EP1680379A2 - Agents pour solubiliser des ions de metal - Google Patents

Agents pour solubiliser des ions de metal

Info

Publication number
EP1680379A2
EP1680379A2 EP04770504A EP04770504A EP1680379A2 EP 1680379 A2 EP1680379 A2 EP 1680379A2 EP 04770504 A EP04770504 A EP 04770504A EP 04770504 A EP04770504 A EP 04770504A EP 1680379 A2 EP1680379 A2 EP 1680379A2
Authority
EP
European Patent Office
Prior art keywords
solution
mis
composition
added
water
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.)
Withdrawn
Application number
EP04770504A
Other languages
German (de)
English (en)
Other versions
EP1680379A4 (fr
Inventor
Yoram Tsivion
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.)
Future Tense Technological Development & Entrepreneurship Ltd
Original Assignee
Future Tense Technological Development & Entrepreneurship Ltd
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 Future Tense Technological Development & Entrepreneurship Ltd filed Critical Future Tense Technological Development & Entrepreneurship Ltd
Publication of EP1680379A2 publication Critical patent/EP1680379A2/fr
Publication of EP1680379A4 publication Critical patent/EP1680379A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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 the sequestration of metal ions, more specifically the invention deals with the administration of chelated metallic nutrients to plants.
  • the metallic nutrients under consideration are such that may form complexes with some organic molecules.
  • a chelate of the art is a combination of an organic molecule (typically referred to as the chelating agent) having several functional groups that bind to a metal cation, yet keep it water soluble.
  • the chelating agents used in agriculture and industry are synthetic such as the chelating molecules based on the ethylene diamine core, and some are natural such as citric acid.
  • Some modified natural products are also known in the art as complexing agents such as lignosulphonates.
  • a chelate comprises a ligand, typically an organic molecule containing at least two functional groups, and a metallic poly - valent cation.
  • a very common ligand use in agriculture is EDTA, often for delivering nutritional metal ions of iron, manganese, copper and zinc.
  • the ligands of choice in agriculture for delivering iron in high - pH soils are EDDHA and EDDHMA. Four properties characterise a proper ligand for iron intended for application to crops through the soil in high pH soils.
  • the fourth property is the overall solubility in aqueous environment when bound to the metal.
  • the need for a comparatively low affinity to Ca +2 stems from the fact that in many cases the high pH in the soil is associated with a high concentration of calcium carbonate. The high calcium concentration in the soil may compete with the bonds on the chelate to eventually displace the iron ion in the chelate. If an iron chelate is to be applied in soils in which the pH is high without the presence of calcium, this requisite may not be relevant.
  • Ion exchange fertilizers have been used to load chelated metals for establishing a controlled release formulation (US 4396412), such ion exchangers are polymers which contain water soluble components such as polyacrylamide.
  • Water soluble polyaspartic acid was disclosed in US 5,593,947 as an enhancer of plant nutrients. This was used alone or in combination with other organic polymers.
  • organic polymers are used to solubilise metal ions in water. With respect to iron, which is more susceptible to precipitation in high pH levels than other commonly occurring cations, the use of some organic polymers was found to be surprisingly effective.
  • the compositions of the present invention can be easily introduced to the agricultural practice, but they can nevertheless be exploited in other fields of the industry in which sequestration of metals is required.
  • the embodiments of the present invention include certain polymer and certain polymer metal ion combinations, that provide beneficial results, as will be further described in the examples, infra. All the polymers contain acidic residues (functional groups).
  • Solution A To a 10 mis (millilitres) solution of poly(acryIic acid) co polymerised with maleic acid (50% in water of poly(acrylic acid-co-maleic acid, average molecular weight 3,000) by Sigma Aldrich, hereinafter referred to as PACM, 5 ml water and 1.0 gram of ferric nitrate nonahydrate were added. To the solution 3.2 grams KOH were added while stirring, causing a gel to form. After a few hours of further stirring, the gel dissipated forming a clear reddish transparent solution. The solution, having a volume of about 22 mis (millilitres), is stable for at least two months, contains about 0.63 % iron.
  • Solution B 5.8 grams of poly(styrenesulfonic acid) copolymerised with maleic acid (poly(styrenesulfonic-co-maleic acid) sodium salt, by Sigma Aldrich) was mixed in 15 mis of water with 0.5 ferric nitrate nonahydrate, forming a gel instantly. While sti ⁇ ing, 2.5 mis of acetic acid were added to the solution, and after a few hours of stirring the gel dissipated completely and a clear reddish transparent solution formed.
  • Solution C 0.4 grams of copper powder was mixed with 15 ml water, to which suspension 3.0 mis of PACM were added, forming a gel. After complete dissolution of the copper, 2 grams of KOH were added and the solution formed was mixed until clear.
  • Solution D To 14 mis of PACM 1.6 grams of MnCO (by Sigma Aldrich) were added. The mixture was stirred for two days until all the solid powder disappeared visually, forming a whitish slurry. 4.5 grams of KOH were gradually introduced while stirring, forming a clear transparent brown solution.
  • Solution E To 0.8 grams of ferric nitrate nonahydrate (by Sigma Aldrich), 13 mis of polymethacrylate (sodium salt, 30% in water, by Sigma Aldrich), were introduced and 5 mis of water were added. To the gel formed, 6 mis of acetic acid were added. The mixture was stirred until the gel dissipated.
  • Solution F Five mis of sodium salt of polyaspartate (40% in water by Sigma Aldrich) was mixed with 30 ml water containing 0.1 gram ferric nitrate nonahydrate. After about 1 hour of sti ⁇ ing the gel initially formed, completely dissipated forming a clear reddish solution having a pH between 8 and 9.
  • Solution Gi Three grams of FeEDDHMA (commercial) was mixed with 40 ml of water. To the deeply coloured purple solution formed, 0.2 grams of K 2 CO 3 were added and the solution mixed.
  • Solution G 2 One gram of FeEDDHMA (commercial) was mixed with 40 ml of water.
  • the maleic acid copolymers were effective sequestrants of ferric ion in basic solutions, which is indicative of the chelate formed by the trivalent iron ions bound to the polymer molecules.
  • the superiority of such polymers as sequestrants of ferric ion in the environment of lime as compared to citric acid and EDTA based chelates, and their comparability to EDDHMA in the high pH high lime environment is suggestive of a fertilising potential of iron and other metallic micronutrients in general. This potential may be exploited for applying poly-valent metals to plant organs, in high pH soils in particular, in combination with the chelating polymers of the invention.
  • Fertigation is a modern agricultural practice in which irrigation and fertilization are combined, being performed by the same systems. Fertigation is unique also in confining the root activity to a limited volume of soil or root medium. Fertilizers in fertigation are supplied solubilised through the irrigation system. The chelating polymers and metal ion solutions of the invention are therefore readily adoptable by fertigation. The exceptional chelating capabilities of the solutions A and B are promising with respect to crops growing in high pH and calcareous soils. However, the solutions of the invention can be employed in any fertilisation scheme, which applies fertilisers to any absorptive organ of the plant, including foliar application, much the same as other chelates are used in foliar application of nutrients.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Fertilizers (AREA)
  • Cultivation Of Plants (AREA)

Abstract

L'invention concerne une composition solubilisable contenant des ions métalliques polyvalents et un polymère chélateur comprenant des groupes fonctionnels acides. Ce polymère est capable de retenir des ions métalliques sinon susceptibles de précipitation avec des ions hydroxyle, solubilisés dans une eau à pH élevé. Une solution de l'invention contenant des ions de fer et un copolymère d'acide maléique est une source de fer pour les racines des plantes. La composition de l'invention est particulièrement utilisée pour fournir du fer aux racines de plantes poussant sur des sols très calcaires.
EP04770504A 2003-09-17 2004-09-12 Agents pour solubiliser des ions de metal Withdrawn EP1680379A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0321771A GB2407577A (en) 2003-09-17 2003-09-17 Water-soluble chelating polymer
PCT/IL2004/000833 WO2005026079A2 (fr) 2003-09-17 2004-09-12 Agents pour solubiliser des ions de metal

Publications (2)

Publication Number Publication Date
EP1680379A2 true EP1680379A2 (fr) 2006-07-19
EP1680379A4 EP1680379A4 (fr) 2007-12-12

Family

ID=29227250

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04770504A Withdrawn EP1680379A4 (fr) 2003-09-17 2004-09-12 Agents pour solubiliser des ions de metal

Country Status (3)

Country Link
EP (1) EP1680379A4 (fr)
GB (1) GB2407577A (fr)
WO (1) WO2005026079A2 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2411896A (en) * 2004-03-11 2005-09-14 Yoram Tsivion Plant feed solutions comprising nutritive metals
TR200800106T2 (tr) * 2005-07-12 2008-02-21 Adelaide Research And Innovation Pty Ltd Mikrobesin gübreler için şelatlama ajanları.
FR2948529B1 (fr) * 2009-07-29 2016-02-19 Pierre Philippe Claude Utilisation de cations pour l'amelioration de la biofertilisation bacterienne de grandes cultures

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3755264A (en) * 1971-07-30 1973-08-28 Amicon Corp Maleic anhydride copolymers and method of making
US3790610A (en) * 1971-09-07 1974-02-05 Colloids Inc Organic polymer chelants for iron and manganese ions
US4663053A (en) * 1982-05-03 1987-05-05 Betz Laboratories, Inc. Method for inhibiting corrosion and deposition in aqueous systems
LU84601A1 (fr) * 1983-01-24 1984-10-24 Sba Chimie Societe Anonyme Procede et compositions pour le conditionnement de sols
US4601758A (en) * 1985-02-25 1986-07-22 Dowell Schlumberger Incorporated Sulfonated poly (vinyl aromatics) as fluid loss additives for salt cement slurries
US5026490A (en) * 1990-08-08 1991-06-25 Exxon Research & Engineering Zwitterionic functionalized polymers as deflocculants in water based drilling fluids
US5350735A (en) * 1992-11-05 1994-09-27 Donlar Corporation Composition and method for enhanced fertilizer uptake by plants
US6297209B1 (en) * 1996-05-10 2001-10-02 The Clorox Company Sequesterants as hypochlorite bleach enhancers
US5985992A (en) * 1997-12-10 1999-11-16 Cytec Technology Corp. Anionic polymer products and processes
GB9907668D0 (en) * 1999-04-01 1999-05-26 Zeneca Ltd Solid composition
US6425959B1 (en) * 1999-06-24 2002-07-30 Ecolab Inc. Detergent compositions for the removal of complex organic or greasy soils
US6703469B2 (en) * 2001-03-05 2004-03-09 Specialty Fertilizer Products, Llc Anionic polymers composed of dicarboxylic acids and uses thereof
GB2411896A (en) * 2004-03-11 2005-09-14 Yoram Tsivion Plant feed solutions comprising nutritive metals

Also Published As

Publication number Publication date
WO2005026079A2 (fr) 2005-03-24
EP1680379A4 (fr) 2007-12-12
GB0321771D0 (en) 2003-10-15
WO2005026079A3 (fr) 2005-08-04
GB2407577A (en) 2005-05-04

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