[go: up one dir, main page]

WO2001070241A1 - Production and use of dissolved bioavailable selenium - Google Patents

Production and use of dissolved bioavailable selenium Download PDF

Info

Publication number
WO2001070241A1
WO2001070241A1 PCT/IL2001/000265 IL0100265W WO0170241A1 WO 2001070241 A1 WO2001070241 A1 WO 2001070241A1 IL 0100265 W IL0100265 W IL 0100265W WO 0170241 A1 WO0170241 A1 WO 0170241A1
Authority
WO
WIPO (PCT)
Prior art keywords
selenium
salt
selenate
supermag
suspension
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IL2001/000265
Other languages
French (fr)
Inventor
Daniel Berman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DARICOM Ltd NATURAL HEALTH PRODUCTS
Original Assignee
DARICOM Ltd NATURAL HEALTH PRODUCTS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DARICOM Ltd NATURAL HEALTH PRODUCTS filed Critical DARICOM Ltd NATURAL HEALTH PRODUCTS
Priority to AU44495/01A priority Critical patent/AU4449501A/en
Publication of WO2001070241A1 publication Critical patent/WO2001070241A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/008—Salts of oxyacids of selenium or tellurium
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/04—Sulfur, selenium or tellurium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/06—Aluminium, calcium or magnesium; Compounds thereof, e.g. clay
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/18—Iodine; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/24—Heavy metals; Compounds thereof
    • A61K33/30—Zinc; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28047—Gels
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions

Definitions

  • the present invention generally relates to the production and use of bioavailable selenium solutions. More specifically, the present invention relates to Magnesium Supermag Complexes and their use in producing bioavailable selenium solutions, and to the use of the bioavailable selenium solutions.
  • Selenium is a naturally occurring substance whose anti-oxidant properties have been found to be beneficial to the body. For example, selenium has been shown to play a role in cancer prevention.
  • the enzyme lodothyronine deiodinase which is essential for the functioning of the thyroid gland, is selenium dependent.
  • selenium is known to be effective in relieving the symptoms of arthritis. This may result from the fact that inflammatory damage in arthritis is produced in large part by free radicals, selenium through its role in the glutathione peroxidase enzyme, acts as a potent detoxifier of free radicals.
  • Selenium is most commonly found in two oxidation states: the 4-valance “selenite” or Se(IV), and the 6-valance “selenate” or Se(VI).
  • the 6-valence selenate form is most effective, being most readily absorbed by the body.
  • large concentrations of up to 4000 ppb (4 ppm) of selenium are present in various forms.
  • Some of the selenium is present in partial solution and colloidal-suspension forms where the selenium is in its 4-valance selenite form as sodium selenite Na 2 SeO 3 .
  • selenium is present in its 6-valance selenate form, mainly in suspended-colloidal forms.
  • the selenium in these water sources appears mainly as magnesium potassium selenate, sometimes associated with sodium selenate: K 2 Mg(SeO4) 2 + Na 2 SeO 4 .
  • the selenium found in these water sources is not bioavailable, since it is in a suspended-colloidal form and is not soluble.
  • the present invention provides a method of obtaining dissolved selenium, comprising the steps of: contacting a suspension comprising selenium with water and a first Supermag Complex to obtain a first mixture; removing water from the first mixture; removing the first Supermag Complex from the first mixture; adding a second Supermag Complex and water to obtain a second mixture; removing water from the second mixture; and isolating the dissolved selenium.
  • the first Supermag Complex is Supermag C as herein defined.
  • the second Supermag Complex is Supermag H as herein defined.
  • the selenium suspension is a 6-valence selenate suspension. In another embodiment, the selenate suspension is a magnesium potassium selenate suspension. In another embodiment, the selenate suspension is a magnesium potassium selenate associated with sodium selenate suspension. In another embodiment, the selenium suspension is a 4-valence selenite suspension. In another embodiment, the selenite suspension is a sodium selenite suspension. In another embodiment, the selenium suspension is a mangnesium selenate suspension, potassium selenate suspension, zinc selenate suspension, sodium selenate suspension, sodium selenite suspension or any combination thereof. In one embodiment, water is removed from the first mixture by distillation.
  • the step of removing the first Supermag Complex comprises manually removing the first Supermag Complex.
  • the water removed from said first mixture is recycled back into the second mixture.
  • the water is removed from the second mixture by distillation.
  • the step of isolating the dissolved selenium comprises removing said selenium solution from the second mixture.
  • the present invention provides a composition comprising dissolved selenium manufactured according to the methods of the present invention, an iodine salt, and a table salt.
  • the iodine salt is an iodide salt.
  • the iodide salt is sodium iodide, potassium iodide, lithium iodide or any combination thereof.
  • the iodine salt is an iodate salt.
  • the iodate salt is sodium iodate, potassium iodate, lithium iodate or any combination thereof.
  • the dissolved selenium is a 6-valence selenate. In one embodiment, the selenate is magnesium potassium selenate. In another embodiment, the selenate is magnesium potassium selenate associated with sodium selenate. In another embodiment, the dissolved selenium is a 4-valence selenite. In another embodiment, the selenite is sodium selenite. In another embodiment, the dissolved selenium is mangnesium selenate, potassium selenate, zinc selenate, sodium selenate, sodium selenite or any combination thereof.
  • the table salt comprises a sodium salt, a potassium salt, a calcium salt, a mangesium salt, a chloride salt, or any combination thereof.
  • the present invention provides a method of producing the salt composition of the present invention.
  • the method comprises the steps of: heating the table salt with water, adding the dissolved selenium to the table salt, adding the iodine salt to the dissolved selenium and the table salt, and drying.
  • the step of adding the dissolved selenium comprises spraying the dissolved selenium onto the table salt.
  • the present invention provides a method of producing dissolved selenium from a suspension comprising selenium.
  • the method comprises adding to the suspension a Magnesium Supermag Complex as herein defined.
  • the present invention further relates to a salt composition comprising the dissolved selenium, and to a method of producing said salt.
  • Supermag Complex is a partial liquid, partial gel complex that is produced by combining a total mineral solution with magnesia (Mgo), magnesium hydroxide (Mg(OH) 2 ) or basic magnesium carbonate ((MgCO 3 ) 2 ' Mg(OH) 2 ' 5H 2 O).
  • Mgo magnesia
  • Mg(OH) 2 magnesium hydroxide
  • the composition and production of various Supermag Complexes is described in detail in provisional application Serial No. 60/190,083, which is incorporated in its entirety by reference herein. Briefly, there are three main types of Supermags, depending on the respective magnesium components.
  • “O” type Supermag Complex contains magnesium Oxide or magnesia (MgO).
  • Supermag H contains magnesium hydroxide (Mg(OH) 2 ).
  • C type Supermag Complex (hereinafter “Supermag C”) contains basic magnesium carbonate (MgCO 3 ) 2 " Mg(OH) 2 ' 5H 2 O.
  • the percentage of the magnesium components [MgO, Mg(OH) 2 or (MgCO 3 ) 2 " Mg(OH) 2 ' 5H 2 O] as a percentage of the total mass determines the potency of the final Supermag product and the speed in which it works.
  • the magnesium components constitute 2.5 wt%- 35wt% based on the total weight of the Supermag composition.
  • Supermag O contains 10% MgO.
  • Supermag O contains 2.5% MgO.
  • Supermag H contains 10% Mg(OH) 2 .
  • Supermag H contains 2.5% Mg(OH) 2 .
  • Supermag C contains 10% (MgCO 3 )2 ' Mg(OH) 2 ' 5H 2 O.
  • Supermag C contains 2.5% (MgCO 3 ) 2 " Mg(OH) 2 • 5H 2 O.
  • the Supermags contain additional ions: magnesium (7%-10% by weight), calcium (1% max by weight), sodium (0.5% max by weight), potassium (0.25% max by weight), chloride (26% max by weight) and bromide (0.6% max by weight).
  • weight percent it is meant the percent weight of the ion based on the total weight of the composition.
  • Tables 1-6 Examples of typical Supermag compositions are provided in Tables 1-6 below.
  • Table 1 represents a typical Supermag O composition comprising 2.5% MgO.
  • Table 2 represents a typical Supermag H composition comprising 2.5% Mg(OH) 2 .
  • Table 3 represents a typical Supermag C composition comprising 2.5% (MgCO 3 ) 2 " Mg(OH) 2 ' 5H 2 O.
  • Table 4 represents a typical Supermag O composition comprising 10% MgO.
  • Table 5 represents a typical Supermag H composition comprising 10% Mg(OH) 2 .
  • Table 6 represents a typical Supermag C composition comprising 10% (MgCO 3 ) 2 ' Mg(OH) 2 • 5H 2 O.
  • Table 1 Supermag O composition comprising 2.5% MgO and
  • Supermag O is particularly useful for selectively adsorbing/attracting metal lauryl sulphates and metal laurate sulphates.
  • Supermag C is particularly useful for dissolving a suspended complex salt in aqueous solution.
  • Supermag C is particularly useful for attraction adsorption of dissolved ions (e.g. Ca 2+ , Mg 2+ , K + , Cl " , Br " ).
  • dissolved ions e.g. Ca 2+ , Mg 2+ , K + , Cl " , Br " .
  • the Supermag complexes are useful in obtaining dissolved selenium from a suspended-colloidal selenium Complex, thus changing the selenium to a soluble bioavailable selenium form.
  • the term "selenium” as used herein refers to a selenium salt such as for example a 6-valence selenate salt of a 4-valence selenite salt. The process of obtaining the dissolved selenium salt from a suspended-colloidal selenium complex is described in detail below.
  • a mass of water, which contains the suspended-colloidal selenium Complex is placed into a distillation apparatus (column) together with a Supermag Complex.
  • the type of selenium Complex may vary.
  • the selenium complex comprises 6-valence selenate.
  • the selenium complex comprises 4-valence selenite.
  • the 6-valence selenate is magnesium potassium selenate
  • the magnesium potassium selenate is associated with sodium selenate (K 2 Mg(SeO4) 2 + Na 2 SeO ).
  • the 4-valence selenite is sodium selenite (Na 2 Se ⁇ 3 ). Examples of other selenium compounds are magnesium selenate, potassium selenate, zinc selenate, sodium selenite and sodium selenate are also applicable. Any of these selenium compounds can be used alone or in combination with each other.
  • the amount of Supermag Complex is typically between 0.5-2% of the total mass of the composition (Supermag + selenium Complex). In one embodiment, the Supermag Complex comprises 0.5% of the total mass of the composition.
  • the Supermag Complex can be any of the Supermag Complexes described hereinabove and in of provisional application Serial No. 60/190,083. In one embodiment, the Supermag Complex is Supermag C, which contains 2.5-35% by weight (MgCO 3 ) 2 " Mg(OH) 2 ' 5H 2 O. In one embodiment, Supermag C contains 2.5
  • the Supermag C contains 10 wt% of (MgCO 3 ) 2 ' Mg(OH) 2 ' 5H 2 O.
  • the Supermag C contains 10 wt% of (MgCO 3 ) 2 ' Mg(OH) 2 " 5H 2 O.
  • Supermag O and Supermag H which contain 2.5-35 wt % of MgO and Mg(OH) 2 , respectively, can also be utilized in this step.
  • Supermag O which contains 2.5 wt% MgO is used.
  • Supermag O that contains 10% wt% MgO is used.
  • Supermag H which contains 2.5% Mg(OH) 2 is used.
  • Supermag H which contains 10% Mg(OH) 2 is used.
  • the Supermag Complex is Supermag C containing 10% (MgCO 3 ) 2 Mg(OH) 2 5H 2 O based on the total mass (mass over mass) of the Supermag, whose overall composition is, for example:
  • composition is within the prescribed ranges of components as shown in Table 6 which shows the specification of Supermag C containing 10% basic magnesium carbonate (MgCO 3 ) 2 ' Mg(OH) 2 ' 5H 2 O.
  • the mixture of Supermag Complex and selenium Suspension is then heated in the distillation apparatus to approximately 100°C-150°C (preferably 120°C) and the evaporated water is channeled through a condenser and refluxed for a number of cycles, e.g. for 3 cycles into a separate vessel of the distillation apparatus.
  • the Supermag Complex begins to adsorb all the salts present apart from the selenate.
  • the salts adsorbed by the Supermag Complex are potassium salts such as KCI and KBr, sodium salts such as NaCI, and NaBr, calcium salts such as CaCI 2 , and CaBr 2 , and magnesium salts such as MgCI 2 and MgBr 2 .
  • Evaporation of the water is continued at a temperature range of 100°C-150°C (preferably 105°C - 120°C) until all minerals apart from the selenate are adsorbed to the Supermag gel.
  • the degree of adsorption is determined by chemical analysis (e.g. atomic absorption, ICP, spectrometry etc) of the evaporated and the non-evaporated water. After this stage there is 1/30 -1/40 of the original quantity of water left together with the selenate suspension.
  • the Supermag Complex containing all the adsorbed concentrated salts apart from the selenates is removed from the distillation apparatus.
  • the way of removing the Supermag can vary. In one embodiment, this is achieved by mechanical removal of the Supermag which is a semi-solid to solid gel mass and is easily removed. However, other ways of removing the Supermag gel are applicable. Such separation methods, for example filtration, centrifugation etc. are known to a person skilled in the art.
  • a second Supermag Complex is added.
  • the amount of the Second Supermag Complex is typically between 0.5-2% of the total mass of the composition (Supermag + selenium Complex).
  • the Supermag Complex comprises 0.5% of the total mass of the composition.
  • the second Supermag Complex can be any of the Supermag Complexes described hereinabove and in of provisional application Serial No. 60/190,083.
  • the second Supermag Complex is Supermag H, which contains 2.5-35% by weight Mg(OH) 2 .
  • the Supermag H contains 2.5 wt% of Mg(OH) 2 .
  • the Supermag H contains 10 wt% of Mg(OH) 2 .
  • Supermag O and Supermag C which contain 2.5-35 wt % of MgO and (MgCO 3 ) 2 «Mg(OH) 2 *5H 2 O, respectively, can also be utilized in this step.
  • Supermag O which contains 2.5 wt% MgO is used.
  • Supermag O that contains 10% wt% MgO is used.
  • Supermag C which contains 2.5 wt% (MgCO 3 ) 2 ' Mg(OH) 2 ' 5H 2 O is used.
  • Supermag C which contains wt% (MgCO 3 ) 2 ' Mg(OH) 2 ' 5H 2 O is used.
  • the Supermag Complex is Supermag H containing 10% of the total mass of Mg(OH) 2 .
  • water is added to the distillation apparatus.
  • the evaporated water previously removed to another vessel is returned to the distillation apparatus.
  • the recycling of the evaporated water back into the distillation apparatus is desired since chemical analysis is carried out periodically on the evaporated water and the remaining water. This aids in ascertaining the constitution of the final product. However, it is not essential to recycle the evaporated water.
  • fresh water is added to the distillation apparatus.
  • distillation is performed at a temperature range of 100°C-150°C, preferably approximately 105°C-120°C.
  • the distillation is carried out with the condensed water, refluxed for an optimum number of 2-3 cycles (approx.), to the distillation vessel.
  • the suspended colloidal selenium (selenate or selenite) is dissolved at this stage.
  • the whole mass is gradually cooled to a temperature range of 40°C-70°C, for example 50°C, without any forced cooling system.
  • the Supermag Complex loses all its free water and remains as a gel with bound water only and settles on the bottom of the apparatus.
  • the selenate solution and any of the above-mentioned selenium-bearing complexes present at the beginning are pumped out of the apparatus, into storage barrels for final applications in whatever dilution is required.
  • Any storage barrels such as non-PVC or non-metal storage barrels can be used.
  • the Supermag Complex is left behind.
  • the leftover Supermag Complex contains the remainder of all the salts/ions that were not adsorbed in the first distillation. The total dissolution of the selenium Complex is thus enabled.
  • the dissolved selenium is bioavailable and can be used in various medicinal and non-medicinal applications.
  • the combination of iodine and selenium has specific therapeutic properties.
  • the enzyme lodothydronine deiodinase that is essential for the functioning of the thyroid gland, is selenium dependent.
  • the dissolved selenium produced by the process of the present invention can be used to produce a salt comprising selenium and iodine.
  • the selenium/Iodine combined salt combines iodine with totally bioavailable inorganic non-toxic selenium salt.
  • a selenium/iodine salt which comprises a dissolved bioavailable selenium manufactured in accordance with the process of the present invention; and an iodine salt.
  • the selenium is 6-valence selenate.
  • the selenium is 4-valence selenite.
  • the iodine salt is an iodide salt (I " ), for example potassium iodide (Kl), sodium iodide (Nal) or lithium iodide (Lil).
  • the iodine salt is an iodate salt (IO 3 ), for example potassium iodate (KIO 3 ), sodium iodate (NalOs) and lithium iodate (LilO 3 ).
  • the selenium/iodine salts are incorporated into any type of known table salt.
  • Typical ingredients of table salts are potassium (such as KCI), magnesium (such as MgCI 2 or MgSO 4 ), calcium (such as CaCI 2 or CaSO ), sodium (such as NaCI), and chloride (such as' KCI, NaCI, MgCl2 or CaCI 2 ). These ingredients can be used alone or in any combination with each other.
  • Examples of applicable table salts are: a low sodium salt which comprises 50% NaCI /50% KCI; and a low sodium salt which comprises or 30% NaCI/70% KCI.
  • the salt can be any known table salt. The process of preparing the selenium/iodine containing table salt is described in detail below.
  • the table salt is heated in a vessel with water.
  • the amount of water may vary. In one embodiment, water comprises 20% of the total mass (water and table salt).
  • the salt is heated to a temperature range of 100°C - 150°C, preferably to 100 °C-110°C and the original water content is evaporated.
  • the selenium solution is a selenate solution.
  • the selenium solution is a selenite solution.
  • the selenium solution is a magnesium potassium selenate (K2Mg(SeO4)2) solution.
  • the selenium solution a magnesium potassium selenate associated with sodium selenate (K 2 Mg(SeO4) 2 + Na 2 SeO ).
  • the selenium solution is sodium selenite (Na 2 SeO 3 ).
  • the selenium solution is magnesium selenate, potassium selenate, zinc selenate, sodium selenite and sodium selenate or any combinations thereof.
  • the concentrated solution comprises more than 5 gr/L of the selenium compound described above. In another embodiment, the concentrated solution comprises between 5-20 gr/L of the selenium compound described above. In yet another embodiment, the concentrated solution comprises more than 20 g/L of the selenium compound described above.
  • the selenium solution is added to the table salt by mixing or by spraying the table salt with the selenium solution by means of a spraying gun or any spraying apparatus. Any concentration of selenium which will produce a table salt/selenium combination within the approved supplemental values for human intake may be used.
  • Iodine is added as a solid additive in either iodide or iodate form, for example sodium iodide, potassium iodide, lithium iodide, sodium iodate, potassium iodate, lithium iodate or any combinations whereof.
  • the whole mass is air dried by heating with dry air.
  • the selenium (selenate or selenite) crystallizes and the result is the original table salt having selenium and iodide/iodate incorporate therein.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Veterinary Medicine (AREA)
  • Medicinal Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Public Health (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

The present invention provides a method for obtaining dissolved selenium from a selenium suspension by adding a magnesium compound containing composition to the suspension, removing water from the resulting mixture and isolating the dissolved selenium. The dissolved selenium is added to a hot aqueous solution of a salt, such as a sodium, potassium, calcium, magnesium or cloride salt, and then an iodine salt is added to the dissolved selenium and salt and the resulting composition is dried to produce a composition containing selenium, iodine and the salt. The combination of the iodine and selenium has therapeutic properties.

Description

PRODUCTION AND USE OF DISSOLVED BIOAVAILABLE SELENIUM
FIELD OF THE INVENTION
The present invention generally relates to the production and use of bioavailable selenium solutions. More specifically, the present invention relates to Magnesium Supermag Complexes and their use in producing bioavailable selenium solutions, and to the use of the bioavailable selenium solutions.
BACKGROUND OF THE INVENTION
Selenium is a naturally occurring substance whose anti-oxidant properties have been found to be beneficial to the body. For example, selenium has been shown to play a role in cancer prevention. In addition, the enzyme lodothyronine deiodinase, which is essential for the functioning of the thyroid gland, is selenium dependent. Furthermore, selenium is known to be effective in relieving the symptoms of arthritis. This may result from the fact that inflammatory damage in arthritis is produced in large part by free radicals, selenium through its role in the glutathione peroxidase enzyme, acts as a potent detoxifier of free radicals.
Selenium is most commonly found in two oxidation states: the 4-valance "selenite" or Se(IV), and the 6-valance "selenate" or Se(VI). The 6-valence selenate form is most effective, being most readily absorbed by the body. In many water sources in Israel, from the very south along the desert (Arava) up to the Western Galilee, large concentrations of up to 4000 ppb (4 ppm) of selenium are present in various forms. Some of the selenium is present in partial solution and colloidal-suspension forms where the selenium is in its 4-valance selenite form as sodium selenite Na2SeO3. However, in most of the water sources selenium is present in its 6-valance selenate form, mainly in suspended-colloidal forms. The selenium in these water sources appears mainly as magnesium potassium selenate, sometimes associated with sodium selenate: K2Mg(SeO4)2 + Na2SeO4. Mixtures containing other selenium compounds, for example, magnesium selenate, potassium selenate, zinc selenate, sodium selenite and sodium selenate, may also occur.
The selenium found in these water sources is not bioavailable, since it is in a suspended-colloidal form and is not soluble. Currently there is no known method for producing bioavailable selenium from suspended-colloidal selenium. There is an urgent need in the art for a method of dissolving the suspended-colloidal selenium, thus changing the selenium into a bioavailable 6-valence selenate form.
SUMMARY OF THE INVENTION
The present invention provides a method of obtaining dissolved selenium, comprising the steps of: contacting a suspension comprising selenium with water and a first Supermag Complex to obtain a first mixture; removing water from the first mixture; removing the first Supermag Complex from the first mixture; adding a second Supermag Complex and water to obtain a second mixture; removing water from the second mixture; and isolating the dissolved selenium.
In one embodiment, the first Supermag Complex is Supermag C as herein defined. In one embodiment the second Supermag Complex is Supermag H as herein defined.
In one embodiment, the selenium suspension is a 6-valence selenate suspension. In another embodiment, the selenate suspension is a magnesium potassium selenate suspension. In another embodiment, the selenate suspension is a magnesium potassium selenate associated with sodium selenate suspension. In another embodiment, the selenium suspension is a 4-valence selenite suspension. In another embodiment, the selenite suspension is a sodium selenite suspension. In another embodiment, the selenium suspension is a mangnesium selenate suspension, potassium selenate suspension, zinc selenate suspension, sodium selenate suspension, sodium selenite suspension or any combination thereof. In one embodiment, water is removed from the first mixture by distillation. In another embodiment, the step of removing the first Supermag Complex comprises manually removing the first Supermag Complex. In another embodiment, the water removed from said first mixture is recycled back into the second mixture. In another embodiment, the water is removed from the second mixture by distillation. In another embodiment, the step of isolating the dissolved selenium comprises removing said selenium solution from the second mixture.
In addition, the present invention provides a composition comprising dissolved selenium manufactured according to the methods of the present invention, an iodine salt, and a table salt.
In one embodiment, the iodine salt is an iodide salt. The iodide salt is sodium iodide, potassium iodide, lithium iodide or any combination thereof. In another embodiment, the iodine salt is an iodate salt. The iodate salt is sodium iodate, potassium iodate, lithium iodate or any combination thereof.
In one embodiment, the dissolved selenium is a 6-valence selenate. In one embodiment, the selenate is magnesium potassium selenate. In another embodiment, the selenate is magnesium potassium selenate associated with sodium selenate. In another embodiment, the dissolved selenium is a 4-valence selenite. In another embodiment, the selenite is sodium selenite. In another embodiment, the dissolved selenium is mangnesium selenate, potassium selenate, zinc selenate, sodium selenate, sodium selenite or any combination thereof.
In one embodiment, the table salt comprises a sodium salt, a potassium salt, a calcium salt, a mangesium salt, a chloride salt, or any combination thereof.
In addition, the present invention provides a method of producing the salt composition of the present invention. The method comprises the steps of: heating the table salt with water, adding the dissolved selenium to the table salt, adding the iodine salt to the dissolved selenium and the table salt, and drying. In one embodiment, the step of adding the dissolved selenium comprises spraying the dissolved selenium onto the table salt.
DETAILED DESCRIPTION OF THE PRESENT INVENTION
The present invention provides a method of producing dissolved selenium from a suspension comprising selenium. The method comprises adding to the suspension a Magnesium Supermag Complex as herein defined. The present invention further relates to a salt composition comprising the dissolved selenium, and to a method of producing said salt.
A Magnesium Supermag Complex (hereinafter "Supermag Complex") is a partial liquid, partial gel complex that is produced by combining a total mineral solution with magnesia (Mgo), magnesium hydroxide (Mg(OH)2) or basic magnesium carbonate ((MgCO3)2 ' Mg(OH)2 ' 5H2O). The composition and production of various Supermag Complexes is described in detail in provisional application Serial No. 60/190,083, which is incorporated in its entirety by reference herein. Briefly, there are three main types of Supermags, depending on the respective magnesium components. "O" type Supermag Complex (hereinafter "Supermag O") contains magnesium Oxide or magnesia (MgO). "H" type Supermag Complex (hereinafter "Supermag H") contains magnesium hydroxide (Mg(OH)2). "C" type Supermag Complex (hereinafter "Supermag C") contains basic magnesium carbonate (MgCO3)2 " Mg(OH)2 ' 5H2O.
The percentage of the magnesium components [MgO, Mg(OH)2 or (MgCO3)2 " Mg(OH)2 ' 5H2O] as a percentage of the total mass determines the potency of the final Supermag product and the speed in which it works. Typically, the magnesium components constitute 2.5 wt%- 35wt% based on the total weight of the Supermag composition. For example, in one embodiment, Supermag O contains 10% MgO. In another embodiment, Supermag O contains 2.5% MgO. In another embodiment, Supermag H contains 10% Mg(OH)2. In another embodiment Supermag H contains 2.5% Mg(OH)2. In another embodiment, Supermag C contains 10% (MgCO3)2 ' Mg(OH)2 ' 5H2O. In another embodiment,
Supermag C contains 2.5% (MgCO3)2 " Mg(OH)2 • 5H2O.
Aside from their respective magnesium components [MgO, Mg(OH)2 or (MgCO3)2 ' Mg(OH)2 ' 5H2O], the Supermags contain additional ions: magnesium (7%-10% by weight), calcium (1% max by weight), sodium (0.5% max by weight), potassium (0.25% max by weight), chloride (26% max by weight) and bromide (0.6% max by weight). By weight percent it is meant the percent weight of the ion based on the total weight of the composition.
Examples of typical Supermag compositions are provided in Tables 1-6 below. Table 1 represents a typical Supermag O composition comprising 2.5% MgO. Table 2 represents a typical Supermag H composition comprising 2.5% Mg(OH)2. Table 3 represents a typical Supermag C composition comprising 2.5% (MgCO3)2 " Mg(OH)2 ' 5H2O. Table 4 represents a typical Supermag O composition comprising 10% MgO. Table 5 represents a typical Supermag H composition comprising 10% Mg(OH)2. Table 6 represents a typical Supermag C composition comprising 10% (MgCO3)2 ' Mg(OH)2 • 5H2O. Table 1 : Supermag O composition comprising 2.5% MgO and
Figure imgf000009_0001
Table 2: Supermag H composition comprising 2.5% Mg(OH)2and
Figure imgf000009_0002
Table 3: Supermag C composition comprising 2.5% (MgCO3)2 ' Mg(OH)2 5H2O and
Figure imgf000009_0003
Table 4: Supermag O composition comprising 10% MgO and
Figure imgf000010_0001
Table 5: Supermag H composition comprising 10% Mg(OH)2and
Figure imgf000010_0002
Table 6: Supermag C composition comprising 10% (MgCO3)2 " Mg(OH)2 5H2O and
Figure imgf000010_0003
The different Supermags have been found to have different utilities. For example, Supermag O is particularly useful for selectively adsorbing/attracting metal lauryl sulphates and metal laurate sulphates. Supermag C is particularly useful for dissolving a suspended complex salt in aqueous solution. Supermag C is particularly useful for attraction adsorption of dissolved ions (e.g. Ca2+, Mg2+, K+, Cl", Br"). In the course of investigating these properties, it has been surprisingly found that Supermag O, Supermag H and Supermag C, alone or in combination with each other, are useful in various applications, particularly in dissolving different minerals found in mineral suspensions. This property of the Supermags is extremely useful since the minerals in mineral suspensions are bioavailable only once they are dissolved.
For example, the Supermag complexes are useful in obtaining dissolved selenium from a suspended-colloidal selenium Complex, thus changing the selenium to a soluble bioavailable selenium form. The term "selenium" as used herein refers to a selenium salt such as for example a 6-valence selenate salt of a 4-valence selenite salt. The process of obtaining the dissolved selenium salt from a suspended-colloidal selenium complex is described in detail below.
In the first step, a mass of water, which contains the suspended-colloidal selenium Complex, is placed into a distillation apparatus (column) together with a Supermag Complex. The type of selenium Complex may vary. In one embodiment, the selenium complex comprises 6-valence selenate. In another embodiment, the selenium complex comprises 4-valence selenite. In one embodiment, the 6-valence selenate is magnesium potassium selenate
Figure imgf000011_0001
In another embodiment, the magnesium potassium selenate is associated with sodium selenate (K2Mg(SeO4)2 + Na2SeO ). In another embodiment, the 4-valence selenite is sodium selenite (Na2Seθ3). Examples of other selenium compounds are magnesium selenate, potassium selenate, zinc selenate, sodium selenite and sodium selenate are also applicable. Any of these selenium compounds can be used alone or in combination with each other.
The amount of Supermag Complex is typically between 0.5-2% of the total mass of the composition (Supermag + selenium Complex). In one embodiment, the Supermag Complex comprises 0.5% of the total mass of the composition. The Supermag Complex can be any of the Supermag Complexes described hereinabove and in of provisional application Serial No. 60/190,083. In one embodiment, the Supermag Complex is Supermag C, which contains 2.5-35% by weight (MgCO3)2 " Mg(OH)2 ' 5H2O. In one embodiment, Supermag C contains 2.5
wt% of (MgCO3)2 ' Mg(OH)2 ' 5H2O. In another embodiment, the Supermag C contains 10 wt% of (MgCO3)2 ' Mg(OH)2 " 5H2O. However, Supermag O and Supermag H which contain 2.5-35 wt % of MgO and Mg(OH)2, respectively, can also be utilized in this step. In one embodiment, Supermag O which contains 2.5 wt% MgO is used. In another embodiment, Supermag O that contains 10% wt% MgO is used. In another embodiment, Supermag H which contains 2.5% Mg(OH)2 is used. In yet another embodiment, Supermag H which contains 10% Mg(OH)2 is used.
In one embodiment, the Supermag Complex is Supermag C containing 10% (MgCO3) 2 Mg(OH) 2 5H2O based on the total mass (mass over mass) of the Supermag, whose overall composition is, for example:
Figure imgf000013_0001
This composition is within the prescribed ranges of components as shown in Table 6 which shows the specification of Supermag C containing 10% basic magnesium carbonate (MgCO3)2 ' Mg(OH)2 ' 5H2O.
The mixture of Supermag Complex and selenium Suspension is then heated in the distillation apparatus to approximately 100°C-150°C (preferably 120°C) and the evaporated water is channeled through a condenser and refluxed for a number of cycles, e.g. for 3 cycles into a separate vessel of the distillation apparatus.
When 0.05-0.10 of the original mass of water is left, a concentrated mineral solution comprising selenate is left. At this stage the Supermag Complex begins to adsorb all the salts present apart from the selenate. Examples of the salts adsorbed by the Supermag Complex are potassium salts such as KCI and KBr, sodium salts such as NaCI, and NaBr, calcium salts such as CaCI2, and CaBr2, and magnesium salts such as MgCI2 and MgBr2.
Evaporation of the water is continued at a temperature range of 100°C-150°C (preferably 105°C - 120°C) until all minerals apart from the selenate are adsorbed to the Supermag gel. The degree of adsorption is determined by chemical analysis (e.g. atomic absorption, ICP, spectrometry etc) of the evaporated and the non-evaporated water. After this stage there is 1/30 -1/40 of the original quantity of water left together with the selenate suspension.
In the next step, the Supermag Complex containing all the adsorbed concentrated salts apart from the selenates is removed from the distillation apparatus. The way of removing the Supermag can vary. In one embodiment, this is achieved by mechanical removal of the Supermag which is a semi-solid to solid gel mass and is easily removed. However, other ways of removing the Supermag gel are applicable. Such separation methods, for example filtration, centrifugation etc. are known to a person skilled in the art.
After the Supermag complex has been removed, a second Supermag Complex is added. The amount of the Second Supermag Complex is typically between 0.5-2% of the total mass of the composition (Supermag + selenium Complex). In one embodiment, the Supermag Complex comprises 0.5% of the total mass of the composition. The second Supermag Complex can be any of the Supermag Complexes described hereinabove and in of provisional application Serial No. 60/190,083. In one embodiment, the second Supermag Complex is Supermag H, which contains 2.5-35% by weight Mg(OH)2. In one embodiment, the Supermag H contains 2.5 wt% of Mg(OH)2. In another embodiment, the Supermag H contains 10 wt% of Mg(OH)2. However, Supermag O and Supermag C, which contain 2.5-35 wt % of MgO and (MgCO3) 2«Mg(OH) 2*5H2O, respectively, can also be utilized in this step. In one embodiment, Supermag O which contains 2.5 wt% MgO is used. In another embodiment, Supermag O that contains 10% wt% MgO is used. In another embodiment, Supermag C which contains 2.5 wt% (MgCO3)2 ' Mg(OH)2 ' 5H2O is used. In yet another embodiment, Supermag C which contains wt% (MgCO3)2 ' Mg(OH)2 ' 5H2O is used.
In one embodiment, the Supermag Complex is Supermag H containing 10% of the total mass of Mg(OH)2.
Next, water is added to the distillation apparatus. In one embodiment, the evaporated water previously removed to another vessel is returned to the distillation apparatus. The recycling of the evaporated water back into the distillation apparatus is desired since chemical analysis is carried out periodically on the evaporated water and the remaining water. This aids in ascertaining the constitution of the final product. However, it is not essential to recycle the evaporated water. In accordance with another embodiment of the present invention, fresh water is added to the distillation apparatus. Following the addition of water, distillation is performed at a temperature range of 100°C-150°C, preferably approximately 105°C-120°C. In one embodiment, the distillation is carried out with the condensed water, refluxed for an optimum number of 2-3 cycles (approx.), to the distillation vessel. The suspended colloidal selenium (selenate or selenite) is dissolved at this stage.
The whole mass is gradually cooled to a temperature range of 40°C-70°C, for example 50°C, without any forced cooling system. During this process the Supermag Complex loses all its free water and remains as a gel with bound water only and settles on the bottom of the apparatus.
The selenate solution and any of the above-mentioned selenium-bearing complexes present at the beginning are pumped out of the apparatus, into storage barrels for final applications in whatever dilution is required. Any storage barrels such as non-PVC or non-metal storage barrels can be used.
The Supermag Complex is left behind. The leftover Supermag Complex contains the remainder of all the salts/ions that were not adsorbed in the first distillation. The total dissolution of the selenium Complex is thus enabled.
The dissolved selenium is bioavailable and can be used in various medicinal and non-medicinal applications. Thus it is a further object of the present invention to provide various uses of the dissolved selenium obtained by the process of the present invention. For example, it is known that the combination of iodine and selenium has specific therapeutic properties. The enzyme lodothydronine deiodinase that is essential for the functioning of the thyroid gland, is selenium dependent. Thus the dissolved selenium produced by the process of the present invention can be used to produce a salt comprising selenium and iodine. The selenium/Iodine combined salt combines iodine with totally bioavailable inorganic non-toxic selenium salt.
Thus, in accordance with an embodiment of the present invention, there is provided a selenium/iodine salt, which comprises a dissolved bioavailable selenium manufactured in accordance with the process of the present invention; and an iodine salt. In one embodiment, the selenium is 6-valence selenate. In another embodiment, the selenium is 4-valence selenite. In one embodiment, the iodine salt is an iodide salt (I"), for example potassium iodide (Kl), sodium iodide (Nal) or lithium iodide (Lil). In another embodiment, the iodine salt is an iodate salt (IO3 ), for example potassium iodate (KIO3), sodium iodate (NalOs) and lithium iodate (LilO3).
The selenium/iodine salts are incorporated into any type of known table salt. Typical ingredients of table salts are potassium (such as KCI), magnesium (such as MgCI2 or MgSO4), calcium (such as CaCI2 or CaSO ), sodium (such as NaCI), and chloride (such as' KCI, NaCI, MgCl2 or CaCI2). These ingredients can be used alone or in any combination with each other. Examples of applicable table salts are: a low sodium salt which comprises 50% NaCI /50% KCI; and a low sodium salt which comprises or 30% NaCI/70% KCI. However, it should be apparent that these examples are in no way limiting, and that the salt can be any known table salt. The process of preparing the selenium/iodine containing table salt is described in detail below.
In the first step, the table salt is heated in a vessel with water. The amount of water may vary. In one embodiment, water comprises 20% of the total mass (water and table salt). The salt is heated to a temperature range of 100°C - 150°C, preferably to 100 °C-110°C and the original water content is evaporated.
In the next step, a concentrated solution of selenium as produced by the process of the present invention is added. In one embodiment, the selenium solution is a selenate solution. In another embodiment, the selenium solution is a selenite solution. In another embodiment, the selenium solution is a magnesium potassium selenate (K2Mg(SeO4)2) solution. In one embodiment, the selenium solution a magnesium potassium selenate associated with sodium selenate (K2Mg(SeO4)2 + Na2SeO ). In another embodiment, the selenium solution is sodium selenite (Na2SeO3). In another embodiment, the selenium solution is magnesium selenate, potassium selenate, zinc selenate, sodium selenite and sodium selenate or any combinations thereof.
In one embodiment, the concentrated solution comprises more than 5 gr/L of the selenium compound described above. In another embodiment, the concentrated solution comprises between 5-20 gr/L of the selenium compound described above. In yet another embodiment, the concentrated solution comprises more than 20 g/L of the selenium compound described above.
The selenium solution is added to the table salt by mixing or by spraying the table salt with the selenium solution by means of a spraying gun or any spraying apparatus. Any concentration of selenium which will produce a table salt/selenium combination within the approved supplemental values for human intake may be used.
In the next step, the water evaporation is continued. Iodine is added as a solid additive in either iodide or iodate form, for example sodium iodide, potassium iodide, lithium iodide, sodium iodate, potassium iodate, lithium iodate or any combinations whereof. The whole mass is air dried by heating with dry air. The selenium (selenate or selenite) crystallizes and the result is the original table salt having selenium and iodide/iodate incorporate therein.
It will be appreciated that the present invention is not limited by what has been described hereinabove and that numerous modifications, all of which fall within the scope of the present invention, exist. Rather the scope of the invention is defined by the claims which follow:

Claims

What is claimed is:
1. A method of obtaining dissolved selenium comprising the steps of: contacting a suspension comprising selenium with water and a first Supermag Complex to obtain a first mixture; removing water from said first mixture;
removing said first Supermag Complex from said first mixture; adding a second Supermag Complex and water to obtain a second mixture;
removing water from said second mixture; and isolating said dissolved selenium.
2. The method of claim 1 , wherein said first Supermag Complex is Supermag
C as herein defined.
3. The method of claim 1 , wherein said second Supermag Complex is
Supermag H as herein defined.
4. The method of claim 1 , wherein said aelenium suspension is a 6-valence aelenate suspension.
5. The method of claim 4, wherein said selenate suspension is a magnesium potassium selenate suspension.
6. The method of claim 4, wherein said selenate suspension is a magnesium potassium selenate associated with sodium selenate suspension.
7. The method of claim 1, wherein said selenium suspension is a 4-valence selenite suspension.
8. The method of claim 7, wherein said selenite suspension is a sodium selenite suspension.
9. The method of claim 1 , wherein said selenium suspension is a mangnesium selenate suspension, potassium selenate suspension, zinc selenate suspension, sodium selenite suspension, sodium selenite suspension or any combination thereof.
10. The method of claim 1 , wherein water is removed from said first mixture by distillation.
11. The method of claim 1 , wherein the step of removing said first Supermag Complex comprises manually removing said first Supermag Complex.
12. The method of claim 1, wherein the water removed from said first mixture is recycled back into said second mixture.
13. The method of claim 1 , wherein water is removed from said second mixture by distillation.
14. The method according to claim 1 , wherein the step of isolating said dissolved selenium comprises removing said selenium solution from said second mixture.
15. A composition comprising dissolved selenium manufactured according to the method of claim 1 ; an iodine salt; and a table salt.
16. The composition of claim 15, wherein said iodine salt is an iodide salt.
17. The composition of claim 16, wherein said iodide salt is sodium iodide, potassium iodide, lithium iodide or any combination thereof.
18. The composition of claim 15, wherein said iodine salt is an iodate salt.
19. The composition of claim 18, wherein said iodate salt is sodium iodate, potassium iodate, lithium iodate or any combination thereof.
20. The composition of claim 15, wherein said dissolved selenium is a
6-valence selenate.
21. The composition of claim 20, wherein said selenate is magnesium potassium selenate.
22. The composition of claim 20, wherein said selenate is magnesium potassium selenate associated with sodium selenate.
23. The composition of claim 15, wherein said dissolved selenium is a 4-valence selenite.
24. The composition of claim 23, wherein said selenite is sodium selenite.
25. The composition of claim 15, wherein dissolved selenium is mangnesium selenate, potassium selenate, zinc selenate, sodium selenite, sodium selenite or any combination thereof.
26. The composition of claim 15, wherein said table salt comprises a sodium salt, a potassium salt, a calcium salt, a mangesium salt, a chloride salt, or any combination thereof.
27. A method of producing the composition of claim 15, comprising the steps of: heating said table salt with water; adding said dissolved selenium to said table salt; adding said iodine salt to said dissolved selenium and said table salt; and drying.
28. The method of claim 27, wherein the step of adding said dissolved selenium comprises spraying said dissolved selenium onto said table salt.
PCT/IL2001/000265 2000-03-20 2001-03-20 Production and use of dissolved bioavailable selenium Ceased WO2001070241A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU44495/01A AU4449501A (en) 2000-03-20 2001-03-20 Production and use of dissolved bioavailable selenium

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US19008300P 2000-03-20 2000-03-20
US19008400P 2000-03-20 2000-03-20
US60/190,083 2000-03-20
US60/190,084 2000-03-20

Publications (1)

Publication Number Publication Date
WO2001070241A1 true WO2001070241A1 (en) 2001-09-27

Family

ID=26885764

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/IL2001/000264 Ceased WO2001070390A1 (en) 2000-03-20 2001-03-20 Production of magnesium supermag complexes
PCT/IL2001/000265 Ceased WO2001070241A1 (en) 2000-03-20 2001-03-20 Production and use of dissolved bioavailable selenium

Family Applications Before (1)

Application Number Title Priority Date Filing Date
PCT/IL2001/000264 Ceased WO2001070390A1 (en) 2000-03-20 2001-03-20 Production of magnesium supermag complexes

Country Status (2)

Country Link
AU (2) AU4449501A (en)
WO (2) WO2001070390A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7854956B2 (en) 2007-03-07 2010-12-21 Exportadora De Sal, S.A. De C.V. Low sodium salt compositions and methods of preparation and uses thereof
CN105645668A (en) * 2014-12-05 2016-06-08 中国石油化工股份有限公司 Processing method of selenium-containing waste water
CN105645667A (en) * 2014-12-05 2016-06-08 中国石油化工股份有限公司 Processing method of selenium-containing waste water

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4806264A (en) * 1987-09-01 1989-02-21 The United Sates Of America As Represented By The Secretary Of The Interior Method of selectively removing selenium ions from an aqueous solution
US5071568A (en) * 1990-10-31 1991-12-10 Union Oil Company Of California Selenium removal process
US5089141A (en) * 1990-11-09 1992-02-18 The United States Of America As Represented By The Secretary Of The Interior Chemical process for removing selenium from water
US5849338A (en) * 1996-04-10 1998-12-15 Chronorx Llc Unit dosage forms for treatment of vasoconstriction and related conditions

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3980753A (en) * 1970-02-20 1976-09-14 Veitscher Magnesitwerke-Aktiengesellschaft Industrial process of preparing magnesia of high purity
US4147665A (en) * 1976-06-07 1979-04-03 Agency Of Industrial Science & Technology Magnesia adsorbent
IE53450B1 (en) * 1981-11-17 1988-11-09 Steetley Refractories Ltd Manufacture of magnesium hydroxide
US5211852A (en) * 1990-12-28 1993-05-18 Martin Marietta Magnesia Specialties Inc. Process for removal of metal ions from water
JPH11322327A (en) * 1998-05-18 1999-11-24 Matsushita Electric Ind Co Ltd Dissolution method of magnesium salt in water

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4806264A (en) * 1987-09-01 1989-02-21 The United Sates Of America As Represented By The Secretary Of The Interior Method of selectively removing selenium ions from an aqueous solution
US5071568A (en) * 1990-10-31 1991-12-10 Union Oil Company Of California Selenium removal process
US5089141A (en) * 1990-11-09 1992-02-18 The United States Of America As Represented By The Secretary Of The Interior Chemical process for removing selenium from water
US5849338A (en) * 1996-04-10 1998-12-15 Chronorx Llc Unit dosage forms for treatment of vasoconstriction and related conditions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MURPHY A.P.: "A water treatment process for selenium removal", JOURNAL OF THE WATER POLLUTION CONTROL FEDERATION, vol. 61, no. 3, March 1989 (1989-03-01), pages 361 - 362, XP002943121 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7854956B2 (en) 2007-03-07 2010-12-21 Exportadora De Sal, S.A. De C.V. Low sodium salt compositions and methods of preparation and uses thereof
US8372463B2 (en) 2007-03-07 2013-02-12 Exportadora De Sal, S.A. De C.V. Methods of preparation of low sodium salt compositions
CN105645668A (en) * 2014-12-05 2016-06-08 中国石油化工股份有限公司 Processing method of selenium-containing waste water
CN105645667A (en) * 2014-12-05 2016-06-08 中国石油化工股份有限公司 Processing method of selenium-containing waste water
CN105645667B (en) * 2014-12-05 2018-04-10 中国石油化工股份有限公司 A kind of processing method of selenium-containing wastewater

Also Published As

Publication number Publication date
WO2001070390A1 (en) 2001-09-27
AU4449501A (en) 2001-10-03
AU4449401A (en) 2001-10-03

Similar Documents

Publication Publication Date Title
Sepehr et al. Surface modification of pumice enhancing its fluoride adsorption capacity: An insight into kinetic and thermodynamic studies
US5356611A (en) Method of recovering iodine
JP2019099901A (en) Method for recovering lithium from lithium-containing solution
CN108144576A (en) A kind of fluorine adsorbent and the method that fluorine is recycled in removing from fluorinated water
JP4958293B2 (en) Adsorbent for bromate ion
JPWO2002010105A1 (en) Treatment method and substance for fluorine-based compounds
JP4111404B2 (en) Method for separating NaCl from LiCl solution
JPS61283342A (en) Lithium adsorbent and its preparation
JPWO2008093628A1 (en) Boron remover and boron removal method using dry glue
US4588565A (en) Separation of lithium chloride from impurities
CN112142076B (en) A method for extracting lithium from brine by adsorption method
WO2001070241A1 (en) Production and use of dissolved bioavailable selenium
CN106745087A (en) A kind of process for purification of glauber salt
Thole et al. Water defluoridation by bauxite-gypsum-magnesite (BG-Mc) based filters calcined at 350–500 C
Olegario-Sanchez et al. Comparative study of As (III) and Zn (II) removal from aqueous solutions using Philippine natural zeolite and alumina
JP4963032B2 (en) Phosphorous adsorbent
KR100351468B1 (en) Making system process mineral salt alkalinity utilizaton nature sea
JP4607847B2 (en) Treatment method and treatment agent for boron-containing wastewater
CN117065719A (en) A kind of mineral composite fluoride removal material and its preparation method and application
CN115160986A (en) Method for preparing snow-melting agent from high-chloride high-acid wastewater
CN1100722C (en) Process for precipitating B and Li in bittern at same time
JPS6362546A (en) Composite type lithium adsorbent and its production
JP2531790B2 (en) Lithium recovery method
JPS6219066A (en) Production of specialty salt
JP4761612B2 (en) Treatment method for boron-containing wastewater

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP