阅读说明：本技术 油基组合物用于在尿素基肥料施用中减少氨挥发的用途 (Use of oil-based compositions for reducing ammonia volatilization in urea-based fertilizer applications ) 是由 斯图尔特·沃德 安德烈斯·费利佩·兰格尔·贝切拉 安科·克瓦斯特 安娜·加吉 于 2020-03-17 设计创作，主要内容包括：包含含硼颗粒的油基组合物在将尿素基肥料颗粒施用于土壤时减少氨挥发的用途,其中在施用于土壤之前,尿素基肥料颗粒包覆有包含含硼颗粒的油基组合物；主要特点是,含硼颗粒主要由在25℃下小于10g/L的低水溶性材料组成；并且至少95％的含硼颗粒通过激光衍射分析测量具有在0.1和60um范围内的粒径。用包含含硼颗粒的油基组合物包覆的尿素基肥料颗粒在将尿素基肥料颗粒施用于土壤时减少氨挥发的用途,其特征在于含硼颗粒基本上由在25℃下小于10g/L的低水溶性材料组成；并且至少95％的含硼颗粒通过激光衍射分析测量具有0.1和60um范围内的粒度。(Use of an oil-based composition comprising boron-containing particles to reduce ammonia volatilization upon application of urea-based fertilizer particles to soil, wherein prior to application to soil, the urea-based fertilizer particles are coated with the oil-based composition comprising boron-containing particles; is mainly characterized in that the boron-containing particles mainly consist of low water-soluble materials with the temperature of 25 ℃ less than 10 g/L; and at least 95% of the boron-containing particles have a particle size in the range of 0.1 and 60um as measured by laser diffraction analysis. Use of urea-based fertilizer particles coated with an oil-based composition comprising boron-containing particles to reduce ammonia volatilization upon application of the urea-based fertilizer particles to soil, characterized in that the boron-containing particles consist essentially of a low water-soluble material of less than 10g/L at 25 ℃; and at least 95% of the boron-containing particles have a particle size in the range of 0.1 and 60um as measured by laser diffraction analysis.)

1. Use of an oil-based composition comprising boron-containing particles to reduce ammonia volatilization upon application of urea-based fertilizer particles to soil, wherein said urea-based fertilizer particles are coated with an oil-based composition comprising boron-containing particles prior to application of said urea-based fertilizer particles to soil;

wherein said boron-containing particles consist essentially of a low water-soluble material less than 10g/L at 25 ℃; and at least 95% of the boron containing particles have a particle size in the range of 0.1 and 60 μm as measured by laser diffraction analysis.

2. Use of urea-based fertilizer particles coated with an oil-based composition comprising boron-containing particles to reduce ammonia volatilization upon application of the urea-based fertilizer particles to soil,

wherein said boron-containing particles consist essentially of a low water-soluble material less than 10g/L at 25 ℃; and at least 95% of the boron containing particles have a particle size in the range of 0.1 and 60 μm as measured by laser diffraction analysis.

3. Use according to any one of claims 1 to 2, wherein the boron-containing particles consist essentially of colemanite.

4. Use according to any one of claims 1 to 3, wherein the boron-containing particles comprise from 30 to 80% by weight, more preferably from 50 to 80% by weight, of the oil-based composition.

5. Use according to any one of claims 1 to 4, characterized in that at least 95% of the boron-containing particles have a size in the range of 0.1 to 50 μm.

6. Use according to any one of claims 1 to 5, wherein the oil in the oil-based composition is selected from natural oils, mineral oils, synthetic oils or any mixture of two or more of the above oils.

7. Use according to claim 6, wherein the natural oil in the oil-based composition is a vegetable oil.

8. Use according to any one of claims 1 to 7, wherein the oil-based composition further comprises one or more of a dispersant, a rheological agent, a thickener, an anti-settling agent and/or a colorant material.

9. Use according to any one of claims 1 to 8, characterized in that said urea-based fertilizer granules are coated with less than 1% by weight, more preferably with less than 0.6% by weight, of an oil-based composition.

10. Use according to any one of claims 1 to 9, wherein the urea-based fertilizer granules are selected from urea, urea calcium sulphate (UCaS), urea calcium nitrate (UCaN), urea magnesium nitrate (UMgN), urea calcium phosphate (UCaP), urea magnesium phosphate (UMgP), urea calcium superphosphate (USP), urea calcium ammonium nitrate (UCaN), Urea Ammonium Sulphate (UAS), urea phosphoric acid, Urea Ammonium Phosphate (UAP), urea potassium salt (UK), urea-based NPK fertilizer granules and mixtures thereof.

11. Use according to any one of claims 1 to 10, characterized in that the fertilizer granule further comprises any secondary nutrient calcium, magnesium, sulphur and/or any source of micronutrients boron, copper, iron, manganese, molybdenum and zinc and mixtures thereof.

Technical Field

The present invention relates to the use of an oil-based composition for reducing ammonia volatilization when applying urea-based fertilizers in soil. The invention also relates to the use of coated urea-based fertilizer particles for reducing ammonia volatilization when applying urea-based fertilizers in soil.

Background

Nitrogen (N) is one of the most important nutrient elements of plants. It is used to construct amino acids, proteins, enzymes (such as chlorophyll) and any other important components of plants or crops.

Plants cannot fix nitrogen from the atmosphere; they rely on the roots to remove Nitrate (NO) from the soil₃ ^-) And ammonium (NH)₄ ⁺) The ionic form absorbs the desired nitrogen. Although all soils contain some nitrogen, farmers often must provide their crops with an additional source of nitrogen to ensure optimal growth and high yield. Fertilizers are the most common method of providing supplemental nitrogen, and there can be two sources: organic (e.g., animal feces) or mineral. Mineral fertilizers can contain nitrogen in three different forms: urea, ammonium salts and nitrates. Today, urea is the most common source of nitrogen in mineral fertilizers because of its high nitrogen content (46% by weight) and low cost. However, urea is difficult to absorb by plants, and it is converted to nitrate or ammonium ions in soil for use by plants.

Urease is a natural enzyme present in all soils that catalyses the conversion of urea to carbamic acid which is then broken down into ammonia and carbon dioxide. At this stage ammonia, a volatile gas, needs to react with water to form ammonium ions, otherwise a large amount of N (30% of the total N content added as urea) is lost by atmospheric evaporation, depending on soil type, water content, pH, climate, etc.

A known method to reduce ammonia volatilization is to reduce urease activity in the soil. When urea is converted to ammonia at a low rate, the conversion to ammonium is more efficient and less ammonia is lost to the atmosphere. A known method of reducing urease activity is to add urease inhibitors to the fertilizer granules. The inhibitor is released into the soil with the urea, reducing urease activity.

Urease inhibitors have been studied intensively and several families of compounds have been disclosed. In addition to the inhibitory effect, these products must be non-toxic to plants, active at low concentrations, stable for long periods of time and compatible with urea fertilizer formulations. One of the most popular classes of urease inhibitors is the phosphoric triamides, found in the mid 80 s (US 4,530,714). Among this family, n-butyl thiophosphoric triamide (nBTPT) is currently the most commonly used urease inhibitor. The compound does not have any inhibitory effect on itself, but is slowly oxidized to N- (N-butyl) triammonium phosphate (nBPT), thereby inhibiting urease.

Fertilizer compositions containing urease inhibitors, mixed with fertilizers or added as coatings, are now well known in the agricultural field. However, the stability of inhibitors in these compositions over time is limited, especially those containing sulfate ions, such as urea ammonium sulfate fertilizer.

Furthermore, it has recently been shown that nBTPT may actually be toxic to plants (front. plant Sci 6:1007 and front. plant Sci 7:845), and therefore the use of this compound may be questioned in the future. Sulfur is one of the secondary nutrients of plants. Modern fertilization practices require the addition of sulfur due to intensive agriculture and industry to reduce sulfur emissions in the air and subsequent supply to the ground by rain.

Good agricultural practice typically requires a nitrogen to sulphur ratio of 10/1 to 5/1 to meet crop demand, for example 150kg nitrogen per hectare per year and 30kg sulphur per hectare per year.

The lack of sulfur results in lower crop quantity and quality, and is generally reflected in protein content and type. Sulfur is indeed a major element entering cellular chemistry in the form of molecules such as amino acids (cysteine, methionine, etc.). It is also a catalyst for photosynthesis and, in some cases, can improve the fixation of atmospheric nitrogen.

Typically, sulphur is applied to the soil in the form of elemental sulphur, either as a compound such as ammonium sulphate, ammonium bisulphate, thiosulphate, sulphide or gypsum, or in combination with other fertiliser materials such as urea, for example a physical mixture of urea and ammonium sulphate, or a co-particulate material of urea and ammonium sulphate, the latter hereinafter being referred to as urea ammonium sulphate, abbreviated to UAS.

It is known that the introduction of boron sources, such as borax or boric acid, can reduce the ammonia emissions produced by the decomposition of urea in the soil.

Us patent application 2012/067094 discloses a fertilizer comprising a source of boron (boric acid or borax) and urea. The boron source is mixed with a binder and the resulting mixture is granulated. The obtained granules were then coated with urea. Alternatively, the boron source may be added to the urea melt and granulated to obtain homogeneous urea granules containing the boron source. The final granules contain 0.3% to 5% by weight boron and release less ammonia when applied to soil than standard urea.

Us patent 3,565,599 discloses homogeneous urea granules comprising 4-8% by weight of a boron source, a metal borate or boric acid and a hydrophobic substance. The boron source is used as urease inhibitor to reduce ammonia volatilization.

WO patent application 2017/024405 discloses a method for reducing ammonia volatilization by providing urea granules coated with a plant available boron source to plants. The boron source may be potassium borate, disodium octaborate tetrahydrate, potassium tetraborate tetrahydrate, boric acid and mixtures thereof. The urea pellets were either dry coated with the boron source in powder form or first coated with 0.5% by weight rapeseed oil and finally coated with the boron source in powder form. The final boron content is 0.1 to 2.5% by weight of the particles, and the examples disclosed in the application contain 1.25 to 1.35% by weight of boron.

The mechanism by which the water-soluble boron source reduces ammonia volatilization is not known, but it is believed that boron inhibits the growth of urease-producing microorganisms and/or directly inhibits urease.

Disclosure of Invention

According to one aspect of the invention, the use of an oil-based composition comprising boron-containing particles for reducing ammonia volatilization when urea-based fertilizer particles are applied to soil, wherein the urea-based fertilizer particles are coated with the oil-based composition comprising boron-containing particles prior to their application to soil. The application is mainly characterized in that the boron-containing particles mainly comprise low water-soluble materials with the temperature of 25 ℃ less than 10 g/L; at least 95% of the boron-containing particles have a particle size in the range of 0.1 to 60 μm as measured by laser diffraction analysis.

According to another aspect, there is provided the use of urea-based fertilizer particles coated with an oil-based composition comprising a boron-containing particle for reducing ammonia volatilization when the urea-based fertilizer particles are applied to soil. The application is mainly characterized in that the boron-containing particles mainly comprise low water-soluble materials with the temperature of 25 ℃ less than 10 g/L; at least 95% of the boron containing particles have a particle size in the range of 0.1-60 μm as measured by laser diffraction analysis.

Detailed Description

Unless defined otherwise, all terms, including technical and scientific terms, used in disclosing the invention, have the meaning commonly understood by one of ordinary skill in the art to which this invention belongs. By way of further guidance, definitions of terms are included to better understand the teachings of the present invention.

All references cited in this specification are herein deemed to be incorporated by reference in their entirety.

As used herein, the following terms have the following meanings:

as used herein, the terms "a", "an" and "the" refer to both the singular and the plural referents unless the context clearly dictates otherwise. For example, "a compartment" refers to one or more compartments.

As used herein, "about" refers to a measurable value, such as a parameter, amount, duration, etc., intended to encompass variations of +/-20% or less, preferably +/-10% or less, more preferably +/-5% or less, even more preferably +/-1% or less, and still more preferably +/-0.1% or less and from the stated value such variations are suitable for the disclosed invention up to now. It should be understood, however, that the value to which the modifier "about" refers is also specifically disclosed per se.

As used herein, "comprising," "including," and "comprises" are synonymous with "including," "includes," "including," or "containing," "comprises," and "comprising," and are open-ended terms that include or specify the presence of, for example, components, and do not exclude or preclude the presence of additional, non-recited components, features, elements, components, steps, or groups thereof, as known in the art or disclosed herein.

The recitation of numerical ranges by endpoints includes all numbers and fractions subsumed within that range, as well as the recited endpoint.

Unless otherwise defined, the expressions "weight%", "weight percent", "% w/w", "wt%" or "% wt" herein and throughout the specification refer to the relative weight of each component relative to the total weight of the formulation.

The present disclosure provides for the use of an oil-based composition comprising boron-containing particles to reduce ammonia volatilization upon application of urea-based fertilizer particles to soil, wherein the urea-based fertilizer particles are coated with the oil-based composition comprising boron-containing particles prior to their application to soil. The application is mainly characterized in that the boron-containing particles mainly comprise low water-soluble materials with the temperature of 25 ℃ less than 10 g/L; and at least 95% of the boron-containing particles have a particle size in the range of 0.1-60 μm as measured by laser diffraction analysis.

It has been surprisingly found that boron sources comprising materials with low water solubility (less than 10g/L at 25 ℃) reduce ammonia volatilization better than other boron sources with high water solubility. In order to obtain the best effect on ammonia volatilization it was found that at least 95% of the boron containing particles need to be in the size range of 0.1-60 μm. In particular, 95% of the particles may have a size in the range of 0.1-55 μm. More specifically, 95% of the particles may have a size in the range of 0.1-50 μm. Even more particularly, 100% of the particles may have a size in the range of 0.1-50 μm. Since boron reduces ammonia volatilization by inhibiting microbial or enzymatic growth, it is expected that boron sources with high water solubility will be more effective than those with low water solubility.

There are a variety of particle size measurement techniques. Laser diffraction analysis was found to be a suitable technique for measuring boron-containing particles used in the present invention. Laser diffraction analysis is a well-known technique in the field of particle size measurement. This analysis provides a size distribution curve of the particles contained in the sample. Based on this, it is relatively simple to characterize a material by a percentage of particles having a particular size range.

The oil-based composition comprising the boron-containing particles may be added to the fertilizer particles by any conventional means, such as spraying.

According to another aspect, there is provided the use of urea-based fertilizer particles coated with an oil-based composition comprising a boron-containing particle for reducing ammonia volatilization when the urea-based fertilizer particles are applied to soil. The application is mainly characterized in that the boron-containing particles mainly comprise low water-soluble materials with the temperature of 25 ℃ less than 10 g/L; and at least 95% of the boron-containing particles have a particle size in the range of 0.1-60 μm as measured by laser diffraction analysis.

According to one embodiment, the boron-containing particles consist essentially of colemanite. Colemanite is a naturally occurring boron-containing mineral with Ca as the chemical component₂B₆O₁₁·5H₂And O. Its water solubility is low (8 g/L at 25 ℃), while the solubility of boric acid and of the sodium and potassium borates is much higher: boric acid (47g/L), borax (51g/L), disodium octaborate tetrahydrate (223g/L), and potassium tetraborate tetrahydrate (158 g/L).

The colemanite particles may be purchased directly from commercial suppliers of the desired grade, such as Etimine, or may be purchased in sizes larger than desired and the particles micronized using suitable techniques, such as jet milling or bead milling. Bead milling has been found to be particularly suitable for providing colemanite particles having the desired dimensions of the present invention.

According to one embodiment, the boron-containing particles comprise 30 to 80% by weight of the oil-based composition, in particular the boron-containing particles comprise 50 to 80% by weight of the oil-based composition. Achieving as high a loading of boron-containing particles as possible in oil-based compositions is advantageous as it allows a sufficiently high boron addition to the fertilizer particles without overloading the fertilizer particles with oil, which can make the final product sticky and difficult to handle. The loading may depend on the other components used in the composition, such as the type of carrier oil, the type of dispersant, and the like.

According to one embodiment, the oil used in the composition may be any suitable natural, mineral or synthetic oil, such as a mineral white oil, but it is preferred to use an environmentally acceptable oil, such as a vegetable oil. Suitable vegetable oils include rapeseed oil, soybean oil, sunflower oil, linseed oil, castor oil or other similar vegetable oils. Other oils, such as methylated oils or modified vegetable oils, can also be used, but water-miscible materials cannot be used. In one embodiment, the oil contained in the oil-based composition is a mixture of two or more of the above oils.

According to one embodiment, the natural oil in the oil-based composition may be a vegetable oil. Surprisingly, vegetable oils, such as rapeseed oil, proved to be a better oil for dispersing the boron-containing particles than mineral white oil.

According to one embodiment, the oil-based composition comprising boron-containing particles may comprise one or more of a dispersant, a rheological agent, a thickener, an anti-settling agent and/or a colorant. It may be desirable for the oil-based composition to have good stability over time to allow storage, and therefore the boron-containing particles must be prevented from rapidly settling out of suspension. Suitable rheological, thickening and antisettling agents include clays such as sepiolite, bentonite, attapulgite, hectorite, palygorskite and organically modified clays; a polyurethane; a polyurea; hydrophilic fumed silica (hydrophilic fumed silica); hydrophobic fumed silica (hydrophic fumed silica); gas phase mixed oxides (fumed mixed oxides).

Colorants (dyes or pigments) may be added to the formulation to help monitor the coating process and enhance the physical appearance of the final fertilizer product. Examples of suitable classes of pigments include, but are not limited to, phthalocyanine blue (e.g., CI pigment blue 15, 15:1, 15:2, 15:3, 15:4) and aluminum chloro phthalocyanine (e.g., CI pigment blue 79); ultramarine blue; red, yellow and green iron oxides.

According to one embodiment, the oil-based composition comprising the boron-containing particles comprises less than 1.0% w/w of the final fertilizer particle. In particular, the oil-based composition comprises less than 0.8% w/w of the final particle. More particularly, the oil-based composition comprises less than 0.6% w/w of the final particle.

To achieve a satisfactory reduction in ammonia volatilization, high boron loadings are required. However, if the loading of the oil-based composition is too high, the physical properties of the fertilizer granules, such as granule strength, anti-caking properties, are reduced, and it is therefore important to balance these aspects.

According to one embodiment, the urea-based fertilizer granule may be selected from urea, urea calcium sulfate (UCaS), urea calcium nitrate (UCaN), urea magnesium nitrate (UMgN), urea calcium phosphate (UCaP), urea magnesium phosphate (UMgP), urea calcium superphosphate (USP), urea calcium ammonium nitrate (UCaN), Urea Ammonium Sulfate (UAS), urea phosphate, Urea Ammonium Phosphate (UAP), urea potassium salt (UK), urea-based NPK fertilizer granules, and mixtures thereof. Among the various nutrients required by plants, urea contains only one nutrient N. The use of fertilizer granules containing multiple nutrients can be advantageous because it reduces the number of applications required to provide all of the nutrients required by a plant or crop. It may also be advantageous to supply nitrogen to the plant using two different nitrogen sources. Urea is not immediately available to plants and so a nitrogen source in the form of ammonium or nitrate ions may provide an advantage. UAS is a well-known urea-based fertilizer and is widely used today. It provides nitrogen, urea and ammonium, as well as sulfur, which is a secondary nutrient, in two different forms. The UAS can provide urea and ammonium sulfate in different ratios to suit the particular needs of the plant.

According to one embodiment, the fertilizer granule may comprise any secondary nutrient calcium, magnesium, sulphur and/or any source of micronutrients boron, copper, iron, manganese, molybdenum and zinc and mixtures thereof. Each of these nutrients plays a critical role in the growth cycle of the crop and may need to be supplied at some point in the growing season. However, plants require lower quality of each nutrient than the three major nutrients.

The calcium content of the mineral fertilizer granules may be from about 0 to about 24 wt% (expressed as CaO).

The magnesium content of the mineral fertilizer granules may be about 0 to 10 wt%, in particular about 0.5 to about 10 wt% (expressed as MgO).

The sulphur content of the mineral fertilizer granules may be up to 40 wt%, in particular may be about 5 to 40 wt% (expressed as SO)₃)。

The boron content of the mineral fertilizer granules may be about 0 to 0.5 wt%, in particular may be at most 0.25 wt%. If present, the boron content may be at least 0.01 wt%.

The copper content of the mineral fertilizer granules may be from about 0 to about 1.0 wt%, in particular up to 0.6 wt%. If present, the copper content may be at least 0.005 wt%.

The iron content of the mineral fertilizer granules may be from about 0 to about 1.5 wt%, in particular up to 0.8 wt%. If present, the iron content may be at least 0.05 wt%.

The manganese content of the mineral fertilizer granules may be from about 0 to about 1.5 wt%, in particular up to 0.8 wt%. If present, the manganese content may be at least 0.02 wt%.

The molybdenum content of the mineral fertilizer particles may be from about 0 to about 1.0 wt%, in particular up to 0.1 wt%. If present, the manganese content may be at least 0.002 wt%.

The zinc content may be from about 0 to about 1.0 wt.%, in particular up to 0.5 wt.%. If present, the zinc content may be at least 0.01 wt%.

Experiment of

Example 1:

fertilizer granules consisting of urea ammonium sulphate with an N content of 40% by weight and an S content of 5.5% by weight were coated with an oil-based composition comprising boron-containing granules. Five different boron sources were investigated: boric acid, 45 μm colemanite (100% of the particles having a size of less than 50 μm), 75 μm colemanite (82% of the particles having a size of less than 75 μm), disodium octaborate and zinc borate. The oil-coated only sample served as a control. The coated fertilizer granules were placed on two different soils with different pH values. The air flow was directed through an Erlenmeyer vessel fitted with fertilizer on the pre-incubation soil and further through a vessel fitted with a boric acid trap. The ammonia lost from the fertilizer is absorbed by boric acid and the rate of ammonia absorption can be measured by titration of the remaining boric acid. Ammonia volatilization was measured at four time points (after 3, 7, 10 and 14 days, respectively). The ammonia volatilization amounts measured are summarized in table i (soil pH 6.2) and table ii (soil pH 7.6). In both cases, the sample coated with 45 μm colemanite showed the best reduction of ammonia volatilization.

Table i: ammonia loss in soil at pH 6.2 (expressed as a percentage of nitrogen application)

Coating of	3 days	7 days	10 days	14 days
					Oil	0.29	2.72	5.70	7.49
Oil + boric acid	0.21	1.74	3.95	5.66
					Oil + colemanite (45 μm)	0.16	1.46	3.28	5.00
Oil + colemanite (75 μm)	0.28	1.85	4.58	6.32
					Oil + disodium octaborate	0.21	1.61	4.43	6.07
Oil plus Zinc Borate	0.12	1.70	3.69	5.21

Table ii: ammonia loss in soil at pH 7.6 (expressed as a percentage of nitrogen application)

Product(s)	3 days	7 days	10 days	14 days
					Oil	1.82	5.78	7.53	8.08
Oil + boric acid	1.09	5.16	6.40	7.02
					Oil + colemanite (45 μm)	1.,05	3.46	4.55	4.94
Oil + colemanite (75 μm)	1.47	5.45	7.22	7.70
					Oil + disodium octaborate	1.92	6.59	8.26	8.77
Oil plus Zinc Borate	1.35	5.68	6.95	7.56

Example 2:

fertilizer granules consisting of urea ammonium sulphate with an N content of 40% by weight and an S content of 5.6% by weight were coated with an oil-based composition comprising 45 μm of colemanite (100% of the granules have a size below 50 μm). Another series of granules with the same fertilizer composition was coated with the same oil as the first series, without any colemanite. Another series of granules with the same fertilizer composition was used without coating. The fertilizer granules were spread on three different soils with different pH values (6.2, 6.4 and 7.6). The air flow was directed through an Erlenmeyer vessel fitted with fertilizer on the pre-incubation soil and further through a vessel fitted with a boric acid trap. The ammonia lost from the fertilizer is absorbed by boric acid and the rate of ammonia absorption can be measured by titration of the remaining boric acid. Ammonia volatilization was measured 14 days after fertilization. The results (in wt% of N volatilized) are set forth in Table III. On all three soils, particles coated with an oil-based composition comprising 45 μm of colemanite showed a reduction in ammonia volatilization.

Table III: ammonia losses in different soils (expressed as a percentage of nitrogen application)

Particle coating	pH of soil is 6.2	pH of soil is 6.4	pH of soil 7.6
				Is free of	7.37	7.54	15.07
Oil	7.28	8.09	13.77
				Oil and colemanite 45 μm	5.77	6.78	13.68