, scones, pastries. A food product is considered
"dry" if it does not contain enough water to dissolve all table
salt present therein; thus salt particles are present in said
product. Typically, the water content of such dry food product is
below 10 wt %, preferably below 5 wt %.
[0017] The term "Primary Particle" is known in the field. It
particularly denotes a chemically uniform particle of 5-5000 nm,
preferably of 20-2000 nm diameter. A particle is considered
chemically uniform, if its chemical composition is similar along
the diameter of the particle. For example, particles made by an FSP
process, such as NaCl or NaCl/KCl particles, are considered
chemically uniform, as such particles form a phase considered as a
solid solution. As another example, NaCl/SiO2 made by FSP consists
of two chemically uniform particle types that can be produced
simultaneously. Electron microscopy images show that such materials
consist of NaCl particles (uniform within the diameter of the
particles) and SiO2 (silica particles, again uniform within the
diameter of these particles). Most preparation methods can be used
to simultaneously manufacture two or more type of chemically
uniform particles within the same production run. This elegant way
to directly make mixtures greatly facilitates production and
removes requirement for an additional mixing step. Further,
particles obtained by a milling process are considered chemically
uniform, as such particles are considered crystalline or
micro-crystalline. The shape of primary particles may vary in a
broad range and depends on its manufacturing; typically rounded
entities or sharp-edged entities of equal dimensions are used.
[0018] In the context of this invention, the term "building block"
is used synonymous to "Primary particle"; this term further
stresses the aim to use such particles for forming
"aggregates".
[0019] The term "Aggregate" is known in the field. It particularly
denotes the aggregation or agglomeration of smaller entities, in
the context of this invention, above all the aggregation or
agglomeration of building blocks.
[0020] The term "Flame Spray Pyrolysis" or "FSP" is known in the
field and is a special form of the general term flame synthesis. It
particularly denotes a process wherein particles are synthesized by
pyrolysis of a sprayed liquid in a flame. Details of suitable
apparatuses and process parameters may be found in the examples or
in US2004126298, US2006229197, or US2007196259.
[0021] The term "Grinding" is known in the field. It particularly
denotes a process wherein particles are crushed down to smaller
particle sizes. In the context of this invention, the term
"grinding" includes, but is not limited to ball milling, e.g.
milling in liquid media using a ball mill.
[0022] In more general terms, in a first aspect, the invention
relates to a dry food product which contains a table salt
formulation characterized in that said table salt formulation
comprises (i.e. contains or consists of) a mixture of at least two
types of particles of one or more physiologically acceptable
inorganic salts and in that at least one of the type of said
particles is composed of primary particles of which at least 50 wt
% (preferably at least 70 wt %) are 5-5000 nanometer in
diameter.
[0023] This inventive formulation food product exhibits a salty
perception while maintaining flavor integrity at reduced sodium
levels. In some specific cases, such food product also provides
salty perception but with reduced or without the metallic or
soap-like off-flavors inherent to aqueous solutions of the similar
composition. Without being bound to theory, it is believed that the
size of the primary particles and their arrangement has a
significant influence to the quality of the food product. Such
small particles of table salts have, until now, not been used for
the manufacturing of dry food products. It is believed that this is
due to the slightly hygroscopic properties of sodium chloride and
other inorganic salts amenable to food application, which makes
handling and storage of such small particles inconvenient or even
impossible. This is typically seen in the form of blocks if salt
has been stored under humid conditions. For comparison, typically
used table salt has a particle size of about 100 to 1000
micrometer. The above identified small primary particles are
available using the manufacturing methods described herein.
[0024] The food product of this invention is explained in further
detail below.
[0025] Primary Particle:
[0026] In a preferred embodiment, the invention relates to a table
salt composition comprising at least 70 wt % particles consisting
of NaCl or a NaCl/KCl mixture and at most 30 wt % of particles of
one or more physiologically acceptable inorganic salts. In a
preferred embodiment, said NaCl/KCl mixtures contain at least 50 wt
% NaCl.
[0027] In a further preferred embodiment, at least 50 wt %
(particular preferably at least 70 wt %) of all primary particles
are 5-5000 nanometer in diameter.
[0028] Aggregates:
[0029] In an advantageous embodiment, the invention relates to a
food product as described herein, wherein said primary particles
are formed to aggregates, said aggregates consisting of
10-10.sup.15, preferably 10.sup.3-10.sup.12, primary particles. The
formation of aggregates out of the primary particles, as defined
above, further increases the quality or the food product. It is
understood and evident to the person skilled in the field that
during aggregate formation, the distinction between individual,
touching primary particles can become difficult due to partial
sintering and formation of so called necks (see e.g. .sup.1). Such
partial sintering helps consolidating the structure of the
aggregate and can be made on purpose by heating or compaction or
exposure to diluted steam or a combination thereof.
[0030] Chemical Composition:
[0031] In an advantageous embodiment, the invention relates to a
food product as described herein, wherein the cation of said one or
more physiologically acceptable inorganic salt is selected from the
group consisting of alkali metal ions (in particular Na, K), earth
alkali ions (in particular Mg, Ca, Sr), transition metal ions (in
particular Zn, Fe, Cu, Mn).
[0032] In an advantageous embodiment, the invention relates to a
food product as described herein, wherein the anion of said one or
more physiologically acceptable inorganic salt is selected from the
group consisting of phosphates (in particular monophosphates:
PO.sub.4.sup.3-, HPO.sub.4.sup.2-, H.sub.2PO.sub.4.sup.-), sulfates
(SO.sub.4.sup.2-), silicates, hydroxides, halogenides (in
particular F, Cl.sup.-, Br.sup.-, I.sup.31 ), carbonate or
hydrogencarbonate.
[0033] In a further advantageous embodiment, the invention relates
to a composition as described herein, wherein said physiologically
acceptable inorganic salt is selected from the group consisting of
NaCl, CaSO4, CaCl2, MgSO4, MgCl2, KCl, as water-free (anhydrous) or
hydrated salts).
[0034] Morphology:
[0035] Enhanced saltiness of the inventive food product can be
realized using structured salts of a specific structure and
substructure, containing other components such as gypsum or
magnesium chloride or magnesium sulfate or potassium chloride. Such
sub-structured salts can be described as complex aggregates
consisting from a major constituent (preferably composed of sodium
chloride or a mixture of sodium and potassium chloride) and minor
constituents (consisting of one or more other physiologically
acceptable salts as disclosed herein). It was surprisingly found
that specific substructures of complex salts can be prepared as to
deliver an enhanced salt perception to a test panel or consumer
group whilst delivering significantly less sodium to the consumers.
This astonishing finding therefore allows maintaining flavor and
salt perception in a dry food product whilst cutting down on sodium
delivery without the application of any artificial additive such as
glutamate or other flavor enhancers. Latter compounds find
wide-spread application in food but have been suspected for a
series of sicknesses and, moreover, are incompatible with the
concept of organic food or natural or nature-identical food
additives. Some of the substructures found in the present invention
contain elements that are also found in sea salts grown from
evaporating natural sea water in shallow ponds in climatically hot
regions. However, latter so called natural sea salts do not have an
optimized substructure and composition and can not be adapted
readily to the preparation or design of a specific flavor
combination. Most natural sea salts are available at very limited
supply and their often manually effected collection is labor and
cost effective. The present invention overcomes these limitations
by providing a toolbox from which optimized salts with an adaptable
substructure can be rapidly prepared for a specific application.
Suitable sub-structured salts furthermore are made in a way as to
exhibit enhanced shelf life since a rapidly aging material can not
be used in processed food applications. There, particularly the
effect of humidity on changes in the materials substructure is
important.
[0036] Distribution:
[0037] In an advantageous embodiment, the invention relates to a
dry food product wherein said table salt formulation is located on
one or more surfaces of said food product. In one embodiment, said
table salt formulation is homogeneously distributed in said food
product, thus also being present on its surfaces. In an alternative
embodiment, said table salt formulation is located or essentially
located, at one or more of the surfaces of said food product.
[0038] In a second aspect, the invention relates to methods for
manufacturing a dry food product as described herein.
[0039] In one embodiment, such processes comprise the steps of a)
manufacturing primary particles in a flame spray process thereby
providing an aerosol and b) directly contacting said dry food
product with said aerosol. This process is described in further
detail below: The production of the building blocks can be made in
a flame spray process and the resulting salt containing off gas
from the reactor (the aerosol) can be directly fed onto a dry food
product. Such direct contact effects aggregation and impaction of
the salt formulation with the dry food product and simultaneously
effects application of the salt to form the desired substructure.
Step a) manufacturing of primary particles is known in the field
and also described herein. The direct contact, as described in step
b) may be achieved by positioning at least one surface of a dry
food product in the off gas of a conventional FSP apparatus which
contains the primary particles. The elegance of such a direct
process is evident as the difficult handling of ultra fine
particles (diameter nanometer to micrometer range) is
sensitive.
[0040] The invention also relates to a dry food product obtainable
by or obtained by a process as described herein.
[0041] In a third aspect, the invention relates to specific table
salt formulation as described herein. These specific table salt
formulations are novel and are found particular suitable to be used
for a dry food product as described herein.
[0042] Thus, the invention relates to a table salt formulation
comprising a mixture of at least two types of particles, wherein
each type of particles contains one or more physiologically
acceptable inorganic salts and each type of said particles is
composed of primary particles of which at least 50 wt % are 5-5000
nanometer in diameter and said primary particles are formed to
aggregates containing 10-10.sup.15 of said primary particles.
[0043] In an advantageous embodiment, the invention relates to a
table salt formulation as described herein wherein the total
content of NaC1 or a NaCl/KCl mixture is at least 70 wt-% and the
total content of other physiologically acceptable salts is at most
30 wt-%.
[0044] In an advantageous embodiment, the invention relates to a
table salt formulation as described herein wherein a first type of
particles contains 90 to 99.5 wt-% NaCl and 0.5-10 wt-% of one or
more, preferably one, compound selected from the group consisting
of SiO2, CaCO3, Ca3(PO4)2, and/or optionally magnesium doped
calcium phosphates. Such magnesium doped calcium phosphates may be
represented by the formula (Ca,Mg)xOwHy(PO4)z and in particular
include hydroxyapatite and tricalciumphosphate (TCP).
[0045] In a fourth aspect, the invention relates to a process for
manufacturing a table salt formulation as described herein. It was
found that these processes are particularly suitable for the
formation of the above defined primary particles which are small
when compared to the particles currently used for table salt
formation. In particular, the processes as described herein do
circumvent the problem of hygroscopic properties occurring by using
the known processes.
[0046] Thus, the invention relates to a method of manufacturing a
table salt formulation as described herein comprising the steps of
forming primary particles of physiologically acceptable inorganic
salts by means of a grinding process (in particular a wet mill
process) and/or a flame synthesis process (in particular a flame
spray pyrolysis process) and/or a precipitation process and/or a
spray drying processes; isolating the particles obtained; forming
aggregates by mixing, applying heat and/or pressure and/or exposure
to diluted steam to the obtained primary particles.
[0047] This process allows large-scale production of the table salt
formulation as described herein.
[0048] The formation of primary particles is known per se and may
also be achieved by a precipitation process or other suitable
processes like spray drying. Flame synthesis processes are
particularly suitable where primary particles are aimed to contain
different salt compositions such as NaCl/SiO2 or NaCl/KCl or more
complex mixtures. Grinding processes are particular suitable where
the corresponding salt is commercially available, but particle size
of the commercial product is too large. It is evident that the
selection of the best process depends on the chemical composition
of said particles; such selection is within the ordinary skill of
person skilled in the art.
[0049] The invention further relates to a table salt formulation
obtained by a process as described herein.
[0050] The invention further relates to a salt toolbox, in
accordance with the invention, as described herein. Manufacturing
of a specific substructure in a table salt formulation as described
herein requires two steps: A) Preparation of specific small
building blocks consisting of crystallites or amorphous particles
of one or several mineral constituents (formation of primary
particles) and B) Combination of the building blocks to a specific
salt with a defined substructure. Steps A) and B) are explained in
further detail below: Step A) Mineral constituents can be alkaline
salts consisting of sodium or/and potassium in the form of chloride
or phosphate or carbonate or silicate or hydroxide or a mixture of
anions (e.g. sodium chloride, potassium chloride, sodium sulphate,
potassium sulphate, sodium carbonate), earth alkaline salts
consisting of calcium or/and magnesium or/and strontium salt in the
form of chloride or sulphate or phosphate or carbonate or silicate
or hydroxide or a mixture of anions (e.g. calcium sulphate in all
different states of hydration or in the anhydrous form, magnesium
carbonate, magnesium hydroxy carbonate), heavy metal salts in
suitable concentrations and mixed compositions thereof. Suitable
heavy metal salts include iron, manganese, zinc, copper (upper
limit: 2 ppm), molybdenum, cobalt and bismuth. These building
blocks can be manufactured by top-down approaches like crushing,
grinding or milling or by bottom-up techniques like precipitation,
spray-drying, sol-gel or combustion processes (flame synthesis,
flame spray pyrolysis), alternatively also freeze drying, vacuum
drying and other more specific methods may be applied and are
evident to the skilled person working in the field or a combination
of these methods. Other methods to prepare small inorganic
particles of a specific salt are known to the ones working in the
field. Typical production methods are e.g. described in, milling
which is incorporated by reference. Step B) Combination can be done
by mechanical blending and intense mixing, or by choosing
production and blending in a combined step. This can e.g. be done
by simultaneously milling specific substances together in a
suitable bead mill (e.g. DYNO Mill Typ Multi Lab, Willy A. Bachofen
AG, 0.6 L standard Inox steel/PA6 grinding vessel, ECM-Accelerators
or KD-agitator discs, 0.5 mm diameter YSZ grinding balls). During
the step of building block combination additional additives like
organic carboxylates and free acids or mixtures thereof including
fruit acids (e.g. glucuronic acid, mucinic acid, algenic acid,
pectinic acid, maleinic acid, mandelic acid, benzoic acid, tartaric
acid, citric acid, malic acid or succinic acid) may be introduced
as well.
[0051] In an advantageous embodiment, the invention relates to a
process wherein the combined building blocks (primary particles)
are consolidated by application of heat or/and pressure or/and
exposure to diluted steam to form aggregates characterized in that
said primary particles are of the same type. This results in
building blocks which are chemically uniform. This provides a
higher flexibility to the manufacturer of a food product, as a
specific combination of aggregates may be adapted to each specific
food product.
[0052] In an advantageous embodiment, the invention relates to a
process wherein the combined building blocks (primary particles)
are consolidated by application of heat or/and pressure or/and
exposure to diluted steam to form aggregates characterized in that
said primary particles are of different types. This results in
building blocks which are not chemically uniform. This provides
ready-to use aggregates which may directly applied to a food
product.
[0053] In a further advantageous embodiment, the invention relates
to a process wherein aggregates obtained, in particular if in the
size above about 1 millimeter, are crushed or broken down and
separated to a specific size fraction amenable for application of
the sub-structured salt. Separation or fractionation may take place
by any means convenient, e.g. sieving.
[0054] In a further advantageous embodiment, the invention relates
to a process wherein the primary particles are obtained by a FSP
process.
[0055] In a further advantageous embodiment, the invention relates
to a process wherein the primary particles are obtained by a wet
milling process using a solvent that is essentially water free,
such as an oil (in particular an oil that is physiologically
acceptable) or a low boiling solvent (in particular a low boiling
alcohol like methanol or ethanol).
[0056] The invention also relates to a table salt formulation
obtained by a process as described herein.
[0057] In a fifth aspect, the invention relates to the use of a
table salt formulation as described herein for the manufacture of a
food product, in particular a dry food product.
[0058] The invention also relates to a method of use of a table
salt formulation as described herein for the manufacture of a food
product, in particular a dry food product.
MODES FOR CARRYING OUT THE INVENTION
[0059] To further illustrate the invention, the following examples
are provided. These examples are provided with no intention to
limit the scope of the invention.
[0060] Analysis:
[0061] The substructure of the salt can be analyzed by a series of
analytical tools.
[0062] a) Element composition: Atom absorption spectroscopy (AAS)
or Laser Ablation Inductively Coupled Plasma Mass Spectrometry
(LA-ICP-MS) after workup and quantitative dissolution as e.g.
described by Gunther.sup.3.
[0063] b) Element distribution: The preferred method to investigate
the spatial distribution of elements in a sample is element mapping
as e.g. possible by energy dispersive X-ray analysis in an SEM as
e.g. described and used in .sup.4. This method is suitable at a
spatial resolution down to the 10 nm level. Alternatively, for
lower resolution (10 micrometer), rastering of a sample with a
laser ablation system can give much more accurate compositions but
at the expense of lower spatial resolution .sup.5. Alternatively, a
micro-X-ray absorption spectrometer can be used.
[0064] c) Phase analysis. The dominant crystal phases give
information of what combination of ions is present in a sample. It
can e.g. distinguish between a mixture of sodium chloride crystals
and calcium sulfate crystallites from a mixture of sodium sulfate
and calcium chloride. While in some cases, the salt perception of
such mixtures may not be affected by different mixtures of
anion/cation pairs, in numerous cases; such distinction plays a
role for the physical properties of the mixture. This is
particularly useful as it allows distinction between presence of
salt crystallites as claimed for group B (see background
information) and absence of distinct salt crystals (as defined for
group A (background info) where the constituents of the salt are
present as aqueous ions. Latter give no diffraction pattern in
X-ray diffraction.
[0065] d) Crystallite size. The size of the crystals or
crystallites or agglomerates of crystallites in the case of a
polycrystalline material can be best derived from scanning electron
microscopy images or using X-ray diffraction and applying the
Scherrer formula.
[0066] Starting materials: Unless otherwise specified, pure grade
laboratory chemicals (solids, liquids, gases) were used as
commercially available without further specific purification.
Commercial food grade table salt was used as "Fine 50 Pure Dried
Vacuum Salt, Glacia, British Salt, United Kingdom". Commercial high
oleic sunflower oil ("HOSO") was used as "food grade, Cargill,
United Kingdom".
EXAMPLE 1
Preparation of NaCl Primary Particles by Milling
[0067] Different amounts (225 g, 450 g, 675 g, and 900 g) of food
grade table salt were dried for 6 hours at 300.degree. C.
Subsequently, 1500 g of high oleic sunflower oil (HOSO) was added
to each of the samples. Subsequently, the samples were strongly
mixed with a magnetic stirrer or a mixing turbine (Ytron-Y, Ytron,
Germany) and milled using a laboratory agitator bead mill
(Dyno-mill multi lab, Willy A. Bachofen AG, Switzerland, 0.6 L
standard Inox steel/PA6 grinding vessel, agitator discs or
ECM-accelerators, 0.5 mm diameter Yttria Stabilized Zirconia (YSZ)
grinding balls, filling degree 60-80%). The milling was run
continuously using silicon tubes (inner diameter 8 mm, Siwa Silikon
Schlauch, Unico-Haberkorn, Switzerland) and a flexible-tube pump
(R17 DT71D4/TF, SEW Eurodrive, Germany). During milling the mill
feed was continuously agitated. In case of sedimentation of mill
material especially at high NaCl concentrations, intake of the salt
into the tube was enhanced by manual picking of the sedimented salt
with the tube opening. The milling was conducted at a maximal flow
rate of 60 L/h and a maximal agitator disc speed of 12 m/s.
Thereby, the pressure at the inlet of the grinding vessel was up to
1 bar and the temperature at the grinding vessel outlet never
exceeded 100.degree. C. For all the samples the grinding time was
between 20 and 60 min. After grinding the samples were diluted with
HOSO to a final concentration of 1.5 wt % and dispersed using an
ultrasonic horn (200 W, cycle 0.5, 1 min, Hielscher GmbH UP-400S,
Germany) for particle size distribution analyses.
[0068] To determine particle size distributions, a BI-XDC X-ray
disk centrifugation system (Brookhaven Instruments) was used. The
geometric mean of the four samples is 0.48 micrometer, 0.53
micrometer, 0.52 micrometer and 0.60 micrometer, respectively. The
particle size distributions were fitted with a lognormal function
which can be described with (mu.sub.1=-0.737, sigma.sub.1=0.091),
(mu.sub.2=-0.642, sigma.sub.2=0.079), (mu.sub.3=-0.648,
sigma.sub.3=0.102) and (mu.sub.4=-0.504, sigma.sub.4=0.140),
respectively.
EXAMPLE 2
Preparation of NaCl Primary Particles by Flame Spray Pyrolysis
[0069] Flame spray pyrolysis was applied to synthesize nanometric
sodium chloride. A precursor containing the corresponding metal
loading Na and Cl was prepared by dissolution of amounts of sodium
hydroxide (Ph. Eur., Fluka, Switzerland) in 2-ethylhexanoic acid
(puriss., SigmaAldrich, Switzerland) at 140.degree. C. and the
addition of corresponding amounts of 1,2-dichloroethane (reinst,
Merckt, Switzerland). The precursor was 2:1 diluted with
tetrahydrofuran (puriss., stabilized, Riedel-de Haen, Switzerland).
This low-viscosity liquid was delivered to a flame spray pyrolysis
apparatus consisting of 4 equal burners by annular gear pumps (HNP
Microsystems, Parchim, Germany) at 10 mL/min. The flames consisted
of a central spray delivery and a circular premix flame. The
precursor solution was pumped through a capillary (diameter 0.4
mm), dispersed with oxygen (Pan Gas, tech.) at 10 L/min and ignited
in a mixture of methane (Pan Gas, tech.) at 1.13 L/min and oxygen
(Pan Gas, tech.) at 2.4 L/min forming the premix flame. All gas
flow rates were controlled by calibrated mass flow controllers
(red-y compact, Vogtlin Instruments, Switzerland). The reactor
setup was fully enclosed and the incoming air filtered by a
conventional HEPA filter system and the offgas containing the
product nanoparticles was conducted to the filtration cylinder and
filtered (Tulona baghouse filters, PTFE on PTFE support, diameter
120 mm, length 1640 mm, Technische Textilien Lorrach GmbH &
Co., Lorrach, Germany) using a total gas flow rate of 600-750 m3/h,
resulting in an average filtration velocity of 7.6-9.4 cm/s. By
applying regular impulses of pressured air, the produced
nanoparticles fell off the filters and into the particle catchment
tank where they could be collected.
[0070] The as prepared sodium chloride nanoparticles are of white
appearance and hydrophilic. The volume-surface-average diameter of
the as produced powder was evaluated by nitrogen adsorption using
the BET method (according to .sup.6). The typical specific surface
area (SSA) was between 40 and 60 m2/g which corresponds to a
volume-surface-average diameter of between 69 and 46 nm.
EXAMPLE 3
Preparation of Mixed Primary Particles NaCl/SiO2 and
NaCl/Ca3(PO4)2
[0071] Flame spray pyrolysis was applied to synthesize
nanoparticulate sodium chloride and sodium chloride in-situ doped
with 5 wt % tricalcium phosphate (TCP) or silica. A precursor
containing the corresponding metal loading Na and Cl was prepared
by dissolution of amounts of sodium hydroxide (Ph. Eur., Fluka,
Switzerland) in 2-ethylhexanoic acid (puriss., SigmaAldrich,
Switzerland) at 140.degree. C. and the addition of corresponding
amounts of 1,2-dichloroethane (reinst, Merckt, Switzerland) or
corresponding amounts of calcium 2-ethylhexanoate prepared from
calcium hydroxide (Ph. Eur., Riedel de Haen, Seelze, Germany)
dissolved in 2-ethylhexanoic acid (puriss., SigmaAldrich,
Switzerland) at 140.degree. C., and tributyl phosphate (Acros
Organics, Geel, Belgium) or hexamethyldisiloxane (98%, Aldrich,
Switzerland) were added to the sodium chloride precursor
(preparation as described in example 2). These three precursors
were 2:1 diluted with tetrahydrofuran. The mixtures were fed
through a capillary (diameter 0.4 mm) into a methane (1.13 L/min,
tech., Pan Gas, Switzerland)-oxygen (2.4 L/min, tech., Pan Gas,
Switzerland) flame using a gear-ring pump (HNP Mikrosysteme,
Parchim, Germany) at 5 mL/min). Oxygen at 5 L/min (tech., Pan Gas,
Switzerland) was used to disperse the liquid leaving the capillary.
Calibrated mass flow controllers (Brooks Instrument, Hatfield, PA,
USA) were used to control all gas flows. The as-formed
nanoparticles were collected on glass fibre filters (GF/A, 25.7 cm
diameter, Whatman, Maidstone, United Kingdom), placed on a cylinder
mounted above the flame, by the aid of a vacuum pump (Seco SV 1040
C, Busch, Switzerland). The specific surface area (SSA) of
as-prepared powders was between 40 and 60 m2/g which corresponds to
a volume-surface-average diameter of between 69 and 46 nm.
EXAMPLE 4
Preparation of a Sub-Structured Salt by Simultaneous Milling
[0072] A "fleur de sel"-type mixture containing 98.9 wt % food
grade table salt, 0.5 wt % CaSO.sub.4.2H20 (reinst, AppliChem), 0.3
wt % MgCl.sub.2.6H20 (Ph. Eur., Fluka), 0.2 wt % MgSO.sub.4.7H20
(Ph. Eur., Fluka) and 0.1 wt % KCl (puriss., Riedel-de Haen) was
filled into a 2L Schott flask and dried for 6 hours at 300.degree.
C. Subsequently, 1500 g of high oleic sunflower oil (HOSO) was
added to the sample. Then, the sample was strongly mixed with a
magnetic stirrer and milled using a laboratory agitator bead mill
(Dyno-mill multi lab, Willy A. Bachofen AG, Basel, Switzerland,
year of manufacture 2006, 0.6 L standard Inox steel/PA6 grinding
vessel, agitator discs or accelerators, 0.5 mm diameter YSZ
grinding balls, filling degree 60-80%). The milling was run
continuously using silicon tubes (inner diameter 8 mm, Siwa Silikon
Schlauch, Unico-Haberkorn, Switzerland) and a flexible-tube pump
(R17 DT71D4/TF, SEW Eurodrive, Germany). During milling the mill
feed was continuously agitated. In case of sedimentation of mill
material, intake of the salt into the tube was enhanced by manual
picking of the sedimented salt with the tube opening. The milling
was conducted at a maximal flow rate of 60 L/h and a maximal
agitator disc speed of 12 m/s. Thereby, the pressure at the inlet
of the grinding vessel was up to 1 bar and the temperature at the
grinding vessel outlet never exceeded 100.degree. C. The grinding
time was 55 min. After grinding the samples were diluted with HOSO
to a final solid content concentration of 1.5 wt % and dispersed
using an ultrasonic horn (200W, cycle 0.5, 1 min, Hielscher GmbH
UP-400S, Germany) for particle size distribution analyses. To
determine particle size distributions a BI-XDC X-ray disk
centrifugation system (Brookhaven Instruments) was used. The
geometric mean of the sample is 0.55 micrometer.
EXAMPLE 5
Stability Test I
[0073] The crystal growth the three as-prepared powders described
in example 3 was further analyzed. Crystal growth inherently
amounts to a lower BET specific surface area (SSA) of the
particles. Therefore, the SSAs of the as-produced powders (see Exp.
3) were compared to the SSAs after 6 days in ambient air. After a
6-day storage time in ambient air the SSA of the pure sodium
chloride particles was 1 m2/g which corresponds to a mean particle
diameter of 2500 nm. This sintering of the nanoparticles was
strongly inhibited by the presence of silica or tricalcium
phosphate. After 6 days, these two samples showed BET SSAs of 59
and 47 m2/g which corresponds to a mean particle diameter of 46 and
58 nm for the 5 wt % silica and the 5 wt % tricalcium phosphate
samples, respectively. Therefore, the in-situ addition of silica or
salts like tricalcium phosphate inhibits crystal growth and hence
prolongs shelf life of the nanoparticles.
EXAMPLE 6
Stability Test II
[0074] Different concentrations of sodium chloride (Fine 50 Pure
Dried Vacuum Salt, Glacia, British Salt, United Kingdom) were
milled in high oleic sunflower oil (Cargill, United Kingdom) to a
particle size of below 1 micrometer (particle size distribution as
measured by XDC, see example 1). These four samples were stored in
closed Schott flasks and the particle size distribution measured
again after a storage time of 30 days.
[0075] The measured particle size distributions still have a log
normal shape. The geometric mean of the four samples is 0.69
micrometer, 0.59 micrometer, 0.68 micrometer and 0.98 micrometer,
respectively, which corresponds to a median shift of 12 to 63%. The
particle size distributions were fitted with a lognormal function
leading to can be described with (mu.sub.1=-0.375,
sigma.sub.1=0.129), (mu.sub.2=-0.530, sigma.sub.2=0.108),
(mu.sub.3=-0.391, sigma.sub.3=0.124) and (mu.sub.4=-0.016,
sigma.sub.4=0.217), respectively. Considering the storage time of
30 days, these results show an enhanced size stability created by a
protecting oil layer on the surface of the milled salts. Thus,
storage under oil improves stability of the NaCl micron-sized
particles.
EXAMPLE 7
Saltiness Testings
[0076] 10 wt % milled pure sodium chloride (Fine 50 Pure Dried
Vacuum Salt, Glacia, British Salt, United Kingdom) in high-oleic
sunflower oil (HOSO) slurries produced as detailed in example 1
with an XDC particle size of around 0.6 micrometer were
homogeneously sprayed onto potato chips (unsalted potato chips,
Walkers, United Kingdom) to a final salt content on the chips of
1.2 wt % and a total HOSO concentration of 33 wt %. These chips
were sensory tested in a triangle test and compared to ready salted
potato chips containing 1.5 wt % salt and 33 wt % HOSO (ready
salted potato chips, Walkers, United Kingdom). In this test 120
consumers compared two samples of the reference (ready salted
potato chips, Walkers, United Kingdom) and one sample of the
salt-in-oil-slurry applied to unsalted chips with a 20 wt % reduced
salt content. The consumers failed to determine any differences
between these samples which means that by the application of
micron-sized pure sodium chloride building blocks the sodium
content could be reduced by 20 wt % without lowering the
saltiness.
[0077] While there are shown and described presently preferred
embodiments of the invention, it is to be distinctly understood
that the invention is not limited thereto but may be otherwise
variously embodied and practiced within the scope of the following
claims.
[0078] The following documents are identified in this specification
and are included by reference. [0079] 1. Friedlander, S. K. Smoke,
dust, and haze (Oxford University Press, New York, 2000). [0080] 2.
Schubert, H. Handbuch der mechanischen Verfahrenstechnik
(Wiley-VCH, Weinheim, 2003). [0081] 3. Gunther, D., Horn, I. &
Hattendorf, B. Recent trends and developments in laser
ablation-ICP-mass spectrometry. Fresenius Journal of Analytical
Chemistry 368, 4-14 (2000). [0082] 4. Vollenweider, M. et al.
Remineralization of human dentin using ultrafine bioactive glass
particles. Acta Biomaterialia 3, 936-43 (2007). [0083] 5. Gunther,
D., Frischknecht, R., Heinrich, C. A. & Kahlert, H. J.
Capabilities of an Argon Fluoride 193 nm excimer laser for laser
ablation inductively coupled plasma mass spectrometry microanalysis
of geological materials. Journal of Analytical Atomic Spectrometry
12, 939-944 (1997). [0084] 6. Janssen, E., Zirkzee, H. F., German,
A. L. & Maxwell, I. A. Particle Sizing of Flocculated
Latex-Particles by Physisorption of Nitrogen. Journal of Applied
Polymer Science 52, 1913-1916 (1994).
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