WO2013119108A1 - Engrais composite à libération contrôlée comprenant de la zéolite - Google Patents

Engrais composite à libération contrôlée comprenant de la zéolite Download PDF

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Publication number
WO2013119108A1
WO2013119108A1 PCT/NL2013/050058 NL2013050058W WO2013119108A1 WO 2013119108 A1 WO2013119108 A1 WO 2013119108A1 NL 2013050058 W NL2013050058 W NL 2013050058W WO 2013119108 A1 WO2013119108 A1 WO 2013119108A1
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WO
WIPO (PCT)
Prior art keywords
composite
zeolite
clinoptilolite
fertilizer
composite according
Prior art date
Application number
PCT/NL2013/050058
Other languages
English (en)
Inventor
Huib VAN DER STOK
Sofyan TAMARA
Original Assignee
United Troika B.V.
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 United Troika B.V. filed Critical United Troika B.V.
Publication of WO2013119108A1 publication Critical patent/WO2013119108A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C9/00—Fertilisers containing urea or urea compounds
    • 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
    • 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
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/80—Soil conditioners

Definitions

  • the present invention relates to a zeolite composite.
  • the present invention further pertains to the use of such a zeolite composite for controlled release of water and nutrients in crops production.
  • CR fertilizer controlled release fertilizers
  • CR fertilizer controlled release fertilizers
  • the gradual release of nutrient release from CR fertilizers may better coincide with plant needs, minimize leaching and improve fertilizer use efficiency.
  • Many different CR fertilizer types are available and products differ in both the technologies by which nutrients are contained and the environment stimulus for a nutrient release; generally, focus is on coating encapsulation.
  • such CR formulations often involve artificial components, and have little effect on water management.
  • WO 2005/075602 discloses a zeolite-based fertilizer composition using a zeolite built from clinoptilolite,, mordenite and smectite, of a kind described in its examples, which contains 5 - 20 % feldspar, rock-forming tectosilicate minerals. These numbers correspond with the amounts of feldspar present in zeolites presently marketed.
  • HU 212261 and SU 763310 describe the usefulness of zeolites together with fertilizer, but fail to describe the source of zeolites and to identify the role of feldspar and quartz in these fertilizers.
  • US Geological Survey USGS has experimented with zeolites applied to several different fertilizers including controlled-release nitrogen, controlled-release
  • the inventors have fulfilled that need and found that a modified zeolite composite comprising clinoptilolite and mordenite which appeared very suited for the purpose of controlled release of water and plant nutrients in agriculture, particularly in wet and dry land cultivation.
  • a zeolite composite comprising predominant amounts of clinoptilolite and significant amounts of mordenite can be modified to such extent that it advantageously affects its properties in terms of water retention and controlled release of plant nutrients.
  • Harvest yields were greatly improved compared with conventional N-fertilization, exemplified for potatoes in the attached experimental studies. A 20 % increase in yield was within reach.
  • a great deal of the advantageous properties is believed - without being restricted to any theory - to rest in the interplay of small-pore clinoptilolite and large-pore mordenite, and in the fact that the zeolite composition is substantially free from interfering minerals and components such as feldspar and quartz otherwise present in significant amounts in commercially available zeolites.
  • clinoptilolite such as obtained from Armenia or Rumania is analyzed to contain about 10 % quartz and about 10 to 15 % feldspar.
  • the clinoptilolite of the invention void of quartz and feldspar renders it more accessible to the active additives and improve the composition efficacy.
  • the composite may therefore interchangeably referred to as a 'biological' or 'natural' composite, indicating that it consists of ingredients which are environmentally friendly and involves naturally occurring materials only.
  • the modified zeolite composite is relatively inexpensive and long-lasting, increases soil fertility through repeated use, and releases water and nutrients to plants as they are needed, thereby eliminating pollution, inefficiencies, and it reduces the need for irrigation.
  • the invention thus pertains to a zeolite composite comprising clinoptilolite and mordenite, said composite further comprising activated charcoal, molasses, and binder, and optionally further minerals.
  • the invention also pertains to the use of such composite as controlled release soil modification or fertilizer. DETAILED DESCRIPTION OF THE INVENTION
  • the composite according to the invention comprises large amounts of zeolite materials, preferably at least 75 %, more preferably 80 - 95 %, most preferably 82 - 92 wt%, based on dry weight of the composite.
  • the term 'composite' or 'composite product' is intended to indicate that the zeolite constituent materials with different physical and chemical properties remain distinct at the macroscopic or microscopic scale within the finished product.
  • the further ingredients and water may be adsorbed or absorbed or otherwise comprised in the pores of the zeolite ingredients.
  • X-ray diffraction is used for zeolite
  • the product is preferably in granular form, preferably packaged in a plastic bag, sack or drum.
  • controlled release fertilizer composite indicates that the composite of the invention has both fertilizing properties and is able to maintain these fertilizing properties over extended periods when in use. It therewith distinguishes from commercially available fertilizer compositions comprising no means to preventing leaching into the soil.
  • zeolites are a subclass of crystalline porous silicates.
  • Clinoptilolite and mordenite are natural zeolites comprising a microporous arrangement of silica and alumina tetrahedra, the latter having a relatively high ratio of silicon to aluminum atoms.
  • mordenite and clinoptilolite are zeolites commercially available, either as blends or as individual zeolite powders. While a predominant part of the zeolites present in the composite is formed from clinoptilolite, is preferred that large amounts of mordenite are also present.
  • the composite preferably comprises more than 50 %, preferably more than 55 %, most preferably 55 - 70 wt% of clinoptilolite, based on the total dry weight of zeolite materials.
  • the clinoptilolite according to the invention preferably comprises less than 1 % of the sum of feldspar and quartz, more preferably less than 0.5 %; most preferably the clinoptilolite is subsantially free from feldspar and quartz, i.e. these are present in amounts below detection limits.
  • the composite preferably comprises at least 25 wt%, more preferably at least 30 wt%, most preferably 30 - 50 %, in particular 35 - 45 wt% of mordenite, based on the total dry weight of zeolite materials.
  • the composite comprises clinoptilolite and mordenite in a weight ratio between 1 : 1 and 3 : 1, preferably between 11 :9 and 7:3.
  • clinoptilolite and mordenite make up at least 90 wt%, more preferably more than 95 wt% of all zeolite materials in the composite. It is preferred that all zeolites present in the composition are naturally occurring zeolites, i.e. it is preferred that synthetic zeolites are excluded from the composite. In one embodiment, clinoptilolite and mordenite make up for all zeolite materials in the composite.
  • the zeolite comprising clinoptilolite and mordenite is preferably activited through heat treatment to increase the zeolite efficacy to take up the otther ingredients such as the activated charcoal, molasses, and binder, and optionally further minerals.
  • a suited heat treatment would involve grinding the zeolite composition to powdered form, and subjecting the powdered zeolite to a temperature of at least 100 °C for a period of at least 60 seconds, more preferably at least 2 minutes, prior to admixing the the zeolite with the fertilizer components. It is found that the heat-treated zeolite advantageously improves the slow-release properties of the composite.
  • the zeolite comrpising clinoptilolite and mordenite preferably comprises less than 1 wt% of the sum of feldspar and quartz, more preferably less than 0.5 wt%; even more preferably less than 0.1 wt%, based on the weight of the zeolite; in one embodiment, the amount of feldspar and quartz, if any, in the composite is less than 0.5 wt%, preferably less than 0.1 wt%, based on the weight of the composite, and more preferably the composite is subsantially free from feldspar and quartz, i.e. if present, these are present in amounts below detection limits.
  • the zeolite of the invention consists of clinoptilolite and mordenite, void from any other (clay) minerals such as quartz, bentonite and feldspar.
  • the zeolite composite may be characterized in terms of its mineral content to a great extent provided by the zeolite materials. It is preferred that the composite comprises at least 65 %, more preferably at least 70 %, most preferably at least 75 % of the sum of Si0 2 and A1 2 0 3 , based on dry weight of the composite. In one embodiment, the molar ratio of Si:Al is at least 3.0, more preferably 3.5 - 8, most preferably 4.0 - 6.0.
  • the zeolite composite advantageously comprises agricultural fertilizer providing nitrogen and phosphorous, valuable plant nutrients.
  • agricultural fertilizer providing nitrogen and phosphorous, valuable plant nutrients.
  • Through its advantageous and characterizing zeolite structure it enables slow and controlled release of such agricultural fertilizer into the soil, ensuring an ongoing supply of nutrients during plant growth.
  • Leaching is therewith controlled. It is preferred to include between 1 and 20 %, more preferably between 2 and 15 %, most preferably between 3 and 10 % of agricultural fertilizer, based on dry weight of the composite.
  • Soil fertilizers may be used as these are commercially available, although it is preferred to use renewable or natural soil fertilizers presently marketed.
  • Organic fertilizers are preferred.
  • the zeolites make it possible to use soluble fertilizers without the known disadvantages of leaching associated with such fertilizers.
  • a suitable source of nitrogen-providing fertilizer composition is livestock or domestic animal organic byproducts, including urea and manure.
  • phosphorous may additionally be provided as phosphoric acid and/or phosphates, and these contributions are considered incorporated in the term 'fertilizer' in the context of the invention.
  • the fertilizer composition may be rated in terms of N-P-K rating, reflecting the relative contents of nitrogen (N), phosphorous (P) and potassium (K) present in the fertilizer, and it rests within the skilled person's knowledge to determine which relative contributions of these nutrients are suited for cultivation purposes. climate, soil type and crop are for instance parameters to be considered.
  • the invention rests in the controlled release of the fertilizer rather than the relative contents of N, P and K of the fertilizer itself.
  • the composite further comprises activated carbon (or 'activated charcoal' or 'activated coal'; all used interchangeably), preferably in amounts of 1 - 5 wt% of the dry composite weight. Molasses are preferably added in amounts of 0.1 - 5 wt%, most preferably up to 3 wt% of the dry composite weight. It is preferred that the composite further comprises minerals in addition to the zeolite minerals, preferably at least Fe, Mn and Zn. It is preferred to include Fe, Mn and Zn in amounts of 0.1 - 3 wt%, more preferably 0.5 - 2 wt% of the dry composite weight.
  • the composite further comprises a natural binder, where the term "binder" means any suitable inorganic or organic material which can serve as matrix to bind the zeolite materials, to render the composite in preferred granular form.
  • a starch-based binder is preferred. With 'starch-based binder' it is understood starch or materials comprising starch in significant proportions, preferably at least 10 %, more preferably at least 20 %, most preferably at least 30 wt% starch (calculated per dry weight of the binder materials).
  • a suitable source is flour, may be preferred.
  • amounts of 0.1 - 5 wt%, more preferably 0.2 - 3 wt%, most preferably 0.3 - 2 wt% of binder is preferred.
  • the zeolite composite comprises 80 - 94 wt% of the above zeolites, 2 - 4 wt% activated carbon, 0.2 - 2 wt% molasses, 0.1 - 0.5 wt% Fe, 0.1 - 0.5 wt% Mn, 0.3 - 1 % Zn, 0.3 - 2 % binder and 3 - 10 % soil fertilizer
  • Quartz and feldspar are preferably present in an amount of less than 0.1 wt%, and more preferably are not detectable at all. The sum of the above constituents preferably amounts to 100 %.
  • the invention pertains to a kit of parts comprising (a) the zeolite materials as characterized above, and (2) a composition comprising agricultural fertilizer as described above, in order to arrive at a zeolite composite according to the invention when mixing both parts. It is thus possible to optimize the controlled release composition to the soil and crop requirements. Any remaining ingredients may be added to either part, although it is preferred to include any further minerals such as Mn, Fe and Zn to the fertilizer part (b). It is preferred to add a binder, as detailed above, in the admixing step.
  • the controlled release composite and kit are particularly useful for controlling agricultural soil fertilization, and for preventing or slowing down leaching - and thus wasting - of agricultural fertilizer into the soil.
  • the zeolite composite product according to the invention may be applied in amounts of 100 - 1000 kg/ha, more preferably 200 - 800 kg/hate composite or kit bring advantages to crops cultivation, for instance by increasing harvest yields.
  • a "crop" is a non-animal species or variety that is grown to be harvested as food, livestock fodder, fuel or for any other economic purpose.
  • Major world crops include maize (corn), wheat, rice, soybeans, hay, potatoes and cotton, but also palm trees (providing palm oil) and vegetables and fruits; and the CR composite and kit are believed to improve the yields in each of these crops.
  • tests with potatoes, palm trees and rice were shown to result in a harvest yield that improved with more than 20 %.
  • the attached potato study stands model. It it noted that the potato study also showed that the controlled release zeolite composition according to the invention is useful in controlling the growth of the potatoes, and helps preventing or reducing (toxic) greening of potatoes caused by light exposure before harvesting.
  • Example 1 composite composition
  • test areas were prepared in May for growing potatoes of the variety ' Seresta' . During growth the potassium content, harvest yield and basic weight of the potatoes was monitored for:
  • Test areas B and D were provided with UTCS-12 in amounts of about 500 kg/ha. Nitrogen fertilization at test areas C and D was carried out according to standard protocols. Seresta is a known early season variety.
  • test areas A and B both no nitrogen fertilization were less developed in terms of crops growth compared to the test areas C and D treated with nitrogen fertilizer.
  • test area D The basic weight of the potato variety Seresta with conventional nitrogen fertilization together with UTCS-12 (test area D) was significantly higher than observed for all other test areas, including that of test area C.
  • test areas were also studied for other potato deficiencies, such as surface defects, potato scab, rotting etc.. Again, potatoes harvested at test area D exhibited far better properties and less deficiencies than the others, also when compared to test area C. When harvesting, it was noticed that there was no greening for test area D. Where in other test areas there was a significant fraction of potatoes that was exposed to light and resulted in greening (i.e. rendering the potatoes toxic), it was found that no such defects arose for test area D.
  • test area D exhibited more controlled shape, thus rendering such potatoes more attractive for subsequent processing.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Cultivation Of Plants (AREA)
  • Fertilizers (AREA)

Abstract

La présente invention concerne un engrais composite à libération contrôlée comprenant au moins 7 % en poids de zéolite comprenant de la clinoptilolite et de la mordenite, ledit composite comprenant en outre un engrais agricole contenant de l'azote, du charbon actif, de la mélasse et une ou plusieurs substances liantes. Une étude expérimentale a démontré que la zéolite composite UTCS-12 selon l'invention améliorait les rendements de récolte d'environ 20 %.
PCT/NL2013/050058 2012-02-06 2013-02-05 Engrais composite à libération contrôlée comprenant de la zéolite WO2013119108A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL2008236 2012-02-06
NL2008236A NL2008236C2 (en) 2012-02-06 2012-02-06 Water and nutrient management in crops production.

Publications (1)

Publication Number Publication Date
WO2013119108A1 true WO2013119108A1 (fr) 2013-08-15

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NL (1) NL2008236C2 (fr)
WO (1) WO2013119108A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104115643A (zh) * 2014-06-27 2014-10-29 和县海豪蔬菜种植有限责任公司 一种白萝卜的栽培方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1253932A (zh) * 1999-10-29 2000-05-24 中国科学院沈阳应用生态研究所 长效复混肥添加剂
WO2002083740A1 (fr) * 2001-04-13 2002-10-24 Odore, Carlo Fertilisant azote a base d'uree enrobe de zeolite
WO2005075602A1 (fr) 2004-02-09 2005-08-18 Ballance Agri-Nutrients Limited Compositions d'engrais
EP1639886A1 (fr) * 2004-09-17 2006-03-29 Martini S.p.A. Procédé pour la préparation d'un substrat composite biodégradable pour la croissance de plantes avec propagation "gamique" et "agamique"
FR2929610A1 (fr) * 2008-04-02 2009-10-09 Serge Bensaid Engrais a base d'une matiere poreuse

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1253932A (zh) * 1999-10-29 2000-05-24 中国科学院沈阳应用生态研究所 长效复混肥添加剂
WO2002083740A1 (fr) * 2001-04-13 2002-10-24 Odore, Carlo Fertilisant azote a base d'uree enrobe de zeolite
WO2005075602A1 (fr) 2004-02-09 2005-08-18 Ballance Agri-Nutrients Limited Compositions d'engrais
EP1639886A1 (fr) * 2004-09-17 2006-03-29 Martini S.p.A. Procédé pour la préparation d'un substrat composite biodégradable pour la croissance de plantes avec propagation "gamique" et "agamique"
FR2929610A1 (fr) * 2008-04-02 2009-10-09 Serge Bensaid Engrais a base d'une matiere poreuse

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 200043, Derwent World Patents Index; AN 2000-483438, XP008110331 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104115643A (zh) * 2014-06-27 2014-10-29 和县海豪蔬菜种植有限责任公司 一种白萝卜的栽培方法

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