Patent Application
20240002309
The invention relates to controlled release potassium chloride fertilizer.
The concept of controlled release fertilizers (CRFs) is well known in the art. These CRFs are typically manufactured by applying a coating to the substrate fertilizer to form a coated mixture and curing the coated mixture, i.e., forming a coated fertilizer with one layer of coating, in a reaction vessel such as a rotating drum or pan. Additional layers of coating may be applied by the same process, i.e., coating and curing in a reaction vessel.
For example, U.S. Pat. No. 3,223,518, discloses granular, particulate, or pelletized fertilizers encapsulated by a water-insoluble, non-hydroscopic organic resinous encapsulating coating. U.S. Pat. No. 3,285,223 discloses coating and encapsulating granular materials with a plurality of coatings with a specifically designed apparatus that provides heating, blowing, and rotating means in a single vessel.
U.S. Pat. Nos. 4,772,490 and 7,722,696 described resins that may be cured at room temperature. Specifically, the resin is a combination of polyol, cardol, cardanol, derivatives or oligomers thereof and polyisocyanate or isocyanate. The resin is cured or encapsulated onto the fertilizer by activation with an amine catalyst.
The granular fertilizers available in the market used as substrate for coating in order to create a CRF vary in composition, size and shape. These fertilizers are manufactured by different means for example: granulation, compaction, prilling or the like. The manufacturing method chosen depends on the nature of the fertilizer, the target market and the production cost.
The shape of the granular fertilizer has a big influence on their performance as substrate for coating to produce CRFs. A fertilizer substrate composed of perfectly spherical granules is preferred for CRFs since it allows to produce a layer with a homogenous thickness and, as a consequence, a homogeneous release. For example prilling or granulation of fertilizers can produce virtually spherical particles, which are very favourable for applying a thin homogeneous coating. Urea is a well-known fertilizer widely available as a prilled or granulated product.
KCl has been available as prilled product but prilling KCl is relatively expensive. Hence, the most widely available KCl fertilizer is obtained from a compaction process. KCl after compaction is known to have very irregular shape. Yet, prilled KCl is relatively small, comprises pin-holes and a hollow core, which is disadvantageous for controlled release fertilizers, as this increases dissolution of the KCl.
The irregular shape of compacted KCl has a number of disadvantages. If the fertilizer is used as neat granules, the sharp edges are causing the formation of dust during transport and handling. In order to reduce the formation of dust during transportation and handling, it is not uncommon to apply a polishing step. Polishing of fertilizers (after compaction, for example) is a procedure either using a rotating drum in a so-called ‘dry’ process, or—more often—in a wet process where water is added, which dissolves sharp edges, and which is then evaporated. The latter process has the disadvantage that energy consumption is increased, but the dust in the product is reduced.
An application of this common polishing knowledge specifically to CRFs was described in CN101381263. This reference describes the use of a rotating barrel/drum polisher. This equipment is equivalent to the type of common use in the fertilizer manufacturing industry as described before. According to this reference, a polishing time of 45-60 minutes per batch is required.
Another example is the paper published by Lu et al. Sci Rep 10, 5763 (2020), where a water polishing pretreatment is described, resulting in increased sphericity (decreased the angle of repose). The result of increased sphericity is described to allow lower coating weights.
Both polishing methods described for CRFs are targeted to smoothen rough surfaces of already relatively spherical granules. There is with no mention to highly irregularly shaped, non-spherical, substrates
These state of the art polishing methods based in rotating drum equipment have not found a widespread application for improving the substrates to be coated to produce CRFs due to several issues. The first issue is generation of dust. A polishing action generates a certain amount of small particles and dust, while more dust is generated the more irregular the product is. Presence of dust in the substrate is considered detrimental for coating, yielding imperfections in the coating layer and loss of costly polymer on coating the small particles. The second issue is cost. A polishing step is an extra step in the process of making CRFs so to be efficient it needs to be made in an equipment involving low investment, low operating costs (avoiding use of water, heat etc.) and with as high throughput (or shorter batch time if not continuous) as possible. If possible, polishing is avoided by using more spherical products; however, for certain fertilizers, such products are not available, or too expensive.
There is, in consequence, a need to have an efficient and cost effective method that can improve irregular fertilizers to be used as substrate for a controlled release fertilizer. It is furthermore a specific object of the invention to provide a process to polish irregular compacted KCl, such that good slow release properties are obtained with an amount of coating comparable to what is used for more spherical granules.
The present invention provides a process for producing a slow release fertilizer of KCl comprising the following steps:
The agitating elements of the intensive mixer type device generally keep a certain gap between the rotating elements and the static elements. For example, the vessel can contain rotating elements on a central shaft, which have a certain gap with static elements on the vessel wall. The distance preferably is between about 1 mm and about 5 cm, preferably between about 5 mm and about 3 cm.
The agitating elements generally move at a certain circumferential tip speed. Preferably, the circumferential tip speed is about 0.3 m/s to about 5 m/s, more preferably about 1 m/s to 3 m/s.
The process is a dry process. Hence, no, or virtually no water is used.
Preferably, the compacted KCl has a d50 of between 2-4 mm, preferably between 2.5 mm and 3.5 mm. The d90 generally is below 5.5 mm, preferably below 5 mm. The d50 is the size of particles at which 50% of the weight of the particles is smaller, and 50% is higher than the d50 value. The d90 defines the size of the particles at which 10 wt % is larger, and 90 wt % is smaller than the stated size.
The process according the present invention allows an efficient and low-cost polishing step. Preferably, the polishing process step is done within 1 hr, preferably within 30 min, and it appeared possible to perform an effective process within 20 min, like for example about 10 min.
The present invention is also related to a polished and coated compacted potassium chloride controlled release fertilizer obtainable with the process according to the present invention. The polished and coated granular fertilizer has a release profile which can be slower than non-polished compacted KCl, prilled KCl or dry-drum polished compacted KCl, and has the following characteristics: lower release at day one, and a more gradual, slower, increase in the first weeks.
The present invention is also related to a polished and coated compacted potassium chloride controlled release fertilizer wherein the KCl has a sphericity between 0.88 and 0.92, and shows, with 6 pph (parts per hundred) (6 parts by weight coating on solid basis relative to 100 parts by weight potassium chloride particles), a release of less than 18%, preferably about 15% or less, at day 7 in a standard test at 21° C.
Preferably, the polished and coated granular KCl according to the invention has a d50 of between 3-4 mm and a d90 below 5.5 mm.
The invention furthermore relates to the use of an intensive mixer type device consisting of a container vessel and at least one set of agitating elements rotating relative to static elements in said vessel, in the treatment of granular material prior to its coating to create a controlled release granular material.
Generally, compacted KCl has a sphericity of below 0.87, like for example about 0.86. Such a substrate reflects a common irregular (not spherical) shape of compacted (also called compacted and granulated) KCl, similarly to commercially available KCl for agriculture. Other fertilizer products are available in much more spherical shape, see for example the following table.
A sphericity of higher than 0.9 generally allows good release properties, and generally little polishing is necessary. However, with compacted KCl, it appears more difficult to achieve a good release profile. Hence dry polishing or wet polishing, both using a standard drum, can be applied. The sphericity of several KCl reference products, and the release properties are given in the below table:
The standard KCl and the dry-drum polished KCl in a standard drum showed fast initial release, and a very flat release profile after about 10-15 days.
The release of unpolished compacted KCl clearly is quite unacceptable. The dry polishing of standard drum-treated KCl takes relatively long (more than 2 hours), and the release of the coated granules is not really up to standard even though a reasonable sphericity is achieved. The wet polished KCl shows better release properties after standard coating, but the treatment is long, and the evaporation of water is relatively costly because of energy usage.
The present invention allows polishing in relatively short time, with low energy input, while coating at low amount results in a release profile which is even improved in comparison to coated prilled KCl with the same coating weight (for example 6 pph).
According to the invention, common compacted and granulated KCl can be used. Compacted and granulated KCl is also simply called compacted KCl. Common KCl comprises an amount of KCl of at least 90%, preferably about 95% or more. Other components generally are sodium chloride (2-3 wt %) and other impurities. The amount of water generally is less than 0.5 wt %, like for example 0.2 wt %.
Compacted potassium chloride (KCl) generally has a d50 of between 2-4 mm, preferably between 2.5 mm and 3.5 mm. The d90 generally is below 5.5 mm, preferably below 5 mm
Compacted KCl generally has a sphericity of below 0.87, like for example between 0.85 and like about 0.86.
Substrate fertilizer morphology and particle size distribution of the products can be analyzed by Particle Size and Particle Shape Analysis with Dynamic Image Analysis, by a RETSCH Camsizer. The main morphology parameter used to evaluate the substrate fertilizer is sphericity (SPHT), defined as:
Where P is the measured perimeter of a particle projection and A is the area covered by a particle projection. For an ideal sphere SPHT=1. The higher the sphericity the rounder the granule and the better the CRF made with that substrate will be. The parameter measured is sphericity at d50. named SPHT3 at Q3[%]50 in the software of the RETSCH Camsizer equipment used.
The polishing device consists of a vessel in which the material to be treated is contained, in which agitating elements in rotating movement relative to static elements in the vessel impart energy to the bed of material providing for mixing. For example, the vessel can contain rotating elements on a central shaft, which have a certain gap with static elements on the vessel wall. Also, the vessel shell having agitating elements can rotate, while static elements are attached to a central shaft of the intensive mixer.
The rotational and static elements can be, but are not restricted to, paddles, blades, ribbons and pins. The rotational and static elements are attached to one or more shafts or axels, or to the inner side of the vessel shell.
The rotating elements keep a certain gap distance between them and the static elements in order to avoid excessive crushing of the granules and at the same time are operated at a high enough tip circumferential speed in order to provide enough polishing effect. The distance generally is about 1 mm or more, but preferably is about the d90 or more, like for example about 5 mm or more. Generally, the distance is about 5 cm or less, as otherwise lower efficiency is achieved. Preferably, the distance is about 3 cm or less. A suitable distance is for example 8 mm, 1 cm, 1.5 cm or 2 cm.
Tip circumferential speed is the speed of the blade tip, which is the closest point of the mixing element to the wall or the furthest point from the rotation axis. The tip speed generally is between 0.3 and 5 m/s. A relatively low tip speed may cause an increase in treatment time and more dust generation and is, therefore, less preferred. Therefore, a tip speed of about 1 m/s or more is preferred. A to high tip speed may cause high energy input, and a tip speed of about 3 m/s is preferred.
The effect of the polishing pretreatment according to the invention is not only to remove the sharp edges of the granules but also at the same time to incorporate part of the dust generated by the friction into the crevasses of the granule surface, providing a superior substrate for being coated into a controlled release fertilizer.
The device can be operated batch-wise or continuously. Due to the short residence time needed for polishing the equipment can be incorporated upstream of a fertilizer coating line without negatively affecting its throughput.
In a batch-type process, at an industrial scale, the device can handle at least one ton or more per batch, preferably 2 ton or more, like for example 3, 4 or 5 ton per batch.
The potassium chloride after polishing has a sphericity of 0.88 or higher. Generally, the sphericity is about 0.92 or lower, and preferably about 0.9 or lower. More preferably, the sphericity is between 0.88 and 0.90, and even more preferably between 0.88 and 0.89, as such sphericity can suffice to provide proper release properties of the controlled release fertilizer, and allows an efficient process. As explained above, the presence of the small dust particles in the (small) cavities of the potassium chloride granules is thought to be instrumental in achieving such advantageous release profile.
The presence of small dust particles can also be observed on microscopy photographs, as shown in
The polymer coating step can be a conventional coating step. The amount of polymer coating is determined by the required performance. More coating is needed to make the controlled release of fertilizer last for longer (longer longevity) which is needed for certain applications. However, more coating means higher cost. Typically, the amount of polymer coating is about 6 pph (parts per hundred) (6 parts by weight coating on solid basis relative to 100 parts by weight potassium chloride particles) for a longevity of around 6-7 months. However, other amounts can be applied as well providing different longevities for different applications. For example, the coating can be applied in an amount of 3-10 pph.
Other types of coatings, like the ones based on elemental sulfur, will also benefit from the use of such polished material. The typical coating weights of sulfur coating are considerably higher than polymer coating. Typically about 15-25 pph or even higher are applied, like up to 50 pph, since the performance of sulfur as barrier is inferior to that of polymer coatings but also since cost is not an issue due to the low cost of elemental sulfur.
The preferred controlled release fertilizer according to the present invention shows a release at 7 days of about 18% or less, preferably about 15 wt % or less. As explained above, the first week release is quite indicative for the controlled release behavior, and slow initial release is considered important.
The preferred controlled release compacted KCl fertilizer according to the present invention preferably shows a release at 10 days of about 20% or less, preferably about 15% or less; and/or a release at 30 days of 40% or less, preferably of 35% or less; and/or a release at 50 days of 50% or less, preferably 45% or less. Even more preferably, at 20 days, the release is about 30% or less. Even more preferably, the KCl fertilizer conforms with the release percentages as described above at all time points.
Materials and Methods
The KCl used in the examples is granular KCl, from ICL (Iberpotash). Composition is: 95% KCl, 2.3% NaCl, 0.2% H2O (moisture). Bulk density is 1 ton/m3. The particle size distribution of the material is shown in the table below.
Maximum diameter is defined as the d90 which is the diameter under which 90% of the weight of the sample is contained. In this case d90 is 4.71 mm.
The device used for the pretreatment according to the invention is a paddle mixer. It has approximately 300 liters working capacity (approximately 50 cm diameter and 150 cm length). It is equipped with a control panel with frequency inverter for speed control of the blade. It has a single shaft with 12 arms mounted perpendicularly to it, finished by adjustable blades. Distance from edge of blade to the wall is adjustable on a range of 1 to 30 mm.
CRFs were prepared using the fertilizers pretreated in the mixing device to compare their performance. In these examples, the CRFs were prepared by coating the fertilizers with a polyurethane based resin made by reacting a liquid polyol and a liquid diisocyanate similarly as described in U.S. Pat. No. 7,722,696. The coating level for all examples is 6 parts of solid coating per 100 parts of fertilizer (6 pph). Samples are prepared in a rotating drum holding 1.5 kg of fertilizer and equipped with a heating system to keep fertilizer at a temperature between 60° C. and 80° C.
Analysis
Dust amount was determined by sieving a representative sample over a standardized sieve of 2.36 mm opening. All material going through the sieve (<2.36 mm) is considered to be dust and needs to be removed prior to coating. This dust is, then, considered waste and needs to be limited.
Substrate fertilizer morphology and particle size distribution of the fraction >2.36 mm were analyzed by Particle Size and Particle Shape Analysis with Dynamic Image Analysis by a RETSCH Camsizer. The main morphology parameter used to evaluate the substrate fertilizer is sphericity (SPHT), defined as:
Where P is the measured perimeter of a particle projection and A is the area covered by a particle projection. For an ideal sphere SPHT=1. The higher the sphericity the rounder the granule and the better the CRF made with that substrate will be. The parameter measured is the value of sphericity at d50, mentioned as SPHT3 at Q3[%]50 in the software of the Camsizer equipment.
The performance of the coated fertilizer was measured by the rate of nutrient release from the granule when contacted with water. Slower release rates indicate longer longevity of the product in terms of releasing its nutrients over time. The industry standards for determining the release characteristics of the product include the water leach release test.
In the water leach release test, CRFs produced were placed in water at 21° C. and tested at different time intervals, 24 hours, 7 days and, in some cases, longer times (for example for preparing
Examples with Different Gaps to the Wall.
Settings: Load 300 kg, Time 30 min, Circumferential speed 1.64 m/s (70 Hz), Coating level: 6 pph (parts of coating per hundred of fertilizer)
Examples with Different Speeds
Settings: Load 300 kg, Time 30 min, Gap to wall 30 mm, Coating level: 6 pph (parts of coating per hundred of fertilizer)
Comparative Treated Vs Untreated
Settings Polishing: Load 300 kg, Time 30 min, Gap to wall 30 mm, Circumferential speed 1.64 m/s (70 Hz)
Coating Weight: 6 pph (parts of coating per hundred of fertilizer)
Comparative Treated Vs Treated Cleaned
Polishing generates a fine dust which is stuck on the fertilizer. In general the presence of dust is seen as detrimental for coating. This dust was removed from the untreated and polished fertilizer by a hexane washing treatment and their performances were compared.
Settings Polishing: Load 300 kg, Time 30 min, Gap to wall 30 mm, Circumferential speed 1.64 m/s (70 Hz); Coating Weight: 6 pph (parts of coating per hundred of fertilizer)
For the untreated sample, the performance remained largely the same while for the polished sample, the dust free sample performed, surprisingly, considerably worse. This suggests that the presence of the dust generated by this novel dry polishing process is beneficial to the coating. Traditional drum polishing and water polishing known in the art used for CRFs will not present this beneficial dust.
| Number | Date | Country | Kind |
|---|---|---|---|
| 20210141.6 | Nov 2020 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2021/083196 | 11/26/2021 | WO |
