EP1434751A1 - Nouvelle composition de chelate de fer - Google Patents

Nouvelle composition de chelate de fer

Info

Publication number
EP1434751A1
EP1434751A1 EP02770358A EP02770358A EP1434751A1 EP 1434751 A1 EP1434751 A1 EP 1434751A1 EP 02770358 A EP02770358 A EP 02770358A EP 02770358 A EP02770358 A EP 02770358A EP 1434751 A1 EP1434751 A1 EP 1434751A1
Authority
EP
European Patent Office
Prior art keywords
composition
iron
iron chelate
agent
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Withdrawn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
EP02770358A
Other languages
German (de)
English (en)
Inventor
Nils Hjelte
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.)
VAN IPEREN B.V.
Original Assignee
Ns Hjelte AB
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 Ns Hjelte AB filed Critical Ns Hjelte AB
Publication of EP1434751A1 publication Critical patent/EP1434751A1/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Withdrawn legal-status Critical Current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
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/10—Solid or semi-solid fertilisers, e.g. powders
    • C05G5/18—Semi-solid fertilisers, e.g. foams or gels
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/20—Liquid fertilisers
    • C05G5/27—Dispersions, e.g. suspensions or emulsions

Definitions

  • the invention relates to a composition to be used for treating iron deficiency in plants as well as method of producing the same.
  • Iron chelates are important iron compounds which supply iron to plants for growth. Most of these compounds comprise a chelate complex with ethylenediiminobis [ (2- hydroxy-phenyl) acetic acid] (EDDHA) or ethylenediimino- bis [ (2-hydroxy-4-methyl-phenyl) acetic acid] (EDDHMA) as
  • EDDHAFe or EDDHMAFe are obtained as high performance iron chelates in the form of EDDHAFeNa (K) and EDDHMAFeNa (K) . They are available as dried powders or granules having about 2-6 % iron contents as a chelated complex. These high performance iron chelates are mainly used in arid areas with calcareous alkaline soils and for high value crops like peaches, grapes for the table, pears and the like.
  • An organic solvent is used to facilitate the formation of liquid iron chelates having a chelated iron content of about 40-50 g/1, which corresponds to about 3 wt% chelated iron. Large amounts of the solvent are used and the products are made from expensive dried iron chelates or involve the removal of water by distillation as well as the filtering of sodium chloride from the distillation residues .
  • a homogeneous trace-element fertil- iser paste which comprises 2-18 wt% polyglycol ether with not less than 9 ethylene oxide units and/or a water-soluble polyglycol ether derivative with not less than 8 ethylene oxide units .
  • the dust from commercial metal chelates can cause industrial hygienic problems since it irritates eyes and mucous membranes. Severe effects, such as asthma, can be obtained both during manufacturing and packaging as well as when the product is handled by the farmer. Exposed personnel may also develop hypersensitivity to the dried product.
  • the products are applied to the soil after they have been partly dissolved and/or dispersed in water for further feeding to irrigation lines . Here the iron chelate particles are further diluted and completely dissolved by the irrigation water.
  • the object of the invention is to provide a new water based composition to be used for treating iron deficiency in plants as well as a method of producing the same, whereby the above-mentioned problems are avoided or eliminated.
  • a method is provided which in an efficient and reliable way allows for the production of and a cheap composition of a high performance iron chelate, whereby the drying and granulation process of chelated products is avoided as is the use of expensive organic solvents and the composition can be used directly as a fertilizer.
  • intermediate products in the form of non-homogenous unstable concentrated sedimenting iron chelate slurries can according to the invention be modified to stable homogenous forms by agitating, i.e. disintegrating and dispersing, such a slurry comprising a particulate phase of at least one iron chelate compound having limited solubility in water.
  • the limited solubility of the iron chelate compounds is utilised.
  • the solubility of an iron chelate compound in the water phase should not be more than 1 % expressed as iron in chelated form.
  • An iron chelate mixture which is prepared according to the state of the art for producing a composition to be used for treating plant iron deficiency in soils for agricultultural purposes, comprises a water phase and a particulate phase of at least one iron chelate compound having limited solubility in water.
  • the particulate phase consists of a solid and/or crystalline and/or amorphous and/or liquid iron chelate complex, the latter for example being large micellar aggregates.
  • a composition with thixo- tropic properties as well as stability after storage at rest can be obtained by agitating such a mixture until the particulate phase is disintegrated and homogeneously dispersed in the water phase.
  • the iron chelate slurry particles are agitated by mechanical means, optionally in the presence of thickening and/or gelation additives, particularly those which increase thixotropic properties to the composition.
  • the size of the disintegrated (finely divided) iron chelate particles is less than 10 micron (100 mesh) . Most preferably, the size of the particles is less than 1 micron.
  • the disintegration of the iron chelate particulate phase results in a more viscous composition.
  • the composition with a large number of dispersed particles turns into a gel-like state.
  • the effect is improved by including a gelation additive in the composition.
  • the inventive "gelled” composition will upon agitation revert to a liquid state.
  • a "gel” produced according to the invention can subsequently be mechanically turned into a liquid of the iron chelate when the composition is to be used. Furthermore, upon standing this liquid again resumes its gel-like state.
  • the stability of the composition can be improved by including a viscosity-increasing agent, whereby the already viscous mixture becomes more viscous or even truly gelled.
  • a viscosity-increasing agent such as sodium EDTA, sodium EDTA, sodium EDTA, sodium EDTA, sodium EDTA, sodium EDTA, sodium EDTA, sodium EDTA, sodium EDTA, sodium EDTA, sodium EDTA, sodium EDTA, sodium EDTA, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate
  • the desired properties of the disintegrated dispersions can be obtained with such typical additives as bento- nites, aluminates, kaolins, silicon oxides, preferably fused silicas, and the like as well as natural products, such as alginates, cellulose derivatives, and gelatines, or synthetic polymers, like polyacrylates . They are preferably supplied as very fine powder forms (micronized) and are used at the rate of maximum two parts for one part of chelated iron. These additives are used in minute amounts from about 0.5 to 5 wt% calculated on the water content of the composition.
  • An inventive composition stabilized in its gelled form is the most stable form of the dispersions.
  • thickened dispersions are sufficiently stable when the storage times are limited, i.e. less than three months.
  • the gelling rate is dependent of both the amount of disintegrated and homogeneously dispersed iron chelate particles and the amount of viscosity increasing agent added to the composition.
  • a synergistic effect is obtained in a dose-response way: At a constant amount of disintegrated and homogeneously dispersed particles an increased gelling is obtained with an increased amount of viscosity increasing agent and vice versa .
  • these additives result in the formation of hydrogen bonds between the particles of the viscosity increasing agent and the iron chelate, whereby a network is formed and a homogenous phase is obtained, which sub- sequently can be broken by mechanical means.
  • the gelling of the mixture caused by this network keeps the particles of the liquid slurry in a dispersed form, whereby sedimentation is avoided.
  • Stable dispersions can be produced with chelated iron contents of 2 % or more.
  • the chelated iron content of the inventive composition is 3-4 %.
  • the 3 % iron products have a dry matter content of about 50-60 %.
  • the 3 % iron content is a practical concentration since iron chelate dose rates generally are based on products having 6 % chelated iron. It is thus a simple calculation to convert a traditional dose rate to a 3 % formulation.
  • Gelled compositions which have a chelated iron content of up to 4 %, can also be produced. In such a case the dry matter content of the dispersion is about 65-70 %. A gelling starts as soon as the agitation is stopped. In the gelled composition the dispersed particles are "locked in” and exhibit no tendency to form sediments upon storing. Samples have been stored for three years without showing any tendency of sedimentation of particles or other change of properties .
  • the liquefaction can be performed for example by agitation, e.g. by vibration or by applying shear forces to the inventive composition. As long as shear forces are applied, no sedimentation will take place. When the shear forces are removed a gel will again be formed. This is especially an advantage when the inventive composition is used as a gel depot for slow release of fertilizing iron, the composition being injected into the soil as a liquid and subsequently gelled. The composition will thus be trapped by the soil particles and will slowly be dissolved by the moisture in the soil.
  • Suitable iron chelating agents to be used in the inventive composition are products manufactured according the processes described in US 4,130,582 as well as US 2,824,128. Strong phenolic amino acids are preferred, such as ethylenediiminobis [ (2-hydroxy-phenyl) acetic acid] (EDDHA) and ethylenediiminobis [ (2-hydroxy-4-methyl-phenyl) - acetic acid] (EDDHMA) as well as a large number of chemical modifications of these compounds.
  • the phenol moiety of the chelating molecule can be substituted by a lower alkyl group or chlorine ( to e.g EDDHC1A) .
  • the ethylenediamine moiety can be substituted by a propyylenediamine .
  • a slurry of particulate iron chelate can also be produced by conventional methods.
  • chelated iron in the trivalent oxidation state is used.
  • a slurry can be obtained which has a chelated iron content of about 2.3 % as EDDHAFe.
  • Such a slurry can be dispersed and physically stabilized according to the present invention. The procedure results in a final product which con- tains 2.2 % Fe thus meeting the EU specifications for liquid iron chelates .
  • the drying process of the chelate mixture is avoided and the chelated product can after storage be used directly.
  • the stored product can easily be made fluid, although the liquid product contains 25-30 % of the dispersed chelate.
  • the inventive method of disintegrating and homogeneously dispersing as well as stabilizing a liquid mixture, which contains an in agriculture accepted iron chelate is cost-efficient compared with conventional drying by means of e.g. spray-granulation.
  • the capital costs for the necessary equipment is only a fraction of the costs for a spray-granulation unit.
  • the productivity of a unit applying the method of the invention is much higher than that of a drying unit for spray-granulation .
  • a concentrated slurry of the iron chelate EDDHAFeNa was prepared according to the state of the art from concentrated water solutions of 0.5 mol of the technical the chelating agent EDDHANa, supplemented with 1.85 mol of caustic, and 0.45 mol of ferric chloride, respectively, by co-currently feeding the solutions into a small heel of artificial iron chelate slurry kept in a beaker provided with a low shear agitator and a pH electrode.
  • the ferric chloride was charged at a constant rate and the chelating agent in an on/off mode in order to keep the pH between pH 6.5 and 7.5.
  • the agitated reaction mixture consists of an almost black slurry of suspended particles in an almost black mother liquid.
  • the suspended particles are not directly visible because of the dark liquid colour, but by stopping the agitation for a while and then tilting the beaker a sediment can be seen, which occupies more than half of the total product volume .
  • the product prepared according to the state of the art is thus not suitable for use in agriculture because of its inhomogeneous character.
  • Comparative Example 1 was placed in ice cooled water and agitated by using a dispersing and disintegrating machine,
  • the agitation was then interrupted and the machine was disconnected.
  • the mixture was now substantially more viscous than the original iron chelate slurry from Compar- ative Example 1, but could easily be poured into a glass jar, which was sealed. After standing at rest for 2 h the mixture had turned into gel as could be seen by tilting the jar.
  • the jar was stored at rest for three months and then opened for sampling. When visually inspected, the jar contained an almost black gel, just as before storage.
  • Example 4 was repeated by using powdered silicate instead of powdered silica. A gelled product was obtained, which exhibited thixotropic properties.
  • Example 4 was repeated by using powdered aluminate instead of powdered silica. A gelled product was obtained, which exhibited thixotropic properties .
  • EXAMPLE 7 was repeated by using powdered aluminate instead of powdered silica. A gelled product was obtained, which exhibited thixotropic properties .
  • a slurry of 300 g of EDDHFeNa in water was prepared from the chelating agent EDDHANa, ferric chloride, and caustic while agitating with an disintegrating device and keeping the pH between 7 and 8 during the chelation step.
  • a liquid slurry was obtained, which contained 12.5 g of chelated iron and 39 g of sodium chloride.
  • Fused silica (7 g) was added to this slurry while agitating with a disintegrating machine for 30 min, which resulted in a more viscous slurry.
  • the agitation was interrupted and the viscous slurry was poured into a plastic container. After one hour a gel was formed, which upon agitation returned to the viscous liquid state. After interrupting this agitation and one hour of standing, the viscous liquid had again turned into a gel.
  • the resulting gel product had a chelated iron content of 4.1 wt%.
  • EXAMPLE 10 Bentonite (20 g) was added to 610 g of an iron chelate mixture, which contained 300 g of technical EDDHFe having a chelated iron content of 20.1 g.
  • the resulting slurry was disintegrated and homogeneously dispersed as in Example 9.
  • a viscous liquid was obtained which gelled within one hour after the interruption of the agitation.
  • the gel so obtained had a chelated iron content of 3.2 wt% .
  • EXAMPLE 11 A water solution of 404 kg, 1.00 k ol, of technical EDDHA di-sodium salt (850 kg) , NSHAB 2002-07-03, was supplied to a container provided with a mixing device. To this solution 112 kg of 50 % caustic was added under agitation. A feeding pump was connected to the container for discharging and the feeding rate was adjusted so that the mixture could be discharged at a constant rate into a chelation reactor for 75 min.
  • a chelation reactor was provided with a heel of 500 kg of 3 % iron chelate slurry from a previously prepared batch.
  • the slurry was kept dispersed by a low shear agitator provided with baffles .
  • the slurry had a pH of about 7.5-8.0.
  • a pH-electrode was immersed in the slurry and con- nected to a pH-stat controlling unit in an on- and off- mode, which in turn was connected to a feeding pump for the chelating agent.
  • the pH-stat was adjusted to open for feeding at pH 6.8 and to close at pH 7.3.
  • the iron chelate was prepared under the following conditions : When starting up, the pH-stat is activated and the feeding of the ferric chloride is started. Initially, the pH of the slurry falls, and at pH 6.8 the feeding of the chelating agent will start automatically.
  • the chelating agent Since the chelating agent is fed at a higher rate than the ferric chloride the pH will rise again. At pH 7.3, the feeding of the chelating agent is automatically interrupted by the pH-stat.
  • the pH is then adjusted to pH 7.5-8.0 by the addition of either of the starting materials. If an adjustment is required, the agitation is allowed to continue for additional 15 min followed by a re-check of the pH. An iron chelate product slurry of 1781 kg was obtained when these conditions were followed.
  • the main part (1281 kg) was transferred to an open storage tank and gently agitated. Then 25 kg of bentonite was added in small portions and mixed into the slurry for 30 min.
  • the contents of the agitated tank were homogenised by feeding for 90 min to a dispersion machine UTL 2000/05 (Kawerke GMBH and Co., Germany) operating on line and run at a speed of 5000 rpm.
  • the resulting product can be directly fed into containers for end users. After about one hour the viscous liquid turns into a gel having thixotropic properties.
  • the final product contains 3 % iron in the form of EDDHAFe.
  • Ultraturrax dispersing machine and run for 20 min at a reduced speed of about 2500 rpm in order to avoid any intrusion of air.
  • the container for the preparation was cooled on the outside with cold running water during the operation of the dispersing machine.
  • the resulting product was a viscous liquid, which in two hours turned into a gel. Upon agitation this gel became a pourable viscous liquid, which when left at rest again turned into a gel.
  • the product contained 2 % iron in the form of EDDHMAFe.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Fertilizers (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne un procédé de production d'une composition destinée aux terres agricoles pour le traitement de la carence en fer des plantes et contenant un mélange d'une phase d'eau et d'une phase de particules d'au moins un composé de chélate de fer ayant une solubilité limitée dans l'eau. Ce mélange est agité jusqu'à ce que la phase de particules soit désintégrée et dispersée de manière homogène dans la phase d'eau. On obtient ainsi une composition correspondante ayant des propriétés thixotropiques et une stabilité après stockage au repos.
EP02770358A 2001-09-12 2002-09-12 Nouvelle composition de chelate de fer Withdrawn EP1434751A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
SE0103014 2001-09-12
SE0103014A SE0103014D0 (sv) 2001-09-12 2001-09-12 A new iron chelate composition
PCT/SE2002/001657 WO2003022782A1 (fr) 2001-09-12 2002-09-12 Nouvelle composition de chelate de fer

Publications (1)

Publication Number Publication Date
EP1434751A1 true EP1434751A1 (fr) 2004-07-07

Family

ID=20285288

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02770358A Withdrawn EP1434751A1 (fr) 2001-09-12 2002-09-12 Nouvelle composition de chelate de fer

Country Status (3)

Country Link
EP (1) EP1434751A1 (fr)
SE (1) SE0103014D0 (fr)
WO (1) WO2003022782A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007148992A1 (fr) * 2006-06-19 2007-12-27 Gavin Frank Murdoch Composition végétale bénéfique
CN107879803A (zh) * 2017-11-27 2018-04-06 岳西县天泰化工有限责任公司 一种用氨基酸螯合微量元素水溶肥料
WO2020222134A1 (fr) * 2019-04-29 2020-11-05 Basf India Limited Libération prolongée de micronutriments
GB2583913B (en) * 2019-05-07 2021-08-04 Yara Uk Ltd Fertilizer particles comprising iron
CN111334220B (zh) * 2020-03-27 2021-07-06 深圳市盛元半导体有限公司 一种铜面黏着改质剂、制备方法及其应用

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2846832B1 (de) * 1978-10-27 1980-02-07 Hoechst Ag Spurenelementduengemittelpasten und Verfahren zu deren Herstellung
GB8807197D0 (en) * 1988-03-25 1988-04-27 Phosyn Group Ltd Iron chelate composition
US5221313A (en) * 1991-09-19 1993-06-22 Tennessee Valley Authority Micronutrient delivery systems using hydrophilic polyacrylamides
FR2808021B1 (fr) * 2000-04-20 2003-07-04 Synthron Compositions aqueuses a base de chelates de fer pour l'agriculture

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03022782A1 *

Also Published As

Publication number Publication date
SE0103014D0 (sv) 2001-09-12
WO2003022782A1 (fr) 2003-03-20

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