阅读说明：本技术 用于制备包含替代性硼源的肥料颗粒的方法 (Method for preparing fertilizer granules comprising alternative boron sources ) 是由 R.穆拉图 A.梅斯塔德 于 2018-02-26 设计创作，主要内容包括：本公开涉及用于制备包含替代性硼源的肥料颗粒的方法。发现可将某些硬硼钙石和硼钠钙石粉末在造粒前不久供应至肥料熔体,而基本上没有溶解到该熔体中。因此,由该熔体制备的肥料颗粒可含有可忽略的量或不可检测水平的硼酸钠或硼酸。此外,该肥料颗粒可以是均质的,这对于供应硼的肥料而言是合意的。还发现该肥料颗粒可以与五水硼砂相当的比率向植物供应硼。(The present disclosure relates to methods for making fertilizer granules comprising an alternative boron source. It was found that certain colemanite and ulexite powders can be supplied to the fertilizer melt shortly before granulation without substantial dissolution into the melt. Thus, fertilizer granules prepared from the melt may contain negligible or undetectable levels of sodium borate or boric acid. Furthermore, the fertilizer granules may be homogeneous, which is desirable for fertilizers supplied with boron. It has also been found that the fertilizer granules can supply boron to plants at a rate comparable to borax pentahydrate.)

1. A process for preparing a fertilizer granule comprising the steps of:

a) Forming a fertilizer melt comprising nitrate, wherein the fertilizer melt is an NPK melt or a calcium nitrate melt;

b) Adding to the melt a boron source in the form of colemanite or ulexite particles having a median particle size in the range of1 to 100 μm in such a way that

-if the fertilizer melt is an NPK melt, the colemanite particles or the colemanite particles are in contact with the fertilizer melt for less than 100 seconds;

Or

-if the fertilizer melt is a calcium nitrate melt, the colemanite granules or the colemanite granules are in contact with the fertilizer melt for less than 600 seconds;

c) And granulating the homogenized fertilizer granules from the prepared homogenized fertilizer melt.

2. The method of claim 1, wherein the nitrate salt is ammonium nitrate.

3. A method according to any one of claims 1 to 2, wherein the melt is an NPK fertilizer melt and the water content of the melt is less than 3% w/w.

4. The method of any one of claims 1 to 2, wherein the fertilizer melt comprises more than 70% w/w calcium nitrate and the water content of the melt is less than 20% w/w.

5. The method of any one of claims 1 to 4, wherein the temperature of the melt upon addition of the colemanite particles or the colemanite particles is in the range of 100 ℃ to 180 ℃.

6. the method of claim 5, further comprising the step of coating the granulated particles.

7. Particles prepared by the method according to any one of claims 1 to 6.

8. The particle of claim 7, comprising less than 0.1% w/w boron in the form of sodium borate or boric acid.

Brief description of the drawings:

Figure 1 shows the boron availability of 5 different NPK fertilizer compositions.

Figure 2 shows the boron availability of 5 different calcium nitrate fertilizer compositions.

FIG. 3 shows the boron content of Canola (Canola) plants after 21 days.

Detailed description of the invention

The present disclosure relates to novel fertilizer granules, which can be prepared by melt granulation. Melt granulation is the most common industrial process for preparing fertilizer granules. Melt granulation typically includes a step involving heating an aqueous mixture containing a fertilizer salt to produce a fertilizer melt. Optionally, the fertilizer melt may be produced by the exothermic neutralization of a mineral acid with ammonia. As used herein, a fertilizer melt is a fluid comprising fully and/or partially dissolved or melted fertilizer salt, which contains a low water content. Accordingly, the fertilizer melt may be solid at ambient temperature, but liquid at elevated temperatures. Water may be evaporated from the fertilizer melt prior to the droplet generation step. The droplet generating step may comprise spraying the fertilizer melt through a nozzle. The droplets can then be solidified by various well-known methods. For example, granulation (pelletizing) is a type of melt granulation process that can produce fairly uniform spherical particles by solidifying droplets as they fall through a cooling fluid. Other examples of melt granulation processes include spheroidisation, pan granulation, drum granulation and cooling belt techniques. For the melt granulation process, it is beneficial to produce a composition having a melting point at a relatively low temperature (but significantly higher than ambient temperature). Subsequently, the solidification of the granules from the fertilizer melt may be promoted by cooling via ambient air.

One advantage of melt granulation processes is that they can produce homogeneous fertilizer granules. Homogeneous fertilizer granules as used herein means that the granules are substantially homogeneous with respect to their nutrient composition throughout the granule. The homogeneous fertilizer granules may be prepared by melt granulation of a homogeneous fertilizer melt. Homogeneous fertilizer melt as used herein means that the fertilizer melt is substantially homogeneous with respect to its composition, however, the homogeneous fertilizer melt may contain some solid particles, wherein those solid particles are homogeneously dispersed throughout the fertilizer melt. If the homogeneous melt comprises solid particles, it may also be considered as a slurry.

NPK particles provide the three major mineral nutrients in plant available form. When NPK particles are prepared by melt granulation, the potassium salt is typically added to the NP melt in powder form. Depending on the composition, temperature and water content, some potassium salts, such as KCl and K2SO4, may be insoluble or only partially soluble in the melt. It is also possible to add potassium in the form of an aqueous solution comprising dissolved potassium salt. When granulation of fertilizer granules is performed from a homogeneous fertilizer melt, the nutrient composition throughout the granules is also substantially homogeneous. Homogeneous fertilizer granules are generally preferred over heterogeneous granules and heterogeneous blends because they allow for a more uniform and reliable release of nutrients. This is particularly important for fertilizers supplied with boron, which may be phytotoxic at high concentration levels.

It has been found that when a boron containing mineral is dissolved in the fertilizer melt there is a significant risk that sodium borate or boric acid will be formed. For example, based on experimental data (not shown), it has been realized that the prior art process described in WO9959938a1 results in the formation of large amounts of boric acid. However, sodium borate and boric acid may also present potential toxicity issues associated with human exposure during fertilizer preparation, transportation and handling. Accordingly, there is a need for alternative boron sources that can be used in homogeneous fertilizer granules and it is desirable that such alternative boron sources do not form sodium borate or boric acid during the manufacturing process. As used herein, "sodium borate" is intended to encompass water-soluble borates as well as hydrates thereof that contain sodium as the only cation. Accordingly, "sodium borate" encompasses anhydrous borax, pentahydrate, decahydrate, borax (tincal), rhombohedral (tincal) and tetrahydrate.

Particle size has been found to be a key parameter that needs to be carefully controlled. For example, boron-containing mineral powders of smaller particle size may increase the risk of dissolving and forming sodium borate or boric acid in the melt. On the other hand, boron-containing mineral powders with larger particle sizes may increase the risk of low boron availability of the plant. Sodium borate for fertilizer applications is typically supplied as a coarse powder having a median particle size of about 500 μm.

It has been found that certain colemanite and ulexite powders can be supplied to nitrate-containing fertilizer melts shortly before granulation without substantial dissolution into the melt, while still being able to provide boron to plants at high rates. The boron-containing mineral colemanite occurs naturally and has a chemical composition that can be represented by Ca2B6O 11.5H 2O. The boron-containing mineral, boronatrocalcite, occurs naturally and has a chemical composition that can be represented by NaCaB5O 9.8H 2O. Accordingly, the resulting fertilizer granules may contain granules of naturally occurring minerals, while at the same time, the fertilizer granules may contain negligible amounts of sodium borate and boric acid. Negligible amounts in the fertilizer granule will represent less than 0.1% w/w boron in the form of sodium borate or boric acid. In particular, a negligible amount may be less than 0.05% w/w boron in the form of sodium borate or boric acid. In particular, a negligible amount may be less than 0.01% w/w boron in the form of sodium borate or boric acid. In particular, the negligible amount may be an undetectable level of boron in the form of sodium borate or boric acid.

Suitable colemanite powders and ulexite powders have a median particle size in the range of1 μm to 100 μm. More particularly, such powders may have a median particle size in the range of 5 μm to 90 μm. More particularly, such powders may have a median particle size in the range of 10 μm to 40 μm. It is particularly desirable that the resulting fertilizer granules are homogeneous with respect to the boron source. In addition, it is particularly desirable to use milled borates. Milled borates as defined herein are amorphous borates having a size of 100 μm or less. Accordingly, suitable colemanite or ulexite powders may have a median particle size in the range of1 μm to 100 μm, a D90 value of less than 100 μm, and a D10 value of greater than 1 μm. D90 indicates that 90% of the particles had a size below this value as measured by laser diffraction analysis. D10 indicates that 10% of the particles had a size below this value as measured by laser diffraction analysis.

Without being limited by theory, the high utilization of boron from the colemanite and ulexite powders in fertilizer granules made by melt granulation may be due to a decrease in the coefficient of activity of borate ions in the salt matrix. In this regard, it has been found that the presence of nitrates (e.g., ammonium nitrate) contribute to the availability of boron from colemanite. In particular, both NPK granules and calcium nitrate granules were tested to contain ammonium nitrate. It is known that colemanite granules are associated with urea fertilizers as disclosed in WO2001021556(Kemira), but urea is considered to be incompatible with ammonium nitrate.

It is assumed that the fertilizer granules produced by melt granulation, wherein a colemanite powder or a colemanite powder is added shortly before the granulation step, comprise colemanite granules or colemanite granules from the respective powder. Accordingly, the median particle size of the colemanite powder or the ulexite powder may most conveniently be measured prior to addition to the fertilizer melt. The median particle size of the powder particles as used herein is the median volume-based value (D50) that can be conveniently obtained using conventional laser diffraction techniques, depending on the assumptions it is applicable to.

To determine the median particle size of colemanite or ulexite in a fertilizer granule, it is possible to dissolve the fertilizer granule in cold water (e.g., 2 ℃ to 8 ℃) and examine the insoluble granules by well-known methods. Insoluble particles can be dried and classified, for example, according to particle size or particle density, after which the fractions are analyzed by x-ray diffraction, Raman spectroscopy, scanning electron microscopy, and the like (see Frost et al Journal of Molecular Structure 1037(2013)23-28 and Celik & Cakal, Physicochem. Probl. Miner. Process.52(1), 2016, 66-76; Allen et al 1849, geographic subclause but 1036-k). By such methods, the fraction comprising colemanite or boronatrocalcite particles can be identified by, for example, x-ray diffraction, the colemanite or boronatrocalcite particles can be isolated, and the median particle size can be obtained by conventional laser diffraction techniques.

It has also been found that in a preferred embodiment, the water content of the fertilizer melt undergoing granulation should be low prior to addition of the colemanite powder or the ulexite powder. Without being limited by theory, excess water in the melt may lead to boric acid formation. In some more particular embodiments, the water content of the NPK fertilizer melt may be in the range of 0% to 4% w/w prior to addition of the colemanite powder or the ulexite powder. More particularly, the water content of the NPK fertilizer melt may be in the range of 0.5% to 3% w/w prior to addition of the colemanite powder or the ulexite powder. In particular, the water content of the calcium nitrate fertilizer melt may be in the range of 0% to 20% w/w prior to addition of the colemanite powder or the ulexite powder. More particularly, the water content of the calcium nitrate fertilizer melt may be in the range of 3% to 18% w/w prior to addition of the colemanite powder or the ulexite powder. As discussed below, calcium nitrate is typically hydrated. Without being limited by theory, the higher amount of water allowed in the calcium nitrate melt compared to the NPK fertilizer melt is due to the water binding to the calcium nitrate and not being free water.

Another parameter that can affect the dissolution of the colemanite powder or the ulexite powder is the time of contact with the fertilizer melt undergoing granulation. Having a shorter contact time has been found to reduce the likelihood of dissolution of the colemanite powder or the ulexite powder in the melt. In particular, the colemanite powder or the ulexite powder may be added shortly before granulation. In this context, the contact time is the time between the addition of colemanite powder or ulexite powder to the melt and the time when the fertilizer melt is granulated to form solid fertilizer granules. This amount of time may vary depending on the fertilizer properties. In particular, the contact time may be the time required to homogenize the melt after the addition of the powder. In this way, a homogeneous melt can be obtained without the conversion of colemanite and boronatrocalcite to toxic boric acid and borate species over extended contact times after the melt has been homogenized. Accordingly, the precise appropriate point in time for adding the colemanite powder or the ulexite powder prior to granulation may vary to some extent. For example, it has been observed that colemanite or ulexite granules can be contacted with NPK fertilizer melts for less than 100 seconds. In particular, the contact time with NPK fertilizer is between 50 and 95 seconds, more particularly between 80 and 95 seconds, and even more particularly between 85 and 95 seconds. In contrast, the kenyaite granules may be in contact with the calcium nitrate fertilizer melt for less than 600 seconds. In particular, the contact time of the kenyaite granules with the calcium nitrate fertilizer melt is between 400 and 580 seconds, more particularly between 500 and 580 seconds, and even more particularly between 550 and 580 seconds.

It has also been found that a melt granulation process combining a low water content of the fertilizer melt with a short contact time of the colemanite powder or the boronatrocalcite powder can provide nitrate-based fertilizer granules without significant levels of sodium borate or boric acid, which are still capable of providing boron to plants in an adequate, uniform and reliable ratio. Both low water content and short contact time are as defined above and depend on the fertilizer properties. This can be achieved by adding a colemanite or ulexite powder having a median particle size in the range of1 to 100 μm to a fertilizer melt containing a low level of water shortly before granulation. The fertilizer melt may be an NPK fertilizer melt or a calcium nitrate melt. More particularly, this can be achieved by adding colemanite or ulexite powder having a median particle size in the range of 10 to 40 μm to the NPK fertilizer melt containing low levels of water shortly before granulation. Alternatively, this may be achieved by adding a colemanite or boronatrocalcite powder having a median particle size in the range of 10 to 40 μm to a calcium nitrate fertilizer melt containing a low level of water shortly before granulation.

An NPK fertilizer melt as used herein is a fertilizer melt comprising significant levels of major mineral nutrients for plants based on nitrogen (N), phosphorus (P) and potassium (K). Accordingly, the main components of the NPK fertilizer melt may be nitrate, phosphate and potassium salts. For example, an NPK fertilizer melt may contain 25% to 50% ammonium nitrate, 5% to 30% w/w ammonium phosphate and 5% to 30% w/w potassium chloride. For example, the NPK fertilizer melt may contain 30% to 50% w/w ammonium nitrate, 30% to 40% w/w phosphate, 5% to 25% w/w potassium chloride. NPK granules can be made from NPK fertilizer melts. NPK granules as used herein are fertilizer granules comprising a primary mineral nutrient content (NPK) of 03-05-05 or higher (according to the X-Y-Z terminology mentioned). Common NPK granules may, for example, have a nutrient content of 15-15-15, 16-16-16, 13-13-21, 20-05-10, 15-09-20, 27-05-05, etc., depending on crop requirements.

NP fertilizer melts as used herein are fertilizer melts containing significant levels of the major mineral nutrients for plants based on nitrogen (N) and phosphorus (P). Accordingly, the main components of NP fertilizer melts can be nitrates and phosphates.

Urea is a common nitrogen source for fertilizers. When applied in the field, urea hydrolysis can produce short-term alkalization next to the urea fertilizer granules. Higher pH results in ammonia loss, especially when urea granules are applied as topdressing for porous and dry soils. The life cycle carbon footprint of urea fertilizers is higher than that of fertilizers based on nitrate as the N source. Therefore, it would be environmentally advantageous to provide fertilizer granules in which the nitrogen source is based on ammonium and/or nitrate (rather than urea). Accordingly, the nitrogen source of the fertilizer granules herein may be any non-toxic nitrate. Ammonium nitrate is particularly suitable because it provides plant available nitrogen from both cations and anions. Calcium nitrate is also particularly suitable because calcium is a desirable secondary nutrient and the salt may be beneficial in acid soils.

A calcium nitrate melt as used herein is a fertilizer melt that contains significant levels of calcium nitrate. Accordingly, the major component of the calcium nitrate melt may be calcium nitrate, for example 60% to 90% w/w calcium nitrate. Calcium nitrate as used herein is a Ca (NO3)2 salt, which may or may not be hydrated. Accordingly, the calcium nitrate may be anhydrous Ca (NO3)2 or hydrates such as Ca (NO3)22H2O, Ca (NO3)23H2O and Ca (NO3)24H 2O. However, as used herein, when referring to X% w/w calcium nitrate, we refer to the relative weight of the calcium nitrate as if it were present in anhydrous form, regardless of the actual degree of hydration. Thus, fertilizer granules comprising calcium nitrate will typically also comprise water as a hydrate. Correspondingly, fertilizer granules comprising e.g. 95% w/w calcium nitrate may also comprise 5% w/w water. In particular, pure anhydrous calcium nitrate has a melting point of 561 deg.C, while calcium nitrate tetrahydrate has a melting point of 42.7 deg.C. Pure calcium nitrate tetrahydrate fertilizer granules are difficult to prepare by conventional melt granulation techniques due to the low melting point, but it is well known that the presence of ammonium nitrate in a calcium nitrate melt improves the setting properties (see WO 200002831).

According to the present invention, the phosphate may be any non-toxic phosphate that provides phosphate ions to plants. Such salts include, but are not limited to, NH4H2PO4, (NH4)2HPO4, CaHPO4, Ca (H2PO4)2, and Ca3(PO4) 2. The term ammonium phosphate includes NH4H2PO4 and (NH4)2HPO 4. Methods for measuring the amount of Phosphate in Fertilizer granules are well known to the skilled person, e.g. as disclosed in "Evaluation of common Used Methods for the Analysis of Acid-Soluble phosphorus in International modified feeding reactors" of the International Fertilizer Industry Association (6 months 2014) or "Testing Methods for feeders" (2013) of the Japan Food and Agricultural Materials Inspection Center registration Authority (Japanese Incorporated assisted cultivation for Food and Agricultural Materials institute).

It is also known that colemanite can react with aqueous ammonium sulfate to form gypsum and boric acid (m., Kocakerim, m., et al, Korean j.chem.eng. (2007) 24: 55). In WO9959938a1(Kemira), sulfate-based NPK fertilizers were manufactured. In this process, a colemanite mineral is fed into a reactor along with potassium sulfate, sodium sulfate, magnesium sulfate, and manganese sulfate, and the solution is subsequently neutralized with ammonia to a pH of 6.0. The temperature before granulation was 133 ℃ and the water content was 6.9%. Neither the colemanite particle size nor its contact time is disclosed.

In accordance with the present disclosure, the potassium salt may be any non-toxic potassium salt that provides potassium ions to plants. However, it is beneficial for the fertilizer melt and fertilizer granules to contain little or no sulfate as it may help dissolve colemanite or ulexite. Thus, in one aspect, a fertilizer melt comprising colemanite or ulexite must not contain significant amounts of sulfate. Accordingly, in some embodiments, the fertilizer granules obtained from such fertilizer melts must not contain significant amounts of sulfate. For example, the fertilizer granule may comprise less than 1.0% w/w sulphate or less than 0.5% w/w sulphate.

methods for measuring the amount of potassium salt or potassium chloride in fertilizer granules are well known to the skilled person, e.g. as disclosed in "Testing Methods for Fertilizers" (2013) of the japan food and agricultural materials Testing center registration authority.

The homogenized fertilizer granules according to the present disclosure may be applied to the field by a spreader (spreading machine). For efficient dispensing by conventional machines, median diameters in the range of 1mm to 10mm may be suitable. It is particularly beneficial that more than 50% by volume of the fertilizer granules have a diameter in the range of 2mm to 5 mm. Some plants are notorious for their high demand for boron during growth, and therefore in one aspect of the present disclosure, the fertilizer granules can be used to fertilize a crop selected from alfalfa, barley, canola, cauliflower, corn, coffee, rice, soybean, and wheat. In one aspect of the present disclosure, the fertilizer granule may be used for fertilizing a crop selected from the group consisting of canola and cauliflower.

Sillimanite appears to be a useful alternative B source when Sherrel et al (1983) examined alternative boron sources for slow release of boron to plants by direct application of powders. Colemanite, although poorly soluble, appears to be very similar to the highly soluble compounds currently used, whereas the B availability in borosilte is low and this material should remain effective for a longer period of time. Furthermore, because of the lower initial availability, it may be possible to administer higher rates of borosillimanite without causing harm, and thus may increase the time that the borosillimanite remains effective ". However, if boron minerals are applied to a fertilizer melt to produce N fertilizer granules, it must be taken into account that they may dissolve or react with the melt. Colemanite is known to be soluble in mineral acids and other aqueous solutions. Particle size, temperature, pH and other parameters may affect dissolution. For example, a small colemanite particle size will increase the likelihood of dissolution in a fertilizer melt, which may be aqueous, acidic, and heated.

If desired, the homogeneous fertilizer particles in the present disclosure may be coated using conventional techniques to further improve their robustness or to provide specific nutrients. If the coating is carried out by conventional techniques without the presence of plant nutrients in the coating, the fertilizer particles will remain homogeneous. However, if desired, it is also possible to obtain heterogeneous particles by coating homogeneous fertilizer particles according to the present disclosure.

As used herein,% w/w represents weight percent. Accordingly, an ingredient of X% w/w in a fertilizer granule means that the ingredient is present in X weight percent relative to the total weight of the granule. Accordingly, an ingredient of X% w/w in the fertilizer melt means that the ingredient is present in X weight percent relative to the total weight of the melt.

As used herein, "about X" means any measured or calculated value that would be rounded to X.

Boron content as used herein is calculated as a relative weight percent of elemental boron (B), regardless of the actual boron source. Commercial fertilizers that provide boron typically have a boron (B) content in the range of 0.01% to 0.5% w/w. Accordingly, if the boron source used is borax pentahydrate, the weight percentage of borax pentahydrate will be in the range of 0.07% to 3.4% w/w.

It is understood that the composition of the fertilizer granules and fertilizer melt in this disclosure will constitute 100%. Correspondingly, a fertilizer comprising 80% w/w calcium nitrate and 5% w/w ammonium nitrate will contain 15% w/w of other ingredients (e.g. water of crystallisation).

Methods for measuring the amount of fertilizer salt in fertilizer granules are well known to the skilled person, e.g. as described in "Testing Methods for Fertilizers" (2013) of the registration authority of the japan food and agricultural materials Testing center or "Methods of sampling and test for converters" (1985) of Bhavan et al, indian standard IS: 6092 (part 6).

The invention is defined by the claims rather than the following examples:

Examples

According to EU method 9.5 in "Regulation (EC) No. 2003/2003of fertilizers by The European Association and Council (13.10.2003) (Regulation (EC) No. 2003/2003of The European Parameter and of The Council of13October 2003relating to fertilizers": boron was analyzed by "Determination of boron in ferrite extracts by means of measurements of spectrometry with azomethine-H".

Water soluble boron was analyzed by: the sample was dissolved in water, the solution was allowed to reach its boiling point and then stirred for 30 minutes before analysis.

Acid soluble boron was analyzed by: the samples were dissolved in 4M hydrochloric acid for 10 minutes at room temperature before analysis.

The boron source in the following examples is a commercially available powder from Eti Maden having the following particle sizes in μm:

	D10	D50	D90	D99
					Col-75	3.05	22	68	115
Col-45	2.5	19	55	87
					Ule-75	2.3	15.7	81	168
Ule-45	1.9	12.3	54	98
					Borax pentahydrate powder	258	641	1297	1822

As described above, the median particle size is represented by the D50 value obtained by laser diffraction analysis.