WO2005086579A2 - Nutritive compositions containing metals - Google Patents

Nutritive compositions containing metals Download PDF

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Publication number
WO2005086579A2
WO2005086579A2 PCT/IL2005/000275 IL2005000275W WO2005086579A2 WO 2005086579 A2 WO2005086579 A2 WO 2005086579A2 IL 2005000275 W IL2005000275 W IL 2005000275W WO 2005086579 A2 WO2005086579 A2 WO 2005086579A2
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WO
WIPO (PCT)
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nutritive
species
composition
metal
nutritive composition
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PCT/IL2005/000275
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French (fr)
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WO2005086579A3 (en
Inventor
Yoram Tsivion
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Future Tense Technological Development & Entrepreneurship Ltd.
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Publication of WO2005086579A2 publication Critical patent/WO2005086579A2/en
Publication of WO2005086579A3 publication Critical patent/WO2005086579A3/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D1/00—Fertilisers containing potassium
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D3/00—Calcareous fertilisers
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00—Other inorganic fertilisers
    • C05D9/02—Other inorganic fertilisers containing trace elements

Definitions

  • the present invention relates generally to solutions of metal ions used for feeding purposes. A more specific use of such solutions is in the fertilization of agricultural crops.
  • Fertilising crops is performed by applying nutritive elements or compounds to the soil or to the foliage to be subsequently taken up by the plants for further consumption by the various organs.
  • Potassium, iron, calcium, manganese, zinc, copper and molybdenum are nutritive metals of which iron, zinc, copper, manganese and to a lesser extent calcium ions, tend to form coordinative bonds with certain active groups of organic materials. This is sometimes referred to as complexing of the metals with ligands. Such complexation is used as practical means for keeping metal ions in a non precipitated form which they would otherwise tend to fall into if no specific measures are taken. When a molecule forms more than one coordinative bond with a metal ion, a chelate is formed.
  • a large variety of commercial products in the market exist which use chelated metal ions for applying such metals to crops for supplying those metals to the crop.
  • Citric acid is a naturally occurring chelating agent (ligand) containing anionic (acidic) groups
  • the preferable source for the ferrous ion in this publication is either iron sulfate or ferrous chloride, and for manganous ions the preferable source is either manganese nitrate, manganese sulfate, manganese chloride or manganous oxide.
  • soluble metal salts such as sulfates, nitrates, chlorides.
  • Insoluble compounds of the nutritive metal are used, for example US patent 4,265,653 mentioned above discloses the use manganese oxide as component of the nutritive preparation.
  • WO 9716395A1 publication two non soluble species of nutritive metals are made to react, namely zinc metal and manganese dioxide are made to interact. The interaction is made in a solution of sulfuric acid, which introduces sulfate to the preparation.
  • sulfuric acid which introduces sulfate to the preparation.
  • especially nitrates and chlorides are considered as potentially phytotoxic, or having a negative effect on the crop, respectively.
  • preparations for applying metal nutrients to crops are made using sources for metal ions which are water insoluble or sparingly water soluble forms of the respective metal.
  • Such forms are typically metals in the metal form, carbonate of metal ions, oxides of metal ions, hydroxides or silicates.
  • the metal ion source is converted to a more available form by a method as will be described below.
  • Oxides of metals typically oxides of zinc, calcium, copper, magnesium and manganese are available in the market to provide the metal ion required.
  • Carbonates of metals such as manganese carbonate, calcium carbonate are available metal in the market.
  • Metals in zero oxidation state are also available in the market, typically iron, copper, manganese and zinc.
  • suspensions of one or more species of the desired metal sources are prepared by reacting them in a solution or a suspension of one acidic reactant species or a plurality of such reactants. Stim ' ng and optionally heating for a long enough period of time to turn the entire amount of insoluble metal source to a soluble metal form.
  • one or more organic acid species are used, to acidify the suspension, containing at least one anionic functional group respectively.
  • Example 1 1 gram of iron powder was stirred with 10 mis (milliliters) of poly(acrylic acid) co polymerised with maleic acid (50% in water of poly(acrylic acid-co-maleic acid) by Sigma Aldrich. After a few days a clear solution formed.
  • Example 2 3 gram of iron powder were stirred in 30 mis water and 10 grams malic acid. After a few days all the iron powder dissolved and a whitish paste formed. This white precipitate could be dissolved by raising the pH gently with bicarbonate and increasing the amount of water.
  • Example 3 2 grams of manganese oxide were mixed and stirred with
  • Example 4 1.5 grams of calcium oxide were mixed and stirred with 10 mis of poly(acrylic acid) co polymerised with maleic acid (50% in water of poly(acrylic acid-co-maleic acid) by Sigma Aldrich and 5 mis water. After a few days of stirring a stable solution formed.
  • Example 5 To the solution of example 4, 0.5 grams of MnO were added and also 1 ml of 85% lactic acid (by Sigma Aldrich). After a few days of stirring a clear solution formed.
  • Example 6 To 15 mis of poly(acrylic acid) co polymerised with maleic acid (50% in water of poly(acrylic acid-co-maleic acid) by Sigma Aldrich mixed with 5 mis (millilitres) of water were added 0.7 grams of CuO. Constant stirring and heating to about 80°C dissolved all the oxide and a green solution formed. To this solution 1.0 grams of CaO were introduced under constant stirring. After a few hours the CaO dissolved as well.
  • Example 7 To 20 mis of water were added 4 grams of ethylene diamine tetra acetic acid EDTA (Sigma Aldrich ) and 0.5 grams of metallic manganese. After a few hours of stirring and heating to about 60°C, the metal dissolved completely and a white precipitate formed.
  • Example 8 Two grams of manganous carbonate were dispersed in 11 mis of water to which were added 3.2 grams of citric acid and 1 ml of 85 % lactic acid. The suspension was stirred for several days until a whitish paste formed, eventually completely replacing the brown carbonate powder suspension. Three grams of KOH were added while stirring, turning the paste into a clear, transparent brownish liquid.
  • Example 9 To 10 grams of poly acrylic acid (35% in water by Sigma Aldrich) were added 1.1 gram ZnO. The mixture was stirred and temperature raised to about 90°C. The reaction was very slow and water was added to keep an overall volume of about 15 ml mixture. After a few days, 1.5 mis of lactic acid was added to finish the conversion process, i.e. solubilise the entire oxide left.
  • Calcium and magnesium These two metals, alone or in a mixture are very effectively solubilised with lactic acid.
  • 2.6 grams of commercial CaO were mixed with 5 mis of water.
  • 11 mis of 85% lactic acid were introduced with mixing.
  • a solution formed.
  • extra 0.5 gram of CaO were added while stirring, the solution solidified.
  • This solid can be further dried and crushed to form powder, that when fine enough, can easily dissolve in water even at a neutral pH.
  • magnesium is very easily solubilised and then solidifies, solubilising readily if crushed. This way it is very convenient to obtain a mixed calcium and magnesium salt with lactic acid.
  • Manganese preferably manganese carbonate is also conveniently introduced into such mixtures.
  • Metal ion solutions or suspensions prepared in accordance with the invention provide potentially a wealth of combinations varying in qualitative and quantities aspects.
  • the presence of sulfates, nitrates, chlorides can be eliminated altogether or largely, while at least some of the neutralizing charges for the metal ions (cations) are provided by organic anions of mono-anions, poly- anions or anionic polymers.
  • a polyanion as an acidifying agent for the conversion process, promotes a reduction in the amount of dissolved molecules in the spraying solutions as compared to the use of soluble metal species as metal source.
  • a nutritive preparation a combination including less molecules altogether potentially decreasing the osmotic effect of the spraying solution.
  • the use of polymers as charge neutralizers decreases potentially the number of molecules in a nutritive preparation even further.
  • Malic acid, citric acid, lactic acid and EDTA are all chelating agents being able to bind the metallic ion specified above.
  • chelated metal solutions can be prepared without using a metal salt source, thereby diversifying the combinations available.
  • anionic compounds useful in a conversion process of the invention are natural products (e.g. malic acid, lactic acid) which may be appealing to customers insisting on the use of natural products in the agricultural practice implemented for raising their food.
  • Iron oxides are rather difficult to extract the metal ion from.
  • extracting the metal ion from iron powder is very convenient and may be quite fast if heat is applied. This way, the inclusion of chloride, nitrate, sulfate which are the most abundant component of commercially available iron salts can be avoided altogether.
  • stock preparations are used for preparing nutritive compositions, in which metal solutions or dispersions are prepared using the conversion process described above generally and in the examples.
  • additional beneficial factors can be added, such as nutrients, for example urea, phosphoric acid, phosphonic (phosphorous) acid, ammonia, nitrate.
  • Other factors are non - nutrients, such as pesticides and hormones. Mixing stock solutions of metal solutions prepared in accordance with the present inventions is possible.
  • potassium hydroxide is typically used as an agent for providing hydroxyl ions.
  • Ammonia which is also nutritive, can be used. Sodium may be less desirable in this respect because it is usually not considered as a nutritive element, although for some crops it may be nutritive.
  • the hydroxide is a component of water and is produced when the ammonia, potassium hydroxide and CaO is introduced to aqueous systems.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Fertilizers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Nutritive compositions containing nutritive metal ions devoid of inorganic anions are disclosed. A method for preparing such compositions is described. The method includes reacting at least one water insoluble metal source with at least one organic compound. The organic compounds useful in the conversion reaction of the invention contain one or more anionic functional groups. Stock solutions can be made in accordance with the invention, into which additional nutrients or beneficial factors can be added. The term beneficial factors relate to non nutritive elements such as pesticides, and hormones.

Description

NUTRITIVE COMPOSITIONS CONTAINING METALS
TECHNICAL FIELD OF THE INVENTION
The present invention relates generally to solutions of metal ions used for feeding purposes. A more specific use of such solutions is in the fertilization of agricultural crops.
BACKGROUND OF THE INVENTION
Fertilising crops is performed by applying nutritive elements or compounds to the soil or to the foliage to be subsequently taken up by the plants for further consumption by the various organs. Potassium, iron, calcium, manganese, zinc, copper and molybdenum are nutritive metals of which iron, zinc, copper, manganese and to a lesser extent calcium ions, tend to form coordinative bonds with certain active groups of organic materials. This is sometimes referred to as complexing of the metals with ligands. Such complexation is used as practical means for keeping metal ions in a non precipitated form which they would otherwise tend to fall into if no specific measures are taken. When a molecule forms more than one coordinative bond with a metal ion, a chelate is formed. A large variety of commercial products in the market exist which use chelated metal ions for applying such metals to crops for supplying those metals to the crop.
In US patent 4,265,653 sources for the preparation of a citric acid metal ion combination is disclosed. Citric acid is a naturally occurring chelating agent (ligand) containing anionic (acidic) groups, but the preferable source for the ferrous ion in this publication is either iron sulfate or ferrous chloride, and for manganous ions the preferable source is either manganese nitrate, manganese sulfate, manganese chloride or manganous oxide.
Preparing the nutritive compositions of the above metals solutions is achieved usually using soluble metal salts such as sulfates, nitrates, chlorides. Insoluble compounds of the nutritive metal are used, for example US patent 4,265,653 mentioned above discloses the use manganese oxide as component of the nutritive preparation. In WO 9716395A1 publication, two non soluble species of nutritive metals are made to react, namely zinc metal and manganese dioxide are made to interact. The interaction is made in a solution of sulfuric acid, which introduces sulfate to the preparation. However, especially nitrates and chlorides are considered as potentially phytotoxic, or having a negative effect on the crop, respectively.
In a co - pending GB patent application 0321771.8 by the same inventor, the solubilising of copper is disclosed, in which polyanion is used as a solubilising agent. DETAILED DESCRIPTION OF THE PRESENT INVENTION
In accordance with the present invention, preparations for applying metal nutrients to crops are made using sources for metal ions which are water insoluble or sparingly water soluble forms of the respective metal. Such forms are typically metals in the metal form, carbonate of metal ions, oxides of metal ions, hydroxides or silicates. The metal ion source is converted to a more available form by a method as will be described below. Oxides of metals, typically oxides of zinc, calcium, copper, magnesium and manganese are available in the market to provide the metal ion required. Carbonates of metals such as manganese carbonate, calcium carbonate are available metal in the market. Metals in zero oxidation state are also available in the market, typically iron, copper, manganese and zinc.
Converting the metal ion sources In general, suspensions of one or more species of the desired metal sources are prepared by reacting them in a solution or a suspension of one acidic reactant species or a plurality of such reactants. Stim'ng and optionally heating for a long enough period of time to turn the entire amount of insoluble metal source to a soluble metal form. Typically, one or more organic acid species are used, to acidify the suspension, containing at least one anionic functional group respectively.
Further are described exemplary conversion schemes, exemplifying the metal sources reacted upon and reactants. Example 1: 1 gram of iron powder was stirred with 10 mis (milliliters) of poly(acrylic acid) co polymerised with maleic acid (50% in water of poly(acrylic acid-co-maleic acid) by Sigma Aldrich. After a few days a clear solution formed. Example 2: 3 gram of iron powder were stirred in 30 mis water and 10 grams malic acid. After a few days all the iron powder dissolved and a whitish paste formed. This white precipitate could be dissolved by raising the pH gently with bicarbonate and increasing the amount of water. Example 3: 2 grams of manganese oxide were mixed and stirred with
5.6 grams of citric acid and 10 mis water. Without warming after a few days all the oxide dissolved forming a white - gray paste. This paste could be dissolved by raising the pH gently with bicarbonate and increasing the amount of water, or by introducing KOH to raise the pH to about neutral. Example 4: 1.5 grams of calcium oxide were mixed and stirred with 10 mis of poly(acrylic acid) co polymerised with maleic acid (50% in water of poly(acrylic acid-co-maleic acid) by Sigma Aldrich and 5 mis water. After a few days of stirring a stable solution formed. Example 5: To the solution of example 4, 0.5 grams of MnO were added and also 1 ml of 85% lactic acid (by Sigma Aldrich). After a few days of stirring a clear solution formed. Example 6. To 15 mis of poly(acrylic acid) co polymerised with maleic acid (50% in water of poly(acrylic acid-co-maleic acid) by Sigma Aldrich mixed with 5 mis (millilitres) of water were added 0.7 grams of CuO. Constant stirring and heating to about 80°C dissolved all the oxide and a green solution formed. To this solution 1.0 grams of CaO were introduced under constant stirring. After a few hours the CaO dissolved as well. Example 7. To 20 mis of water were added 4 grams of ethylene diamine tetra acetic acid EDTA (Sigma Aldrich ) and 0.5 grams of metallic manganese. After a few hours of stirring and heating to about 60°C, the metal dissolved completely and a white precipitate formed. Adding 1.5 grams KOH while stirring cleared the solution, forming a reddish brown transparent solution. To this, 10 mis of the solution of example 6 were added, forming a green solution. Example 8. Two grams of manganous carbonate were dispersed in 11 mis of water to which were added 3.2 grams of citric acid and 1 ml of 85 % lactic acid. The suspension was stirred for several days until a whitish paste formed, eventually completely replacing the brown carbonate powder suspension. Three grams of KOH were added while stirring, turning the paste into a clear, transparent brownish liquid. Example 9. To 10 grams of poly acrylic acid (35% in water by Sigma Aldrich) were added 1.1 gram ZnO. The mixture was stirred and temperature raised to about 90°C. The reaction was very slow and water was added to keep an overall volume of about 15 ml mixture. After a few days, 1.5 mis of lactic acid was added to finish the conversion process, i.e. solubilise the entire oxide left.
Expediting the solubilising reactions As mentioned above, heating the source material (metal, metal oxide, etc.) enhances the rate of solubilisation. Other ways for practically expediting the reactions are using peroxides, typically hydrogen peroxide instead of some of the water in the solubilisation reaction. The use of hydrogen peroxide has a very pronounced effect of expediting the solubilisation of iron powder, and copper powder. With manganese it is essential to that the metal ion does not go into the higher oxidation states. Metallic magnesium powder can be used as a quich to dissolve source of magnesium, also with caution because the reaction with acid water may be very exothermic.
Calcium and magnesium These two metals, alone or in a mixture are very effectively solubilised with lactic acid. For example 2.6 grams of commercial CaO were mixed with 5 mis of water. To the slurry, 11 mis of 85% lactic acid were introduced with mixing. A solution formed. When extra 0.5 gram of CaO were added while stirring, the solution solidified. This solid can be further dried and crushed to form powder, that when fine enough, can easily dissolve in water even at a neutral pH. Likewise, magnesium is very easily solubilised and then solidifies, solubilising readily if crushed. This way it is very convenient to obtain a mixed calcium and magnesium salt with lactic acid. Manganese, preferably manganese carbonate is also conveniently introduced into such mixtures.
Some benefits of compositions of the invention
Metal ion solutions or suspensions prepared in accordance with the invention provide potentially a wealth of combinations varying in qualitative and quantities aspects. Thus, the presence of sulfates, nitrates, chlorides, can be eliminated altogether or largely, while at least some of the neutralizing charges for the metal ions (cations) are provided by organic anions of mono-anions, poly- anions or anionic polymers. In accordance with the present invention it is possible to prepare virtually any combination of nutritive metals in one suspension or solution.
Using a polyanion as an acidifying agent for the conversion process, promotes a reduction in the amount of dissolved molecules in the spraying solutions as compared to the use of soluble metal species as metal source. Using as a nutritive preparation a combination including less molecules altogether potentially decreasing the osmotic effect of the spraying solution. The use of polymers as charge neutralizers decreases potentially the number of molecules in a nutritive preparation even further. Malic acid, citric acid, lactic acid and EDTA are all chelating agents being able to bind the metallic ion specified above. In accordance with the present invention, chelated metal solutions can be prepared without using a metal salt source, thereby diversifying the combinations available. Some of the anionic compounds useful in a conversion process of the invention are natural products (e.g. malic acid, lactic acid) which may be appealing to customers insisting on the use of natural products in the agricultural practice implemented for raising their food. Iron oxides are rather difficult to extract the metal ion from. In the method of the present invention, extracting the metal ion from iron powder is very convenient and may be quite fast if heat is applied. This way, the inclusion of chloride, nitrate, sulfate which are the most abundant component of commercially available iron salts can be avoided altogether.
In another embodiment of the invention, stock preparations are used for preparing nutritive compositions, in which metal solutions or dispersions are prepared using the conversion process described above generally and in the examples. To such stock preparations additional beneficial factors can be added, such as nutrients, for example urea, phosphoric acid, phosphonic (phosphorous) acid, ammonia, nitrate. Other factors are non - nutrients, such as pesticides and hormones. Mixing stock solutions of metal solutions prepared in accordance with the present inventions is possible.
To raise the pH, typically after the conversion process has terminated, potassium hydroxide is typically used as an agent for providing hydroxyl ions. Ammonia, which is also nutritive, can be used. Sodium may be less desirable in this respect because it is usually not considered as a nutritive element, although for some crops it may be nutritive. The hydroxide, is a component of water and is produced when the ammonia, potassium hydroxide and CaO is introduced to aqueous systems.

Claims

1. A nutritive composition comprising in total: • at least one species of nutritive metal ion; • at least one organic compound species having at least an anionic functional group for at least neutralizing the charges of said at least one species of nutritive ions, and • water and water components.
2. A nutritive composition as in claim 1, containing at least one organic chelating agent.
3. A nutritive composition as in claim 1 , wherein said composition is devoid of nitrate, chloride and sulphate.
4. A nutritive composition as in claim 1 and wherein said at least one organic compound species is a natural product.
5. A nutritive composition as in claim 4 and wherein said at least one organic compound species is lactic acid and wherein said at least one species of nutritive metal ion is magnesium.
6. A nutritive composition as in claim 1 and wherein said at least one organic compound species is an ionic polymer.
7. A nutritive composition as in claim 1 containing iron ions.
8. A nutritive composition as in claim 1 containing three metal ion species.
9. A nutritive composition as in claim 1 containing at least two metal ion species.
10. A nutritive composition as in claim 9 wherein one metal ion species is potassium ion.
11. A nutritive composition as in claim 9 wherein said at least two metal species are magnesium and calcium and wherein said at least one organic compound species is lactic acid.
12. A nutritive composition comprising at least one metal ion dissolved in water and water components, wherein any other ions present are anionic functional groups of organic molecules.
13. A method for preparing nutritive compositions comprising reacting at least one water insoluble source of nutritive metal species with at least one organic compound containing at least one anionic functional group, in water. 5
14. A method for preparing nutritive composition as in claim 13, comprising reacting two water insoluble sources of nutritive metal species.
10 15. A method for preparing nutritive composition as in claim 13, and wherein one nutritive metal species is calcium.
16. A method for preparing nutritive composition as in claim 13, and wherein one metal species is potassium.
15 17. A method for preparing nutritive composition as in claim 13, and wherein said composition is a stock preparation.
18. A method for preparing nutritive composition as in claim 13, and 0 wherein said reacting is expedited by replacing at least some of said water with hydrogen peroxide.
19. A method for preparing nutritive composition as in claim 13, and wherein at least some of said organic compound is a non - 5 nutrient.
PCT/IL2005/000275 2004-03-11 2005-03-09 Nutritive compositions containing metals WO2005086579A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0405446A GB2411896A (en) 2004-03-11 2004-03-11 Plant feed solutions comprising nutritive metals
GB0405446.6 2004-03-11

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WO2005086579A2 true WO2005086579A2 (en) 2005-09-22
WO2005086579A3 WO2005086579A3 (en) 2005-12-15

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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2407577A (en) * 2003-09-17 2005-05-04 Yoram Tsivion Water-soluble chelating polymer
WO2007006078A1 (en) 2005-07-12 2007-01-18 Adelaide Research And Innovation Pty Ltd Chelating agents for micronutrient fertilisers

Citations (6)

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Publication number Priority date Publication date Assignee Title
US3131048A (en) * 1960-05-02 1964-04-28 Leslie L Balassa Stable metal chelate preparations
US3200136A (en) * 1962-04-24 1965-08-10 Beecham Res Lab Metal chelates of alpha-hydroxy-carboxylic acids and their preparation
US5372626A (en) * 1990-07-31 1994-12-13 Zivion; Yoram Fertilizer compositions for administering ionic metal microelements to plant roots
WO1999008982A1 (en) * 1997-08-17 1999-02-25 Leket Bar Chemicals Ltd. Compositions comprising iron chelates
US5997600A (en) * 1996-11-13 1999-12-07 Stoller Enterprises, Inc. Fertilizer compositions including chelated metal ions
US6177581B1 (en) * 1999-10-12 2001-01-23 The Dow Chemical Company Mixed-metal chelates and process for the preparation thereof

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Publication number Priority date Publication date Assignee Title
US4265653A (en) * 1979-07-05 1981-05-05 Pfizer Inc. Manganese micronutrient solutions
DE3044903A1 (en) * 1980-11-28 1982-07-08 Basf Ag, 6700 Ludwigshafen METHOD FOR PRODUCING MULTIPLE TRACK NUTRIENT FUELS
IT1244865B (en) * 1989-07-12 1994-09-12 Nat Energy Council SOIL TREATMENT
US5772723A (en) * 1996-11-22 1998-06-30 Frit, Inc. Method of manufacturing citric acid chelates
US6515090B1 (en) * 2000-05-01 2003-02-04 John Larry Sanders Anionic vinyl/dicarboxylic acid polymers and uses thereof
GB2407577A (en) * 2003-09-17 2005-05-04 Yoram Tsivion Water-soluble chelating polymer

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3131048A (en) * 1960-05-02 1964-04-28 Leslie L Balassa Stable metal chelate preparations
US3200136A (en) * 1962-04-24 1965-08-10 Beecham Res Lab Metal chelates of alpha-hydroxy-carboxylic acids and their preparation
US5372626A (en) * 1990-07-31 1994-12-13 Zivion; Yoram Fertilizer compositions for administering ionic metal microelements to plant roots
US5997600A (en) * 1996-11-13 1999-12-07 Stoller Enterprises, Inc. Fertilizer compositions including chelated metal ions
WO1999008982A1 (en) * 1997-08-17 1999-02-25 Leket Bar Chemicals Ltd. Compositions comprising iron chelates
US6177581B1 (en) * 1999-10-12 2001-01-23 The Dow Chemical Company Mixed-metal chelates and process for the preparation thereof

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WO2005086579A3 (en) 2005-12-15
GB2411896A (en) 2005-09-14

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