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    • 专利摘要:
    COMPACTED POTASSIUM CHLORIDE FERTILIZERS CONTAINING MICRONUTRIENTS AND METHODS FOR MANUFACTURING THE SAME. Granular cohesive MOP fertilizer that contains one or more micronutrients and one or more binding ingredients. The fertilizer is prepared by compacting the MOP feedstock with one or more micronutrients and one or more optional binders to form a cohesive MOP composition. The cohesive MOP composition is then further processed, such as by crushing and sizing, to form a cohesive granular MOP product containing micronutrients. The process yields a fertilizer product containing micronutrients with granule size and superior element distribution, without compromising handling and storage qualities.
    公开号:BR112014002749B1
    申请号:R112014002749-8
    申请日:2012-08-02
    公开日:2021-02-09
    发明作者:Del Ferguson；Ronald Olson；Carey Heinbigner
    申请人:The Mosaic Company；
    IPC主号:
    专利说明:

    CORRELATE ORDER
    [001] This application claims the benefit of US Provisional Application number 61 / 514,952 filed on August 4, 2011, which is incorporated into this document in its entirety as a reference. FIELD OF THE INVENTION
    [002] The invention refers generally to fertilizer compositions. More specifically, the invention relates to the entry of micronutrients in potassium muriate based fertilizers by means of compaction processes. BACKGROUND OF THE INVENTION
    [003] Essential nutrients for plants include primary, secondary or macronutrients and traits or micronutrients. Primary nutrients include carbon, hydrogen, oxygen, nitrogen, phosphorus and potassium. Carbon and oxygen are absorbed from the air, while other nutrients, including water (hydrogen source), nitrogen, phosphorus, and potassium are obtained from the soil. Fertilizers containing nitrogen, phosphorus and / or potassium sources are used to complement soils that are lacking in these nutrients.
    [004] In accordance with conventional fertilizer standards, the chemical constitution or analysis of fertilizers is expressed as a percentage (by weight) of the essential primary nutrients, nitrogen, phosphorus and potassium. More specifically, when expressed in the fertilizer formula, the first number represents the percentage of nitrogen, expressed on an elementary basis as "total nitrogen" (N), the second number represents the percentage of phosphorus, expressed on an oxide basis as "acid phosphoric available "(P2O5), and the third value represents the percentage of potassium also expressed at the base of the oxide as" available potassium oxide "(K2O), or otherwise known as the expression (N-P2O5-K2O).
    [005] Although the amounts of phosphorus and potassium are expressed in their oxide forms, there is no P2O5 or K2O in fertilizers. Phosphorus most commonly exists as monocalcium phosphate, but it also occurs as other calcium or ammonium phosphates. Potassium is usually in the form of potassium chloride or sulphate. Conversions of oxide forms of P and K to elemental expression (NPK) can be done using the following formulas:% P =% P2O5 x 0.437% K =% K2O X 0.826% P2O5 =% PX 2.29% K2O =% K x 1.21
    [006] Potassium muriate (MOP), also known as potassium chloride, KC1, is an agricultural fertilizer, and is the most common source of potassium fertilizer. MOP by definition contains 48% to 62% of soluble K2O, mainly as chloride. MOP is usually extracted from natural mineral sources underground, either by conventional mining or solution extraction techniques. Once extracted, MOP can be transformed into several different forms or finished products of KC1 suitable for industrial, chemical, human or animal nutrients, specific or agricultural applications as desired by individual consumers.
    [007] Finished MOP, for the purpose of agricultural consumption, is normally sold in granular form. The size and purity of the granules may vary, depending on the end use for which the product will be used. The granules are produced through crushing and sizing processes known to a person skilled in the art, such as by compaction and subsequent crushing and sizing, which thus break the larger pieces of the MOP into small granules. Compaction implies the continuous lamination of the MOP raw material at high pressures, producing material cohesion in the resulting product. The classification of MOP, and, consequently, its market value, also depend on both the purity and granule size of the product. Typically, MOP is sieved to the desired particle size for a specific need.
    [008] A typical MOP feed stock has a granule size that is comparable to table salt, which is less than the desired granule size. In order to obtain larger granules, this raw material is compacted first through a compaction process, such as a single roller compactor or the like, to produce a product similar to a cohesive sheet. Subsequent processing typically involves controlled breaking of the MOP sheet into granules, which are then classified to a desired size range by classification or other methods known in the industry. A non-limiting example of a standard roller compactor known in the industry is the KR Komareck B220B Compactor (or any of the "B" or high pressure briquetting models and compaction machines) available from KR Komarek, Inc. of Wood Dale, IL.
    [009] In addition to the primary nutrients, such as the potassium that becomes available to plants through the MOP fertilizer added to the soil, micronutrients and secondary nutrients are also essential for plant growth. These are needed in much smaller quantities than the primary nutrients. Secondary nutrients may include, but are not limited to, sulfur (SO4), calcium (Ca), magnesium (Mg), or combinations thereof. Micronutrients may include, but are not limited to, for example, boron (B), zinc (Zn), manganese (Mn), nickel (Ni), molybdenum (Mo), copper (Cu), iron (Fe), chlorine (Cl) or their combinations. From that point, below and throughout the specification, for the sake of simplicity, the term "micronutrient" refers to and includes both secondary nutrients and micronutrients.
    [010] A common method of applying micronutrients to crops is application to the soil. Application rates generally recommended are less than 10 lb / acre (4.53 kg / acre) on an elementary basis. Applications of separate micronutrients at these low rates are difficult and are prone to result in low uniformity of distribution. The inclusion of micronutrients with mixed fertilizers is a convenient method of application and some methods allow for more uniform distribution with conventional application equipment. Costs are also reduced by eliminating a separate application step. Four methods of applying micronutrients with mixed fertilizers may include incorporation during manufacture, combining by volume with granular fertilizers, coating on granular fertilizers and seeds, and mixing with liquid herbicides or fluid fertilizers.
    [011] Combination by volume with granulated fertilizers is the practice of combining volume of micronutrient compounds with phosphate, nitrogen and potassium-based fertilizers. The main advantage of this practice is that better fertilizers can be produced, which will provide the recommended micronutrient rates for a given field, at the usual fertilizer application rates. The main disadvantage is that the segregation of nutrients can occur during the mixing operation and with the subsequent handling. Micronutrients are often present in small particle sizes, which can result in the segregation of a mixture by volume. In order to reduce or avoid size segregation during handling and transport, ideal micronutrient granules should be close to the same size as phosphate, nitrogen and potassium granules. Since micronutrients are needed in very small amounts for plant nutrition, this practice has resulted in micronutrient granules distributed unevenly and, generally, far from most plants to constitute an immediate benefit, like most elements of micronutrients migrate in the soil solution just a few millimeters throughout the growing season.
    [012] Coatings reduce the possibility of segregation. However, some surface bonding materials are unsatisfactory, as they do not maintain micronutrient coatings during bagging, storage and handling, which results in segregation of micronutrient sources from granular fertilizer components.
    [013] Measures have been implemented to reduce the problem of segregation, for example, as in the case of sulfur or sulfur platelets in the fertilizer portion, as described in US Patent No. 6,544,313, entitled "Sulfur-Containing Fertilizer Composition and Method for Preparing Same "and in the case of micronutrients, as described in US Patent number 7,497,891, entitled" Method for Producing a Fertilizer with Micronutrients "both being incorporated herein by reference in their entirety. This method of preparation, however, refers to a granulation process.
    [014] Some applications of pelletizing and compacting micronutrients exist in products, such as sodium chloride (salt) and kieserite (magnesium sulfate monohydrate), however, the inclusion of micronutrients in a primary nutrient, such as MOP, using a roller compactor is not known in the prior art and is known to the inventors.
    [015] The addition of micronutrients has historically been carried out in downstream operations outside the MOP processing limits for miners and millers. There is a long, well-documented need to increase crop yields in order to feed a growing world population. Therefore, there is still a need to create a value-added, granular, sized, milled and compacted MOP fertilizer product that contains one or more micronutrients that maximize the introduction of the micronutrient (s) into the soil solution and, finally, to the root area of the plants. SUMMARY OF THE INVENTION
    [016] Modalities of the invention include a cohesive granular MOP fertilizer featuring one or more micronutrients, such as, but not limited to boron (B), zinc (Zn), manganese (Mn), molybdenum (Mo), nickel (Ni) , copper (Cu), iron (Fe), chlorine (Cl), sulfur (S), in its elemental form, sulfur in its oxidized sulfate form (SO4) and their combinations in various concentrations. The fertilizer can also include a compaction aid, coloring agent, and / or one or more binding ingredients, such as sodium hexametaphosphate (SHMP). Micronutrients, when compacted in MOP, remain soluble and dissolve easily when applied using conventional fertilization practices.
    [017] According to the modalities of the invention, the fertilizer is prepared by compacting the raw material of MOP with one or more micronutrients and one or more optional binders to form a cohesive MOP product. The cohesive MOP product is then processed, such as by crushing and sizing, to form a cohesive MOP granular product containing micronutrients. The process produces a fertilizer product containing micronutrients with a higher and more uniform granule and element size distribution, without compromising handling or storage qualities, compared to the aforementioned micronutrient applications. The uniform distribution of a fertilizer containing micronutrients compared to existing dry application methods allows individual plants to have better access to nutrients.
    [018] The summary of the invention described above is not intended for each illustrated modality or for each implementation of the present invention. The following detailed description more specifically exemplifies these modalities. BRIEF DESCRIPTION OF THE DRAWINGS
    [019] Figure 1 is a process flow chart for injecting micronutrients into an MOP feed.
    [020] Figure 2 is a graph showing the results of the MOP Hersey Rupture 0-0-62 (based on N-P2O5-K2O), plus samples of micronutrients (HM).
    [021] Figure 3 is a graph showing the Production Yields of MOP Carlsbad 0-0-60 (based on N-P2O5 - K2O), plus micronutrient test MOP product using sulfur.
    [022] Figure 4 is a graph illustrating the Production Yields of MOP Carlsbad 0-0-60 (based on N — P2O5 — K2O) plus micronutrient test MOP product using molybdenum.
    [023] Figure 5 is a graph showing the results of Rupture MOP Carlsbad 0-0-60 (based on N-P2O5-K2O), plus micronutrient test MOP product.
    [024] Figure 6 is a graph showing the results for Carlsbad MOP Powder 0-0-60 (based on N-P2O5 -K2O), plus micronutrient test MOP product.
    [025] Figure 7 is a graph showing the MOP Carlsbad 0-0-60 Moisture Absorption results (based on N-P2O5-K2O), plus micronutrient test MOP product.
    [026] Figure 8 is a final photo of the MOP Carlsbad 0-060 (based on N-P2O5 -K2O), plus MOP product for micronutrient testing.
    [027] Figure 9 represents a spectrum of the X-ray Energy-Dispersive Spectrograph (EDS) of a sample of a compacted MOP granule containing micronutrients according to one embodiment of the invention.
    [028] Figure 10 is a micrograph of the Scanning Electron Microscope (SEM) of the sample in Figure 9.
    [029] Figure 11A is a chlorine EDS map of the SEM of figure 10.
    [030] Figure 11B is a potassium EDS map of the SEM of figure 10.
    [031] Figure 11C is a manganese EDS map of the SEM of figure 10.
    [032] Figure 11D is a sodium EDS map of the SEM of figure 10.
    [033] Figure 11E is a zinc EDS map of the SEM of figure 10.
    [034] Figure 11F is an oxygen EDS map of the SEM of figure 10.
    [035] Figure 11G is a sulfur EDS map of the SEM of figure 10.
    [036] Figure 12A is an EDS spectrum of a sample of a crushed compacted MOP granule containing micronutrients according to an embodiment of the invention.
    [037] Figure 12B is an EDS spectrum of a sample of the complete compacted MOP granule containing micronutrients from Figure 12A.
    [038] Although the invention is subject to several modifications and alternative forms, the specifics of them having been shown by way of example in the drawings being described in more detail. It should be understood, however, that the intention is not to limit the invention to the particular modalities described. On the contrary, the intention is to cover all modifications, equivalent and alternative, that fit the spirit and scope of the invention. DETAILED DESCRIPTION
    [039] A cohesive granular fertilizer product according to the modalities of the invention generally includes a MOP fertilizer base and one or more micronutrients (or secondary nutrients), including, but not limited to, boron (B), zinc (Zn ), manganese (Mn), molybdenum (Mo), nickel (Ni), copper (Cu), iron (Fe), chlorine (Cl), sulfur (S), in its elemental form, sulfur in its oxidized sulphate form ( SO4) or their combinations in various concentrations. As revealed above, the term "micronutrients" refers to and includes both secondary nutrients and micronutrients. The concentration of one or more micronutrients can vary from about 0.001 to about 99, 99 weight percent and more particularly between about 0.001 to about 10 weight percent.
    [040] The base of the MOP fertilizer can be any one of a variety of commercially available MOP sources, such as, but not limited to, for example, a MOP feedstock having a K2O content (on the N- scale) P2O5-KXO) ranging from about 20 weight percent to about 80 weight percent. In a specific non-limiting example, the chemical analysis of the MOP raw material is 0-0-60% by weight, in another non-limiting example, the chemical analysis of the MOP raw material is 0-0-62% by weight, and in yet another non-limiting example, the chemical analysis of the MOP raw material is 0-0-55% by weight.
    [041] The fertilizer may also include one or more binding agents or ingredients in order to improve the strength or handling capacity of the finished, compacted, granular MOP product so that the granules are less susceptible to wear or break during handling or transportation, as described in US Patent number 7,727,501, entitled "Compacted Granular Potassium Chloride, and Method and Apparatus for Production of same" incorporated herein by reference in its entirety. A bonding agent is a chemical that is added to the feed of a compaction circuit to improve the strength and quality of the compacted particles. The binding agent works by sequestering or chelating impurities in the raw material MOP, while providing adhesive properties to the compacted mixture. Binders can include, for example, sodium hexametaphosphate (SHMP), tetra-sodium pyrophosphate (TSPP), tetrapotassium pyrophosphate (TKPP), sodium tripolyphosphate (STPP), diamonium phosphate (DAP), monoammonium phosphate (MAP), granular monoammonium phosphate (GMAP), potassium silicate, sodium silicate, starch, dextran, lignosulfonate, bentonite, montmorillonite, kaolin, or combinations thereof. In addition or as an alternative to binding agents, some of the micronutrients themselves can act as binding agents to increase the resistance of the particles.
    [042] In accordance with an embodiment of the invention, a cohesive granulated MOP fertilizer containing micronutrients is obtained by mixing one or more micronutrients in the MOP feed of a compaction circuit. Micronutrients can be added to the feed before compaction. The compaction of this MOP feed load and then the conventional after-treatment, such as crushing and sizing, yields cohesive granules of the MOP fertilizer containing micronutrients that are uniformly distributed throughout the granular product.
    [043] A production line or production circuit for obtaining compacted granular MOP generally includes a material feeding device, such as a belt conveyor, pneumatic conveyor or the like that feeds several MOP chains into particles, classifying the material of recovered or discarded MOP, one or more micronutrients and one or more optional binding agents for a compactor. The compactor then presses the raw material at high pressure into a cohesive MOP sheet or intermediate cake, which can then be crushed, graded, resized, or otherwise re-finished in a finished and desired MOP product.
    [044] Figure 1 is a flow chart that illustrates the steps involved in a contemplated modality of the production method of the present invention. Specifically, figure 1 shows the injection of a micronutrient into the MOP supply of a production circuit. The micronutrient (s) can be added to the MOP feedstock at various locations in the circuit by an injector, including measuring equipment to allow more precise control of the quantities of each component added per unit of MOP feedstock.
    [045] After adding the micronutrients (s) and, optionally, the binding agent (s) to the MOP raw material, the MOP additives and raw material are mixed MOP. The mixing step can be performed passively, allowing these materials to come together or mix during their joint transportation through the feeding mechanism or, alternatively, specific mixing equipment between the injector and the compactor to provide more aggressive or active mixing of the micronutrient (s), optional binders and raw material of MOP before compaction.
    [046] The combined MOP raw material, now properly mixed with the micronutrients, is then compacted. The compaction process can be carried out using conventional compaction equipment, such as a roller compactor or the like. The cohesive intermediate produced can then be made into the desired finished granular product, using methods such as milling, or other conventional sorting methods suitable to produce a finished product of the desired particle size or type. These steps are also shown in the flowchart in figure 1.
    [047] In a specific embodiment of the invention, it is desirable to incorporate two or more different micronutrients in combination, and this can be achieved either by injection of a pre-combined combination of several micronutrients or by means of separate placement or injection of quantities of micronutrients to MOP. It will be understood that any process in use or modifications of equipment so as to allow the addition of one or more micronutrients and / or binding agents, both simultaneously and separately, to the raw material MOP are contemplated by the scope of the present invention.
    [048] The following representative examples further define the modalities of the present invention. Example 1
    [049] Several MOP fertilizer compositions compacted with numerous micronutrients were obtained and evaluated in terms of technical feasibility. The raw material of MOP supplied by Mosaic Hersey Potash Mine of Michigan, USA (hereinafter "Mosaic Hersey") was compacted with various micronutrients in different concentrations. The chemical analysis of MOP was 98.8% by weight of KOI, 1.1% by weight of sodium chloride (NaCl), 283 ppm of calcium (Ca), 11 ppm of iron (Fe), 59 ppm of magnesium (Mg) and 287 ppm of sulfate (SO4). The total moisture content of the MOP raw material was 0.1439% by weight. The MOP raw material supplied by Mosaico Hersey is a 0-0-62% K2O product (expressed in terms of N-P2O5-K2O) produced using solution mining techniques. The raw material of MOP is white in color as it is inherent in the nature of MOP produced with the solution mining technique.
    [050] The micronutrients used in the production of Hersey Micronutrient (HM) samples (Table 1 below) included boron (in the form of anhydrous sodium borate Na2B4θ ), Zinc (in the form of ZnSθ4.H2θ monohydrate zinc sulphate), zinc (in the form of ZnO zinc oxide), manganese (in the form of manganese sulphate MnSθ4.H2θ) and / or molybdenum (in the form of sodium molybdate Na2 M0O4.2H2O).
    [051] The following compositions have been produced (hereinafter referred to as "the products of HM"): Table 1 - Description of the test of elaboration of the

    [052] Each product was generated using the same process flowchart: MOP and micronutrient (s) were mixed in a batch mixing drum. The mixed product was then distributed to the compaction circuit. The compaction circuit used included a compactor producing a sinusoidal flake, a flake breaker, a disintegrator (crusher) and a 2-deck vibrating screen providing a Tyler 4 x 10 mesh product. Large and small granules were recycled for processing later.
    [053] Samples of each of HM's products were analyzed for K2O content by an independent external laboratory. Table 2 presents the Analytical Values (independent laboratory) versus theoretical K2O value (% Calc) based on the content of the micronutrient compound and the MOP feed base of 62% K2O. Table 2 - K2O Analysis of HM Products

    [054] Samples of each of HM's products were analyzed for micronutrient content (boron, molybdenum, manganese and zinc) by an independent external laboratory. The micronutrients found in sodium tetraborate, anhydrous, molybdate, manganese sulfate monohydrate and zinc sulfate monohydrate are effectively retained in a compacted granule. The results are shown in Table 3. Table 3 - Analysis of micronutrients of the Products of the
    Quality Metrics
    [055] Each of HM's products has been classified in order to perform a size analysis. Table 4 below shows the standard fertilizer combination metrics, including the Size Guide Number (SGN) and the Uniformity Index (UI) for each of the product streams along with a baseline. The formulas for these sizing metrics are as follows: - SGN = d5o (μm) / 10, or otherwise defined as the particle size in millimeters of which 50% by weight of the sample is thicker and 50% thinner times 100. - UI = [ds (μm) / 1,000) / (dgo (μm) / 1,000)] * 100, or otherwise defined as the particle size in which 95% of the material is retained, divided by the size of particle in which 10% of the material is retained, multiplied by 100. Table 4 - SGN and UI of HM Products

    [056] The SGN and UI for a basic product (without the addition of micronutrients) is 307 and 36, respectively. While the UI for HM products is similar to the baseline, the SGN is lower. The average SGN for HM products is 271.
    [057] Two disruption procedures were performed to compare HM products with the baseline scenario. These were the wear and conditioned break tests. The wear rupture test is used to assess the rigidity of a product that has been exposed to a relative humidity of 72% for 24 hours. The conditioned rupture test is used to assess the product's stiffness after 24 hours of exposure to 26% relative humidity. The difference between the conditioned and wear values is assumed to be the amount of wear that has occurred.
    [058] A test sample for each HM product of the same or similar size analysis was measured. For the wear rupture test, the samples were exposed to the respective relative humidity for 24 hours. After a period of agitation, the quantity of the broken sample was measured, that is, the percentage of rupture retained in a mesh screen of specified size.
    [059] Figure 2 reveals that each of HM's products has a slightly higher wear break value compared to the baseline. The rupture values in figure 2 do not indicate a concern with the quality of the product, however they can be reduced if so desired, using a bonding agent.
    [060] In another series of rupture tests with the Ag-granular Hersey product, it was observed that the rupture values could optionally be reduced to less than 10% in addition to 700 ppm of SHMP binder (Table 5). Table 5 - Hersey granule rupture results
    Example 2
    [061] MOP raw material from Mosaic Carlsbad New Mexico (also known as Dyna-K) was compacted with various micronutrients and evaluated for its technical viability. Carlsbad's MOP is generated using conventional underground mining techniques. The MOP generated from this process is a 0-0-60% K2O product (expressed in terms of N-P2O5-K2O) and is red in color as is the inherent nature of the MOP produced from underground mining techniques.
    [062] The added micronutrients included 0.5% by weight of boron (3.47% by weight of Na2B4θ . 5H2O), 1.0% by weight of manganese (3.03% of MnSO7.H2O), 1, 0 wt% Zn (4.41 wt% ZnSO4.7H2O), 1.0 wt% copper (4.10 wt% CUSO4.5H2O), 1.0 wt% iron ( 4.98 percent by weight of FeSC> 4.7H2O), and 0.05% by weight of molybdenum (via 0.13% by weight of Na2MoC> 4.2H2O). Each of the operations was repeated with the addition of 5% by weight of sulfur.
    [063] In the compaction method, the initial drag pressures of 1,000 psi (6,895 kPa) and 2,500 psi (17,237 kPa), where 1,000 psi (6,895 kPa) of the drag pressure correspond to about 2,000 psi (137,895 kPa) applied to the material being compacted, with the yields of the final product, that is, the actual percentage of the final product compared to an initial feed weight, are 51% and 75%, respectively. It was observed that the dust levels were visually lower with the increase of the drag pressure, which was used for the test operations.
    [064] The combined boron and boron / sulfur products worked well, yielding 67% and 60%, respectively. There were no negative effects of the products, and the products flowed well, with no equipment problems.
    [065] The products of manganese sulphate and the manganese sulphate / sulfur combination resulted in a slight negative effect on the feed screw with a few stops, suggesting that the manganese had a binding effect on the power feeder. Yields were 67% and 64%, respectively.
    [066] The zinc compound of zinc sulphate products and zinc sulphate / sulfur combination have an inherent surface moisture of about three to about five percent. This moisture migrates to the raw material, making it moist, which could potentially impact the flow in the reservoir. However, yields were not influenced, and products showed yields of 65% and 77%, respectively.
    [067] Copper sulphate and copper sulphate / sulfur combination products were required in several handling operations. Although copper had a moist texture, this moisture was not necessarily transferred to the raw material when mixing, unlike observations with the zinc compound. The copper was received in the form of flakes (particles 1/4 "= 6.35 mm), which were sprayed before being mixed with the raw material. Feed rates were reduced to reduce the risk of ash binding from the system Blue particles were observed in the final product.
    [068] The combination of iron sulfate and sulfur impacted the feeding activity, however, the yields were higher when the iron compound was added without sulfur. This is illustrated in the graph in figure 3.
    [069] Sodium molybdate and the sodium molybdate / sulfur combination were treated in two ratios of 0.05 weight percent and 0.13 weight percent. Once recycling has entered the system, steady state has been achieved, yields have increased and run time has exceeded normal operating time by about twenty minutes of compaction even from the normally discarded dust. This is illustrated by the graph in figure 4, which compares the yield in grams of production to the test interval.
    [070] Sulfur compounds, in general, are well compacted in the raw material of MOP in general and the yield of the flakes in general was slightly increased by the addition of sulfur.
    [071] The finished products have undergone three quality tests, including degradation (wear breakage), tendency to fragmentation and moisture absorption properties. Zinc / sulfur products tended to have increased rupture characteristics, increased fragmentation and increased moisture absorption compared to the standard MOP product. Breakage and dust values can be further reduced if desired, using binding agents and antifragmentation treatment oils.
    [072] Iron and iron / sulfate products tend to turn black during the moisture absorption test and emit a strong hydrogen sulfide odor. The sulfur-treated product generally had a lighter appearance than the sulfur-free product with the same additive.
    [073] Wear and etch breaks are shown in figure 5, fragmentation results are shown in figure 6 and moisture absorption results are shown in figure 7. Visual comparison of all products is included in figure 8.
    [074] The moisture absorption test determines the critical relative humidity of a sample, which is defined as the relative humidity at which the absorption of a water sample increases markedly. The higher the critical relative humidity of a product, the less moisture the product absorbs, thus maintaining better product integrity during handling and storage. Specifically, the moisture absorption test determines the amount of moisture absorbed by a product (as a percentage of weight gained) at various points in time in various humidity settings, such as, for example, 24 hours, 48 hours and 72 hours , when exposed to 26% relative humidity (RH), 40% RH, 60% RH, 72% RH, 76% RH, 80% RH, 85% RH, and 100% relative humidity.
    [075] The fragmentation results are from a defragmentation test which is an abrasion test used to study the degradation characteristics of a sample. Abrasion of the product is created by tipping the product over a period of time with a series of steel balls. The dust inherent in the air is removed from the tipper and weighed. The short-term defragmentation test is performed on samples that have been exposed to 40% RH for 24 hours, while the long-term defragmentation test is performed on samples that have been exposed to seven 24-hour cycling days between 26 and 72% RH. Example 3
    [076] MOP feed provided by Mosaic Potash Esterhazy Kl in Esterhazy, Saskatchewan, Canada (hereinafter "Mosaic Kl" or "Kl") was compacted with various micronutrients in two separate systems and assessed for their technical viability. This example documents the tests and test results performed by an outsourced compaction planning facility. Chemical analysis of MOP is typically 96.25% by weight of KC1, 2.87% by weight of sodium chloride (NaCl), 300 ppm of calcium (Ca), 300 ppm of magnesium (Mg), and 600 ppm sulfate (SO4). The total moisture content of the MOP feed is typically 0.02% by weight at 130 ° C. The MOP feed provided by the Kl mosaic is a 0-0-60% K2O product (expressed in terms of N-P2O5-K2O) and is generated using conventional underground mining techniques. The MOP generated from this process is red / pink in color as is the inherent nature of MOP produced from the underground mining technique.
    [077] The micronutrients used in this production of Kl (EM) micronutrient samples (Table 6 below) included boron (in the form of sodium tetraborate, anhydrous Na2B4O ), Zinc (in the form of ZnSθ4.H2θ monohydrate zinc sulphate) ), and manganese (in the form of manganese sulfate monohydrate MnSCU.foO).
    [078] The following compositions were produced (hereinafter referred to as "the EM products"): Table 6 - Description of the micronutrient elaboration test

    [079] Each of these products was generated using the same process flowchart (figure 1). The MOP and micronutrient (s) were mixed in a batch mix drum. The mixed product was then heated and supplied to the compaction circuit. The compaction circuit consisted of a compactor producing a sinusoidal flake, a flake breaker, a disintegrator and a two-deck vibrating screen providing a 4 x 10 mesh Tyler product. In this circuit, the large and smaller particles were recycled for further processing.
    [080] In the compaction method, a drag pressure of 1,000 psi (6,895 kPa) was used, in which 1000 psi (6,895 kPa) corresponding to approximately 20,000 psi (137,895 kPa) applied to the material being compacted. The product yield ranged from 29.3% to 34.4%. There were no negative effects on the production parameters of the micronutrient products, and the products flowed well, without equipment problems.
    [081] Samples of each of the EM products were analyzed for micronutrient content (boron, zinc and manganese) by an independent external laboratory. The micronutrients found in sodium tetraborate, anhydrous, molybdate, manganese sulfate monohydrate and zinc sulfate monohydrate are effectively retained in a compacted granule. The results are shown in Table 7. Table 7 - Analysis of micronutrients of EM products

    [082] Some adaptations of the dust removal systems may be necessary, since smaller micronutrients can be removed with the dust. Each of the EM products was displayed in order to perform a size analysis. Table 8 below shows the Size Guide Number (SGN) and the Uniformity Index (UI) for each of the current products, along with a baseline. Table 8 - SGN and UI of EM Products

    [083] The SGN and UI for the baseline products (without the addition of micronutrients) were 292/280 and 42/41 respectively. While the UI for EM products is similar to the baseline, there is some variation with the SGN values. The average SGN of EM products is 27 9. By keeping the SGN and UI at acceptable levels, this provides for the generation of less segregation, resulting in a better distribution of micronutrients in the field and increased accessibility of micronutrients for each plant.
    [084] The finished products were treated with defragmented oil and subjected to initial and long-term tests of tendency to fragmentation for quality purposes. The percentage results of powder are shown below in Table 9. Table 9 - Results of initial and long-term fragmentation of EM products

    [085] It was observed from these tests that the addition of zinc (EM-2) improved the baseline fragmentation values, but did not absorb more moisture during the cycling period of this test and the product was visually observed as being defined during the experimental process. The combinations of manganese with zinc (EM-3 and EM-4) did not exhibit such hygroscopic properties. Meanwhile, the addition of boron (EM-1) produced more powder (specifically in the long term), while the rest of the samples (which all contained manganese) showed the worst results in terms of initial and long-term powder. However, although some of these powder values may be higher than desired, they can be reduced and so desired using alternative binders and treatment oils for defragmentation. Example 4
    [086] MOP feed provided by Mosaic Potash Esterhazy Kl in Esterhazy, Saskatchewan, Canada (hereinafter "Mosaic Kl" or "Kl") was compacted with various micronutrients in two separate systems and assessed for their technical viability. This example documents the tests and test results carried out on an industrial scale at Mosaic Kl's facilities. Again, the chemical analysis of MOP is typically 96.25% by weight of KOI, 2.87% by weight of sodium chloride (NaCl), 300 ppm of calcium (Ca), 300 ppm of magnesium (Mg, and 600 ppm of sulfate (SO4). The total moisture content of the MOP feed is typically 0.02% by weight at 130 ° C. The MOP feed provided by the Kl mosaic is a K2O product 0-0-60% ( expressed in terms of N-P2O5-K2O) and is generated using conventional underground mining techniques.The MOP generated from this process is red / pink in color as is the inherent nature of MOP produced from the underground mining technique.
    [087] The micronutrients used in this production of Kl (EM) micronutrient samples (Table 10 below) included zinc (in the form of ZnSO4.H2O monohydrate sulphate), and manganese (in the form of MnSO4 manganese sulphate). H2O).
    [088] The following compositions have been produced (hereinafter - "EM products"). Table 10: Description of the micronutrient elaboration test

    [089] During manufacture, two micronutrients were transported from the granaries on two separate conveyors controlled by variable frequency drives. These conveyors fed a mixing spindle conveyor that mixed the two micronutrients with the preheated MOP and released the mixture into a compaction system. The compaction circuit consisted of a compactor producing a sinusoidal flake, a flake breaker, a crusher and a two deck vibrating screen providing a 4 x 8 or 4 x 9 Tyler Mesh product. In this circuit, the large and small granules dimensions were recycled for further processing. This circuit also employed a finish / polish rating that provided a 4.5 x 8 Tyler Mesh product.
    [090] Eleven samples of the EM-4 product were analyzed for micronutrient content (zinc and manganese) by an independent external laboratory. It was verified that the micronutrients zinc and manganese were contained in a compacted granule.
    [091] The results are shown in Table 11. Table 11 - Analysis of micronutrients in EM products


    [092] Again, there are differences between the concentrations of added micronutrients and those of the final product. Additional adjustments can be made to the dust removal systems, since it is believed that micronutrients can escape the system with the loss of dust. Additionally or alternatively, micronutrients may need to be formulated in excess to ensure that the target concentrations are met.
    [093] Seven samples of the EM-4 product were tested in order to perform a size analysis. Table 12 below shows the Size Guide Number (SGN) and the Uniformity Index (UI) for each of the product streams together with a baseline. Table 12 - SGN and UI of EM products


    [094] The typical SGN and UI values for the baseline product (without adding micronutrients) are 300 and 50, respectively. The results show a cohesive granular particle, of appropriate size that is suitable for combination or direct application, in order to obtain a uniform distribution of the micronutrient components in the field.
    [095] Nine samples of finished product EM-4 were subjected to quality tests, including degradation (rupture) and moisture absorption properties. The results of both tests can be seen below in Table 13. Table 13 - Results of the quality test for EM-4 products

    [096] Results that indicate moisture and product breakdown are not significantly affected after micronutrients have entered each fertilizer particle. Scanning Electron Microscope and X-ray Energy-Dispersive Spectrograph
    [097] With reference to figures 9-12B, four samples of the cohesive granular MPO EM fertilizers containing micronutrients from Example 4 passed through the Scanning Electron Microscope (SEM) and the Energy-Dispersive Spectrograph (EDS) in an external, independent laboratory . The samples were analyzed to determine the relative proportions and distributions of each element of interest within an individual granule and ensure a micronutrient distribution with each micronutrient particle + cohesive MOP. One of these samples was then ground and passed through a new scan to compare the results obtained with the sweeps of the same sample in granular form. The images were collected for each sample, then analyzed by EDS to produce a first spectrum identifying the distribution of the components of potassium (K), chlorine (Cl), sodium (Na), zinc (Zn), manganese (Mn), sulfur (S) and oxygen (O) and then creating a visual map of each element in the SEM image. Scanning and EDS micrographs are shown in figures 9-12B.
    [098] An EDS scan of an SEM image can determine the presence of an element and can give an idea of the relative proportion of the elements that make up the sample, although the quantitative results are not determined by EDS. It should be noted that zinc in its Zn2 + state (added as ZnSO1) emits a low energy response, which is read at the same energy level, as the response generated from Na. Since granular MOP samples containing micronutrients are expected to have both Na and Zn2 +, it cannot be determined which element is responsible for the peaks read in the spectra. All results marked as Zn and Na should therefore be considered as a composite of Zn and Na.
    [099] With reference to figures 9 and 11A-F, all five samples showed consistent results and contained all possible components, without any significant amount of unexpected elements. The EDS results shown in figures 9 and 11A-F show the expected high proportion of K and Cl. As mentioned earlier, the responses marked "Zn" and "Na" must be considered together to demonstrate the presence of Zn and Na. However, since both Zn and Mn are added in the form of sulfate (SO4), the EDS maps of O and S (figures 11F and 11G) can be compared with the EDS map of Mn (figure 11B) to verify the existence of areas where S and O are present, where there is no Mn response. From this comparison, it is reasonable to deduce that these sulphate responses are due to zinc sulphate.
    [0100] As shown in the maps of figures 11A-11F, the distribution of the components, specifically Zn and Mn, is quite uniform, with only small areas of greater concentration of approximately <100 μm in size. Since there is agreement on the values of the crushed and granular forms of the same sample (see figures 12A-12B), it can be inferred that the distribution of the components is probably uniform throughout the sample.
    [0101] During the scan, a quick overview of the entire sample was completed and confirmed that there were no large deposits (ie, complete granules) visible in the subset samples.
    [0102] The results of the SEM and EDS scans confirm that distribution and relative proportions of the constituents of the micronutrients containing MPO Granular are uniform and coherent among the samples. The distribution of manganese and sulfates can be confirmed with good confidence and can be used to suggest the distribution of zinc. The uniform distribution of micronutrients within each granule results in better distribution of micronutrients in the field and greater availability of micronutrients for each plant.
    [0103] The invention can be realized in other specific ways without departing from its essential attributes and, therefore, the illustrated modalities must be considered in all aspects as illustrative and not restrictive.
    权利要求:
    Claims (20)
    [0001]
    1. Cohesive potassium muriate product (MOP) containing one or more secondary nutrients or micronutrients, the MOP product characterized by being formed from a compacted MOP composition, the composition comprising: potassium chloride containing 48.0 per weight percent to 62.0 weight percent K2O; and sodium tetraborate present in an amount such that the MOP product comprises a boron content between 0.001 percent by weight and 1.0 percent by weight, wherein the MOP product exhibits a wear break value and a value conditioned break of 10% or less.
    [0002]
    2. MOP product according to claim 1, characterized by the fact that the MOP product comprises a plurality of cohesive MOP granules formed from the crushing and size classification of compacted MOP composition.
    [0003]
    3. MOP product according to claim 2, characterized by the fact that sodium tetraborate is distributed throughout each of the cohesive MOP granules, thus being adapted to provide a uniform application of micronutrients to a growing area, facilitating micronutrient access to a root zone of a plant in the growing area, compared to dry, non-compacted mixtures.
    [0004]
    4. MOP product according to claim 2, characterized by the fact that the plurality of cohesive MOP granules has a uniform size distribution to reduce or eliminate segregation during material handling and transfer otherwise due to migration by granule size.
    [0005]
    5. MOP product according to claim 1, characterized by the fact that potassium muriate has a chemical profile in the range of 0-0-48 weight percent K2O to 0-0-62 weight percent of K2O, based on an N-P2O5-K2O convention.
    [0006]
    6. MOP product according to claim 5, characterized by the fact that potassium muriate has a chemical profile of 0-0-60 weight percent K2O, based on the N-P2O5-K2O convention.
    [0007]
    7. MOP product according to claim 5, characterized by the fact that potassium muriate has a chemical profile of 0-0-62 weight percent K2O based on the N-P2O5-K2O convention.
    [0008]
    8. MOP product according to claim 1, characterized by the fact that at least one source of micronutrient or secondary nutrient provides one or more micronutrients selected from the group consisting of boron (B), zinc (Zn), manganese (Mn), molybdenum (Mo), nickel (Ni), iron (Fe), copper (Cu), sulfur (S) in its elemental form, sulfur in its oxidized sulphate form (SO4) and combinations thereof.
    [0009]
    9. MOP product according to claim 1, characterized in that it further comprises a source of a secondary micronutrient or nutrient, in which the source of secondary micronutrient or nutrient provides one or more secondary micronutrients and / or nutrients present in the composition in a range from 0.001 to 10 weight percent.
    [0010]
    10. MOP product according to claim 1, characterized in that the composition additionally comprises a binding agent.
    [0011]
    11. MOP product according to claim 10, characterized by the fact that the binding agent is selected from the group consisting of sodium hexametaphosphate (SHMP), tetra-sodium pyrophosphate (TSPP), tetrapotassium pyrophosphate (TKPP) , sodium tripolyphosphate (STPP), diamonium phosphate (DAP), monoammonium phosphate (MAP), granular monoammonium phosphate (GMAP), potassium silicate, sodium silicate, starch, dextran, lignosulfonate, bentonite, montmorillonite, kaolin combinations thereof.
    [0012]
    12. Method of producing a cohesive potassium muriate product (MOP) containing micronutrients, as defined in claim 1, characterized by: providing a composition of MOP including potassium chloride containing from 48.0 weight percent to 62.0 weight percent K2O, and at least one source of micronutrient; compacting the MOP composition to form a compacted MOP composition; crushing the MOP composition into granules to produce the cohesive MOP product, wherein the at least one micronutrient source comprises sodium tetraborate present in an amount such that the MOP product comprises a boron content between 0.001 and 1.0 per weight percent, where the MOP product exhibits a wear break value and a conditioned break value of 10% or less.
    [0013]
    Method according to claim 12, characterized in that it further comprises: classifying the cohesive MOP product granules by size.
    [0014]
    14. Method according to claim 13, characterized by the fact that a size distribution of the granules is uniform, and in which granules that do not conform are resized to conformity.
    [0015]
    15. Method according to claim 12, characterized by the fact that at least one source of micronutrient provides one or more micronutrients selected from the group consisting of boron (B), zinc (Zn), manganese (Mn), molybdenum (Mo), nickel (Ni), copper (Cu), sulfur (S) in its elemental form, sulfur in its oxidized sulphate form (SO4) and combinations thereof.
    [0016]
    16. Method according to claim 12, characterized in that providing a MOP composition includes providing a plurality of micronutrient sources to the potassium muriate, each of the micronutrient sources being added separately and mixed before compaction.
    [0017]
    17. Method according to claim 12, characterized in that providing a MOP composition includes supplying a plurality of micronutrient sources to the potassium muriate, the micronutrient sources being mixed in large quantities, prior to the addition to the muriate of potassium.
    [0018]
    Method according to claim 12, characterized in that it further comprises adding a binding agent to the MOP composition prior to compaction.
    [0019]
    19. Method according to claim 18, characterized in that the binding agent is selected from the group consisting of sodium hexametaphosphate (SHMP), tetra-sodium pyrophosphate (TSPP), tetrapotassium pyrophosphate (TKPP), tripolyphosphate sodium (STPP), diamonium phosphate (DAP), monoammonium phosphate (MAP), granular monoammonium phosphate (GMAP), potassium silicate, sodium silicate, starch, dextran, lignosulfonate, bentonite, montmorillonite, kaolin and combinations of themselves.
    [0020]
    20. Method according to claim 12, further comprising: adding one second of a micronutrient or secondary nutrient, in which the second provides one or more micronutrients or secondary nutrients present in the composition in a range of 0.001 to 10 percent in weight.
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    同族专利:
    公开号 | 公开日
    CA2784661C|2017-01-10|
    RU2607105C2|2017-01-10|
    RU2014108161A|2015-11-27|
    EP2739589A2|2014-06-11|
    US9266784B2|2016-02-23|
    US20160168040A1|2016-06-16|
    WO2013019935A2|2013-02-07|
    CA2784661A1|2013-02-04|
    BR112014002749A2|2017-02-21|
    CL2014000279A1|2014-08-29|
    CN103930387A|2014-07-16|
    US20190292111A1|2019-09-26|
    EP2739589A4|2015-04-22|
    AU2012290064A1|2014-02-27|
    AU2012290064B2|2017-08-17|
    AR087464A1|2014-03-26|
    MX2014001394A|2014-11-13|
    MX362110B|2019-01-07|
    CO6890110A2|2014-03-10|
    WO2013019935A3|2013-04-25|
    IL230764D0|2014-03-31|
    NZ620866A|2016-06-24|
    US20130031943A1|2013-02-07|
    CN108276099A|2018-07-13|
    JO3174B1|2018-03-08|
    IL230764A|2018-06-28|
    JP2014524400A|2014-09-22|
    MY172623A|2019-12-06|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2935387A|1957-05-31|1960-05-03|Duval Sulphur & Potash Company|Compacting process for producing a granular product|
    US3005696A|1957-12-06|1961-10-24|Tennessee Valley Authority|Process for production of ammonium phosphate fertilizers|
    US3135473A|1962-03-21|1964-06-02|American Metal Climax Inc|Process of converting potassium chloride fines into a relatively coarse granular product by compaction|
    US3794478A|1972-09-29|1974-02-26|Kalium Chemicals Ltd|Fertilizer composition containing micronutrients|
    US3961932A|1974-01-07|1976-06-08|Ciba-Geigy Corporation|Process for coating granular fertilizers with chelated micronutrients|
    FR2301497B1|1975-02-24|1978-05-19|Sumitomo Chemical Co|
    US4025329A|1975-12-04|1977-05-24|O. M. Scott & Sons Company|Particulate urea-formaldehyde fertilizer composition and process|
    US4154593A|1976-08-27|1979-05-15|Mississippi Chemical Corporation|Process for granulating ammonium phosphate containing fertilizers|
    US4832728A|1981-09-25|1989-05-23|Melamine Chemicals, Inc.|Fertilizer compositions, processes of making them, and pocesses of using them|
    US4789391A|1985-07-08|1988-12-06|Reed Lignin Inc.|Controlled release formulation for fertilizers|
    NL8700913A|1987-04-16|1988-11-16|Nl Stikstof|METHOD FOR MANUFACTURING FERTILIZER GRANULES|
    US4758261A|1987-11-30|1988-07-19|Tennessee Valley Authority|Diammonium phosphate produced with a high-pressure pipe reactor|
    US5653782A|1994-12-26|1997-08-05|Rotem Amfert Negev Ltd.|Process for the manufacture of sulfur-containing fertilizers|
    IL110241A|1994-07-07|1998-10-30|Baran Advanced Materials Ltd|Controlled release fertilizers|
    US6413291B1|1995-03-03|2002-07-02|Magic Green Corporation|Soil conditioning agglomerates containing calcium|
    DE19826570C2|1998-06-15|2002-10-31|Piesteritz Stickstoff|Process for the production of fertilizer granules containing urea and ammonium sulfate|
    US6254655B1|1999-03-18|2001-07-03|Oms Investments, Inc.|Processes for preparing granular composite fertilizer compositions and products produced thereby|
    DE19919233C2|1999-04-28|2002-06-20|Kali & Salz Ag|Process for the production of fertilizer granules|
    CA2375983C|1999-06-25|2007-09-18|Henri Dinel|Organic fertilizer containing compost|
    US6241796B1|1999-07-21|2001-06-05|Imc-Agrico Company|Method for producing fertilizer grade DAP having an increased nitrogen concentration from recycle|
    CN100434399C|2000-05-17|2008-11-19|美盛公司|Sulfur-containing fertilizer composition and method for preparing same|
    RU2182142C1|2001-04-11|2002-05-10|Открытое акционерное общество "Научно-исследовательский институт по удобрениям и инсектофунгицидам им. Я.В. Самойлова"|Method to obtain granulated nitroammophoska|
    US6749660B2|2001-06-04|2004-06-15|Geovation Technologies, Inc.|Solid-chemical composition and method of preparation for the anaerobic bioremediation of environmental contaminants coupled to denitrification|
    CA2444099A1|2003-08-11|2005-02-11|Dave Zirk|Compacted granular potassium chloride, and method and apparatus for production of same|
    US7497891B2|2004-08-31|2009-03-03|The Mosaic Company|Method for producing a fertilizer with micronutrients|
    US20060148646A1|2004-09-23|2006-07-06|Taylor Pursell|Controlled release fertilizers containing calcium sulfate and processes for making same|
    US7789932B2|2006-02-08|2010-09-07|The Andersons, Inc.|Dispersible potash pellets|
    CA2638704C|2008-08-13|2014-04-08|Karnalyte Resources Inc.|Process for producing potassium chloride granulars|
    CN101429064A|2008-12-19|2009-05-13|邢台绿洲农肥有限责任公司|Process for producing sulfate of calcium-potash-magnesia|
    US9181137B2|2009-03-20|2015-11-10|Agtec Innovations, Inc.|Micronutrient fertilizers and methods of making and using the same|
    CA2663119A1|2009-04-16|2010-10-16|Sulphur Solutions Inc.|Dispersible sulphur fertilizer pellets|
    US8282898B2|2009-11-23|2012-10-09|Karnalyte Resources Inc.|Process for the formulation of potassium chloride from a carnallite source|
    MX2012010144A|2010-03-03|2013-02-21|Mos Holdings Inc|Fertilizer composition containing micronutrients and methods of making same.|
    NZ620866A|2011-08-04|2016-06-24|Mos Holdings Inc|Compacted muriate of potash fertilizers containing micronutrients and methods of making same|
    CN102320879A|2011-09-06|2012-01-18|李子先|High nutrient compound selenium fertilizer and preparation method thereof|
    WO2014152994A1|2013-03-14|2014-09-25|Mos Holdings Inc.|Fertilizer composition and method for preparing the same|NZ620866A|2011-08-04|2016-06-24|Mos Holdings Inc|Compacted muriate of potash fertilizers containing micronutrients and methods of making same|
    CA2821909A1|2012-07-27|2014-01-27|Carbon Basis Company Ltd.|Biochar products and method of manufacture thereof|
    EP3359617A4|2015-10-08|2019-08-14|The Carbon Basis Company Ltd.|Biochar products and method of manufacture thereof|
    US10031183B2|2013-03-07|2018-07-24|Rai Strategic Holdings, Inc.|Spent cartridge detection method and system for an electronic smoking article|
    WO2014152994A1|2013-03-14|2014-09-25|Mos Holdings Inc.|Fertilizer composition and method for preparing the same|
    US9220302B2|2013-03-15|2015-12-29|R.J. Reynolds Tobacco Company|Cartridge for an aerosol delivery device and method for assembling a cartridge for a smoking article|
    UA123582C2|2015-05-19|2021-04-28|Сулваріс Інк.|Fertilizer pellets with micronized sulphur|
    US20200071241A1|2016-09-02|2020-03-05|Harvey M. Goertz|Particulate compositions and methods of use|
    EP3601200A4|2017-03-31|2021-01-13|The Mosaic Company|Fertilizers containing slow and fast release sources of boron|
    US10611701B2|2017-05-23|2020-04-07|The Mosaic Company|Swellable fertilizer granules containing elemental sulfur with increased oxidation rates|
    BR112020015159A2|2018-02-27|2021-01-19|Dead Sea Works Ltd.|POTASSA POWDER GRANULATION PROCESS|
    CN108947672A|2018-08-13|2018-12-07|合肥工业大学|A kind of borosilicate kalium liquid fertilizer material and preparation method thereof|
    US11180424B1|2018-12-07|2021-11-23|Fertile Peat Products, Llc|Phosphate fertilizer with finely ground elemental sulfur, swelling agent and rock phosphate|
    CN110105138A|2019-05-15|2019-08-09|金正生物化工有限公司|A kind of high concentration organic-inorganic compound fertilizer granulating agent|
    DE102019007587A1|2019-10-31|2021-05-06|K+S Aktiengesellschaft|Process for the production of sulphurous potash granules|
    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-07-30| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-04-07| B25A| Requested transfer of rights approved|Owner name: THE MOSAIC COMPANY (US) |
    2020-06-30| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-12-01| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-02-09| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 02/08/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161514952P| true| 2011-08-04|2011-08-04|
    US61/514,952|2011-08-04|
    PCT/US2012/049301|WO2013019935A2|2011-08-04|2012-08-02|Compacted muriate of potash fertilizers containing nutrients and methods of making same|
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