WO2009117702A2 - Carnallite-like food salts and products thereof - Google Patents

Carnallite-like food salts and products thereof Download PDF

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Publication number
WO2009117702A2
WO2009117702A2 PCT/US2009/037877 US2009037877W WO2009117702A2 WO 2009117702 A2 WO2009117702 A2 WO 2009117702A2 US 2009037877 W US2009037877 W US 2009037877W WO 2009117702 A2 WO2009117702 A2 WO 2009117702A2
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WO
WIPO (PCT)
Prior art keywords
salt
chloride
food product
aqueous medium
ammonium
Prior art date
Application number
PCT/US2009/037877
Other languages
French (fr)
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WO2009117702A3 (en
Inventor
Juhani MÄKI
Tapio MÄKI
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Smart Salt, Inc.
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Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=40138192&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2009117702(A2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority to NZ588531A priority Critical patent/NZ588531A/en
Priority to US12/933,871 priority patent/US8501253B2/en
Priority to EP09722520.5A priority patent/EP2268159A4/en
Priority to JP2011500997A priority patent/JP2011528893A/en
Priority to CN2009801094446A priority patent/CN101977517A/en
Application filed by Smart Salt, Inc. filed Critical Smart Salt, Inc.
Priority to MX2010010202A priority patent/MX2010010202A/en
Priority to EA201001495A priority patent/EA201001495A1/en
Priority to AU2009225467A priority patent/AU2009225467A1/en
Publication of WO2009117702A2 publication Critical patent/WO2009117702A2/en
Publication of WO2009117702A3 publication Critical patent/WO2009117702A3/en
Priority to IL208228A priority patent/IL208228A0/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/26—Magnesium halides
    • C01F5/30—Chlorides
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/16—Inorganic salts, minerals or trace elements
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B4/00—General methods for preserving meat, sausages, fish or fish products
    • A23B4/02—Preserving by means of inorganic salts
    • A23B4/023—Preserving by means of inorganic salts by kitchen salt or mixtures thereof with inorganic or organic compounds
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B4/00—General methods for preserving meat, sausages, fish or fish products
    • A23B4/02—Preserving by means of inorganic salts
    • A23B4/027—Preserving by means of inorganic salts by inorganic salts other than kitchen salt, or mixtures thereof with organic compounds, e.g. biochemical compounds
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/40—Table salts; Dietetic salt substitutes

Definitions

  • Sodium-based salts are used in a variety of food products
  • sodium chloride also known as table salt
  • excess consumption of sodium chloride has been linked to high blood pressure (hypertension) SUMMARY OF THE INVENTION
  • the food salts and food salt products have a superior taste and also provide an enhanced taste to other types of spices
  • the food salts and food salt products also have superior properties for the preservation of foods
  • the food salts and food salt products achieve the aforementioned results with lower, or little, or no sodium as compared to sodium chloride
  • the food salt products are a healthy alternative to sodium chloride
  • the food salts and food salt products taste like sodium chloride, season like sodium chloride, and/or bake and cook like sodium chloride
  • the food salts and food salt products described herein have no carbon-based ingredients
  • substantially non-hygroscopic salts for use in a food products having the formula
  • a substantially non-hygroscopic salt for use m a food product having the formula
  • the salts for use in food products described herein are prepared by a) dissolving in or wetting with an aqueous medium (i) magnesium chloride, and (u) ammonium chloride, potassium chloride or a combination thereof, b) boiling the aqueous medium, and c) removing the aqueous medium by evaporation to afford the salt for use in a food product, wherein the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is 1 x y
  • the salts for use in food product descnbed herein are prepared by a) dissolving in or wetting with an aqueous medium (i) magnesium chloride, (ii) ammonium chloride, potassium chloride or a combination thereof, and (in) an acid scavenger; b) boiling the aqueous medium, c) precipitating the salt for use in a food product from the aqueous medium, d) filtering the precipitated salt for use in a food product, and e) optionally recycling the filtrate, wherein the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is 1 x y
  • the salt for use in a food product is prepared by a filtration process, a semi-dry filtration process, a spray drying process, a bulk process or a drum dryer process [0011] In some embodiments, the salts for use in a food product are prepared by dissolving m or wetting with the aqueous medium an additional amount of about 1-10 mol% of ammonium chloride In some embodiments, the salts for use in a food product are prepared by dissolving in or wetting with the aqueous medium an additional amount of about 2 mol% of ammonium chloride [0012] In some embodiments of the salts, x is about 025 and y is about 0 75 [0013] In some embodiments, provided herein is a particle comprising a core and at least one layer, wherein the core composes a salt descnbed herein and wherein at least one layer of the particle composes sodium chloride, potassium chloride, or a combination thereof [0014] Also provided herein is
  • the composition comprises (i) a salt for use m a food product described herein and (u) an aqueous medium, wherein the salt for use in a food product is dissolved and dissociated in the aqueous medium
  • an aqueous solution is prepared by dissolving a salt for use in a food product described herein in potable water
  • the aqueous solution comprises magnesium cations, potassium cations and ammonium cations in a molar ratio of 1 x y
  • the aqueous solution is prepared by further dissolving sodium chloride and potassium chloride in the aqueous medium
  • the aqueous solution comprises sodium cations, potassium cations, magnesium cations, and ammonium cations, wherein the molar ratio of sodium cations to potassium cations is from 1 0005 to 1 0 5, the molar ratio of sodium cations to magnesium cations is from 1 0005 to 1 0 1, and wherein the molar ratio of sodium cations to ammonium cations is from 1 0 to 1 0 1
  • the nutrient substance, semi-finished food product, or processed food product is selected from meats, fish, vegetables, snack foods, soups, sauces, dairy products, and yeast based products
  • a method of decreasing the sodium content of a food product by at least partially substituting a sodium containing salt in the food product with a salt for use in a food product descnbed herein, a composition of descnbed herein, or a solution described herein
  • a food product containing a salt descnbed herein does not have a substantially decreased taste or shelf-life
  • Further provided herem is a method of preparing a substantially non-hygroscopic salt for use m a food product having the formula.
  • Formula m comprising a) dissolving in or wetting with an aqueous medium (l) magnesium chlonde, and (u) ammonium chlonde, potassium chlonde or a combination thereof, and b) removing the aqueous medium by evaporation to afford the salt for use in a food product, wherein the sum of x and y is about 1, wherein 0 ⁇ x ⁇ 1, wherein 0 ⁇ y ⁇ 1, wherein g is about 3, wherein z is about 4-6, and wherein the molar ratio of magnesium chlonde to potassium chlonde to ammonium chlonde is 1 x y
  • the sum of x and y is about 1, x is about 005 to about 045, y is about 0 5 to about 095, g is about 3, z is about 4-6, and the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is 1 x y
  • step (b) further comprises dissolving in or wetting with the aqueous medium an additional about 1 - 10 mol% of ammonium chloride In some embodiments, the method further comprises dissolving in or wetting with the aqueous medium an additional about 2 mol% of ammonium chloride
  • a method of preparing a substantially non-hygroscopic salt for use in a food product having the formula MgK x (NH 4 ⁇ Cl 8 ZH 2 O Formula III comprising a) dissolving in or wetting with an aqueous medium (i) magnesium chloride, (li) ammonium chloride, potassium chloride or a combination thereof, and (m) an acid scavenger, b) removing the aqueous medium by evaporation to affoid the salt for use in a food product, wherein the sum of x and y is about 1, wherein 0 ⁇ x ⁇ 1, wherein 0 ⁇ y ⁇ l, wherein g is about 3, wherein z is about 4-6, and wherem the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is 1 x y [0025] In some embodiments of the method x is about 005 to about 045, y is about 05 to about 095,
  • removing the aqueous medium by evaporation comprises boiling the aqueous medium
  • Formula m comprising- a) dissolving in or wetfang with an aqueous medium (i) magnesium chloride, (ii) ammonium chloride, potassium chloride or a combination thereof, and (ui) an acid scavenger, b) precipitating the salt for use in a food product from the aqueous medium, d) filtering the precipitate, and e) optionally recycling the filtrate,
  • step (b) further comprises dissolving in or wetting with the aqueous medium an additional amount of about 1 - 10 mol% of ammonium chloride In some embodiments, step (b) further compnses dissolving in or wetting with the aqueous medium an additional amount of about 2 mol% of ammonium chloride
  • the salt is prepared by a filtration process, a semi-dry filtration process, a spray drying process, a bulk process or a drum dryer process
  • a substantially non-hygroscopic salt for use in a food product having the formula MgK x (NH 4 ) J Cl 8 ZH 2 O Formula m wherein the sum of x and y is about 1, wherein 0 ⁇ x ⁇ 1, wherein 0 ⁇ y ⁇ l, wherein g is about 3, and wherein z is about 4-6, wherein less than about 5% of the K ions in the salt for use in a food product are optionally substituted with a physiologically acceptable cation, wherein less than about 5% of the NH 4 ions in the salt for use m a food product are optionally substituted with a physiologically acceptable cation, wherein less than about 5% of the Cl ions m the salt for use in a food product are optionally substituted with a physiologically acceptable anion, and wherein the salt for use in a food product is substantially non-hygroscopic
  • the physiologically acceptable cation is selected from calcium, zinc, selenium, copper, cobalt, chromium, manganese, molybdenum and combinations thereof
  • the physiologically acceptable anion is selected from fluoride, iodide, phosphate, silicate, selenate, sulfate, mt ⁇ te and combinations thereof
  • the physiologically acceptable cation is selected from calcium, zinc, selenium, copper, cobalt, chromium, manganese, molybdenum and combinations thereof
  • the physiologically acceptable anion is selected from fluoride, iodide, phosphate, silicate, selenate, sulfate, nitrite and combinations thereof BRIEF DESCRIPTION OF THE DRAWINGS
  • Figure 1 illustrates the powder X-Ray Diffiaction (XRD) pattern for a salt product having the formula MgCl 2 xKCl VNH 4 Cl zH 2 O, wherein x is about 025, y is about 0 75 and z is about 6, with a stick pattern reference for NH 4 MgCl 3 6H 2 O
  • Figure 2 illustrates the X-Ray Diffraction (XRD) pattern for a salt product having the formula MgCl 2 xKCl yNR t Cl zH 2 0, wherein x is about 025, y is about 0 75 and z is about 6, with a stick pattern reference for KMgCl 3 6H 2 O
  • XRD X-Ray Diffraction
  • Figure 3 illustrates the X-Ray Diffraction (XRD) pattern for a salt product having the formula MgCl 2 xKCl yNI ⁇ Cl zH 2 O, wherein x is about 025, y is about 0 75 and z is about 6, with a sbck pattern reference for MgCl 2
  • Figure 4 illustrates the X-Ray Diffraction (XRD) pattern for a salt product having the formula MgCl 2 xKCl VNH 4 Cl zH 2 O, wherein x is about 025, y is about 0 75 and z is about 6, with a stick pattern reference for NH 4 Cl
  • Figure 5 illustrates the X-Ray Diffraction (XRD) pattern for a salt product having the formula MgCl 2 xKCl yNHiCl zH 2 O, wherein x is about 025, y is about 0 75 and z is about 6, with a stick pattern reference for KCl
  • Figure 6 illustrates the X-Ray Diffraction (XRD) pattern for a salt product having the formula MgCl 2 xKCl yNHtCl zH 2 O, wherein x is about 025, y is about 0 75 and z is about 6, with a suck pattern reference for NH 4 MgCl 3 6H 2 O
  • Sodium salts e g , sodium chlo ⁇ de
  • magnesium salts reduce blood pressure and ammonium salts serve as preservatives that slow the growth of bacteria in food materials and products
  • ammonium is a normal metabolic product in the metabolism of nitrogen containing compounds, such as protein Excess physiological ammonium is captured by carbon dioxide and converted into urea, which is excreted from the body in the form of unne
  • nitrogen containing compounds such as protein
  • sodium-salt substitutes are chloride salts
  • Other salts such as sulfate, carbonate and/or phosphate salts have limited utility in sodium-salt substitutes because of their bitter taste and/or limited solubility
  • Chloride salts of alkali metals (e g , potassium) and/or alkaline earth metals (e g , magnesium, calcium) are physiologically acceptable substitutes for sodium-based salts, but such chloride salts are limited by being unduly hygroscopic which limits their utility as food salts
  • hydrochloric acid is released from the product and/or by other acidic components which leads to an unpleasant (e g , metallic or bitter) taste or lingering after-taste
  • Carnalhte is a naturally occurring double salt mineral composing alkali metal chlorides (e g , potassium chloride) and alkaline earth metal chlorides (e g , magnesium chloride)
  • a carnalhte salt is an ammonium carnalhte, e g , a tnple salt comprising potassium chloride, magnesium chloride and ammonium chloride
  • the presence of physiologically acceptable salts m carnalhte and carnallite-type salts makes them good candidates for food salt substitutes
  • U S Patent Nos 3,312,607, and 3,337,432 describe industrial applications of ammonium carnalhte salts (e g , as cell feed in magnesium cells)
  • salts prepared by methods of preparation described therein are not described as suitable for human consumption Generally such industrial salts are not used in food products or human consumption
  • the salts described herein serve as complete or partial replacements for sodium-based salts m food products and provide low sodium products
  • the salt products and salts provided herein possess good preservative characteristics, good physical properties (e g , ability to spnnkle or pour even under damp or humid conditions) and/or good flavor
  • the salts for use in food products descnbed herein are palatable with no discernible difference in taste compared to conventional sodium-based salts and are suitable for use m a vanety of food
  • food salts desc ⁇ bed herein are substantially non- hygroscopic, substantially free of hydrochloric acid and/or free ammonium chloride, and have a pleasant taste
  • food salts desc ⁇ bed herein are prepared by novel methods that provide salts that are suitable for human consumption The methods of preparation described herein allow for ease of manufacturing via a cost-effective process and provide free flowing non- hygroscopic salts that are substantially free of hydrochloric acid and/or free ammonium chloride [0047]
  • the food salts desc ⁇ bed herein are prepared by the dissolution or wetting of the salt components (e g , potassium chloride, ammonium chloride, magnesium chloride, calcium chloride) in an aqueous medium.
  • the presence of dissolved ammonium chloride results m a solution pH-value of 5 0 — 5 5
  • ammonium chloride breaks down to ammonia and hydrogen chloride in the presence of concentrated solutions comprising magnesium chloride
  • the released hydrogen chloride is occluded in the formed crystal lattice and the food salt product has sharp taste with reduced stability (i e , the product is hygroscopic)
  • aqueous solutions prepared according to processes desc ⁇ bed herein are subjected to heat and/or reduced pressure to exhaust the hydrogen chloride and obtain a food salt product that is substantially free of HCl and substantially non-hygroscopic
  • subjecting the aqueous solutions prepared according to processes described to heat and/or reduced pressure leads to hydrolyzation of ammonium chlo ⁇ de (e g , in some instances about 1-10% of the ammonium chlo ⁇ de is hydro lyzed)
  • an additional amount of ammonium chlonde e g about 1-10% molar excess
  • addition of excess ammonium chlo ⁇ de provides a salt, m a subsequent step desc ⁇ bed herein, wherein there is no hydrogen chlonde occluded in the crystal lattice and wherein the stoichiometry of
  • methods of preparation of carnallite salts desc ⁇ bed herein are also applicable to the preparation of naturally occurnng carnallite (i e , a magnesium chlonde, potassium chlo ⁇ de double salt) Addition of a 1-10% molar excess of NH 4 CI to an aqueous solution of magnesium chlonde and potassium chlonde prepared according to processes descnbed
  • non-sodium salts low sodium salt compositions and/or low sodium food products
  • salts composing (i) magnesium cations, (u) potassium cations, ammonium cations, or combinations thereof, and (in) chloride
  • the salts provided herein are hydrates
  • low or no sodium salt compositions and food products compnsmg (i) magnesium cations, (n) potassium cations, ammonium cations, or combinations thereof, and (m) chloride Food Salts for Use in Food Products
  • a salt for use m a food product having the Formula I MgC12 xKCl yNH4Cl zH2O Formula I [0052]
  • the sum of the terms x and y is about 1
  • the term x is is greater than or equal to zero and less than 1
  • the term y is greater than zero and less than or equal to 1 hi further or alternative embodiments
  • the term z is about 4 to about 6
  • the term z is about 6
  • the term y is greater than 0
  • x is greater than 0
  • the term x is about 005 to about 045, about 0 1 to about 04, about 0 1 to about 03, about 02 to about 03, about 025, about 0 55 to about 0 95, about 06 to about 0 9, about 07 to about 0 8, or about 075
  • the term y is about 005 to
  • anions such as, by way of non-limiting example, fluoride, iodide, phosphate, silicate, selenate, sulfate, mt ⁇ te, combinations thereof, and the like are physiologically acceptable Ih certain embodiments, a physiologically acceptable amount, less than 5%, less than 3%, less than 2%, less than 1%, less than 05%, less than 0 1%, or less than 001 % of the chloride anions are substituted with a physiologically acceptable anion
  • the salt product is formulated such that less than 100 mg per day of selenium (e g , from selenate and other sources) is consumed Accordingly, m certain embodiments, provided herein are salts for use in a food product of Formula HI
  • the terms x, y and z are as defined above In some embodiments, the term g is from about 29 to about 3 In specific embodiments, the term g is about 3 [0056]
  • the physiologically acceptable cations are selected from, by way of non-limitmg example, calcium, zinc, selenium, copper, cobalt, chromium, manganese, molybdenum and combinations thereof In certain embodiments, a physiologically acceptable amount, less than 10%, less than 5%, less than 3%, less than 2%, less than 1%, less than 05%, less than 0 1%, or less than 001% of the potassium and/or ammonium cations are substituted with a physiologically acceptable cation. [0057
  • M is a physiologically acceptable cation and the sum of f* (the charge of M), x and y is about 1
  • M is Ca 2+ and in such instances, the sum of 2f, x and y is about 1
  • term f is from 0 to about 0 1 , from 0 to about 005, or from about 0 01 to about 005
  • X is a physiologically acceptable anion and the term h is equal to about 3-g
  • term h is from 0 to about 02, from 0 to about 005, or from about 001 to about 005
  • f is from about 001 to about 0 1 and h is zero
  • h is from about 001 to about 02 and f is zero
  • any of the salt products of Formulas I-IV comprises one or
  • zinc is present in either of Formulas III or IV as a cation substitute of magnesium in an amount such that less than 15 mg per day of zinc is consumed by an individual
  • the salt product is formulated such that less than 250 ⁇ g, or less than 100 ⁇ g per day of selenium (e g , from selenium cations and/or selenate anion sources) is consumed by an individual
  • the salt products described herein comprise less than a detectable amount (e g , by taste), less than 3%, less than 1%, less than 0 5%, or less than 0 1% by weight OfNH 4 Cl free from (i e , outside the lattice of) a magnesium chloride and ammonium chloride double salt and/or a magnesium chloride, potassium chloride and ammonium chloride triple salt
  • the salt products descnbed herein comprise less than a detectable amount (e g , by smell or taste), less than 3%, less than 1%, less than 05%, less than 0 1%, or less than 0 01% by weight of HCl
  • the salt for use in a food product of any of Formulas I-IV is substantially non-hygroscopic In one embodiment, such salt product adsorbs less than 1 wt-% per month upon extended storage in the absence of a dessicant
  • the salt product described herein has a critical relative humidity value of greater than 70%, greater than 75%, greater than 80%, or about 75% to about 80% at 30° C
  • a salt product of Formula 1 has a CRH value of about 70% at 30° C, e g , wherein x is zero and y is one
  • any numerical value, whether descnbed exactly or as about that numerical value includes the disclosure of about that amount and exactly that amount
  • the disclosure of less than about 3% includes the disclosure of less than 3% and the disclosure of less than 3% includes the disclosure of less than about 3%
  • any of the salt products of Formulas I-IV is a food salt, an edible salt, a physiologically acceptable food salt, or the like In preferred embodiments, the salt product is non-toxic In certain embodiments, any of the salt products of Formulas I-IV is suitable for use in any food product descnbed herein
  • the term "food salt” represents a salt (e g , any salt descnbed herein) suitable for use m or with food products
  • a food salt is suitable for human consumption
  • a food salt has no toxicity, or a reduced toxicity, when used in amounts that are similar to amounts of sodium chlonde or sodium-based salts
  • a food salt is a free flowing non-hygroscopic salt that is substantially free of hydrogen chlonde
  • a food salt is also substantially free of free ammonium chlonde
  • the food salts or salts for use in food products descnbed herein are pleasant tasting palatable salts (i e , there is no discernible difference between the taste of the salts descnbed herein and sodium chlonde and/or sodium-based salts) and do not have a metallic taste or after-taste Process of Making
  • the salts for use in a food product described herein are prepared in any manner
  • a processes desc ⁇ bed herein is utilized to prepare a salt product of any of Formulas I-IV
  • a process descnbed herein is utilized to prepare a non-hygroscopic salt product of any of Formulas I-IV
  • a salt product of any of Formulas I-IV is prepared by a dissolving in or wetting with an aqueous medium i magnesium chloride, and u ammonium chloride, potassium chloride or a combination thereof, b removing the aqueous medium by evaporation to afford the salt
  • the molar ratio of chlorides dissolved in the aqueous medium is 1 part magnesium chloride to x parts potassium chloride to y parts ammonium chloride
  • the aqueous medium is removed by e
  • aqueous medium is or comprises water (e g , distilled water)
  • the excess ammonium chloride e g , the excess amount above y moles
  • a salt product of any of Formulas I-IV is prepared by 0 a dissolving in or wetting with an aqueous medium i magnesium chloride, u ammonium chloride, potassium chloride or a combination thereof, and Ui an acid scavenger, b removing
  • any acid scavenger suitable is utilized in some embodiments, the acid scavenger is ammonia In certain embodiments, the acid scavenger is a buffering system, e g ,0 a citnc acid buffer system, a tartanc buffer system, or a malic acid buffer system.
  • the acid scavenger is an ampholytic acid scavenger In more specific embodiments, the ampholytic acid scavenger is an ammo acid In some embodiments, the ampholytic acid scavenger is glycine hi certain embodiments, the acid scavenger is suitable and is used m a suitable amount to maintain the pH of the aqueous medium at less than 7, about 5 5 to about 7, or5 about 6 to about 6 5
  • the aqueous medium is removed in any process described herein under reduced pressure, subject to increased temperature, by evaporation, or a combination thereof.
  • the aqueous medium is removed by heating the aqueous medium, to at least 50 °C, at least 70 "C, at least 90 °C, or at least 100 "C, or boiling.
  • the aqueous medium is removed under reduced pressure.
  • a salt product of any of Formulas I-IV is prepared by: a. dissolving in or wetting with an aqueous medium i. magnesium chloride, ii. ammonium chloride, potassium chloride or a combination thereof, and ⁇ i. an acid scavenger, b. precipitating the salt from the aqueous medium; c. filtering the precipitate; and d. optionally recycling the filtrate.
  • an aqueous medium i. magnesium chloride, ii. ammonium chloride, potassium chloride or a combination thereof, and ⁇ i. an acid scavenger
  • the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is about 1 : x : y. In some embodiments, the molar ratio of magnesium chloride to ammonium chloride is from about 1:1. Oly to about 1:1. Iy and the molar ratio of magnesium chloride to potassium chloride is about 1 : x.
  • any acid scavenger suitable is utilized.
  • the acid scavenger is an amph ⁇ lytic acid scavenger.
  • the ampholytic acid scavenger is an amino acid.
  • the ampholytic acid scavenger is glycine.
  • the acid scavenger is a buffering system, e.g., a citric acid buffer system, a tartaric buffer system, or a malic acid buffer system.
  • the acid scavenger is not ammonia or an ammonia/ammonium buffer system.
  • the acid scavenger is ammonia (e.g., additional or excess ammonium, such as about 2 mol % excess).
  • the acid scavenger is an ampholytic acid scavenger.
  • the ampholytic acid scavenger is an amino acid.
  • the ampholytic acid scavenger is glycine.
  • the acid scavenger is suitable and is used in a suitable amount to maintain the pH of the aqueous medium at less than 7, about 5.5 to about 7, or about 6 to about 6.5.
  • the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is about 1 : x : y. In some embodiments, the molar ratio of magnesium chloride to ammonium chloride is from about 1 : 1.01 y to about 1:1. Iy and the molar ratio of magnesium chloride to potassium chloride is about 1 :x. In certain embodiments, the molar ratio of magnesium chloride to ampholytic acid scavenger is about 1:0.001 to about 1:0.1, or about 1 :0.01 to about 1 :0.05. In specific embodiments, the molar ratio of magnesium chloride to potassium chloride to ammonium chloride to glycine is about 1 : x : y : about 0.02. In those
  • a process of preparing a salt product of Formula IV further comprises dissolving in or wetting with the aqueous medium at least one physiologically acceptable salt comprising either or both of M and X
  • the physiologically acceptable salt is M,X b , wherein the terms a and b are determined based on the charge of the ions, e g , independently selected from 1 and 2
  • the physiologically acceptable salt is selected from, by way of non- limiting example, M 8 CIi,, K «Xt » (NHt) 3 Xt and me
  • dissolving includes at least partially dissolving Ih some embodiments, the step of dissolving the components into the aqueous medium described herein includes heating the aqueous medium in order to dissolve the components Ih certain embodiments, heating the aqueous medium causes the solubility of one or more of the individual components to be increased in the aqueous medium As used herein, heating includes heating to any temperature above room temperature, including, e g , above about 20° C, up to about 100° C, up to boiling, or to boiling In some instances, evaporation includes sublimation and/or lyophihzation.
  • a salt product of any of Formulas I-IV is precipitated from the aqueous medium
  • the individual components are dissolved in a heated aqueous medium and precipitation occurs upon cooling
  • precipitation of the salt product of any of Formulas I-IV is accomplished by decreasing the volume of the aqueous medium
  • the volume of the aqueous medium is decreased by evaporation.
  • evaporation is achieved under reduced pressure and/or increased temperature
  • evaporation is achieved by increasing the temperature of the aqueous medium.
  • a substantially non-hygroscopic salt product e g , a substantially non-hygroscopic salt product of any of Formulas I-IV is prepared by mixing, grinding and/or blending a hygroscopic salt with ammonium chloride
  • the amount of ammonium chloride is mixed, ground or blended with the hygroscopic salt in about 1 mol-% to about 99 mol-%, about 5 mol-% to about 50 mol-%, about 10 mol-% to about 30 mol-%, or about 25 mol-% of the hygroscopic salt
  • the hygroscopic salt is a natural salt
  • the hygroscopic salt is a natural salt
  • the hygroscopic carnalhte is a double salt of magnesium chloride and potassium chloride where
  • the hygroscopic salt is top or surface hygroscopic
  • the mixture is dried
  • the salts of any of Formulas I-IV for use m food products, salt blends thereof, or particles described herein are prepared by a "bulk process,” a “filtration process,” a “semi-dry filtration process,” a “spray drying process” or a “drum dryer process”
  • food salt products of any of Formulas I-IV are prepared by a dissolving in or wetting with an aqueous medium i magnesium chloride, ii ammonium chloride, and ui optionally an acid scavenger, and b contacting the magnesium chloride-ammonium chloride composition (e g , solution) of (a) with solid potassium chloride
  • the volume of the aqueous medium is reduced (e g , by boiling and/or evaporation under reduced pressure and/or increased temperature) by about 30%, about 40% or about 50% prior to contacting with solid potassium chloride
  • the solid potassium chloride is crystalline potassium chloride
  • some or all of the aqueous medium is removed (e g absorbed by the solid potassium chloride) from the composition of (a) upon addition of the solid potassium chloride
  • a dry salt blend is formed upon addition of the solid potassium chloride
  • a semi-dry salt blend is formed upon addition of solid potassium chloride
  • a semi-dry salt blend is dried using any process described herein [0087]
  • an excess mol % of potassium chloride and/or sodium chloride is utilized In some of such embodiments, use of an excess of potassium chloride and/or sodium chloride allows for the formation a "blend" or "salt blend” or "blended salt” of potassium chloride
  • solid potassium chloride is in a fluidized bed and the magnesium chloride-ammonium chloride composition (e g , solution) is deposited (e g , sprayed) onto the fluidized bed (e g , the potassium chloride particles)
  • the magnesium chloride-ammonium chloride composition e g , solution
  • the magnesium chloride-ammonium chloride composition e g , solution
  • the magnesium chloride-ammonium chloride composition e g , solution
  • the magnesium chloride-ammonium chloride composition e g , solution
  • the magnesium chloride-ammonium chloride composition e g , solution
  • a blended salt product of any of Formulas I-IV depending on the products utilized
  • 17 WSGRDocketNo 36626-701 601 containing at least one layer on the surface of the salt crystals is formed at the interface between the composition of (a) and the solid potassium chloride.
  • a coated particle comprising a salt of any of Formulas I-IV that is coated with potassium chloride and/or sodium chloride.
  • a particle comprising a potassium chloride core and a layer comprising a salt of any of Formulas I-IV.
  • such a particle is prepared according to any process described herein.
  • such a particle is further blended with sodium chloride.
  • a particle comprising a potassium chloride core, a layer of a salt of any of Formulas I-IV and a layer of sodium chloride.
  • such a particle comprises an inner layer of a salt of any of Formulas I-IV and an outer layer of sodium chloride. In specific embodiments, such a particle comprises an inner layer of a salt of any of Formulas I-IV and an outer layer of potassium chloride. In further embodiments, such particles further comprise additional salt layers between the core and the inner layer, between the inner layer and the outer layer, on top of the outer layer, or a combination thereof.
  • the food salts described herein are prepared by end-drying or a "bulk process.”
  • the aqueous solutions prepared by any process described herein are evaporated to dryness.
  • evaporating to dryness allows all of the salt components, with the exception of hydrolyzed ammonium chloride, that were dissolved hi the aqueous medium to crystallize out as a salt (e.g., a double salt, a triple salt or the like).
  • analytical evaluations are not needed.
  • solutions are prepared with amount of water being about 100 ml/mol of solute(s).
  • the amount of hydrolyzed ammonium chloride is about the same as the excess mole% of ammonium chloride added to the aqueous medium in any process described herein.
  • the food salts and/or food salt blends are prepared by a "filtration process.”
  • the raw-materials are weighed to a reactor and water is added to the reactor.
  • an aqueous solution described herein is evaporated to about 70%, about 60% or about 50% of the initial volume when a thick crystal mass is formed.
  • the thick crystal mass is cooled and filtered, and the filtrate is recycled.
  • moist filter cake is dried and used in the preparation of salt blends described herein.
  • the filtration process described above is modified to a "semi-dry filtration process.”
  • an aqueous solution prepared by methods described herein is evaporated to about 50% of the original volume, and dry potassium chloride or a mixture of potassium chloride and sodium chloride is added to the moist crystal mass.
  • the additional dry potassium chloride absorbs the remainder of the water and a dry salt product is obtained In certain embodiments, the additional dry potassium chloride absorbs the remainder of the water and a "semi-dry" salt product is obtained In some instances, a semi-dry salt product is further dried by a process descnbed herein In some instances, semi-dry salts are easier to handle m drying equipment In some instances, a semi-dry filtration process yields carnallite- type salts with reduced stratification (e g , uneven composition or mixture) Ui the final salt blend [00941 In some embodiments, the moist filter-cake from the filtration process is treated with dry potassium chloride or a mixture of potassium chloride and sodium chloride to absorb moisture and afford a semi-dry salt blend.
  • the salts and blended salts for use in food products described herein are prepared by a "drum dryer” process
  • a drum dryer process composes (a) optionally moisturizing or treating with water or water vapour (i e , wetting) the components of the food salts and/or blended food salts descnbed herein, (b) rolling the components of the food salts and/or blended food salts for a prolonged time (e g , about 8 hours, about 12 hours, about 16 hours or about 24 hours or more) in a drum dryer and (c) drying the resulting salt or salt blend using any method described herein
  • step (a) is omitted and the components of the food salts are moisturized or wetted by the water present in one or more of the component salts (e g , when one or more of the component salts are salt hydrates)
  • a drum dryer process achieves ion- exchange between the crystals and/or salt components
  • food salts obtained from a drum dryer process have lower CRH values
  • salts prepared by a drum dryer process are used to prepare salt blends that are used to prepare food salt solutions
  • Food salts used as solutions are added to food products (e g liquid food products (e g soups, sauces)) that are boiled or heat-treated prior to consumption
  • the component salts utilized m the process are salt particles
  • the component salts e g , magnesium chlonde, potassium chloride or ammonium chlonde
  • the component salts are of the same
  • the ampholytic acid scavenger is an amino acid In some embodiments, the ampholytic acid scavenger is glycine In some embodiments, the acid scavenger is a basic salt (e g , calcium phosphate, calcium carbonate, magnesium phosphate, magnesium carbonate or the like) In certain embodiments, the acid scavenger is used in a suitable amount to maintain the pH of the aqueous medium at less than 7, about 5 5 to about 7, or about 6 to about 65 In certain embodiments, the molar ratio of magnesium chloride to ampholytic acid scavenger is about 1 0001 to about 1 0 1, or about 1 001 to about 1 005 In specific embodiments, the molar ratio of magnesium chloride to potassium chloride to ammonium chloride to an acid scavenger is about 1 x y about 0 02 [0099] In various embodiments, any two or more of the component
  • composition comprising a salt product of any of Formulas I-IV
  • the composition compnses a salt product of any of Formulas I-IV and at least one additional salt
  • the at least one additional salt is selected from potassium chloride, sodium chloride and combinations thereof
  • the composition comprises a salt component composing a salt product of any of Formulas I-IV and potassium chloride and/or sodium chloride
  • the salt component compnses, by weight, about 0 to about 99%, about 1% to about 99%, about 50% to about 99%, about 50% to about 90%, or about 50% to about 75% sodium chloride
  • the salt component comprises, by weight, 0% to about 99%, about 1% to about 99%, 0% to about 50%, greater than 0% to about 25%, about 1% to about 25%, or about 5% to about 25% potassium chloride
  • the salt component compnses, by weight, about 1% to about
  • particles comprising (i) a salt product of any of Formulas I-IV, and (ii) potassium chloride, sodium chloride, or a combination thereof
  • the particle composes a core and at least one layer
  • the core composes a salt product of any of Formulas I-IV
  • the at least one layer comprises potassium chloride and/or sodium chloride hi certain embodiments, coating the salt core with at least one layer provides an improved taste compared to an uncoated salt particle
  • such particles are prepared by mixing particles comprising a salt product of any of Formulas I-IV with potassium chloride and/or sodium chloride
  • the potassium chloride and/or sodium chloride are in the form of a powder or fine particulates
  • the particulates of the salt product are mixed with the potassium chloride and/or sodium chloride for at least 1 hour, at least 4 hours, at least 8 hours, at least 12 hours, at least 16 hours, or at least 24
  • the composition comprising a salt product of any of Formulas I-IV composes a salt product of any of Formulas I-IV in associated, dissociated or partially dissociated form
  • a composition comprising a salt product of any of Formulas I-IV that has been dissolved in an aqueous medium
  • the aqueous medium is or comprises potable water
  • dissolved includes, e g , completely dissolved or partially dissolved, including at least 99% dissolved, at least 95% dissolved, or at least 50% dissolved
  • the aqueous composition is saturated with a salt product of any of Formulas I-IV hi certain embodiments, the aqueous composition comprises a salt component, wherein the salt component comprises a salt product of any of Formulas I-IV, and one or more of sodium chloride and potassium chloride hi specific embodiments, the salt component comprises, by weight, about 0 to about 99%, about 1%
  • the salt component comprises, by weight, 0% to about 99%, about 1% to about 99%, 0% to about 50%, greater than 0% to about 25%, about 1% to about 25%, or about 5% to about 25% potassium chlo ⁇ de
  • the salt component comprises, by weight, about 1 % to about 99%, about 5% to about 50%, or about 25% of a salt product of any of Formulas I-IV
  • the aqueous composition is saturated with the salt component In some embodiments, up to about 40% (w/w), or up to about 30% (w/w) of the aqueous composition is the salt component [00104]
  • an aqueous composition prepared by dissolving a salt component in an aqueous medium In specific embodiments, the aqueous
  • an aqueous solution comprising magnesium cations, potassium cations and ammonium cations
  • the molar ratio of magnesium cations to potassium cations to ammonium cations is about 1 x y, wherein the sum of the terms x and y is about 1 and wherein y is from greater than 0 to about 1 and x is from 0 to about 1
  • the aqueous solution further compnses chlo ⁇ de anions
  • the molar ratio of magnesium cations to chionde anions is from about 1 2 to about 1 3, about 1 2 9 to about 1 3, or about 1 295 to about 1 3
  • the molar ratio of sodium cations to chloride anions is 1 3 00 [00106]
  • an aqueous solution comprising sodium cations, potassium cations, magnesium cations, and ammonium cations In
  • the molar ratio of sodium cations to magnesium cations is from about 1 005 to about 1 0 1
  • the molar ratio of sodium cations to ammonium cations is from 1 0 to 1 0 1, or from 1 0001 to 1 0 1
  • the molar ratio of sodium cations to potassium cations is from 1 0005 to 1 0 5
  • the molar ratio of sodium cations to magnesium cations is from 1 0 005 to 1 0 1
  • the aqueous solution further comprises chloride anions [00107]
  • an aqueous solution comprising sodium cations, potassium cations, magnesium cations, and ammonium cations, as described herein further comprises an in
  • an insignificant amount of gold cations, silver cations and/or selenium cations is an amount less than about 25 ppm, less than about 5 ppm, less than about 1 ppm, or less than about 0 1 ppm
  • an aqueous solution described herein further compnses a physiologically important ion including, e g , sulfate, phosphate, silicate, nitrite, selenate, iodide, copper cations, cobalt cations, manganese cations, molybdenum cations and combinations thereof [00108]
  • the pH of any of the aqueous compositions/solutions descnbed herein is about 6 to about 7, or about 6 to about 6 8
  • the aqueous solutions descnbed herein are prepared by dissolving in or wetting with an aqueous medium, a salt product of any of Formulas I-IV and one or more of potassium chloride and sodium chloride [00110]
  • Table 2 provides illustrative examples of the compositions descnbed herein. Table 2:
  • composition A Composition B Composition C Composition D
  • the salts descnbed herein are dissolved in an aqueous medium.
  • Compositions A, B and/or C are dissolved in an aqueous medium
  • Table 3 illustrates various forms of the salt product of any of Formulas I-IV that are utilized in the Compositions A, B and/or C of Table 1 and the concentrations (% w/w) at which aqueous solutions of such compositions become saturated Saturation concentrations are determined by
  • composition A Composition B
  • Composition C Composition B
  • any of the aqueous solutions provided herein is potable [00113]
  • the salt products disclosed herein are blended with a polyhydroxy compound
  • the polyhydroxy compound is mannitol, sorbitol, xylitol, or combinations thereof
  • blending the salt products disclosed herein with a polyhydroxy compound (e g mannitol, sorbitol, xylitol) improves the stability of the salt products in humid conditions
  • blending a polyhydroxy compound (e g mannitol, sorbitol, xylitol) with a salt product disclosed herein inhibits (either partially or fully) the ability of a water molecule to bind to a salt product
  • about 1-5 grams of polyhydroxy compound (e g mannitol, sorbitol, xyhtol) is blended with about 1 raol of salt product In some embodiments, about
  • the salt aqueous solutions disclosed herein are blended with a polyhydroxy compound
  • the polyhydroxy compound is mannitol, sorbitol, xylitol, or combinations thereof Li some embodiments, about 1-5 grams of polyhydroxy compound (e g mannitol, sorbitol, xyhtol) is blended with about 1 mol of salt product In some embodiments, about 2-4 grains of polyhydroxy compound (e g mannitol, sorbitol, xylitol) is blended with about 1 mol of salt product In some embodiments, about 3 grams of polyhydroxy compound (e g manmtol, sorbitol, xylitol) is blended with about 1 mol of salt product Uses [00115] In certain embodiments, a salt product desc ⁇ bed herein is utilized as a seasoning In further or alternative embodiments, a salt product desc ⁇ bed herein is a sodium salt (e g , sodium chloride)
  • a salt product or composition provided herein is used in food products
  • salt products provided herein are used as salt substitutes for sodium salts
  • a salt product provided herein is utilized as a flavoring agent and/or as a preservative agent and is, optionally, utilized in food products
  • a product or composition descnbed herein is utilized as a substitute for a flavoring agent or preservative m a food or nutrient product
  • the salt products or compositions described herein are utilized in a process of preparing a food product wherein the salt products or compositions descnbed herein at least partially replace or substitute a sodium salt (e g , sodium chloride)
  • a salt product of any of Formulas I-IV or a composition descnbed herein is utilized as a flavoring agent and/or preservative in food products, including, by way of non-limiting example, meats (e g)
  • a salt product of any of Formulas I-IV or a composition descnbed herein is utilized as or in a seasoning product, a spice product, or a food salt product [00118]
  • food products comprise food acids, acidity regulators, anti-caking agents, anti-foaming agents, antioxidants, bulking agents, food coloring, color retention agents, emulsifiers, flavors, flavor enhancers, flour treatment agents, humectants, tracer gas, preservatives, stabilizers, sweeten
  • anti-oxidants such as vitamin C act as preservatives by inhibiting the effects of oxygen on the food and can be beneficial to health
  • bulking agents such as starch are additives that increase the bulk of a food without affecting its nutritional value
  • food colorings are added to food to replace colors lost during preparation or to improve the aesthetics of a food
  • color retention agents are used to preserve a food's existing color
  • emulsifiers allow water and oils to remain mixed together in an emulsion, as in mayonnaise, ice cream and homogenized milk.
  • flavors are additives that give food a particular taste or smell and may be derived from natural ingredients or created artificially
  • flour treatment agents are added to flour to improve its color or its use m baking
  • humectants prevent foods from drying out
  • tracer gas allows for package integrity testing to prevent foods from being exposed to atmosphere, thus guaranteeing shelf life
  • preservatives prevent or inhibit spoilage of food due to fungi, bacteria and other microorganisms
  • stabilizers, thickeners and gelling agents like agar or pectin (used in jam for example) give foods a firmer texture
  • stabilizers are not true emulsifiers, they help to stabilize emulsions
  • sweeteners are added to foods for flavoring Ih certain instances, sweeteners other than sugar are added to keep the food energy (calories) low, or because they have beneficial effects for diabetes mellitus and tooth decay and diarrhea
  • thickeners are added to foods for flavoring Ih certain instances, sweeteners other than sugar are added to keep the food energy (calories
  • frozen foods compnse spices e g , black pepper, chih, white pepper, oregano, paprika, garlic, and the like
  • flavors e g , pork flavor, beef flavor, steak flavor, chicken flavor, onion flavor, and the like
  • sodium nitrite sodium ascorbate, dextrose, sodium phosphates, corn syrup solids, sodium stearoyl lactylate, sodium aluminum phosphate, ascorbic acid, BHA,
  • a salt product or a composition descnbed herein is present m or is utilized m preparing a frozen food product to reduce the amount of or substitute one or more of a spice, a flavor, sodium nitrite, sodium ascorbate, dextrose, sodium phosphate, a corn syrup solid, sodium stearoyl lactylate, sodium aluminum phosphate, ascorbic acid, BHA, BHT, and/or citric acid used therein
  • snack foods comprise TBHQ, maltodext ⁇ n, natural flavors (e g , cheese), disodium mosinate, drsodmm guanylate, sodium casemate, spices (e g , black pepper, chili, white pepper, oregano, paprika, garlic, cajun pepper, and the like), and combinations thereof
  • a salt product or a composition described herein is present in or is utilized in preparing snack food (e g , dry snacks and/or baked cheese snacks) to reduce the amount of or substitute one or more of TBHQ, maltodext ⁇ n, a natural flavor, disodium inosinate, disodium guanylate, sodium casemate, and/or a spice used therein
  • dairy foods compose stabilizers (e g , carob bean, xanthan and/or guar
  • the salts descnbed herein are also utilized m, by way of non- hmiting example, mouth-flush mixtures, antiseptics (e g , pastes and ointments) and pastes for reducing the formation of varicose veins
  • the salts described herein are utilized in protein hydrolysates, flavonoids, steroids and the like Thus, in certain embodiments, such products are provided for herein.
  • a salt product or composition descnbed herein is utilized as a salt substitute by an individual to treat hypomagnesia
  • aqueous solutions of the salts and/or salt blends described herem are used as electrolyte replenishing mixtures in the treatment of, e g , travellers' diarrhea, dehydration due to cholera, gastrointestinal distress, salmonella or E coll infections and the like 100125]
  • the salts described herem are utilized as a flavoring enhancing agent
  • a composition (a flavoring product) comprising a salt (or salt blend) descnbed herein and a flavoring agent
  • such a composition is a food additive
  • provided herem is a method of reducing the amount of a flavoring agent necessary to achieve a desired flavor in a food (or other
  • Flavoring agents suitable for combination with spices e g , peppers, curry, heibes de provence, five spice powder, garam masala, black pepper, chili, chili peppers, white pepper, oregano, papnka, garlic, and the like
  • salts e g , sodium chloride
  • other flavors e g , pork flavor, beef flavor, steak flavor, chicken flavor, onion flavor, hoisin sauce, oyster sauce
  • a reduced sodium soy sauce comprising a food salt product of any of Formulas I-IV
  • the example describes a method to produce a mixed carnallite containing 25 mol- % of potassium chloride and 75 mol-% of ammonium chloride by filtering method 2 mol-% excess of ammonium chloride was included into the method
  • Example 2 [00131] The example describes a method to produce ammonium carnallite with total evaporation to dryness including 2 mol-% of excess ammonium chlonde
  • the example describes a method to produce potassium carnallite by total evaporation of water in the presence of glycine ( 1 mol-%) and ammonium chlonde (2 mol-%)
  • the example desc ⁇ bes a method to produce a mixed carnallite containing 25 mol- % of ammonium chloride and 75 mol-% of potassium chloride by filtering method 2 mol-% excess of ammonium chloride was present in the mixture
  • the example desc ⁇ bes a method to produce a mixed carnallite containing 50 mol- % of potassium chloride and 50 mol-% of ammonium chloride by total evaporation to dryness
  • Salt products composing different amounts of potassium and ammonium are prepared in similar manners by adjusting the mol-% of ammonium chloride and mol-% of potassium chloride dissolved into water Example 6
  • Salt products and compositions described herein including e g , those of Tables 1-3, are deposited in incrementally increasing amounts on a food product (e g from 001 mg of salt product per gram of food product) The food products are then tasted by a sample of healthy volunteers and the taste is rated on a scale of 1 -10 The food
  • the best salt products or compositions described herein are determined based on potassium to ammonium ratios produce the best taste and best preservative characteristic
  • the salt product or compositions described herein are utilized as a flavoring agent alone, only the taste of the salt need be considered.
  • Example 7 Two pieces of 10 g were cut from a "market-fresh" salmon, both pieces having a remarkable area of the typical silver-colored skin Both of the pieces were salted, the first with 0 5 g of table salt and the other with 0 5 g of the salt product of Example 3 Both of the samples were stored in a refrigerate room in a temperature of 12° C and the chemiluminence of the salmon skin were observed visually from time to time It was found that the luminence of the sample salted with table salt disappeared after storage for 48 hours The luminence of the salted sample continued for an additional 55 hours before fading Thus, the salt product of Example 2 is illustrated to have an ability to prevent the formation of formic acid in the deterioration of the fish flesh Similar effects have been found in ham and other meat products
  • Salt products and compositions described herein, including e g , those of Tables 1 - 3, are formulated in combination with a flavoring agent (e g , a salt or a spice) in incrementally increasing weight % amounts
  • a flavoring agent e g , a salt or a spice
  • Each of the combinations are then tasted by a sample of healthy volunteers in increasing amounts (e g , from 1 mg of combination)
  • the combinations are then tasted by a sample of healthy volunteers and the taste is rated on a scale of 1 - 10
  • each of the combinations are placed on a food product m increasing amounts (e g from 001 mg of salt product per gram of food product)
  • the food products are then tasted by a sample of healthy volunteers and the taste is rated on a scale of 1-10
  • Example 9 [00149] The example describes a method to produce a mixed carnallite containing 25 mol- % of potassium chloride and 75 mol-% of ammonium chloride by filtering method 2 mol-% excess of ammonium chloride is included into the method
  • the example describes a method to produce a mixed carnalhte containing 25 mol-
  • Figure 1 illustrates the XRD pattern for Sample 1, which is an MgCl 2 XNH 4 Cl 6 H 2 O sample prepared by concentration in a rotary evaporator and filtration (85% yield), the XRD pattern for Sample 2, which is an MgCl 2 x 075 NH 4 Cl x 025 KCl 6 H 2 O sample by the total evaporation of solvent ( ⁇ 100% yield), and a stick pattern for reference NH 4 MgCl 3
  • XRD patterns of salt products provided herein according to Formula I wherein x is about 025, y is about 0 75, z is about 6, and g is about 3, were compared to and found to be distinct from KMgCl 3 6H 2 O ( Figure 2), MgCl 2 ( Figure 3), NHCl, ( Figure 4), KCl ( Figure 5) and NH 4 MgCl 3 6H 2 O ( Figure 6)
  • a sample comprising (1) one or more peak having a 2 ⁇ value that is approximately equal to

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Abstract

Provided herein are salts for use in food products having the formula: MgCl2•xKCl•yNH4Cl•zH2O, wherein x + y is about 1, wherein x is greater than or equal to zero and less than 1, wherein y is greater than zero and less than or equal to 1, and wherein z is from about 4 to about 6.

Description

WSGR Docket No. [36626-701.601 ]
PATENT APPLICATION CARNALLITE-LIKE FOOD SALTS AND PRODUCTS THEREOF
Inventor(s): Juhani MAKL
Citizen of Finland, Residing at
Vanha Palkaneentie 157
SF-36570 Kaivanto
Finland
Tapio MAKI,
Citizen of Finland, Residing at 2240 Shelter Island Dr. San Diego, CA 92106
Assignee: SMART SALT, INC.
1261 Prospect St, Suite 9 La JoIIa5 CA 92037
A California corporation
Entity: Small Business Concern ytfez
Wilson Sonsini Goodrich & Rosati
P ROFESStO NAL CO R P ORATI ON
650 Page Mill Road Palo Alto, CA 94304
(650) 493-9300
(650) 493-6811
CABNALLITE-LIKE FOOD SALTS AND PRODUCTS THEREOF
RELATED APPLICATIONS
[0001] This patent application claims the benefit of U S Provisional Application Ser No 61/038,706, filed March 21, 2008, and UK Application 08200560 filed October 31, 2008, both of which are herein incorporated by reference in their entirety
BACKGROUND
[0002] Sodium-based salts are used in a variety of food products For example, sodium chloride, also known as table salt, is commonly used in food However, excess consumption of sodium chloride has been linked to high blood pressure (hypertension) SUMMARY OF THE INVENTION
[0003] Descnbed herein are food salts and food salt products The food salts and food salt products have a superior taste and also provide an enhanced taste to other types of spices The food salts and food salt products also have superior properties for the preservation of foods In addition, the food salts and food salt products achieve the aforementioned results with lower, or little, or no sodium as compared to sodium chloride As a result, the food salt products are a healthy alternative to sodium chloride In some embodiments, the food salts and food salt products taste like sodium chloride, season like sodium chloride, and/or bake and cook like sodium chloride In some embodiments, the food salts and food salt products described herein have no carbon-based ingredients
[0004] Provided herein are substantially non-hygroscopic salts for use in a food products having the formula
MgKx(NH4)JCIg ZH2O Formula m wherein the sum of x and y is about 1 , wherein 0 ≤x < 1 , wherein 0 < y ≤l , wherein g is about 3, wherein z is about 4-6, and wherein the salt for use in a food product is substantially non- hygroscopic and substantially free of hydrogen chloride
[0005] In some embodiments, provided herein is a substantially non-hygroscopic salt for use m a food product having the formula
MgK51(NH4)JCl11 ZH2O Formula ffl wherein the sum of x and y is about 1 , wherein x is about 005 to about 045, wherein y is about 0 55 to about 095, wherein g is about 3, wherein z is about 4-6, and wherein the salt for use in a food product is substantially non-hygroscopic and substantially free of hydrogen chloπde [0006] In some embodiments, z is 6
WSGR Docket No 36626 701 601 [0007] Descnbed herein are camallite salts that are suitable for use as salts in food products The salts are substantially non-hygroscopic and substantially free of hydrochloric acid and/or free ammonium chloride and are suitable replacements for sodium-based salts in a variety of food products [0008] In some embodiments, the salts for use in food products described herein are prepared by a) dissolving in or wetting with an aqueous medium (i) magnesium chloride, and (u) ammonium chloride, potassium chloride or a combination thereof, b) boiling the aqueous medium, and c) removing the aqueous medium by evaporation to afford the salt for use in a food product, wherein the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is 1 x y
[0009] In some embodiments, the salts for use in food product descnbed herein are prepared by a) dissolving in or wetting with an aqueous medium (i) magnesium chloride, (ii) ammonium chloride, potassium chloride or a combination thereof, and (in) an acid scavenger; b) boiling the aqueous medium, c) precipitating the salt for use in a food product from the aqueous medium, d) filtering the precipitated salt for use in a food product, and e) optionally recycling the filtrate, wherein the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is 1 x y
[0010] In some embodiments, the salt for use in a food product is prepared by a filtration process, a semi-dry filtration process, a spray drying process, a bulk process or a drum dryer process [0011] In some embodiments, the salts for use in a food product are prepared by dissolving m or wetting with the aqueous medium an additional amount of about 1-10 mol% of ammonium chloride In some embodiments, the salts for use in a food product are prepared by dissolving in or wetting with the aqueous medium an additional amount of about 2 mol% of ammonium chloride [0012] In some embodiments of the salts, x is about 025 and y is about 0 75 [0013] In some embodiments, provided herein is a particle comprising a core and at least one layer, wherein the core composes a salt descnbed herein and wherein at least one layer of the particle composes sodium chloride, potassium chloride, or a combination thereof [0014] Also provided herein is a composition comprising (i) a salt for use in a food product descnbed herein and (u) sodium chloπde, potassium chloride, or a combination thereof
WSOR Docket No 36626-701 601 [0015] Ia some embodiments, the composition comprises (i) a salt for use m a food product described herein and (u) an aqueous medium, wherein the salt for use in a food product is dissolved and dissociated in the aqueous medium
[0016] In some embodiments, an aqueous solution is prepared by dissolving a salt for use in a food product described herein in potable water In some embodiments, the aqueous solution comprises magnesium cations, potassium cations and ammonium cations in a molar ratio of 1 x y In some embodiments, the aqueous solution is prepared by further dissolving sodium chloride and potassium chloride in the aqueous medium In some embodiments, the aqueous solution comprises sodium cations, potassium cations, magnesium cations, and ammonium cations, wherein the molar ratio of sodium cations to potassium cations is from 1 0005 to 1 0 5, the molar ratio of sodium cations to magnesium cations is from 1 0005 to 1 0 1, and wherein the molar ratio of sodium cations to ammonium cations is from 1 0 to 1 0 1
[0017] Also provided herein is a nutrient substance, a semi-fimshed food product, a flavoring product, a processed food product that has, during the preparation thereof, been processed or preserved with a salt for use m a food product described herein, a composition descnbed herein, or a solution described herein
[0018] In some embodiments, the nutrient substance, semi-finished food product, or processed food product is selected from meats, fish, vegetables, snack foods, soups, sauces, dairy products, and yeast based products [0019] Also provided herein is a method of decreasing the sodium content of a food product by at least partially substituting a sodium containing salt in the food product with a salt for use in a food product descnbed herein, a composition of descnbed herein, or a solution described herein [0020] In some embodiments, a food product containing a salt descnbed herein does not have a substantially decreased taste or shelf-life [0021] Further provided herem is a method of preparing a substantially non-hygroscopic salt for use m a food product having the formula.
Figure imgf000006_0001
Formula m comprising a) dissolving in or wetting with an aqueous medium (l) magnesium chlonde, and (u) ammonium chlonde, potassium chlonde or a combination thereof, and b) removing the aqueous medium by evaporation to afford the salt for use in a food product, wherein the sum of x and y is about 1, wherein 0 ≤x < 1, wherein 0 < y <1, wherein g is about 3, wherein z is about 4-6, and wherein the molar ratio of magnesium chlonde to potassium chlonde to ammonium chlonde is 1 x y
WSGR Docket No 36626 701 601 [0022] In some embodiments, the sum of x and y is about 1, x is about 005 to about 045, y is about 0 5 to about 095, g is about 3, z is about 4-6, and the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is 1 x y
[0023] In some embodiments, step (b) further comprises dissolving in or wetting with the aqueous medium an additional about 1 - 10 mol% of ammonium chloride In some embodiments, the method further comprises dissolving in or wetting with the aqueous medium an additional about 2 mol% of ammonium chloride
[0024] Also provided herein is a method of preparing a substantially non-hygroscopic salt for use in a food product having the formula MgKx(NH4^Cl8 ZH2O Formula III comprising a) dissolving in or wetting with an aqueous medium (i) magnesium chloride, (li) ammonium chloride, potassium chloride or a combination thereof, and (m) an acid scavenger, b) removing the aqueous medium by evaporation to affoid the salt for use in a food product, wherein the sum of x and y is about 1, wherein 0 ≤x < 1, wherein 0 < y ≤l, wherein g is about 3, wherein z is about 4-6, and wherem the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is 1 x y [0025] In some embodiments of the method x is about 005 to about 045, y is about 05 to about 095, g is about 3, z is about 4-6, and the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is about 1 x y
[0026] In some embodiments, removing the aqueous medium by evaporation comprises boiling the aqueous medium [0027] Provided herein is a method of preparing a salt for use in a food product having the formula
MgKx(NH4)JCl8 ZH2O Formula m comprising- a) dissolving in or wetfang with an aqueous medium (i) magnesium chloride, (ii) ammonium chloride, potassium chloride or a combination thereof, and (ui) an acid scavenger, b) precipitating the salt for use in a food product from the aqueous medium, d) filtering the precipitate, and e) optionally recycling the filtrate,
WSGR DockaNo 36626 701 601 wherein the sum of x and y is about 1, wherein 0 ≤x < 1, wherein 0 < y ≤l, wherein g is about 3, wherein z is about 4-6, and wherein the molar ratio of magnesium chloride to potassium chloride to ammonium chloride il l i y
[0028] In some embodiments of the method, the sum of x and y is about 1 , x is about 005 to about 045, y is about 05 to about 0 95, wherein g is about 3, z is about 4-6, and the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is 1 x y [0029] In some embodiments, step (b) further comprises dissolving in or wetting with the aqueous medium an additional amount of about 1 - 10 mol% of ammonium chloride In some embodiments, step (b) further compnses dissolving in or wetting with the aqueous medium an additional amount of about 2 mol% of ammonium chloride
[0030] In some embodiments, the salt is prepared by a filtration process, a semi-dry filtration process, a spray drying process, a bulk process or a drum dryer process
[0031] Provided herein is a substantially non-hygroscopic salt for use in a food product having the formula MgKx(NH4)JCl8 ZH2O Formula m wherein the sum of x and y is about 1, wherein 0 ≤x < 1, wherein 0 < y ≤l, wherein g is about 3, and wherein z is about 4-6, wherein less than about 5% of the K ions in the salt for use in a food product are optionally substituted with a physiologically acceptable cation, wherein less than about 5% of the NH4 ions in the salt for use m a food product are optionally substituted with a physiologically acceptable cation, wherein less than about 5% of the Cl ions m the salt for use in a food product are optionally substituted with a physiologically acceptable anion, and wherein the salt for use in a food product is substantially non-hygroscopic
[0032] In some embodiments, the physiologically acceptable cation is selected from calcium, zinc, selenium, copper, cobalt, chromium, manganese, molybdenum and combinations thereof In some embodiments, the physiologically acceptable anion is selected from fluoride, iodide, phosphate, silicate, selenate, sulfate, mtπte and combinations thereof [0033] Also provided herein is a substantially non-hygroscopic salt for use m a food product having the formula
Figure imgf000008_0001
Formula m wherein the sum of x and y is about 1 , wherein x is about 005 to about 045, wherein y is about 05 to about 095, wherein g is about 3, wherein z is about 4-6, wherein less than about 5% of the K ions in the salt for use in a food product are optionally substituted with a physiologically acceptable cation, wherein less than about 5% of the NEI4 ions in the salt for use in a food product are optionally substituted with a physiologically acceptable cation, wherem less than about 5% of the Cl ions in the salt for use in a food product are optionally substituted with a physiologically acceptable anion, and wherein the salt for use m a food product is substantially non-hygroscopic
A WSGR Docket No 36626-701 601 [0034] In some embodiments, the physiologically acceptable cation is selected from calcium, zinc, selenium, copper, cobalt, chromium, manganese, molybdenum and combinations thereof In some embodiments, the physiologically acceptable anion is selected from fluoride, iodide, phosphate, silicate, selenate, sulfate, nitrite and combinations thereof BRIEF DESCRIPTION OF THE DRAWINGS
[0035] The novel features of the invention are set forth with particularity m the appended claims A better understanding of the features and advantages of the present invention will be obtained by reference to the following detailed description that sets forth illustrative embodiments, in which the principles of the invention are utilized, and the accompanying drawings of which. [0036] Figure 1 illustrates the powder X-Ray Diffiaction (XRD) pattern for a salt product having the formula MgCl2 xKCl VNH4Cl zH2O, wherein x is about 025, y is about 0 75 and z is about 6, with a stick pattern reference for NH4MgCl3 6H2O
[0037] Figure 2 illustrates the X-Ray Diffraction (XRD) pattern for a salt product having the formula MgCl2 xKCl yNRtCl zH20, wherein x is about 025, y is about 0 75 and z is about 6, with a stick pattern reference for KMgCl3 6H2O
[0038] Figure 3 illustrates the X-Ray Diffraction (XRD) pattern for a salt product having the formula MgCl2 xKCl yNI^Cl zH2O, wherein x is about 025, y is about 0 75 and z is about 6, with a sbck pattern reference for MgCl2 [0039] Figure 4 illustrates the X-Ray Diffraction (XRD) pattern for a salt product having the formula MgCl2 xKCl VNH4Cl zH2O, wherein x is about 025, y is about 0 75 and z is about 6, with a stick pattern reference for NH4Cl
[0040] Figure 5 illustrates the X-Ray Diffraction (XRD) pattern for a salt product having the formula MgCl2 xKCl yNHiCl zH2O, wherein x is about 025, y is about 0 75 and z is about 6, with a stick pattern reference for KCl [0041] Figure 6 illustrates the X-Ray Diffraction (XRD) pattern for a salt product having the formula MgCl2 xKCl yNHtCl zH2O, wherein x is about 025, y is about 0 75 and z is about 6, with a suck pattern reference for NH4MgCl36H2O
DETAILED DESCRIPTION OF THE INVENTION
[0042] Sodium salts, e g , sodium chloπde, have a harmful effect on human health Diets composing high levels of sodium lead to morbidity in arterial hypertension and mortality in myocardial infarction. Conversely, magnesium salts reduce blood pressure and ammonium salts serve as preservatives that slow the growth of bacteria in food materials and products Moreover, ammonium is a normal metabolic product in the metabolism of nitrogen containing compounds, such as protein Excess physiological ammonium is captured by carbon dioxide and converted into urea, which is excreted from the body in the form of unne Thus, magnesium and ammonium
7 WSGR Docket No 36626-701 601 salts can serve as suitable substitutes in sodium-salt preparations if requirements related to taste, nutritional properties and ease of manufacturing and/or processing are met
[0043] Preferably, sodium-salt substitutes are chloride salts Other salts such as sulfate, carbonate and/or phosphate salts have limited utility in sodium-salt substitutes because of their bitter taste and/or limited solubility Chloride salts of alkali metals (e g , potassium) and/or alkaline earth metals (e g , magnesium, calcium) are physiologically acceptable substitutes for sodium-based salts, but such chloride salts are limited by being unduly hygroscopic which limits their utility as food salts Moreover, when the salts are dried, hydrochloric acid is released from the product and/or by other acidic components which leads to an unpleasant (e g , metallic or bitter) taste or lingering after-taste
[0044] Carnalhte is a naturally occurring double salt mineral composing alkali metal chlorides (e g , potassium chloride) and alkaline earth metal chlorides (e g , magnesium chloride) In some instances, a carnalhte salt is an ammonium carnalhte, e g , a tnple salt comprising potassium chloride, magnesium chloride and ammonium chloride The presence of physiologically acceptable salts m carnalhte and carnallite-type salts makes them good candidates for food salt substitutes U S Patent Nos 3,312,607, and 3,337,432, describe industrial applications of ammonium carnalhte salts (e g , as cell feed in magnesium cells) However, salts prepared by methods of preparation described therein are not described as suitable for human consumption Generally such industrial salts are not used in food products or human consumption U S Patent Nos 3,323,875, 3,536,444, 3,798,314, U S Patent Appl No 20Q8/0025908, GB 1308084, GB 1219969 and GBl 130183 descnbe industrial applications of carnalhte double salts (e g , salts comprising magnesium and potassium chlorides, or magnesium and ammonium chlorides), for example, in recovery of magnesium salts from bπnes None of these references describes physiological compatibility of carnalhte salts or the applicability of carnalhte salts as food salts WO 00/44245 does not specifically descnbe stability, hygroscopicity or hydrochloric acid content of salts described therem
[0045] Accordingly, provided herein are food salts for use in food products comprising magnesium chloride, potassium chloride and ammonium chloride that are suitable substitutes for sodium-based food salts Substitution of sodium-based salts with the salts descnbe herein provides food products with reduced levels of sodium In some instances, the salts described herein serve as complete or partial replacements for sodium-based salts m food products and provide low sodium products Furthermore, in certain embodiments, the salt products and salts provided herein possess good preservative characteristics, good physical properties (e g , ability to spnnkle or pour even under damp or humid conditions) and/or good flavor In certain instances, the salts for use in food products descnbed herein are palatable with no discernible difference in taste compared to conventional sodium-based salts and are suitable for use m a vanety of food
8 WSGR DocketNo 36626-701 601 products described herein In some instances, food salts descπbed herein are substantially non- hygroscopic, substantially free of hydrochloric acid and/or free ammonium chloride, and have a pleasant taste
[0046] In some embodiments, food salts descπbed herein are prepared by novel methods that provide salts that are suitable for human consumption The methods of preparation described herein allow for ease of manufacturing via a cost-effective process and provide free flowing non- hygroscopic salts that are substantially free of hydrochloric acid and/or free ammonium chloride [0047] In some embodiments, the food salts descπbed herein are prepared by the dissolution or wetting of the salt components (e g , potassium chloride, ammonium chloride, magnesium chloride, calcium chloride) in an aqueous medium. In some instances, the presence of dissolved ammonium chloride results m a solution pH-value of 5 0 — 5 5 In certain instances, ammonium chloride breaks down to ammonia and hydrogen chloride in the presence of concentrated solutions comprising magnesium chloride In certain conventional dissolving and coolmg methods of preparation, the released hydrogen chloride is occluded in the formed crystal lattice and the food salt product has sharp taste with reduced stability (i e , the product is hygroscopic)
[0048] In certain instances, aqueous solutions prepared according to processes descπbed herein are subjected to heat and/or reduced pressure to exhaust the hydrogen chloride and obtain a food salt product that is substantially free of HCl and substantially non-hygroscopic In some instances, subjecting the aqueous solutions prepared according to processes described to heat and/or reduced pressure leads to hydrolyzation of ammonium chloπde (e g , in some instances about 1-10% of the ammonium chloπde is hydro lyzed) In some embodiments, an additional amount of ammonium chlonde (e g about 1-10% molar excess) is added to an aqueous mixture that has been subjected to heat and/or reduced pressure In some instances, addition of excess ammonium chloπde provides a salt, m a subsequent step descπbed herein, wherein there is no hydrogen chlonde occluded in the crystal lattice and wherein the stoichiometry of ammonium chlonde is such that there is no free ammonium chlonde left outside the crystal lattice of the salt product The addition of about 1-10% molar excess of ammonium chlonde to an aqueous solution prepared according to processes descπbed herein, that is subjected to heat and/or reduced pressure, represents an advance over pnor art as this method of producing carnallite salts that are substantially free of hydrogen chlonde and ammonium chloπde has not been disclosed m pnor art Ammonium carnallite salts prepared by the methods descπbed herein have improved Cntical Relative Humidity values and are stable even in humid conditions (e g , 70% humidity)
[0049] In some embodiments, methods of preparation of carnallite salts descπbed herein are also applicable to the preparation of naturally occurnng carnallite (i e , a magnesium chlonde, potassium chloπde double salt) Addition of a 1-10% molar excess of NH4CI to an aqueous solution of magnesium chlonde and potassium chlonde prepared according to processes descnbed
9 WSGR Docket No 36626-701 601 herein and subjecting the aqueous solution to heat and/or reduce pressure affords, in a subsequent step descπbed herein, salt products that are suitable for human consumption and have improved stability in atmospheric humidity Such natural carnallite salts that are substantially free of hydrogen chloride and are substantially non-hygroscopic are of value when ammonium-free food salts are desired
[0050] Provided herein are non-sodium salts, low sodium salt compositions and/or low sodium food products In certain embodiments, provided herein are salts composing (i) magnesium cations, (u) potassium cations, ammonium cations, or combinations thereof, and (in) chloride In further embodiments, the salts provided herein are hydrates Further provided herein are low or no sodium salt compositions and food products compnsmg (i) magnesium cations, (n) potassium cations, ammonium cations, or combinations thereof, and (m) chloride Food Salts for Use in Food Products
[0051] Provided herein is a salt for use m a food product having the Formula I MgC12 xKCl yNH4Cl zH2O Formula I [0052] In certain embodiments, the sum of the terms x and y is about 1 In further or alternative embodiments, the term x is is greater than or equal to zero and less than 1 In further or alternative embodiments, the term y is greater than zero and less than or equal to 1 hi further or alternative embodiments, the term z is about 4 to about 6 In specific embodiments, the term z is about 6 In certain embodiments, the term y is greater than 0 In further or alternative embodiments, x is greater than 0 In some embodiments, the term x is about 005 to about 045, about 0 1 to about 04, about 0 1 to about 03, about 02 to about 03, about 025, about 0 55 to about 0 95, about 06 to about 0 9, about 07 to about 0 8, or about 075 In certain embodiments, the term y is about 005 to about 045, about 0 1 to about 0 4, about 0 1 to about 0 3, about 02 to about 0 3, about 025, about 0 55 to about 0 95, about 06 to about 0 9, about 07 to about 0 8, about 075 In specific embodiments, the term x is about 0 25 and the term y is about 075 In more specific embodiments, provided herein is a salt wherein x is about 025, y is about 075 and the XRD pattern of the salt comprises any one or more peaks with a 2Θ value about that of the peaks set forth in Sample 1 or Sample 2 of Figure 1 In certain embodiments, the term x is from about 005 to about 0045 and the term y is from about 0 55 to about 095 In other specific embodiments, the term x is about 0 75 and the term y is about 025 In still other specific embodiments, the term x is about 0 5 and the term y is about 0 5
[0053] Salts for use m a food product of Formula I, wherein x + y = 1 , can also be written as Formula II, wherein x, y and z are as defined above
MgKx(NH4)yC13 zH2O Formula II [0054] In certain embodiments, m any of the food salts or other compositions described herein, a small portion of the chloride anions are substituted with another anion, e g , a physiologically
10 WSOR Docket No 36626-701 601 acceptable anion In certain amounts, anions such as, by way of non-limiting example, fluoride, iodide, phosphate, silicate, selenate, sulfate, mtπte, combinations thereof, and the like are physiologically acceptable Ih certain embodiments, a physiologically acceptable amount, less than 5%, less than 3%, less than 2%, less than 1%, less than 05%, less than 0 1%, or less than 001 % of the chloride anions are substituted with a physiologically acceptable anion In certain embodiments, the salt product is formulated such that less than 100 mg per day of selenium (e g , from selenate and other sources) is consumed Accordingly, m certain embodiments, provided herein are salts for use in a food product of Formula HI
MgKx(NH4)yClg zH2O Formula IH [0055] In certain embodiments, the terms x, y and z are as defined above In some embodiments, the term g is from about 29 to about 3 In specific embodiments, the term g is about 3 [0056] Similarly, in certain embodiments, provided herein are salt products wherein a portion of the potassium and/or ammonium cations are replaced with other physiologically acceptable cations In certain embodiments, the physiologically acceptable cations are selected from, by way of non-limitmg example, calcium, zinc, selenium, copper, cobalt, chromium, manganese, molybdenum and combinations thereof In certain embodiments, a physiologically acceptable amount, less than 10%, less than 5%, less than 3%, less than 2%, less than 1%, less than 05%, less than 0 1%, or less than 001% of the potassium and/or ammonium cations are substituted with a physiologically acceptable cation. [0057] Thus, in certain embodiments, provided herein is a salt for use rn a food product of Formula IV
MgMfKx(NH4)yClgXlLzH2O Formula IV
[0058] In certain embodiments, M is a physiologically acceptable cation and the sum of f* (the charge of M), x and y is about 1 For example, in certain embodiments, M is Ca2+ and in such instances, the sum of 2f, x and y is about 1 In certain embodiments term f is from 0 to about 0 1 , from 0 to about 005, or from about 0 01 to about 005 In some embodiments, X is a physiologically acceptable anion and the term h is equal to about 3-g In certain embodiments term h is from 0 to about 02, from 0 to about 005, or from about 001 to about 005 In specific embodiments, f is from about 001 to about 0 1 and h is zero In alternative embodiments, h is from about 001 to about 02 and f is zero The terms x, y, g and z are as descnbed herein above [0059] In certain embodiments, any of the salt products of Formulas I-IV comprises one or more of the following (i) a magnesium chloride and potassium chloride double salt, (π) a magnesium chloride and ammonium chloride double salt, and (ui) a magnesium chloride, potassium chloride and ammonium chloride triple salt In further embodiments, the salt products of either of Formulas HI-IV further comprises a double salt of zinc chloride and ammonium chloride
11 WSGR Docket No 36626-701 601 [0060] In specific embodiments, zinc is present in either of Formulas III or IV as a cation substitute of magnesium in an amount such that less than 15 mg per day of zinc is consumed by an individual In certain embodiments, the salt product is formulated such that less than 250 μg, or less than 100 μg per day of selenium (e g , from selenium cations and/or selenate anion sources) is consumed by an individual
[0061] Furthermore, m certain embodiments, the salt products described herein comprise less than a detectable amount (e g , by taste), less than 3%, less than 1%, less than 0 5%, or less than 0 1% by weight OfNH4Cl free from (i e , outside the lattice of) a magnesium chloride and ammonium chloride double salt and/or a magnesium chloride, potassium chloride and ammonium chloride triple salt Furthermore, in certain embodiments, the salt products descnbed herein comprise less than a detectable amount (e g , by smell or taste), less than 3%, less than 1%, less than 05%, less than 0 1%, or less than 0 01% by weight of HCl
[0062] In certain embodiments, the salt for use in a food product of any of Formulas I-IV is substantially non-hygroscopic In one embodiment, such salt product adsorbs less than 1 wt-% per month upon extended storage in the absence of a dessicant In certain embodiments, the salt product described herein has a critical relative humidity value of greater than 70%, greater than 75%, greater than 80%, or about 75% to about 80% at 30° C In certain instances, a salt product of Formula 1 has a CRH value of about 70% at 30° C, e g , wherein x is zero and y is one [0063] It is to be understood that as used herein, any numerical value, whether descnbed exactly or as about that numerical value, includes the disclosure of about that amount and exactly that amount Thus, the disclosure of less than about 3% includes the disclosure of less than 3% and the disclosure of less than 3% includes the disclosure of less than about 3%
[0064] In certain embodiments, any of the salt products of Formulas I-IV is a food salt, an edible salt, a physiologically acceptable food salt, or the like In preferred embodiments, the salt product is non-toxic In certain embodiments, any of the salt products of Formulas I-IV is suitable for use in any food product descnbed herein
[0065] The term "food salt" represents a salt (e g , any salt descnbed herein) suitable for use m or with food products A food salt is suitable for human consumption A food salt has no toxicity, or a reduced toxicity, when used in amounts that are similar to amounts of sodium chlonde or sodium-based salts A food salt is a free flowing non-hygroscopic salt that is substantially free of hydrogen chlonde A food salt is also substantially free of free ammonium chlonde The food salts or salts for use in food products descnbed herein are pleasant tasting palatable salts (i e , there is no discernible difference between the taste of the salts descnbed herein and sodium chlonde and/or sodium-based salts) and do not have a metallic taste or after-taste Process of Making
12 WSGR Docket No 36626-701 601 [0066] In various embodiments, the salts for use in a food product described herein are prepared in any manner In specific embodiments, a processes descπbed herein is utilized to prepare a salt product of any of Formulas I-IV In more specific embodiments, a process descnbed herein is utilized to prepare a non-hygroscopic salt product of any of Formulas I-IV [0067] In certain embodiments, a salt product of any of Formulas I-IV is prepared by a dissolving in or wetting with an aqueous medium i magnesium chloride, and u ammonium chloride, potassium chloride or a combination thereof, b removing the aqueous medium by evaporation to afford the salt [0068] In some embodiments, the molar ratio of chlorides dissolved in the aqueous medium is 1 part magnesium chloride to x parts potassium chloride to y parts ammonium chloride In some instances, the aqueous medium is removed by evaporation (e g , by boiling and/or otherwise removing by heat and/or reduced pressure) In some instances, boiling leads to hydrolysis of a small mole percent ( ≤l 0%) of ammonium chloride In some embodiments, a slight molar excess of ammonium chloride is added to the aqueous medium when the aqueous medium is subj ected to boiling and/or heat and/or reduced pressure In some embodiments, the molar excess of ammonium chloride added to the aqueous medium is from about 1 - 10 mole% In some specific embodiments, the molar excess of ammonium chloride added to the aqueous medium is from about 1 - 5 mole% In some specific embodiments, the molar excess of ammomum chloride added to the aqueous medium is about 2 mole% In some embodiments, the molar excess of ammomum chloπde is added pπor to boiling the aqueous solution, e g , prior to heating the aqueous solution, or when the temperature of the aqueous solution is about 35 0C, about 45 0C, about 55 0C, about 65 0C, about 75 0C, about 85 0C, or about 95 °C [0069] In some embodiments, the molar ratio of magnesium chloπde to ammomum chloride utilized in the process is from about 1 1 Oly to about I l ly In certain embodiments, the molar ratio of magnesium chloride to potassium chloride to ammonium chloride utilized in the process is about 1 x >y, about 1 x y, or from about 1 x 1 Oly to about 1 x 1 Iy In certain embodiments, the molar ratio of magnesium chloπde to potassium chloπde to ammomum chloπde is from about 1 x 1 Oly to about 1 x 1 05y In more specific embodiments, the molar ratio of magnesium chloπde to potassium chloπde to ammomum chloride is about 1 x 1 02y Thus, for example, wherein the salt prepared hereby is MgCl2 (KCl)05 (NH4Cl)05 zH2O (1 e , wherein x = y = 0 5), the molar ratio of magnesium chloπde to potassium chloπde to ammonium chloride utilized m the process is about 1 05 051 [0070] In certain embodiments, the aqueous medium of any process descπbed herein is removed/evaporated by reduced pressure and/or increased temperature In specific embodiments, the aqueous medium is removed/concentrated by heating aqueous medium to a boil (e g , to at least
!3 WSOR Docket No 36626-701 601 about 100° C under ambient pressure or to lower temperatures under reduced pressure) Furthermore, in certain embodiments, commercial MgCk used in the process is contaminated with residual hydrochloride originated from the process of preparing the MgCk In some of such embodiments, this residual hydrochloride is removed during the process of removing/evaporating S the aqueous medium In certain embodiments, the aqueous medium is or comprises water (e g , distilled water) In some embodiments, the excess ammonium chloride (e g , the excess amount above y moles) added in the boiling step is consumed during the process of removing/evaporating the aqueous medium [0071] In some embodiments, a salt product of any of Formulas I-IV is prepared by 0 a dissolving in or wetting with an aqueous medium i magnesium chloride, u ammonium chloride, potassium chloride or a combination thereof, and Ui an acid scavenger, b removing the aqueous medium by evaporation to afford the salt S [0072] In some embodiments, the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is about 1 x y Ih some embodiments, the molar ratio of magnesium chloride to ammonium chloride is from about 1 1 Oly to about I l ly and the molar ratio of magnesium chloride to potassium chloride is about 1 x In certain embodiments, the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is from about 1 x 1 Oly to0 about 1 x 1 Iy In certain embodiments, the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is from about 1 x 1 Oly to about 1 x 1 OSy In more specific embodiments, the molar ratio of magnesium chloride to potassium chloπde to ammonium chloride is about 1 x 1 02y [0073] In certain embodiments, the molar ratio of magnesium chloride to ampholytic acid5 scavenger is about 1 0 001 to about 1 0 1, or about 1 0 01 to about 1 005 In specific embodiments, the molar ratio of magnesium chloπde to potassium chloπde to ammonium chloπde to glycme is about 1 x y about 0 02
[0074] In certain embodiments, any acid scavenger suitable is utilized In some embodiments, the acid scavenger is ammonia In certain embodiments, the acid scavenger is a buffering system, e g ,0 a citnc acid buffer system, a tartanc buffer system, or a malic acid buffer system. In some embodiments, the acid scavenger is an ampholytic acid scavenger In more specific embodiments, the ampholytic acid scavenger is an ammo acid In some embodiments, the ampholytic acid scavenger is glycine hi certain embodiments, the acid scavenger is suitable and is used m a suitable amount to maintain the pH of the aqueous medium at less than 7, about 5 5 to about 7, or5 about 6 to about 6 5
14 WSOR Docket No 36626-701 601 [0075] In various embodiments, the aqueous medium is removed in any process described herein under reduced pressure, subject to increased temperature, by evaporation, or a combination thereof. In specific embodiments, the aqueous medium is removed by heating the aqueous medium, to at least 50 °C, at least 70 "C, at least 90 °C, or at least 100 "C, or boiling. In other specific embodiments, the aqueous medium is removed under reduced pressure.
[0076] In some embodiments, a salt product of any of Formulas I-IV is prepared by: a. dissolving in or wetting with an aqueous medium i. magnesium chloride, ii. ammonium chloride, potassium chloride or a combination thereof, and ϋi. an acid scavenger, b. precipitating the salt from the aqueous medium; c. filtering the precipitate; and d. optionally recycling the filtrate.
[0077] In some embodiments, the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is about 1 : x : y. In some embodiments, the molar ratio of magnesium chloride to ammonium chloride is from about 1:1. Oly to about 1:1. Iy and the molar ratio of magnesium chloride to potassium chloride is about 1 : x.
[0078] In certain embodiments, any acid scavenger suitable is utilized. In specific embodiments, the acid scavenger is an amphσlytic acid scavenger. In more specific embodiments, the ampholytic acid scavenger is an amino acid. In some embodiments, the ampholytic acid scavenger is glycine. In certain embodiments, the acid scavenger is a buffering system, e.g., a citric acid buffer system, a tartaric buffer system, or a malic acid buffer system. In certain embodiments, the acid scavenger is not ammonia or an ammonia/ammonium buffer system. In some embodiments, the acid scavenger is ammonia (e.g., additional or excess ammonium, such as about 2 mol % excess). In some embodiments, the acid scavenger is an ampholytic acid scavenger. In more specific embodiments, the ampholytic acid scavenger is an amino acid. In some embodiments, the ampholytic acid scavenger is glycine. In certain embodiments, the acid scavenger is suitable and is used in a suitable amount to maintain the pH of the aqueous medium at less than 7, about 5.5 to about 7, or about 6 to about 6.5. [0079] In some embodiments, wherein the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is about 1 : x : y. In some embodiments, the molar ratio of magnesium chloride to ammonium chloride is from about 1 : 1.01 y to about 1:1. Iy and the molar ratio of magnesium chloride to potassium chloride is about 1 :x. In certain embodiments, the molar ratio of magnesium chloride to ampholytic acid scavenger is about 1:0.001 to about 1:0.1, or about 1 :0.01 to about 1 :0.05. In specific embodiments, the molar ratio of magnesium chloride to potassium chloride to ammonium chloride to glycine is about 1 : x : y : about 0.02. In those
15 WSGR Docket No 36626-701 601 embodiments, wherein the acid scavenger is ammonium chloride, the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is 1 x > y In certain embodiments, the acid scavenger is ammonia, in other embodiments, the acid scavenger is not ammonia [0080] In certain embodiments of any of the processes described herein, a process of preparing a salt product of Formula IV further comprises dissolving in or wetting with the aqueous medium at least one physiologically acceptable salt comprising either or both of M and X In specific embodiments, the physiologically acceptable salt is M,Xb, wherein the terms a and b are determined based on the charge of the ions, e g , independently selected from 1 and 2 In further or alternative embodiments, the physiologically acceptable salt is selected from, by way of non- limiting example, M8CIi,, K«Xt» (NHt)3Xt and me ϋks, wherein a and b are as defined above
[00811 As used herein, dissolving includes at least partially dissolving Ih some embodiments, the step of dissolving the components into the aqueous medium described herein includes heating the aqueous medium in order to dissolve the components Ih certain embodiments, heating the aqueous medium causes the solubility of one or more of the individual components to be increased in the aqueous medium As used herein, heating includes heating to any temperature above room temperature, including, e g , above about 20° C, up to about 100° C, up to boiling, or to boiling In some instances, evaporation includes sublimation and/or lyophihzation. [0082] In certain embodiments wherein a salt product of any of Formulas I-IV is precipitated from the aqueous medium, the individual components are dissolved in a heated aqueous medium and precipitation occurs upon cooling In some embodiments, once the individual components are dissolved, precipitation of the salt product of any of Formulas I-IV is accomplished by decreasing the volume of the aqueous medium In certain embodiments, the volume of the aqueous medium is decreased by evaporation. In some embodiments, evaporation is achieved under reduced pressure and/or increased temperature In some embodiments, evaporation is achieved by increasing the temperature of the aqueous medium. In more specific embodiments, evaporation is achieved by increasing the temperature of the aqueous medium under reduced pressure [0083] In some embodiments, a substantially non-hygroscopic salt product, e g , a substantially non-hygroscopic salt product of any of Formulas I-IV is prepared by mixing, grinding and/or blending a hygroscopic salt with ammonium chloride In certain embodiments, the amount of ammonium chloride is mixed, ground or blended with the hygroscopic salt in about 1 mol-% to about 99 mol-%, about 5 mol-% to about 50 mol-%, about 10 mol-% to about 30 mol-%, or about 25 mol-% of the hygroscopic salt In some embodiments, the hygroscopic salt is a natural salt In certain embodiments, the hygroscopic salt is a natural salt In some embodiments, the hygroscopic carnalhte is a double salt of magnesium chloride and potassium chloride wherein the potassium chloride is present in less than stoichiometric amount to magnesium chloride (i e ,
MgCl2 xKCl VNH4Cl zH2O, wherein y is zero and x is less than 1) In some embodiments, the
i6 WSOR Docket No 36626-701 601 hygroscopic salt is mixed, ground and/or blended with ammonium chloride until the sum of the amount of potassium chloride and ammonium chloride is equal to a stoichiometric amount of magnesium chloride (i e , MgCl2 xKCl yNHCl zH2O, wherein y > 0 and x+y = 1) In certain embodiments, the hygroscopic salt is top or surface hygroscopic In further embodiments, following mixing, grinding and/or blending, the mixture is dried
[0084] In some embodiments, the salts of any of Formulas I-IV for use m food products, salt blends thereof, or particles described herein are prepared by a "bulk process," a "filtration process," a "semi-dry filtration process," a "spray drying process" or a "drum dryer process " [0085] In certain embodiments, food salt products of any of Formulas I-IV are prepared by a dissolving in or wetting with an aqueous medium i magnesium chloride, ii ammonium chloride, and ui optionally an acid scavenger, and b contacting the magnesium chloride-ammonium chloride composition (e g , solution) of (a) with solid potassium chloride
[0086] In some embodiments, the volume of the aqueous medium is reduced (e g , by boiling and/or evaporation under reduced pressure and/or increased temperature) by about 30%, about 40% or about 50% prior to contacting with solid potassium chloride In some embodiments, the solid potassium chloride is crystalline potassium chloride In some instances, some or all of the aqueous medium is removed (e g absorbed by the solid potassium chloride) from the composition of (a) upon addition of the solid potassium chloride In some instances, a dry salt blend is formed upon addition of the solid potassium chloride In some instances, a semi-dry salt blend is formed upon addition of solid potassium chloride Ih some instances, a semi-dry salt blend is dried using any process described herein [0087] In some embodiments, an excess mol % of potassium chloride and/or sodium chloride is utilized In some of such embodiments, use of an excess of potassium chloride and/or sodium chloride allows for the formation a "blend" or "salt blend" or "blended salt" of potassium chloride and/or sodium chloride and a salt of any of Formulas I-IV [0088] In some embodiments, a food salt blend is produced by a "spray drying process " A solution containing at least one component of a food salt is sprayed over at least one other component of the blend on a iluidized bed
[0089] In certain embodiments of a spray drying process, solid potassium chloride is in a fluidized bed and the magnesium chloride-ammonium chloride composition (e g , solution) is deposited (e g , sprayed) onto the fluidized bed (e g , the potassium chloride particles) In some embodiments, once the composition of (a) is deposited (e g , sprayed) upon the solid potassium chloride, a blended salt product of any of Formulas I-IV (depending on the products utilized)
17 WSGRDocketNo 36626-701 601 containing at least one layer on the surface of the salt crystals is formed at the interface between the composition of (a) and the solid potassium chloride.
[0090] hi some of such embodiments, use of an excess of potassium chloride and/or sodium chloride allows for the formation of a coated particle comprising a salt of any of Formulas I-IV that is coated with potassium chloride and/or sodium chloride. In certain embodiments, provided herein is a particle comprising a potassium chloride core and a layer comprising a salt of any of Formulas I-IV. In some embodiments, such a particle (or "blend") is prepared according to any process described herein. In certain embodiments, such a particle is further blended with sodium chloride. Ih some embodiments, provided herein is a particle comprising a potassium chloride core, a layer of a salt of any of Formulas I-IV and a layer of sodium chloride. In specific embodiments, such a particle comprises an inner layer of a salt of any of Formulas I-IV and an outer layer of sodium chloride. In specific embodiments, such a particle comprises an inner layer of a salt of any of Formulas I-IV and an outer layer of potassium chloride. In further embodiments, such particles further comprise additional salt layers between the core and the inner layer, between the inner layer and the outer layer, on top of the outer layer, or a combination thereof.
[0091] In some embodiments, the food salts described herein are prepared by end-drying or a "bulk process." The aqueous solutions prepared by any process described herein are evaporated to dryness. In some embodiments, evaporating to dryness allows all of the salt components, with the exception of hydrolyzed ammonium chloride, that were dissolved hi the aqueous medium to crystallize out as a salt (e.g., a double salt, a triple salt or the like). In some instances, analytical evaluations are not needed. In certain instances, solutions are prepared with amount of water being about 100 ml/mol of solute(s). In certain embodiments, the amount of hydrolyzed ammonium chloride is about the same as the excess mole% of ammonium chloride added to the aqueous medium in any process described herein.
[0092] In some embodiments, the food salts and/or food salt blends are prepared by a "filtration process." In some instances, the raw-materials are weighed to a reactor and water is added to the reactor. In certain embodiments of the filtration process, an aqueous solution described herein is evaporated to about 70%, about 60% or about 50% of the initial volume when a thick crystal mass is formed. In some embodiments, the thick crystal mass is cooled and filtered, and the filtrate is recycled. Li some embodiments, moist filter cake is dried and used in the preparation of salt blends described herein.
[0093] In some embodiments, the filtration process described above is modified to a "semi-dry filtration process." In some embodiments, an aqueous solution prepared by methods described herein is evaporated to about 50% of the original volume, and dry potassium chloride or a mixture of potassium chloride and sodium chloride is added to the moist crystal mass. In certain
18 WSOR Docket No M626-70I 601 embodiments, the additional dry potassium chloride absorbs the remainder of the water and a dry salt product is obtained In certain embodiments, the additional dry potassium chloride absorbs the remainder of the water and a "semi-dry" salt product is obtained In some instances, a semi-dry salt product is further dried by a process descnbed herein In some instances, semi-dry salts are easier to handle m drying equipment In some instances, a semi-dry filtration process yields carnallite- type salts with reduced stratification (e g , uneven composition or mixture) Ui the final salt blend [00941 In some embodiments, the moist filter-cake from the filtration process is treated with dry potassium chloride or a mixture of potassium chloride and sodium chloride to absorb moisture and afford a semi-dry salt blend. [0095] In some embodiments, the salts and blended salts for use in food products described herein are prepared by a "drum dryer" process In some embodiments, a drum dryer process composes (a) optionally moisturizing or treating with water or water vapour (i e , wetting) the components of the food salts and/or blended food salts descnbed herein, (b) rolling the components of the food salts and/or blended food salts for a prolonged time (e g , about 8 hours, about 12 hours, about 16 hours or about 24 hours or more) in a drum dryer and (c) drying the resulting salt or salt blend using any method described herein
[0096] In some instances step (a) is omitted and the components of the food salts are moisturized or wetted by the water present in one or more of the component salts (e g , when one or more of the component salts are salt hydrates) In some instances, a drum dryer process achieves ion- exchange between the crystals and/or salt components In some instances, food salts obtained from a drum dryer process have lower CRH values In some instances, salts prepared by a drum dryer process are used to prepare salt blends that are used to prepare food salt solutions Food salts used as solutions are added to food products (e g liquid food products (e g soups, sauces)) that are boiled or heat-treated prior to consumption [0097] In some embodiments of any process descnbed herein, the component salts utilized m the process are salt particles In some embodiments of any process descnbed herein, the component salts (e g , magnesium chlonde, potassium chloride or ammonium chlonde) are of the same particle size In some embodiments of any process descnbed herein, the component salts (e g , magnesium chlonde, potassium chlonde or ammonium chlonde) are of different particle sizes [0098] In certain embodiments of any method of preparation of a food salt or a blend of a food salt descnbed herein, any suitable acid scavenger suitable is utilized In some embodiments, the acid scavenger is ammonia In some embodiments, ammonia is added in an amount that maintains the pH at about 7 In those embodiments wherein the acid scavenger is ammonia, excess ammonium chlonde is optionally not added to the aqueous medium In certain embodiments, the acid scavenger is a buffering system, e g , a citπc acid buffer system, a tartanc buffer system, or a malic acid buffer system. In some embodiments, the acid scavenger is an ampholytic acid
19 WSQR Docket No 36626 701 601 scavenger In some embodiments, the ampholytic acid scavenger is an amino acid In some embodiments, the ampholytic acid scavenger is glycine In some embodiments, the acid scavenger is a basic salt (e g , calcium phosphate, calcium carbonate, magnesium phosphate, magnesium carbonate or the like) In certain embodiments, the acid scavenger is used in a suitable amount to maintain the pH of the aqueous medium at less than 7, about 5 5 to about 7, or about 6 to about 65 In certain embodiments, the molar ratio of magnesium chloride to ampholytic acid scavenger is about 1 0001 to about 1 0 1, or about 1 001 to about 1 005 In specific embodiments, the molar ratio of magnesium chloride to potassium chloride to ammonium chloride to an acid scavenger is about 1 x y about 0 02 [0099] In various embodiments, any two or more of the component salts descπbed herem (e g , magnesium chloride and potassium chloride) are utilized in any of the processes descπbed herem in the form of a double salt, a triple salt, or the like, such as a natural carnallite, a modified carnalhte, a hygroscopic carnallite, a poor tasting carnallite, or the like In a specific embodiment, magnesium chloride and potassium chloride are provided in the form of a carnalhte salt and are processed according to any of the processes descπbed herem with ammonium chloride
Salt Compositions
(00100] In certain embodiments, provided herem is a composition comprising a salt product of any of Formulas I-IV In some embodiments, the composition compnses a salt product of any of Formulas I-IV and at least one additional salt In specific embodiments, the at least one additional salt is selected from potassium chloride, sodium chloride and combinations thereof In certain embodiments, the composition comprises a salt component composing a salt product of any of Formulas I-IV and potassium chloride and/or sodium chloride In specific embodiments, the salt component compnses, by weight, about 0 to about 99%, about 1% to about 99%, about 50% to about 99%, about 50% to about 90%, or about 50% to about 75% sodium chloride In further or alternative embodiments, the salt component comprises, by weight, 0% to about 99%, about 1% to about 99%, 0% to about 50%, greater than 0% to about 25%, about 1% to about 25%, or about 5% to about 25% potassium chloride Ih further or alternative embodiment, the salt component compnses, by weight, about 1% to about 99%, about 5% to about 50%, or about 25% of a salt product of any of Formulas I-IV In further embodiments, the composition comprises one or more additional salts In specific embodiments, blends provided herem comprise a combination of salts (w/w%) as set forth in Table 1 or Table 2
20 WSGR DocketNo 36626-701 601 Table 1
Salt Composition I Composition π Composition m Composition IV
NaCl 0-90% 25-75% 40-70% 45-60%
KCl 0-90% 5-50% 10-30% 15-25%
Salt Product 0 1-90% 5-50% 10-30% 15-25%
(00101] In some embodiments, provided herein are particles comprising (i) a salt product of any of Formulas I-IV, and (ii) potassium chloride, sodium chloride, or a combination thereof In certain embodiments, the particle composes a core and at least one layer In some embodiments, the core composes a salt product of any of Formulas I-IV In further embodiments, the at least one layer comprises potassium chloride and/or sodium chloride hi certain embodiments, coating the salt core with at least one layer provides an improved taste compared to an uncoated salt particle In some embodiments, such particles are prepared by mixing particles comprising a salt product of any of Formulas I-IV with potassium chloride and/or sodium chloride In specific embodiments, the potassium chloride and/or sodium chloride are in the form of a powder or fine particulates In some embodiments, the particulates of the salt product are mixed with the potassium chloride and/or sodium chloride for at least 1 hour, at least 4 hours, at least 8 hours, at least 12 hours, at least 16 hours, or at least 24 hours [00102] In certain embodiments, the salt product blended with an additional salt (e g , sodium chloride and/or potassium chloride) as descnbed herein, the blend has a critical relative humidity (CRH) value of greater than about 70%, greater than about 75%, greater than about 80%, greater than 85%, greater than 90%, or greater than 95% at 30° C In specific embodiments, the salt product blended with an additional salt (e g , sodium chloride and/or potassium chloride) has a CRH value greater than the CRH value for the salt product alone
[00103] In some embodiments, the composition comprising a salt product of any of Formulas I-IV composes a salt product of any of Formulas I-IV in associated, dissociated or partially dissociated form Accordingly, in certain embodiments, provided herein is a composition comprising a salt product of any of Formulas I-IV that has been dissolved in an aqueous medium In specific embodiments, the aqueous medium is or comprises potable water In certain embodiments, dissolved includes, e g , completely dissolved or partially dissolved, including at least 99% dissolved, at least 95% dissolved, or at least 50% dissolved In some embodiments, the aqueous composition is saturated with a salt product of any of Formulas I-IV hi certain embodiments, the aqueous composition comprises a salt component, wherein the salt component comprises a salt product of any of Formulas I-IV, and one or more of sodium chloride and potassium chloride hi specific embodiments, the salt component comprises, by weight, about 0 to about 99%, about 1%
21 WSQR Docket No 36626 701 601 to about 99%, about 50% to about 99%, about 50% to about 90%, or about 50% to about 75% sodium chloπde In further or alternative embodiments, the salt component comprises, by weight, 0% to about 99%, about 1% to about 99%, 0% to about 50%, greater than 0% to about 25%, about 1% to about 25%, or about 5% to about 25% potassium chloπde In further or alternative embodiment, the salt component comprises, by weight, about 1 % to about 99%, about 5% to about 50%, or about 25% of a salt product of any of Formulas I-IV In certain embodiments, the aqueous composition is saturated with the salt component In some embodiments, up to about 40% (w/w), or up to about 30% (w/w) of the aqueous composition is the salt component [00104] In certain embodiments, provided herein is an aqueous composition prepared by dissolving a salt component in an aqueous medium In specific embodiments, the aqueous medium is or comprises potable water In certain embodiments, the aqueous composition is prepared by dissolving a salt product of any of Formulas I-IV in an aqueous medium In further embodiments, the aqueous composition is prepared by dissolving a salt product of any of Formulas I-IV and one or more of sodium chloπde and potassium chloride in an aqueous medium In specific embodiments, the salt component comprises, by weight, about 0 to about 99%, about 1% to about 99%, about 50% to about 99%, about 50% to about 90%, or about 50% to about 75% sodium chloπde In further or alternative embodiments, the salt component comprises, by weight, 0% to about 99%, about 1% to about 99%, 0% to about 50%, greater than 0% to about 25%, about 1% to about 25%, or about 5% to about 25% potassium chloπde In further or alternative embodiment, the salt component compπses, by weight, about 1% to about 99%, about 5% to about 50%, or about 25% of a salt product of any of Formulas I-IV In some embodiments, up to about 40% (w/w), or up to about 30% (w/w) of the aqueous composition is the salt component In various embodiments, the salt product of any of Formulas I-IV, the sodium chloride and/or the potassium chloride are dissolved concurrently, or individually In further embodiments, one or more additional salts are also dissolved m the aqueous medium
[00105] In some embodiments, provided herein is an aqueous solution comprising magnesium cations, potassium cations and ammonium cations In certain embodiments, the molar ratio of magnesium cations to potassium cations to ammonium cations is about 1 x y, wherein the sum of the terms x and y is about 1 and wherein y is from greater than 0 to about 1 and x is from 0 to about 1 In further or alternative embodiments, the aqueous solution further compnses chloπde anions In certain embodiments, the molar ratio of magnesium cations to chionde anions is from about 1 2 to about 1 3, about 1 2 9 to about 1 3, or about 1 295 to about 1 3 In certain embodiments, the molar ratio of sodium cations to chloride anions is 1 3 00 [00106] In further or alternative embodiments, provided herein is an aqueous solution comprising sodium cations, potassium cations, magnesium cations, and ammonium cations In specific embodiments, the molar ratio of the sodium cations to potassium cations is from about 1 005 to
22 WSOR Docket No 36626-701 601 about 1 05 In further or alternative embodiments, the molar ratio of sodium cations to magnesium cations is from about 1 005 to about 1 0 1 In further or alternative embodiments, the molar ratio of sodium cations to ammonium cations is from 1 0 to 1 0 1, or from 1 0001 to 1 0 1 In other embodiments, the molar ratio of sodium cations to potassium cations is from 1 0005 to 1 0 5, the molar ratio of sodium cations to magnesium cations is from 1 0 005 to 1 0 1 , and wherein the molar ratio of sodium cations to ammonium cations is from 1 0 to 1 0 1 In further or alternative embodiments, the aqueous solution further comprises chloride anions [00107] In certain embodiments, an aqueous solution comprising sodium cations, potassium cations, magnesium cations, and ammonium cations, as described herein, further comprises an insignificant amount of one or more of sulfate ions, gold ions, silver ions, bromide ions, iodide ions, phosphate ions, and/or sulfide ions In specific embodiments, an insignificant amount of an ion is, by way of non-limiting example, less than about 100 ppm, less than about 50 ppm, less than about 25 ppm, or less than about 5 ppm. In certain embodiments, an insignificant amount of gold cations, silver cations and/or selenium cations is an amount less than about 25 ppm, less than about 5 ppm, less than about 1 ppm, or less than about 0 1 ppm In further or alternative embodiments, an aqueous solution described herein further compnses a physiologically important ion including, e g , sulfate, phosphate, silicate, nitrite, selenate, iodide, copper cations, cobalt cations, manganese cations, molybdenum cations and combinations thereof [00108] In certain embodiments, the pH of any of the aqueous compositions/solutions descnbed herein is about 6 to about 7, or about 6 to about 6 8
[00109] In some embodiments, the aqueous solutions descnbed herein are prepared by dissolving in or wetting with an aqueous medium, a salt product of any of Formulas I-IV and one or more of potassium chloride and sodium chloride [00110] Table 2 provides illustrative examples of the compositions descnbed herein. Table 2:
Salt Composition A Composition B Composition C Composition D
NaCl 70% 625% 55% 50%
KCl 5% 125% 20% 25%
Salt Product 25% 25% 25% 25%
[00111] In certain embodiments, the salts descnbed herein are dissolved in an aqueous medium. In certain embodiments, Compositions A, B and/or C are dissolved in an aqueous medium Table 3 illustrates various forms of the salt product of any of Formulas I-IV that are utilized in the Compositions A, B and/or C of Table 1 and the concentrations (% w/w) at which aqueous solutions of such compositions become saturated Saturation concentrations are determined by
23 WSGR Docket No M626-701601 dissolving salt compositions into 50 mL of water at about 167" C adding 05 grams of the salts at a tune to reach the saturated solutions usmg a magnetic stirrer Table 3:
Saturation Concentration in Water (% Ww)
Salt Product
Composition A Composition B Composition C
MgCl2 KCI oH2O 26 5% 29 5% 32 5%
MgCl2 HKCl '/,NH4Cl 6H2O 290% 31 0% 33 0%
MgCl2 HKCl '/2NH4Cl 6H2O 32 5% 3S 0% 375%
MgCl2 '4KCl '/4NH4Cl 6H2O 290% 30 5% 320%
MgCl2 NH4CI oH2O 28 5% 31 0% 340%
[00112] In specific embodiments, any of the aqueous solutions provided herein is potable [00113] In certain embodiments, the salt products disclosed herein are blended with a polyhydroxy compound In some embodiments, the polyhydroxy compound is mannitol, sorbitol, xylitol, or combinations thereof In some embodiments, blending the salt products disclosed herein with a polyhydroxy compound (e g mannitol, sorbitol, xylitol) improves the stability of the salt products in humid conditions In some embodiments, blending a polyhydroxy compound (e g mannitol, sorbitol, xylitol) with a salt product disclosed herein inhibits (either partially or fully) the ability of a water molecule to bind to a salt product In some embodiments, about 1-5 grams of polyhydroxy compound (e g mannitol, sorbitol, xyhtol) is blended with about 1 raol of salt product In some embodiments, about 2-4 grams of polyhydroxy compound (e g mannitol, sorbitol, xylitol) is blended with about 1 mol of salt product Ih some embodiments, about 3 grams of polyhydroxy compound (e g mannitol, sorbitol, xylitol) is blended with about 1 mol of salt product
[00114] In certain embodiments, the salt aqueous solutions disclosed herein are blended with a polyhydroxy compound In some embodiments, the polyhydroxy compound is mannitol, sorbitol, xylitol, or combinations thereof Li some embodiments, about 1-5 grams of polyhydroxy compound (e g mannitol, sorbitol, xyhtol) is blended with about 1 mol of salt product In some embodiments, about 2-4 grains of polyhydroxy compound (e g mannitol, sorbitol, xylitol) is blended with about 1 mol of salt product In some embodiments, about 3 grams of polyhydroxy compound (e g manmtol, sorbitol, xylitol) is blended with about 1 mol of salt product Uses [00115] In certain embodiments, a salt product descπbed herein is utilized as a seasoning In further or alternative embodiments, a salt product descπbed herein is a sodium salt (e g , sodium chloride) substitute In certain embodiments, provided herein is a composition composing a salt
24 WSGR Docket No 36626 701 601 product of any of Formulas I-IV and sodium chloride (β g , a portion of the sodium salt is substituted with a salt product of any of Formulas I-IV)
[00116] In some embodiments, a salt product or composition provided herein is used in food products In certain embodiments, salt products provided herein are used as salt substitutes for sodium salts In further or alternative embodiments, a salt product provided herein is utilized as a flavoring agent and/or as a preservative agent and is, optionally, utilized in food products In certain embodiments, a product or composition descnbed herein is utilized as a substitute for a flavoring agent or preservative m a food or nutrient product In further or alternative embodiments, the salt products or compositions described herein are utilized in a process of preparing a food product wherein the salt products or compositions descnbed herein at least partially replace or substitute a sodium salt (e g , sodium chloride) [00117] In specific embodiments, a salt product of any of Formulas I-IV or a composition descnbed herein is utilized as a flavoring agent and/or preservative in food products, including, by way of non-limiting example, meats (e g , cooked meat products, ground meat products, sausages and hot dogs), snack foods (e g , dry snacks, baked cheese snacks, potato chips, sweet crackers, snack bars, granola bars, candy bars, breakfast bars, and salty crackers), dairy foods (e g , conventional cheese, cheese spread, cheeses), dried or dehydrated foods (e g , dned soups and milk powder), canned foods (e g , canned sauces, and canned soup), ready meals, (frozen and non- frozen), frozen foods (e g , frozen pizza, frozen television dinners), fish, vegetables, yeast-based or products (e g , conventional breads, breads and pastnes), spices (e g , curry or garam masala). condiments (e g , ketchup, mayonnaise, pasta sauce, salad dressing, soy sauce, and barbeque sauce), soy products, beverages (e g , sports dπnks and soda pop) and the like In some embodiments, a salt product of any of Formulas I-IV or a composition descnbed herein is utilized as or in a seasoning product, a spice product, or a food salt product [00118] Thus, provided in certain embodiments herein are food products, nutrient substances, semi-finished food products, and a processed food products that have, during the preparation thereof, been processed, flavored or preserved with any salt or salt composition descnbed herein [00119] In certain instances, food products comprise food acids, acidity regulators, anti-caking agents, anti-foaming agents, antioxidants, bulking agents, food coloring, color retention agents, emulsifiers, flavors, flavor enhancers, flour treatment agents, humectants, tracer gas, preservatives, stabilizers, sweeteners, thickeners and the like In some embodiments, food acids are added to make flavors "sharper" and also act as a preservative and antioxidant Common food acids include, by way of non-limiting example, vinegar, citnc acid, tartic acid, malic acid, fumanc acid and lactic acid. In certain embodiments, acidity regulators are used to change or otherwise control the acidity and alkalinity of foods In some embodiments, ann-caking agents keep powders such as milk powder from caking or sticking In certain embodiments, anti-foaming agents reduce or
25 WSGR Docket No 36626-701 601 prevent foaming in foods Ih some embodiments, anti-oxidants such as vitamin C act as preservatives by inhibiting the effects of oxygen on the food and can be beneficial to health In certain embodiments, bulking agents such as starch are additives that increase the bulk of a food without affecting its nutritional value In some embodiments, food colorings are added to food to replace colors lost during preparation or to improve the aesthetics of a food In some embodiments, color retention agents are used to preserve a food's existing color In certain embodiments, emulsifiers allow water and oils to remain mixed together in an emulsion, as in mayonnaise, ice cream and homogenized milk. In some embodiments, flavors are additives that give food a particular taste or smell and may be derived from natural ingredients or created artificially In some embodiments, flour treatment agents are added to flour to improve its color or its use m baking In certain embodiments, humectants prevent foods from drying out In some embodiments, tracer gas allows for package integrity testing to prevent foods from being exposed to atmosphere, thus guaranteeing shelf life In some embodiments, preservatives prevent or inhibit spoilage of food due to fungi, bacteria and other microorganisms In certain embodiments, stabilizers, thickeners and gelling agents, like agar or pectin (used in jam for example) give foods a firmer texture In some cases, while stabilizers are not true emulsifiers, they help to stabilize emulsions In some embodiments, sweeteners are added to foods for flavoring Ih certain instances, sweeteners other than sugar are added to keep the food energy (calories) low, or because they have beneficial effects for diabetes mellitus and tooth decay and diarrhea In some embodiments, thickeners are substances which, when added to the mixture, increase its viscosity without substantially modifying its other properties In some embodiments, a salt product or a composition descnbed herein is present m or is utilized in preparing a food product to reduce the amount of or substitute one or more of a spice, a food acids, acidity regulators, anti-caking agents, anti-foaming agents, antioxidants, bulking agents, food coloπng, color retention agents, emulsifiers, flavors, flavor enhancers, flour treatment agents, humectants, tracer gas, preservatives, stabilizers, sweeteners, thickeners and the like used therein
[00120] In certain instances, frozen foods compnse spices (e g , black pepper, chih, white pepper, oregano, paprika, garlic, and the like), flavors (e g , pork flavor, beef flavor, steak flavor, chicken flavor, onion flavor, and the like), sodium nitrite, sodium ascorbate, dextrose, sodium phosphates, corn syrup solids, sodium stearoyl lactylate, sodium aluminum phosphate, ascorbic acid, BHA,
BHT, citπc acid, and combinations thereof Bi some embodiments, a salt product or a composition descnbed herein is present m or is utilized m preparing a frozen food product to reduce the amount of or substitute one or more of a spice, a flavor, sodium nitrite, sodium ascorbate, dextrose, sodium phosphate, a corn syrup solid, sodium stearoyl lactylate, sodium aluminum phosphate, ascorbic acid, BHA, BHT, and/or citric acid used therein
26 WSGR Docket No 36626 701 601 [00121] In some instances, snack foods (e g , dry snacks and/or baked cheese snacks) comprise TBHQ, maltodextπn, natural flavors (e g , cheese), disodium mosinate, drsodmm guanylate, sodium casemate, spices (e g , black pepper, chili, white pepper, oregano, paprika, garlic, cajun pepper, and the like), and combinations thereof In some embodiments, a salt product or a composition described herein is present in or is utilized in preparing snack food (e g , dry snacks and/or baked cheese snacks) to reduce the amount of or substitute one or more of TBHQ, maltodextπn, a natural flavor, disodium inosinate, disodium guanylate, sodium casemate, and/or a spice used therein [00122] hi some instances, dairy foods compose stabilizers (e g , carob bean, xanthan and/or guar gums), potassium sorbate, sodium diacetate, preservatives (e g , sorbic acid), and combinations thereof In certain embodiments, a salt product or composition described herein is present in or is utilized in preparing a dairy food product to reduce the amount of or substitute one or more of a stabilizer, potassium sorbate, sodium diacetate, and/or a preservative used therein [00123] In certain embodiments, the compositions described herein are utilized in any of the uses described herein In certain embodiments, aqueous compositions comprising a salt product of any of Formulas I-IV, and one or more of sodium chloride and potassium chloride having salt concentrations of up to about 40% (w/w), or up to about 30% (w/w), up to about 20% (w/w), up to about 15% (w/w), up to about 10% (w/w) or up to about 5% (w/w) are utilized In certain embodiments, the compositions further comprise additional additives In specific embodiments, the additional additives mclude additives suitable for enhancing the flavor and/or the preservative characteristics of the salts In further or alternative embodiments, the additional additives mclude any seasoning and/or food additive
[00124] In certain embodiments, the salts descnbed herein are also utilized m, by way of non- hmiting example, mouth-flush mixtures, antiseptics (e g , pastes and ointments) and pastes for reducing the formation of varicose veins In some embodiments, the salts described herein are utilized in protein hydrolysates, flavonoids, steroids and the like Thus, in certain embodiments, such products are provided for herein. In some embodiments, a salt product or composition descnbed herein is utilized as a salt substitute by an individual to treat hypomagnesia In certain embodiments, aqueous solutions of the salts and/or salt blends described herem are used as electrolyte replenishing mixtures in the treatment of, e g , travellers' diarrhea, dehydration due to cholera, gastrointestinal distress, salmonella or E coll infections and the like 100125] In some embodiments, the salts described herem are utilized as a flavoring enhancing agent Thus, in certain embodiments, provided herem is a composition (a flavoring product) comprising a salt (or salt blend) descnbed herein and a flavoring agent In specific embodiments, such a composition is a food additive In some embodiments, provided herem is a method of reducing the amount of a flavoring agent necessary to achieve a desired flavor in a food (or other
27 WSGR Docket No 36626-701 601 item that is inserted into the mouth, such as mouth-flush mixtures, antiseptics, or the like) by combining an effective amount of a salt or salt blend described herein with the flavoring agent [00126] Flavoring agents suitable for combination with spices (e g , peppers, curry, heibes de provence, five spice powder, garam masala, black pepper, chili, chili peppers, white pepper, oregano, papnka, garlic, and the like), salts (e g , sodium chloride), other flavors (e g , pork flavor, beef flavor, steak flavor, chicken flavor, onion flavor, hoisin sauce, oyster sauce), and the like In specific embodiments, provided herein is a reduced sodium soy sauce comprising a food salt product of any of Formulas I-IV
Examples
[00127] The examples described below provide non-limiting illustrative examples of the products and processes descnbed herein
Example 1
[00128] The example describes a method to produce a mixed carnallite containing 25 mol- % of potassium chloride and 75 mol-% of ammonium chloride by filtering method 2 mol-% excess of ammonium chloride was included into the method
[00129] 1 0 mol (203 3 g) of magnesium chloride hexahydrate, 025 mol (18 64 g) of potassium chloride and 0 765 mol (4093 g) of ammonium chlonde were dissolved to 125 ml of water The mixture was concentrated by boiling until 50 ml of water was left in the mixture The mixture was cooled, filtered by suction and the crystal mass was dried in a rotating drum in a temperature of 5O0C
[00130] Yield 236 g (90%) of white crystalline product with pleasant taste The product is virtually unhygroscopic
Example 2 [00131] The example describes a method to produce ammonium carnallite with total evaporation to dryness including 2 mol-% of excess ammonium chlonde
[00132] 1 02 mol (54 6 g) of ammonium chlonde and 1 0 mol (203 3 g) of magnesium chlonde hexahydrate were added to 120 ml of water The mixture was heated to boiling with stirring to evaporate most of the water The formed thick moist crystal mass was mixed with spatula and heated gently until dry product was formed
[00133] Yield 256 g (theor ) of white salt having a pleasant, slightly sour taste The product is virtually unhygroscopic
Example 3
[00134] The example describes a method to produce potassium carnallite by total evaporation of water in the presence of glycine ( 1 mol-%) and ammonium chlonde (2 mol-%)
28 WSGR Docka No 36626 701 601 [00135] 1 0 mol (203 3 g) of magnesium chloride hexahydrate and 1 0 mol (7455 g) of potassium chloride were added to 125 ml of water Glycine (0 75 g) and ammonium chloride (1 07 g) were added and the mixture was treated as described in example 2 Both of the buffering agents were mainly exhausted in the final stages of the drying [00136] Yield 278 g (theor ) of white salt having a note of sea water The product is slightly hygroscopic m a humidity over 70% RH but is stabilized when mixed with alkali chlorides
Example 4
[00137] The example descπbes a method to produce a mixed carnallite containing 25 mol- % of ammonium chloride and 75 mol-% of potassium chloride by filtering method 2 mol-% excess of ammonium chloride was present in the mixture
[00138] 1 0 mol (203 3 g) of magnesium chloride hexahydrate, 075 mol (55 91 g) of potassium chloride and 0255 mol (13 65 g) of ammonium chloride were added to 125 ml of water
The excess of water was evaporated by boiling to a point having 40 ml of water left in the mixture The mixture was cooled, filtered by suction and dried in a rotating drum (5O0C)
[00139] Yield 231 g (85%) of white, virtually unhygroscopic material with small crystal size The taste is pleasing
Example 5
[00140] The example descπbes a method to produce a mixed carnallite containing 50 mol- % of potassium chloride and 50 mol-% of ammonium chloride by total evaporation to dryness
Excess of ammonium chloride (2 mol-%) is present in the mixture
[00141] 1 0 mol (203 3 g) of magnesium chloride, 0 5 mol (3728 g) of potassium chloride and 051 mol (2729 g) of ammonium chloride were dissolved to 125 ml of water The mixture was treated as described in the example 2 to produce a freely flowing salt [00142] Yield 224 g (84%) of white, virtually unhygroscopic material with small crystal size and a pleasant salty taste
[00143] Salt products composing different amounts of potassium and ammonium are prepared in similar manners by adjusting the mol-% of ammonium chloride and mol-% of potassium chloride dissolved into water Example 6
[00144] Depending on the use, different ratios of potassium to ammonium are utilized m salt products and compositions described herein. Salt products and compositions described herein, including e g , those of Tables 1-3, are deposited in incrementally increasing amounts on a food product (e g from 001 mg of salt product per gram of food product) The food products are then tasted by a sample of healthy volunteers and the taste is rated on a scale of 1 -10 The food
29 WSQR Docket No 36626 701 601 products are then stored and the preservative characteristic of the salt product or composition is rated on a scale of 1-10
[00145] In certain instances, wherein the salt products or compositions described herein are utilized as a preservative, the best salt products or compositions described herein are determined based on potassium to ammonium ratios produce the best taste and best preservative characteristic In certain instances, wherein the salt product or compositions described herein are utilized as a flavoring agent alone, only the taste of the salt need be considered. Example 7 [00146] Two pieces of 10 g were cut from a "market-fresh" salmon, both pieces having a remarkable area of the typical silver-colored skin Both of the pieces were salted, the first with 0 5 g of table salt and the other with 0 5 g of the salt product of Example 3 Both of the samples were stored in a refrigerate room in a temperature of 12° C and the chemiluminence of the salmon skin were observed visually from time to time It was found that the luminence of the sample salted with table salt disappeared after storage for 48 hours The luminence of the salted sample continued for an additional 55 hours before fading Thus, the salt product of Example 2 is illustrated to have an ability to prevent the formation of formic acid in the deterioration of the fish flesh Similar effects have been found in ham and other meat products
Example 8
[00147] Salt products and compositions described herein, including e g , those of Tables 1 - 3, are formulated in combination with a flavoring agent (e g , a salt or a spice) in incrementally increasing weight % amounts Each of the combinations are then tasted by a sample of healthy volunteers in increasing amounts (e g , from 1 mg of combination) The combinations are then tasted by a sample of healthy volunteers and the taste is rated on a scale of 1 - 10 [00148] Additionally, or alternatively, each of the combinations are placed on a food product m increasing amounts (e g from 001 mg of salt product per gram of food product) The food products are then tasted by a sample of healthy volunteers and the taste is rated on a scale of 1-10
Example 9 [00149] The example describes a method to produce a mixed carnallite containing 25 mol- % of potassium chloride and 75 mol-% of ammonium chloride by filtering method 2 mol-% excess of ammonium chloride is included into the method
[00150] 1 0 mol (203 3 g) of magnesium chloride hexahydrate, 025 mol (18 64 g) of potassium chloride and 0765 mol (40 93 g) of ammonium chloπde are dissolved to 125 ml of water The mixture is concentrated by boiling until 50 ml of water was left in the mixture The mixture is heated to boiling with stirring to evaporate most of the water The formed thick moist crystal mass is agitated and heated gently until dry product is formed
30 WSGR Docket No 36626-701 601 Example 10
[00151] The example describes a method to produce a mixed carnalhte containing 25 mol-
% of potassium chloride and 75 mol-% of ammonium chloπde by filtering method 2 mol-% excess of ammonium chloπde is mcluded into the method [00152] 1 Omol (203 3 g) of magnesium chloπde hexahydrate, 025 mol (18 64 g) of potassium chloπde and 0 765 mol (40 93 g) of ammonium chloπde are dissolved to 125 ml of water The mixture was concentrated by boiling until 50 ml of water was left m the mixture The mixture was cooled, filtered by suction and the crystal mass was dπed in a rotating drum in a temperature of 500C Example 11
[00153] X-Ray Diffraction (XRD) patterns were obtained for salts descπbed herein
Figure 1 illustrates the XRD pattern for Sample 1, which is an MgCl2XNH4Cl 6 H2O sample prepared by concentration in a rotary evaporator and filtration (85% yield), the XRD pattern for Sample 2, which is an MgCl2 x 075 NH4Cl x 025 KCl 6 H2O sample by the total evaporation of solvent (~100% yield), and a stick pattern for reference NH4MgCl3 Similarly, XRD patterns of salt products provided herein according to Formula I, wherein x is about 025, y is about 0 75, z is about 6, and g is about 3, were compared to and found to be distinct from KMgCl3 6H2O (Figure 2), MgCl2 (Figure 3), NHCl, (Figure 4), KCl (Figure 5) and NH4MgCl3 6H2O (Figure 6) In some embodiments, provided herein is a sample comprising (1) one or more peak having a 2Θ value that is approximately equal to that of a MgCl2 x 0 75 NH4Cl x 025 KCl 6 H2O pattern of any of Figures 1-5, (2) substantially free of one or more peak having a 2Θ value that is approximately equal to that found in the stick figures (m any of Figures 1-6) of any of KMgCl3 6H2O, MgCl2, NHCl4, KCl, NH4MgCl36H2O or a combination thereof, 3) a peak intensity ratio of a first peak having a first 26 to a second peak having a second 26 that is different from a peak intensity ratio of any one or more OfKMgCl3 6H2O, MgCl2, NHCl4, KCl, NH4MgCl3 6H2O having a pan- of peaks with similar or identical 26 values (e g , as set forth in the stick figures of any of Figures 1-6), or a combination thereof In some embodiments, the relative intensities of one or more peaks when comparing a salt provided herein to one or more OfKMgCl36H2O, MgCl2, NHCl4, KCl, NH4MgCl3 6H2O are different [00154] While preferred embodiments of the present invention have been shown and descπbed herein, it will be obvious to those skilled m the art that such embodiments are provided by way of example only Numerous vaπations, changes, and substitutions will now occur to those skilled m the art without departing from the invention It should be understood that various alternatives to the embodiments of the invention described herein may be employed m practicing the mvention It is intended that the following claims define the scope of the invention and that methods and structures within the scope of these claims and their equivalents be covered thereby
3! WSGRD∞kΛNo 36626-701601

Claims

WHAT IS CLAIMED IS:
1. A substantially non-hygroscopic salt for use in a food product having the formula:
MgKx(NH4)yClg-zH2O Formula III wherein the sum of x and y is about 1 , wherein 0 <x < 1 , wherein 0 < y <1 , wherein g is about 3, wherein z is about 4-6, and wherein the salt for use in a food product is substantially non-hygroscopic and substantially free of hydrogen chloride.
2 A substantially non-hygroscopic salt for use in a food product having the formula:
MgKx(NaOyCIg-ZH2O Formula III wherein the sum of x and y is about 1, wherein x is about 0.05 to about 0.45, wherein y is about 0.55 to about 0.95, wherein g is about 3, wherein z is about 4-6, and wherein the salt for use in a food product is substantially non-hygroscopic and substantially free of hydrogen chloride.
3 The salt for use in a food product of claim 1 or 2, wherein z is 6. 4 The salt for use in a food product of claim 1 or claim 2, wherein the salt is prepared by a) dissolving in or wetting with an aqueous medium (i) magnesium chloride, and (ii) ammonium chloride, potassium chloride or a combination thereof; b) boiling the aqueous medium; and c) removing the aqueous medium by evaporation to afford the salt for use in a food product; wherein the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is 1 : x : y.
5 The salt for use in a food product of claim 1 or claim 2, wherein the salt is prepared by: a) dissolving in or wetting with an aqueous medium (i) magnesium chloride, (ii) ammonium chloride, potassium chloride or a combination thereof, and (iii) an acid scavenger; b) boiling the aqueous medium; c) precipitating the salt for use in a food product from the aqueous medium; d) filtering the precipitated salt; and e) optionally recycling the filtrate; wherein the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is 1 : x : : y.
6 The salt for use in a food product of claim 5 wherein the salt is prepared by a filtration process, a semi-dry filtration process, a spray drying process, a bulk process or a drum dryer process.
32 WSGR DocketNo. 36626-701.601 7 The salt for use in a food product of claim 4 or claim 5, wherein step (b) further comprises dissolving in the aqueous medium an additional amount of about 1-10 mol% of ammonium chloride.
8 The salt for use in a food product of claim 4 or claim 5, wherein step (b) further comprises dissolving in the aqueous medium an additional amount of about 2 mol% of ammonium chloride.
9 The salt for use in a food product of any of claims 1 -9, wherein x is about 0.25 and y is about 0.75.
10 A particle comprising a core and at least one layer, wherein the core comprises a salt of any of claims 1-9, and wherein at least one layer of the particle comprises sodium chloride, potassium chloride, or a combination thereof.
11 A composition comprising (i) a salt for use in a food product of any of claims 1 -9 and (ii) sodium chloride, potassium chloride, or a combination thereof.
12 A composition comprising (i) a salt for use in a food product of any of claims 1 -9 and (ii) an aqueous medium, wherein the salt is dissolved and dissociated in the aqueous medium. 13 An aqueous solution prepared by dissolving a salt for use in a food product of any of claims 1-9 in potable water.
14 The aqueous solution of claim 13, comprising magnesium cations, potassium cations and ammonium cations in a molar ratio of 1 : x : y.
15 The aqueous solution of claim 14, wherein the aqueous solution is prepared by further dissolving sodium chloride and potassium chloride in the aqueous medium.
16 The aqueous solution of claim 15 , comprising sodium cations, potassium cations, magnesium cations, and ammonium cations, wherein the molar ratio of sodium cations to potassium cations is from 1 :0.005 to 1 :0.5, the molar ratio of sodium cations to magnesium cations is from 1 :0.005 to 1:0.1, and wherein the molar ratio of sodium cations to ammonium cations is from 1:0 to 1:0.1.
17 A nutrient substance, a semi-finished food product, a flavoring product, a processed food product that has, during the preparation thereof, been processed or preserved with a salt for use in a food product of any of claims 1 -9, a composition of either of claims 11 -12, or a solution of any of claims 13-16. 18 The nutrient substance, semi-finished food product, or processed food product of claim 15, wherein the processed food product is selected from meats, fish, vegetables, snack foods, soups, sauces, dairy products, and yeast based products.
19 A method of decreasing the sodium content of a food product by at least partially substituting a sodium containing salt in the food product with a salt for use in a food product of any of claims 1-9, a composition of either of claims 11-12, or a solution of any of claims 13-16.
33 WSGR Docket No. 36626-701.601 20 The method of claim 19, wherein the food product does not have a substantially decreased taste or shelf-life.
21 A method of preparing a substantially non-hygroscopic salt for use in a food product having the formula: MgKx(NHOyCIg-ZH2O Formula III comprising: a) dissolving in or wetting with an aqueous medium (i) magnesium chloride, and (ii) ammonium chloride, potassium chloride or a combination thereof; and b) removing the aqueous medium by evaporation to afford the salt for use in a food product; wherein the sum of x and y is about 1 , wherein 0 ≤x < 1 , wherein 0 < y ≤l , wherein g is about 3, wherein z is about 4-6, and wherein the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is about 1 : x : y.
22 The method of claim 21 wherein the sum of x and y is about 1 , wherein x is about 0.05 to about 0.45, wherein y is about 0.5 to about 0.95, wherein g is about 3, wherein z is about 4-6, and wherein the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is 1 : x : y.
23 The method of claim 21 or claim 22, further comprising dissolving in or wetting with the aqueous medium an additional about 1-10 mol% of ammonium chloride. 24 The method of claim 21 or claim 22, further comprising dissolving in or wetting with the aqueous medium an additional about 2 mol% of ammonium chloride.
25 A method of preparing a substantially non-hygroscopic salt for use in a food product having the formula:
MgKx(NH4JyCIg-ZH2O Formula m comprising: a) dissolving in or wetting with an aqueous medium (i) magnesium chloride, (ii) ammonium chloride, potassium chloride or a combination thereof, and (iii) an acid scavenger; and b) removing the aqueous medium by evaporation to afford the salt for use in a food product; wherein the sum of x and y is about 1 , wherein 0 ≤x < 1 , wherein 0 < y ≤l , wherein g is about 3, wherein z is about 4-6, and wherein the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is 1 : x : y.
26 The method of claim 25 wherein the sum of x and y is about 1 , wherein x is about 0.05 to about 0.45, wherein y is about 0.5 to about 0.95, wherein g is about 3, wherein z is about 4-6, and
34 WSGR Docket No. 36626-701.601 wherein the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is about 1 : x : y.
27 The method of any of claims 21 to 26 wherein removing the aqueous medium by evaporation comprises boiling the aqueous medium. 28 A method of preparing a salt for use in a food product having the formula:
MgKx(NH4)yClg-zH2O Formula DI comprising: a) dissolving in or wetting with an aqueous medium (i) magnesium chloride, (ii) ammonium chloride, potassium chloride or a combination thereof, and (iii) an acid scavenger; b) precipitating the salt for use in a food product from the aqueous medium; c) filtering the precipitate; and d) optionally recycling the filtrate; wherein the sum of x and y is about 1 , wherein 0 ≤x < 1 , wherein 0 < y ≤l , wherein g is about 3, wherein z is about 4-6, and wherein the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is 1 : x : y.
29 The method of claim 28 wherein the sum of x and y is about 1 , wherein x is about 0.05 to about 0.45, wherein y is about 0.5 to about 0.95, wherein g is about 3, wherein z is about 4-6, and wherein the molar ratio of magnesium chloride to potassium chloride to ammonium chloride is 1 : x : y.
30 The method of claim 28 or 29 wherein the salt is prepared by a filtration process, a semi- dry filtration process, a spray drying process, a bulk process or a drum dryer process.
31 A substantially non-hygroscopic salt for use in a food product having the formula:
MgKx(NH4XCIg ZH2O Formula HI wherein the sum of x and y is about 1 , wherein 0 ≤ x < 1 , wherein 0 < y <1 , wherein g is about 3, wherein z is about 4-6; wherein less than about 5% of the K ions in the salt for use in a food product are optionally substituted with a physiologically acceptable cation; wherein less than about 5% of the NH4 ions in the salt for use in a food product are optionally substituted with a physiologically acceptable cation; wherein less than about 5% of the Cl ions in the salt for use in a food product are optionally substituted with a physiologically acceptable anion, and wherein the salt for use in a food product is substantially non-hygroscopic.
32 The salt of claim 31 wherein the sum of x and y is about 1 , wherein x is about 0.05 to about 0.45, wherein y is about 0.5 to about 0.95, wherein g is about 3, and wherein z is about 4-6.
35 WSGR Docket No. 36626-701.601 33 The salt for use in a food product of claim 31 or 32, wherein the physiologically acceptable cation is selected from calcium, zinc, selenium, copper, cobalt, chromium, manganese, molybdenum and combinations thereof.
34 The salt for use in a food product of claim 31 or 32, wherein the physiologically acceptable anion is selected from fluoride, iodide, phosphate, silicate, selenate, sulfate, nitrite and combinations thereof.
36 WSGR Docket No. 36626-701.601
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CL2009000682A1 (en) 2010-10-08
CN101977517A (en) 2011-02-16
NZ588531A (en) 2012-07-27
EA201001495A1 (en) 2011-10-31
JP2011528893A (en) 2011-12-01
AU2009225467A1 (en) 2009-09-24
WO2009117702A3 (en) 2010-03-18
EP2268159A4 (en) 2015-04-01
EP2268159A2 (en) 2011-01-05

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