CONTROLLED RELEASE POTASSIUM CHLORIDE FERTILIZER

Abstract

The invention relates to a process for producing a controlled release fertilizer of potassium chloride comprising the following steps: a. providing compacted KCl, having a sphericity of below 0.87; b. dry polishing the KCl in an intensive mixer type device consisting of a container vessel and at least one set of agitating elements such that the KCl has a sphericity of between 0.88 and 0.92; c. providing a coating on said polished KCl. The polished and coated compacted KCl can show with 6 pph coating a release of about 18% after 7 days measured with a water leach test at 21 C. The polished and coated compacted KCl may have one or more of the following release properties: a release at 10 days of about 20% or less; and/or a release at 30 days of 40% or less; and/or a release at 50 days of 50% or less.

Claims

1. Process for producing a controlled release fertilizer of potassium chloride comprising the following steps: a. providing compacted KCl, having a sphericity of below 0.87; b. dry polishing the KCl in 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 such that the KCl has a sphericity of between 0.88 and 0.92; c. providing a coating on said polished KCl.

2. Process according to claim 1, wherein the agitating elements keep a certain gap between them and the static elements, wherein the distance is between 1 mm and 5 cm, preferably between 5 mm and 3 cm.

3. Process according to any one of claims 1-2, wherein the agitating elements move at a certain circumferential tip speed, wherein the circumferential tip speed is between 0.3 and 5 m/s, preferably between 1 m/s and 3 m/s.

4. Process according to any one of claims 1-3, wherein the agitating elements are rotating agitating elements on a central shaft, and wherein the static elements are parts of the inside of the vessel wall.

5. Process according to any one of claims 1-4, wherein the compacted KCl has a d50 of between 2-4 mm, preferably between 2.5 mm and 3.5 mm and a d90 of below 5.5 mm, preferably below 5 mm

6. Process according to any one of claims 1-5, wherein the polishing process step is done within 1 hr, preferably within 30 min, and even more preferably within 20 min.

7. Process according to any one of claims 1-6, wherein the coating is a polymer coating applied in an amount of 3 pph to 10 pph, preferably between 4 pph to 7 pph on polished KCl.

8. Process according to any one of claims 1-6, wherein the coating is a sulphur coating applied in an amount of 15 pph to 50 pph, preferably between 15 pph to 25 pph coating on polished KCl

9. Polished compacted KCl granules, ready for coating, having a sphericity of between 0.88 and 0.92, and having visible dust patches under a microscope at 15 magnification.

10. Polished and coated granular material obtainable with the process according to any one of claims 1-8.

11. Coated and polished KCl material according to claim 10, and having with 6 pph or less a release of about 18% or less at 7 days measured with a water leach test at 21 C., preferably about 15% or less.

12. Coated and polished compacted KCl having a sphericity between 0.88 and 0.92, and having with 6 pph coating with a release of about 18% or less at day 7 measured with a water leach test at 21 C., preferably about 15% or less.

13. Coated and polished compacted KCl according claim 12, having one or more of the following release properties: 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.

14. Coated and polished compacted KCl according to any one of claims 10-13, wherein the polished and coated compacted KCl has an d50 of between 3-4 mm and a d90 below mm.

15. 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.

Description

DESCRIPTION OF THE FIGURES

[0027] FIG. 1 are photographs of untreated compacted KCl and dry-polished compacted KCl according to the present invention.

[0028] FIG. 2 is a graph representing several release profiles of coated KCl products.

DETAILED DESCRIPTION OF THE INVENTION

[0029] 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.

TABLE-US-00001 Manufacturing Sphericity Fertilizer method (SPHT at 50% Q3) KCl Prilled 0.966 Urea Prilled 0.980 NPK (21-7-14) Prilled 0.973 Urea Granulated 0.958 MAP Granulated 0.952 NPK (17-10-13) Granulated 0.966 SOP (Potassium Sulphate) Granulated 0.967 KCl Compacted 0.860

[0030] 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:

TABLE-US-00002 Pre-treatment Sphericity (SPHT Release 30 d Sample time (min) at 50% Q3) (% K2O) (6 pph) Prilled KCl 0.966 44 Standard KCl 0 0.863 68 Dry drum 150 0.877 48 polished KCl Water drum 130 0.90 43 polished KCl

[0031] 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.

[0032] 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.

[0033] 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).

[0034] 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 %.

[0035] 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

[0036] Compacted KCl generally has a sphericity of below 0.87, like for example between 0.85 and like about 0.86.

[0037] 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:

[00001]$\mathrm{SPHT}=4\frac{A}{P^2}$

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] The presence of small dust particles can also be observed on microscopy photographs, as shown in FIG. 1. FIG. 1A is a photograph of unpolished compacted KCl, while FIG. 1B shows a picture of blender polished compacted KCl according to the present invention. In FIG. 1B white patches of dust are visibly incorporated on the surface. The dust integrated in the surface of the granule of the polished material is thought to provide the surprising increased performance. The invention thus also relates to polished, compacted KCl granules, ready for coating, having a sphericity of between 0.88 and 0.92, and having visible dust patches under a microscope at 15 magnification.

[0048] 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.

[0049] 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.

[0050] FIG. 2 shows a comparison of the release in a water leach test of different KCl fertilizers, non-polished (prilled or compacted) and polished by different methods. The products were all coated with 6 pph of polyurethane polymer coating. As is apparent from the graphs, unpolished compacted and coated KCl (compacted standard KCl) shows a release of KCl in a standard test (as described below in the experimental section) of about 50% in about 10 days. After about 20 days, the release is relatively slow, leading to about 65% release at 30 days, and 70% release at 50 days. Prilled and coated KCl (prilled KCl), just like standard drum polished KCl (drum polished KCl) shows about 30% release at 10 days, about 50% at 30 days and 55% release at 50 days. The KCl polished according to the present invention (BLENDER POLISHING KCl) shows only 10% release at 10 days, about 25% at 30 days, and about 40% at 50 days. The graphs show that the polished KCl according to the present invention allows a controlled release fertilizer with improved controlled release over prior art type of products.

[0051] 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.

[0052] 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.

Examples

[0053] Materials and Methods

[0054] The KCl used in the examples is granular KCl, from ICL (Iberpotash). Composition is: 95% KCl, 2.3% NaCl, 0.2% H.sub.2O (moisture). Bulk density is 1 ton/m.sup.3. The particle size distribution of the material is shown in the table below.

TABLE-US-00003 Particle size diameter range (mm) Cumulative Weight percentage [%] 0 2 2.1 2 3 19.2 3 4 64.3 4 5 95.2 5 6 99.9 6 7 100

[0055] 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.

[0056] 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.

[0057] 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.

[0058] Analysis

[0059] 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.

[00002]$\mathrm{Dust}\mathrm{amount}\left(\%\right)=100*\frac{\mathrm{Weight}\mathrm{of}\mathrm{particles}<2.36\mathrm{mm}\mathrm{in}\mathrm{sample}\left(g\right)}{\mathrm{Weight}\mathrm{of}\mathrm{total}\mathrm{sample}\left(g\right)}$

[0060] 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:

[00003]$\mathrm{SPHT}=4\frac{A}{P^2}$

[0061] 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.

[0062] 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.

[0063] 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 FIG. 2). In particular, twenty grams of coated fertilizer were placed into a flask with 400 mL of de-mineralized water. The flask containing the sample was inverted three times to allow for mixing and kept at 21 C. After a 24 hour period, the flask was inverted three times and a sample was taken to determine the amount of nutrients (K.sub.2O) in the water. The water was replaced and renewed with 400 mL of fresh de-mineralized water. The measurement was repeated again after 7 days. Extra measurement points can be obtained to be able to plot the release profile during the working time of the controlled release fertilizer. After the last measurement, the remaining particles were milled, dissolved to a known volume and analyzed to check closure of the mass balance for each component. Results are given as weight % of nutrient K.sub.2O released into the solution at different times intervals.

[0064] Examples with Different Gaps to the Wall.

[0065] 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)

TABLE-US-00004 Dust Sphericity Release at 1 d Release at 7 d Gap to wall Amount (SPHT at (% K2O) lab (% K2O) lab (mm) (%) 50% Q3) scale coating scale coating untreated 4.3 0.861 27 48 1 8.3 0.886 9.9 19.7 5 7.1 0.887 8.4 17.7 15 6.4 0.882 2.7 10.3 30 6.1 0.884 1.8 6.5

[0066] Examples with Different Speeds

[0067] Settings: Load 300 kg, Time 30 min, Gap to wall 30 mm, Coating level: 6 pph (parts of coating per hundred of fertilizer)

TABLE-US-00005 Circumferential Dust Sphericity Release at 1 d Release at 7 d Tip Amount (SPHT at (% K2O) lab (% K2O) lab Speed (m/s) (%) 50% Q3) scale coating scale coating untreated 4.3 0.861 27 48 0.82 (35 Hz) 7.5 0.876 26 38 1.17 (50 Hz) 6.4 0.881 6 21 1.64 (70 Hz) 6.3 0.884 2 7

[0068] Comparative Treated Vs Untreated

[0069] Settings Polishing: Load 300 kg, Time 30 min, Gap to wall 30 mm, Circumferential speed 1.64 m/s (70 Hz)

[0070] Coating Weight: 6 pph (parts of coating per hundred of fertilizer)

TABLE-US-00006 Dust Sphericity Release at 1 d Release at 7 d Amount (SPHT at (% K2O) lab (% K2O) lab (%) 50% Q3) scale coating scale coating untreated 4.3 0.861 27 48 polished 6.3 0.884 2 7

[0071] Comparative Treated Vs Treated Cleaned

[0072] 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.

[0073] 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)

TABLE-US-00007 Release Increase by Washing At 1 day At 7 days Untreated 14% 6% Polished 106% 154%

[0074] 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.