NL2008236C2

NL2008236C2 - Water and nutrient management in crops production.

Info

Publication number: NL2008236C2
Application number: NL2008236A
Authority: NL
Inventors: Huib Stok; Sofyan Tamara
Original assignee: Holding Company Belgie Nv
Priority date: 2012-02-06
Filing date: 2012-02-06
Publication date: 2013-08-08
Also published as: WO2013119108A1

Abstract

The invention pertains to a controlled release fertilizer composite comprising at least 7 wt% of zeolite comprising clinoptilolite and mordenite, said composite further comprising nitrogen-comprising agricultural fertilizer, activated coal, molasses, and one or more binder materials.In an experimental study it was shown that the zeolite composite UTCS-12 according to the invention improved harvest yields with about 20 %.

Description

Water and nutrient management in crops production

Field

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 5 nutrients in crops production.

Background of the invention

The availability of water and nutrients is an issue both in wet and dry land cultivation. Improper water and nutrient levels management is at the penalty of reduced harvesting. 10 Irrigation and fertilization are key in farming crops, to account for leaching of nutrients and water to lower grounds, outside the reach of the crops. At the same time, environmental concerns put restraints on copious use of water and fertilizer in crops production.

15 Nowadays scientists are engaged in the development of various delivery systems of fertilizers with an objective to control their release. Application of controlled release fertilizers (CR fertilizer) at the time of planting offers a means to improve the establishment of forest tree seedlings. As compared to conventional fertilizer, the gradual release of nutrient release from CR fertilizers may better coincide with plant 20 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. However, such CR formulations often involve artificial components, and have little effect on water management.

25

In the art there is however a continuous search for improving the controlled release of water and fertilizer components in a cost-effective, simple and environmentally-friendly manner. The ultimate goal is to develop a product that delivers water and nutrients at a rate matching the plant demand, thus improving crop yield and 30 minimizing the loss of water and nutrients due to leaching.

2

The US Geological Survey (USGS) has experimented with zeolites applied to several different fertilizers including controlled-release nitrogen, controlled-release phosphorous fertilizers, and in the release of trace nutrients (http://www.usgs.gov/tech-transfer/factsheets/94-066b.htmO. The experiments indicated that zeolite in soil can aid 5 in the release of some trace nutrients and in their uptake by plants. However, at the same time it is observed that many zeolites can be harmful as well as helpful to plant growth, and there is the need to find the appropriate zeolites during agricultural experimentation. Hitherto, in the art the search for such appropriate zeolites continues.

10 It is an object of the present invention to provide the use of an improved zeolite composition for controlled release of water and/or substances beneficial to plant growth.

Summary of the invention

The inventors have fulfilled that need and found that a modified zeolite composite 15 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.

The inventors have found that a zeolite composite comprising predominant amounts of 20 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 25 properties is believed - without being restricted to any theory - to rest in the interplay of small-pore clinoptilolite and large-pore mordenite.

All is achieved without the need for any artificial components. The composite may therefore interchangeably referred to as a ‘biological’ or ‘natural’ composite, indicating 30 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 3 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 5 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.

List of preferred embodiments 10 1. A controlled release fertilizer composite comprising at least 75 wt% of zeolite comprising clinoptilolite and mordenite, said composite further comprising nitrogen-comprising agricultural fertilizer, activated coal, molasses, and one or more binder materials.

15 2. The composite according to embodiment 1, comprising more than 50 %, preferably more than 55 % of clinoptilolite, based on the total dry weight of zeolite.

3. The composite according to embodiment 1 or 2, comprising clinoptilolite and mordenite in a weight ratio between 1:1 and 3:1, preferably between 11:9 and 7:3.

20 4. The composite according to any one of the preceding embodiments, wherein clinoptilolite and mordenite make up at least 90 wt%, more preferably more than 95 wt% of all zeolite materials.

25 5. The composite according to any one of the preceding embodiments, comprising between 1 and 20 %, preferably between 2 and 15 %, most preferably between 3 and 10 % of nitrogen-comprising agricultural fertilizer, based on dry weight of the composite.

30 6. The composite according to any one of the preceding embodiments, wherein said fertilizer comprises livestock or domestic animal organic byproducts, including urea and manure 4 7. The composite according to any one of the preceding embodiments, comprising 1 -5 wt% of said activated coal, 0.1-5 wt% of said molasses and/or 0.1-5 wt% of starch-based binder, preferably comprising 1-5 wt% of said activated coal, 0.1-5 wt% of said molasses and 0.1-5 wt% of starch-based binder, based on dry weight 5 of the composite.

8. The composite according to any one of the preceding embodiments, being in granulated form.

10 9. The composite according to any one of the preceding embodiments, comprising 80 - 94 wt% of zeolite comprising clinoptilolite and mordenite, 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 % nitrogen-comprising agricultural fertilizer, all numbers based on dry composite weight.

15 10. A kit of parts comprising: (a) zeolite composite comprising clinoptilolite and mordenite in a weight ratio between 1:1 and 3:1, preferably between 11:9 and 7:3; (b) nitrogen-comprising agricultural fertilizer.

20 11. Use of the composite according to any one of embodiments 1 - 9 or the kit of parts according to embodiment 10 for soil modification or fertilization, more particular for controlled release of water and nutrients in crops cultivation.

25 12. A method for cultivating crops, comprising sowing or planting the grains or seeds in soil which has been provided with the controlled release fertilizer composite according to any one of embodiments 1-9.

Detailed Description of the invention 30 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.

5

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 5 of the zeolite ingredients. In the art, X-ray diffraction is used for zeolite characterization purposes, considered to fall within the ambits of the skilled person’s knowledge. The product is preferably in granular form, preferably packaged in a plastic bag, sack or drum.

10 The term ‘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.

15

In the art, 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. Both mordenite and clinoptilolite are zeolites commercially available, either as 20 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 composite preferably comprises at least 25 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.

In one embodiment, the composite comprises clinoptilolite and mordenite in a weight ratio between 1:1 and 3:1, preferably between 11:9 and 7:3.In one embodiment, 30 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 6 zeolites are excluded from the composite. In one embodiment, clinoptilolite and mordenite make up for all zeolite materials in the composite.

Additionally or alternatively, the zeolite composite may be characterized in terms of its 5 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 SiOi and AI2O3, 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.

10

The zeolite composite advantageously comprises 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 15 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 20 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. Depending on the source, phosphorous may additionally be provided as phosphoric acid and/or phosphates, and these contributions are considered incorporated 25 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 30 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.

7

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 5 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 10 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 15 materials). A suitable source is flour, may be preferred. As a guide, amounts of 0.1 - 5 wt%, more preferably 0.2 - 3 wt%, most preferably 0.3 - 2 wt% of binder is preferred.

In one preferred embodiment, 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, 20 0.1 -0.5 wt% Mn, 0.3 - 1 % Zn, 0.3 - 2 % binder and 3 - 10 % soil fertilizer (including optionally added phosphates), all numbers based on dry composite weight. The sum of the above constituents preferably amounts to 100 %.

In one aspect, the invention pertains to a kit of parts comprising (a) the zeolite materials 25 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, 30 Fe and Zn to the fertilizer part (b). It is preferred to add a binder, as detailed above, in the admixing step.

8

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. As a guide, the zeolite composite product according to the invention may be applied in amounts of 100 - 1000 kg/ha, 5 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 pal trees (providing palm oil) and vegetables and fruits; 10 and the CR composite and kit are believed to improve the yields in each of these crops. The attached potato study stands model. It is noted that the same observations were made in a similar experimental study on palm trees.

Examples 15

Example 1 - composite compositionAA

Zeolite* 88.0 % activated carbon 3.0% natural nitrogen** 3.0% phosphoric acid** 3.5%

Molasses 0.5 %

Te 0.3 % ~Mn 0.3 % ~Zn 0.8 % natural binder * * * 0.6 % * comprising about 68 % clinoptilolite and 32 % mordenite ** provided as livestock organic waste to which phosphoric acid is added ***provided as flour 20 ^ will be marketed as ‘UTCS-12’ 9

Comparative experimental study I

Four 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: 5 (A) a test area without any fertilization (control); (B) a test area treated with the composite according to example 1; (C) a test area treated with conventional nitrogenous fertilization; and (D) a test area treated with both the composite according to example 1 and conventional nitrogenous fertilization.

10

The ‘composite according to example 1’ will be referred to herein below as ‘UTCS-12’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.

15

From the start onwards the crops were analyzed at fixed intervals. At the first assessment, after one month, there was a clear difference: 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.

20

Effects of UTCS-12 became apparent after 3 months, in the second part of summer. The potatoes of test area C showed symptoms of potassium deficiencies (in Dutch ‘kaligebrek’). These deficiencies became more pronounced in time.

25 At harvesting near the end of October significant differences were observed between those test areas A and B not fertilized with nitrogenous fertilizer compared to test areas C and D. Positive effects were also observed when using UTCS-12 together with the fertilizer. Harvest yields were significantly improved, i.e. by about 20 %, for test area D.

Differences were also observed in starch content, measured in terms of underwater weight, or ‘OWG’ (short for Dutch ‘onderwatergewicht’). The unfertilized test areas A and B showed higher OWG than the fertilized areas C and D. This parameter is 30 10 indicative for the immature crops growth. For a combination of field weight (‘veldgewicht’) and OWGto the so called basic weight (‘basisgewicht’) there were significant differences between the various areas, and improvements were observed when using UTCS-12. The basic weight of the potato variety Seresta with conventional 5 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.

The various 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 10 better properties and less deficiencies than the others, also when compared to test area C.

Comparative experimental study II

The above results were obtained with test areas on ‘lichte veenkoloniale dalgrond’, a 15 wetland. The same results and conclusions were however reproduced for test areas based on marine clay (in Dutch ‘zeeklei’), at a different location. In the soil the zeolite composite according to the invention is thus believed to absorb plant nutrients and water, and prevent leaching. These plant nutrients and water become available to the crops in a controlled way.

20

Claims

Controlled-release fertilizer or fertilizer composition comprising at least 75% by weight of zeolite comprising clinoptilolite and mordenite, the assembly further comprising nitrogen-containing agricultural fertilizer or agricultural fertilizer, activated carbon, molasses, and one or more binder materials.

The composition of claim 1, comprising more than 50% by weight, preferably more than 55% by weight of clinoptilolite, based on the zeolite dry weight. 10

Composition according to claim 1 or 2, comprising clinoptilolite and mordenite in a weight ratio between 1: 1 and 3: 1, preferably between 11: 9 and 7: 3.

4. A composition according to any one of the preceding claims, wherein the clinoptilolite and mordenite make up at least 90% by weight, preferably more than 95% by weight of all zeolite materials.

Composition according to any one of the preceding claims, comprising between 1 and 20% by weight, preferably between 2 and 15% by weight, most preferably between 3 and 10% by weight, of nitrogen-containing agricultural fertilizer or agricultural fertilizer, based on the dry weight of the composition.

6. A composition according to any one of the preceding claims, wherein the nitrogen-containing agricultural fertilizer or agricultural fertilizer comprises organic waste from livestock or from domestic animals, including urea and manure.

Composition according to any one of the preceding claims, comprising 1 to 5% by weight of activated carbon, 0.1 to 5% by weight of molasses and / or 0.1 to 5% by weight of starch-containing binding material, preferably 1 to 5% by weight of activated carbon, 0 , 1-5% by weight of molasses and 0.1 to 5% by weight of starch-containing binding material, based on the dry weight of the composition.

A composition according to any one of the preceding claims, in the form of granules.

A composition according to any one of the preceding claims, comprising 80 - 94% by weight of zeolite comprising clinoptilolite and mordenite, 2-4% by weight of activated carbon, 0.2 - 2% by weight molasses, 0.1 - 0.5% by weight Fe, 0 , 1 - 0.5 wt% Mn, 0.3 - 1 wt% Zn, 0.3 - 2 wt% binding material and 3 - 10 wt% nitrogen-containing agricultural fertilizer or agricultural fertilizer, based on the dry weight of the composition.

An assembly comprising: (a) zeolite comprising clinoptilolite and mordenite in a weight ratio between 1: 1 and 3: 1, preferably between 11: 9 and 7: 3; (b) nitrogen-containing agricultural fertilizer or agricultural fertilizer.

11. Use of the composition according to any of claims 1-9 or the assembly according to claim 10 for soil improver or soil fertilization, preferably for controlled release of water and nutrients in arable farming.

A method for growing crop, comprising planting or sowing in a soil provided with the controlled release composition according to any of claims 1-9. 20