Calcium sulfate urea granules and methods for producing and using the same

Abstract

A calcium sulfate urea (UCS) fertilizer granule and methods for making and using the same are disclosed. The granule can include urea, calcium sulfate, and a calcium sulfate urea adduct. The granule can contain 33 wt. % to 40 wt. % elemental nitrogen, 2 wt. % to 5 wt. % elemental calcium, and 2 wt. % to 5 wt. % elemental sulfur.

Claims

1. A method of making a calcium sulfate urea (UCS) fertilizer granule comprising urea, calcium sulfate, and a calcium sulfate urea adduct, wherein the calcium sulfate urea (UCS) fertilizer granule comprises 33 wt. % to 40 wt. % elemental nitrogen, 2 wt. % to 5 wt. % elemental calcium, and 2 wt. % to 5 wt. % elemental sulfur, and wherein at least 30 wt. % of the urea in the calcium sulfate urea (UCS) fertilizer granule is comprised in the calcium sulfate urea adduct, the method comprising: combining urea, calcium sulfate, and water to form an aqueous slurry, wherein urea is combined in excess of the stoichiometric ratio for production of a calcium sulfate urea adduct; mixing the aqueous slurry under conditions sufficient to produce a calcium sulfate urea adduct; and removing at least a portion of the water from the aqueous slurry to form the calcium sulfate urea (UCS) fertilizer granule, wherein removing at least a portion of the water from the aqueous slurry comprises adding sulfuric acid and ammonia to cause an exothermic reaction, and wherein heat generated from the exothermic reaction is sufficient to remove at least a portion of the water from the aqueous slurry.

2. The method of claim 1, wherein the aqueous slurry comprises 12 wt. % to 16 wt. % water.

3. The method of claim 1, wherein the amount of sulfuric acid added is from about 5% to 15% of the weight of the aqueous slurry.

4. The method of claim 1, wherein from about 1.5 to 2.5 moles of ammonia are added for every one mole of sulfuric acid.

5. The method of claim 1, further comprising adding a sufficient amount of MgSO.sub.4 to obtain a calcium sulfate urea (UCS) fertilizer granule further comprising 1.5 wt. % to 5 wt. % MgO.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) Advantages of the present invention may become apparent to those skilled in the art with the benefit of the following detailed description and upon reference to the accompanying drawings.

(2) FIGS. 1A-1C are: 1A a schematic of a system that can be used to produce UCS fertilizer granules of the present invention in which solid urea can be used as a starting material; 1B a schematic of a system that can be used where urea solution, urea melt, or a calcium sulfate slurry can be used as reactants material; and 1C a schematic of a system that can be used where an exothermic reaction can be used to remove part of the water of a UCS adduct containing slurry.

(3) While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings. The drawings may not be to scale.

DETAILED DESCRIPTION OF THE INVENTION

(4) The UCS granule of the present invention can include a UCS adduct formed from the following reaction:
CaSO.sub.4.nH.sub.2O+4CO(NH.sub.2).sub.2.fwdarw.CaSO.sub.4.4CO(NH.sub.2).sub.2+nH2O,
where n is a value from 0 to 2 (e.g., 0, 0.5, 1, 2).

(5) The UCS granule can be produced by using urea in excess of the stoichiometric ratio for production of a UCS adduct (e.g., more than four moles of urea for every one mole of calcium sulfate). The UCS granule produced is stable and can contain elemental nitrogen at concentrations above 27 wt. % (e.g., at least, equal to, or between any two of 27 wt. %, 28 wt. %, 29 wt. %, 30 wt. %, 31 wt. %, 32 wt. %, 33 wt. %, 34 wt. %, 35 wt. %, 36 wt. %, 37 wt. %, 38 wt. %, and 40 wt. %). For example, UCS granules of the present invention can include 33, 34, 35, 36, 37, 38, 39, or 40 wt. % elemental nitrogen, 2, 3, 4, or 5 wt. % elemental calcium, and 2, 3, 4, or 5 wt. % elemental sulfur. UCS granules of the present invention can include 33 wt. % to 37 wt. % elemental nitrogen, 3 wt. % to 5 wt. % elemental calcium, and 3 wt. % to 5 wt. % elemental sulfur. The UCS fertilizer granule can include 33 wt. % to 35 wt. % elemental nitrogen, 4 wt. % to 5 wt. % elemental calcium, and 4 wt. % to 5 wt. % elemental sulfur. UCS granules of the present invention can include 33 wt. %, 34 wt. %, or 35 wt. % elemental nitrogen, 4 wt. % or 5 wt. % elemental calcium, and 4 wt. % or 5 wt. % elemental sulfur. UCS granules of the present invention can include 33 wt. % or 34 wt. % elemental nitrogen, 4 wt. % or 5 wt. % elemental calcium, and 4 wt. % or 5 wt. % elemental sulfur. UCS granules of the present invention can include 33 wt. % elemental nitrogen, 5 wt. % elemental calcium, and 5 wt. % elemental sulfur. UCS granules of the present invention can include 34 wt. % elemental nitrogen, 5.5 wt. % elemental calcium, and 5 wt. % elemental sulfur. In some instances, the granule does not include phosphorus, potassium, or both. In some preferred instances, the UCS granule can be a 33-0-0-based fertilizer. This can be beneficial where higher concentrations of nitrogen are desired in a stable granulated fertilizer and can be beneficial by reducing the amount of material needed to provide nitrogen in a stable fertilizer.

(6) The UCS granule produced can also contain low amounts of moisture. The free-moisture content of the granule can be less than 1 wt. %, preferably less than 0.8 wt. %, less than 0.5 wt. % water or 0.25 wt. % to 0.7 wt. % water. In some instances, the free moisture content is 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, or 0 wt. %.

(7) Further, it was unexpectedly found that when using excess urea to produce the UCS adduct, less water is needed to create a slurry that is capable of being transported (e.g., pumped) and is suitable for granulation. This is beneficial in reducing the energy and costs of drying the slurry, recycling the water, and providing fresh water. In addition, it was determined that combining sulfuric acid and ammonia into the UCS adduct slurry causes an exothermic reaction sufficient to remove all or part of the water in the slurry. This is beneficial in reducing the energy and costs in drying the slurry. The product of the exothermic reaction, ammonium sulfate, also benefits the fertilizer, as ammonium sulfate is a readily soluble fertilizer that can be quickly available to crops once applied. Also, it was determined that a UCS granule containing MgO substantially increases the hardness and stability of the UCS granule. In some instances, MgSO.sub.4 can be added into the UCS granule or UCS adduct slurry to provide the MgO. In particularly preferred embodiments, fertilizer compositions comprising a plurality of granules of the present invention are in a dry form and not in a slurry form.

(8) In some instances, the surface of the UCS adduct can include a layer having urea, calcium sulfate, or additional UCS adduct, or any combination thereof or all thereof. By way of example the layer can be formed on at least a portion of the outer surface of the UCS adduct, and the layer can include: (1) urea; (2) calcium sulfate; (3) additional UCS adduct; (4) urea and calcium sulfate; (5) urea and additional UCS adduct; (6) calcium sulfate and additional UCS adduct; (7) or urea, calcium sulfate, and additional UCS adduct. The layer can self-form or self-assemble during the production process of the UCS granule. The urea, calcium sulfate, and/or UCS adduct in the layer can be in particulate form. The USC adduct can also include a layer that has urea, calcium sulfate, or additional UCS adduct, or a combination thereof or all thereof. The layer can be particles of urea, calcium sulfate, or additional UCS adduct. Also, and without wishing to be bound by theory, it is believed that the layer self-assembles during the manufacture of the granule.

(9) The granule can be comprised of one or more particles. A first portion of the particles can be the calcium sulfate urea adduct, and a second portion of the particles can form a layer that covers at least a portion of the calcium sulfate urea adduct. In certain non-limiting aspects, the first portion of the particles can have an average particle size of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 micrometers, and the second portion of the particles can have an average particle size of 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, or 900 micrometers or any size there between. The layer can be made up of particles of urea, particles of calcium sulfate, and/or particles of calcium sulfate urea adduct, or any combination, or all thereof. In some embodiments, the smaller and larger particles can be elongated particles or can be substantially spherical particles or other shapes, or combinations of such shapes. Non-limiting examples of shapes include a spherical, a puck, an oval, a rod, an oblong, or a random shape.

(10) The UCS granules can have a crush strength of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 kg/granule, or more, or any amount there between, preferably 2 kg/granule to 5 kg/granule.

(11) An additional non-limiting benefits of the UCS granules of the present invention is that they can be a good acidifier, which can contribute to efficient nutrient distribution to the soil and/or plants. Even further, the granules can increase nutrient uptake by the plants due, at least in part, to these acidic feature. In some particular aspects, the granules can have a pH of 3, 3.5, 4, 4.5, 5, 5.5, or 6, preferably 4 to 5 when mixed with water. Also, the granules of the present invention can have an average size of 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or 5 mm, preferably about 2 mm to 4 mm. It is also believed that the contents and/or structure of the granules of the present invention can aid in reducing nitrogen volatilization.

(12) These and other non-limiting aspects of the present invention are discussed in further detail in the following sections.

A. Process to Produce UCS Fertilizer Granules

(13) The UCS granules of the present invention can be made using a granulation system shown in FIG. 1A, FIG. 1B, or FIG. 1C, or a combination thereof. The granulation system can be a continuous process capable of handling slurries. The granulation system can include a mixing zone (mixing). The mixing zone can be in a continuous stirred-tank reactor. In the mixing zone, solid urea (e.g., fresh urea prills) (FIG. 1A), calcium sulfate (e.g., gypsum), and water can be combined in a mixing unit (e.g., a continuous stirred-tank reactor) to form an aqueous slurry. In some instances, a stoichiometric excess of urea, such as more than four moles of urea for every one mole of calcium sulfate, is mixed in the mixing zone. In some instances, the excess urea is at least, equal to, or between any two of 5 moles, 6 moles, 7 moles, 8 moles, 9 moles, and 10 moles or more of urea for every one mole of calcium sulfate. In some instances, the water content of the aqueous slurry is 12% to 20% by weight, 12% to 16% by weight, or 13% to 15% by weight. It was unexpectedly found that using this amount of water still produced a slurry that acted like a fluid and was pumpable. In some instances, the water content is provided by water that is not bound or contained in the urea or calcium sulfate. A high level of mixing (e.g., agitator rpm of greater than 200 rpm) can be used to promote formation of the UCS adduct to decrease the amount of heat required for the formation. Additionally or alternatively, urea solution (See, FIG. 1B) and/or urea melt can be used, and can be introduced to the mixing zone. Calcium sulfate in any form of hydration or non-hydration, (e.g., anhydrous calcium sulfate, calcium sulfate hemihydrate, and calcium sulfate dihydrate) can be used as the calcium sulfate. These calcium sulfates with varying degrees on hydration can then be converted to calcium sulfate dihydrate suitable for the UCS adduct formation. Additionally or alternatively, a calcium sulfate slurry (See, FIG. 1B) can be used, and can be introduced to the mixing zone. Urea dissolution is an endothermic process. Optionally, the temperature of the mixing zone can be increased to 1) increase the formation of the adduct, 2) decrease the amount of water needed, and/or 3) decrease the viscosity of the aqueous slurry. Heat can be provided by any means suitable or known. In some instances, steam is used. The optional use of steam can inhibit absorption of heat from the surroundings and hence lowering the temperature requirement in the mixing zone without additional energy. With steam injection, the urea can be rapidly dissolved while the surrounding material is maintained at the high temperature, which can preferably be about 80° C. to 100° C. or any range or value therein. Without wishing to be bound by theory, it is believed that the urea should be in solution (partially or fully solubilized) to exchange urea for water in the calcium sulfate dihydrate composition so as to form the USC adduct. Additional active or inactive ingredients can be added to the aqueous slurry while in the mixing zone or at any other time.

(14) Alternatively, urea can be dissolved in an aqueous solution, calcium sulfate can be formed into a slurry, or both can be performed before entry into the mixing zone (premixing) (FIG. 1B). Accordingly, all or part of the water that enters the mixing zone can enter in a urea solution and/or calcium sulfate slurry.

(15) Also as an alternative, the aqueous slurry containing UCS adduct produced in the mixing zone can exit the mixing zone and enter a second mixing zone where additional active or inactive ingredients can be added to the aqueous slurry. In some embodiments, ammonia and sulfuric acid are added to produce ammonium sulfate in an exothermic reaction, which can further drive production of UCS adduct and evaporate water from the slurry. Ammonia and sulfuric acid can be added to any one of the zones to produce ammonium sulfate and/or to produce heat.

(16) In some instances, the aqueous slurry exits the mixing zone or second mixing zone and can enter a bound water release zone (bound water release). In the bound water release zone, the aqueous slurry can be mixed with unreacted calcium sulfate and optional recycled UCS adduct and/or optional urea. As UCS adduct is produced, bound water within the calcium sulfate is released, further promoting the conversion to UCS adduct. The temperature of the bound water release zone can be 80° C. to 100° C., preferably 85° C. to 95° C., or at least, equal to, or between any two of 80° C., 85° C., 90° C., and 95° C.

(17) Though shown in the figures, optionally, the slurry can exit the bound water release zone and enter a stabilizing zone (stabilizing) where mixing of the mixture of urea, calcium sulfate, UCS adduct, and water can be continued. In some embodiments, UCS adduct recycle (UCS recycle) can be added to any one of the zones to help maintain consistency of the mixture. Additional active or inactive ingredients can be added to the slurry.

(18) The conditions of the material exiting the stabilizing zone, bound water zone, mixing zone, or second mixing zone can be a semi-wet granule, which can easily form “balls when compresses with the hands.” If the material is too dry, then granulation is decreased leading to smaller product fraction in the material exiting the dryer. If the material is too “wet” (tending towards mud) then there is a risk that the UCS “mud” will stick to the surfaces of the dryer, leading to building up on the dryer surface. In some instances, the material can be formed into granules during or after exiting the stabilizing zone.

(19) Drying the granule can enable agglomeration to form solid granules and can also create crystal bridges to enable crystallization of the UCS adduct. In some embodiments, ammonia and sulfuric acid are added to the material in the stabilizing zone, and/or an optional granulation zone (FIG. 1C), and/or added to the material after leaving the bound water release zone and/or the stabilizing zone. In some embodiments, the granules are dried or further dried in a drying zone (drying) (FIG. 1C). The addition of ammonia and sulfuric acid produces ammonium sulfate in an exothermic reaction, which can further drive production of UCS adduct and/or evaporate water from the material. In some instances, sufficient amounts of ammonia and sulfuric acid are added to remove all or substantially all of the free water. In some instances, the material is sufficiently dried by the exothermic reaction so that the material does not or does not need to subsequently enter a dryer or drying zone.

(20) The material can enter a dryer (dryer) (e.g., a rotating dryer) to reduce the amount of free water in the material (FIG. 1A and FIG. 1C). The formation of granules can also occur or continue during the drying of the material. Observations of the material entering and exiting the drying zone confirmed that granulation and UCS adduct conversion continues within the dryer. Operating conditions of the dryer were found to be highly significant to achieve the desired level of drying while promoting urea adduct conversion. The operating temperature of the dryer can also be used to adjust the temperature at which the UCS recycle materials re-enters the granulation system. Continuous operation can be achieved with dryer exit temperatures (as measured by the exit gas) between 80° C. to 90° C., preferably 85° C. to 88° C. or any value or range therein. If the exit temperature rises above 90° C. to 95° C., the composition may melt creating a molten mass inside the drier.

B. Blended or Compounded Fertilizer Compositions

(21) The UCS granules of the present invention can also be included in a blended or compounded fertilizer composition comprising other fertilizers, such as other fertilizer granules. Additional fertilizers can be chosen based on the particular needs of certain types of soil, climate, or other growing conditions to maximize the efficacy of the UCS granules in enhancing plant growth and crop yield. The other fertilizer granules can be granules of urea, single super phosphate (SSP), triple super phosphate (TSP), ammonium sulfate, monoammonium phosphate (MAP), diammonium phosphate (DAP), muriate of potash (MOP), and/or sulfate of potash (SOP), and the like.

C. Method of Using the UCS Fertilizer Granules

(22) The UCS fertilizer granules of the present invention can be used in methods of increasing the amount of nitrogen in soil and of enhancing plant growth. Such methods can include applying to the soil an effective amount of a composition comprising the UCS fertilizer granule of the present invention. The method may include increasing the growth and yield of crops, trees, ornamentals, etc. such as, for example, palm, coconut, rice, wheat, corn, barley, oats, and soybeans. The method can include applying UCS fertilizer granules of the present invention to at least one of a soil, an organism, a liquid carrier, a liquid solvent, etc.

(23) Non-limiting examples of plants that can benefit from the fertilizer of the present invention include vines, trees, shrubs, stalked plants, ferns, etc. The plants may include orchard crops, vines, ornamental plants, food crops, timber, and harvested plants. The plants may include Gymnosperms, Angiosperms, and/or Pteridophytes. The Gymnosperms may include plants from the Araucariaceae, Cupressaceae, Pinaceae, Podocarpaceae, Sciadopitaceae, Taxaceae, Cycadaceae, and Ginkgoaceae families. The Angiosperms may include plants from the Aceraceae, Agavaceae, Anacardiaceae, Annonaceae, Apocynaceae, Aquifoliaceae, Araliaceae, Arecaceae, Asphodelaceae, Asteraceae, Berberidaceae, Betulaceae, Bignoniaceae, Bombacaceae, Boraginaceae, Burseraceae, Buxaceae, Canellaceae, Cannabaceae, Capparidaceae, Caprifoliaceae, Caricaceae, Casuarinaceae, Celastraceae, Cercidiphyllaceae, Chrysobalanaceae, Clusiaceae, Combretaceae, Cornaceae, Cyrillaceae, Davidsoniaceae, Ebenaceae, Elaeagnaceae, Ericaceae, Euphorbiaceae, Fabaceae, Fagaceae, Grossulariaceae, Hamamelidaceae, Hippocastanaceae, Illiciaceae, Juglandaceae, Lauraceae, Lecythidaceae, Lythraceae, Magnoliaceae, Malpighiaceae, Malvaceae, Melastomataceae, Meliaceae, Moraceae, Moringaceae, Muntingiaceae, Myoporaceae, Myricaceae, Myrsinaceae, Myrtaceae, Nothofagaceae, Nyctaginaceae, Nyssaceae, Olacaceae, Oleaceae, Oxalidaceae, Pandanaceae, Papaveraceae, Phyllanthaceae, Pittosporaceae, Platanaceae, Poaceae, Polygonaceae, Proteaceae, Punicaceae, Rhamnaceae, Rhizophoraceae, Rosaceae, Rubiaceae, Rutaceae, Salicaceae, Sapindaceae, Sapotaceae, Simaroubaceae, Solanaceae, Staphyleaceae, Sterculiaceae, Strelitziaceae, Styracaceae, Surianaceae, Symplocaceae, Tamaricaceae, Theaceae, Theophrastaceae, Thymelaeaceae, Tiliaceae, Ulmaceae, Verbenaceae, and/or Vitaceae family.

(24) The effectiveness of compositions comprising the UCS fertilizer granules of the present invention can be ascertained by measuring the amount of nitrogen in the soil at various times after applying the fertilizer composition to the soil. It is understood that different soils have different characteristics, which can affect the stability of the nitrogen in the soil. The effectiveness of a fertilizer composition can also be directly compared to other fertilizer compositions by doing a side-by-side comparison in the same soil under the same conditions.

(25) As discussed above, one of the unique aspects of the UCS fertilizer granules of the present invention is that they can have a density that is greater than water. This can allow the granules to sink in water rather than float in water. This can be especially beneficial in instances where application is intended to a crop that is at least partially or fully submerged in water. A non-limiting example of such a crop is rice, as the ground in a rice paddy is typically submerged in water. Thus, application of UCS granules to such crops can be performed such that the granules are homogenously distributed on the ground that is submerged under water. By comparison, granules that have a density that is less than water would have a tendency to remain in or on the water surface, which could result in washing away of the granules and/or coalescence of the granules, either of which would not achieve homogenous distribution of the granules to the ground that is submerged under water.

D. Compositions

(26) The UCS granules can be used alone or in combination with other fertilizer actives and micronutrients. The other fertilizer actives and micronutrients can be added with urea and calcium sulfate at the beginning of the granulation process or at any later stage.

(27) Non-limiting examples of additional additives can be micronutrients, primary nutrients, and secondary nutrients. A micronutrient is a botanically acceptable form of an inorganic or organometallic compound such as boron, copper, iron, chloride, manganese, molybdenum, nickel, or zinc. A primary nutrient is a material that can deliver nitrogen, phosphorous, and/or potassium to a plant. Nitrogen-containing primary nutrients may include urea, ammonium nitrate, ammonium sulfate, diammonium phosphate, monoammonium phosphate, urea-formaldehyde, or combinations thereof. A secondary nutrient is a substance that can deliver calcium, magnesium, and/or sulfur to a plant. Secondary nutrients may include lime, gypsum, superphosphate, or a combination thereof. For example, in some instances the UCS granule can contain calcium sulfate, potassium sulfate, magnesium sulfate or a combination thereof.

(28) In one aspect, the UCS granules can comprise one or more inhibitors. The inhibitor can be a urease inhibitor or a nitrification inhibitor, or a combination thereof. In one aspect, UCS granule can comprise a urease inhibitor and a nitrification inhibitor. In one aspect, the inhibitor can be a urease inhibitor. Suitable urease inhibitors include, but are not limited to, N-(n-butyl) thiophosphoric triamide (NBTPT) and phenylphosphorodiamidate (PPDA). In one aspect, the UCS fertilizer granule can comprise NBTPT or PPDA, or a combination thereof. In another aspect, the inhibitor can be a nitrification inhibitor. Suitable nitrification inhibitors include, but are not limited to, 3,4-dimethylpyrazole phosphate (DMPP), dicyandiamide (DCD), thiourea (TU), 2-chloro-6-(trichloromethyl)-pyridine (Nitrapyrin), 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazol, which is sold under the tradename Terrazole®, by OHP Inc., USA, 2-amino 4-chloro 6-methyl pyrimidine (AM), 2-mercaptobenzothiazole (MBT), or 2-sulfanilamidothiazole (ST), and any combination thereof. In one aspect, nitrification inhibitor can comprise DMPP, DCD, TU, nitrapyrin, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazol, AM, MBT or ST, or a combination thereof. In one aspect, the UCS fertilizer granule can comprise NBTPT, DMPP, TU, DCD, PPDA, nitrapyrin, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazol, AM, MBT, or ST or a combination thereof.

EXAMPLES

(29) The present invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes only, and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters which can be changed or modified to yield essentially the same results.

Example 1

(30) (Lab Scale Process to Prepare UCS Fertilizer Granules)

(31) A lab scale process for making a UCS fertilizer granule of the present invention was performed by using the system described in FIGS. 1A-1C and in Section A of the Detailed Description of the Invention. It was unexpectedly found that when a stoichiometric excess of urea (e.g., more than four moles of urea for every one mole of calcium sulfate) was used in the reaction having moisture contents as low as 12 wt. % ensured rapid conversion and maintained the slurry within an acceptable fluid like or “pumpable” condition.

(32) Mixtures of urea and gypsum (CaSO.sub.4.2H.sub.2O) were added to hot water with different ratios of urea, gypsum, and water. The urea had a nitrogen content of about 46 wt. % and a moisture content of about 0.3 wt. % or less. The gypsum had a calcium content of about 24 wt. % and sulfur content of about 18 wt. % and a moisture content of about 25 wt. %. Extra water was added to form a slurry. The aqueous mixture was heated to about 90° C. and stirred constantly for 15 minutes. Repeat sample preparation at different reaction temperatures (80° C., 90° C., 100° C., 110° C.) and different stirring (resident) times (10 & 15 minutes) were tested. The reactions used prilled urea, grinded urea, melt urea, and 70 wt. % urea solution, or combinations thereof. The reactions were performed at room temperature.

(33) Conclusions about the lab scale process include the following. (1) Experiments based on slurry formation determined that a temperature of 80° C. was optimal for urea conversion. Increasing the temperature to formation of urea conversion to 110° C. provided few improvements. Using urea melt for the urea conversion also did not provide improvements to the urea conversion. (2) Water content of the raw materials was determined to be significant. Without wishing to be bound by theory, it is believed that water acted as the conversion “initiator,” dissolving the urea and, thus making it available to replace the hydration water within the gypsum. From the slurry experiments it was determined that a moisture content of 18 wt. % to 22 wt. % when using urea concentrations at or below stoichiometric concentrations for the formation of UCS adduct ensured both rapid conversion of the urea and maintained the slurry within an acceptable fluid like or “pumpable” condition without solidification of the slurry. Surprisingly, when a stoichiometric excess of urea was used in the reaction with moisture contents as low as 12 wt. % rapid conversion was realized and the slurry was maintained within an acceptable fluid like “pumpable” condition without solidification of the slurry. From the drum granulation tests it was determined that a moisture content above 5 wt. % was preferred to observe urea conversion. However, the lab drum tests were unable to “maintain” the moisture conditions once started so it was likely that moisture was lost throughout the tests, thus slowing the rate of conversion. (3) Agitation promoted interaction between the urea (which rapidly dissolved to form a solution) and the gypsum.

Example 2

(34) (Characterization of the UCS Slurry and UCS Fertilizer Granules)

(35) Fertilizer blends or compounded fertilizers containing free urea (urea not bound in an adduct), are difficult to granulate and are typically not stable because of urea's reactivity with other fertilizers. Urea can react to produce water, which can dissolve the remaining free urea and increase the ability of urea to react with the other components in the fertilizer. This chain reaction can quickly render a fertilizer unusable. Accordingly, in the past, the aim of production of urea adducts for use in fertilizers, such as UCS adducts, has been to bind as much free urea in the adduct as possible. Therefore, production schemes for UCS adducts have in the past avoided using urea in stoichiometric excesses amounts, so that free urea in the product can be minimized or avoided.

(36) It was unexpectedly found that using a stoichiometric excess of urea in the production of the UCS adduct (more than four moles of urea for every one mole of calcium sulfate) produced a stable UCS adduct containing product that also contained a higher amount of elemental nitrogen (e.g. 33 wt. % to 40 wt. %) than was possible using other methods (e.g., maximum 27 wt. % elemental nitrogen using stoichiometric amounts of urea). The stable product provided an attractive fertilizer alone or in combination with other beneficial agents for plants. Not to be bound by theory, it is believed that the crystal structure of the UCS adduct can allow for additional urea molecules to be bound in UCS adduct crystals either as part of the crystal lattice or UCS adduct crystallizes around free urea, shielding it from reacting with other components of the UCS granule and other fertilizers.

(37) Table 1 provide characterization data for the UCS slurry and UCS granules using the slurry production process described in FIGS. 1A-1C and in Section A of the Detailed Description of the Invention. The reaction was performed with ratios of reactants to provide about ˜717 kg of urea/metric ton of UCS final product and ˜283 kg gypsum/metric ton of UCS final product.

(38) TABLE-US-00001 TABLE 1 (Average Chemical & Physical Analysis for UCS Granule 33 − 0 − 0 + 5% S + 5% Ca) ANALYSIS OF UCS SLURRY FOR PRODUCTION OF UCS GRANULE Water Quantity Total Nitrogen Sulfur Calcium (wt. %) (wt. %) (wt. %) (wt. %) 0 33 5 5 1 32.67 4.95 4.95 2 32.34 4.9 4.9 3 32.01 4.85 4.85 4 31.68 4.8 4.8 5 31.35 4.75 4.75 6 31.02 4.7 4.7 7 30.69 4.65 4.65 8 30.36 4.6 4.6 9 30.03 4.55 4.55 10 29.7 4.5 4.5 11 29.37 4.45 4.45 12 29.04 4.4 4.4 13 28.71 4.35 4.35 14 28.38 4.3 4.3 15 28.05 4.25 4.25 16 27.72 4.2 4.2 17 27.39 4.15 4.15 18 27.06 4.1 4.1 19 26.73 4.05 4.05 20 26.4 4 4 21 26.07 3.95 3.95 22 25.74 3.9 3.9 23 25.41 3.85 3.85 24 25.08 3.8 3.8 25 24.75 3.75 3.75 26 24.42 3.7 3.7 27 24.09 3.65 3.65 28 23.76 3.6 3.6 29 23.43 3.55 3.55 30 23.1 3.5 3.5 ANALYSIS OF GRANULE Chemical Analysis of Granule (wt. % of Granule) Total Nitrogen 34.2 Sulfur 5.1 Calcium 5.5 Moisture 0.54 Physical Analysis of Granule % of batch with 20% Particle size >4 mm % of batch with 58% Particle size 2-4 mm % of batch with 78% Particle size 1-4 mm % of batch with 20% Particle size 1-2 mm % of batch with  1% Particle size <1 mm Crush Strength 5.1 kgf/granule

(39) Chemical analysis for nitrogen content was determined by the Total Nitrogen in Fertilizer by Combustion Technique described in AOAC official Method 993.13.1996 (AOAC International). Calcium content was determined by the Calcium by Atomic Absorption Spectrometric Method described in ISO 10084, 1992 (International Organization for Standardization). Sulfur content was determined by the Gravimetric Barium Sulfate Method described in ISO 10084, 1992 (International Organization for Standardization).

(40) Particle size was determined using standard sieve test methods.

(41) Crush strength was determined by a commercial compression tester (Chatillon Compression Tester). Individual granules between 2 to 4 mm in diameter were placed on a mounted flat (stainless steel) surface and pressure was applied by a flat-end rod (stainless steel) attached to the compression tester. A gauge mounted in the compression tester measured the pressure (in kilograms) required to fracture the granule. At least 25 granules were tested and the average of these measurements was taken as crush strength in kilograms. (Ref. method #IFDC S-115 Manual for determining physical properties of fertilizer-IFDC 1993). It was shown that the formulation had an acceptable crush strength (>2 kgf/granule). See Table 1.

Example 3

(42) (Addition of Sulfuric Acid and Ammonia)

(43) When UCS is manufactured via slurry processes, the resulting slurry requires a water content sufficient to maintain the fluid like condition of the slurry from the reactor system to a granulator. This water has two main disadvantages. First, the recycle ratio in the granulation has to be increased significantly to absorb the slurry moisture. Recycle ratio can be around 8-10:1 which leads to higher energy costs and less flexible operating conditions. Second, most of the slurry water has to be evaporated to produce a granulated product.

(44) It has been determined that by manufacturing ammonium sulfate in the aqueous slurry (in-situ) by utilizing the exothermic reaction of ammonia with sulfuric acid, all or a portion of the water in the aqueous slurry was evaporated from the slurry. In this way, the costs of drying the aqueous slurry by other means was avoided or reduced. In addition, the presence of ammonium sulfate within the UCS product enhanced the fertilizer performance, as ammonium sulfate, a water soluble fertilizer, was readily available to crops once the UCS product was applied. It was also found that the quantity of ammonium sulfate produced removed all or almost all of the free water in the aqueous slurry and did not adversely affect the elemental nitrogen or elemental sulfur content of the UCS product.

(45) The amount of water that was removed from the aqueous slurry was determined by varying amounts of ammonia and sulfuric acid for production of ammonium sulfate. Two moles of ammonium were used for every one mole of sulfuric acid. Anhydrous ammonium and a solution of 98 wt. % sulfuric acid were used to minimize the amount of water added to the slurry. Table 2 includes a summary of the results for removal of water by production of ammonium sulfate. It was found that production of ammonium sulfate in amounts of 9 wt. % to 10 wt. % of the aqueous slurry can remove up to 78.4 kg water/metric ton of UCS produced. Use of additional ammonium sulfate can evaporate a larger amount of water. As discussed above, it was also found, that less than 20 wt. % water was needed in the aqueous slurry to produce the UCS product, in some instances as low as 12 wt. % water was used and the slurry maintained a fluid like condition. Accordingly, producing ammonium sulfate in the aqueous slurry can remove all, substantially all, or part of the free water in the aqueous slurry. Additional amounts of ammonium sulfate can be produced in situ or added into the slurry as well. In some cases, ammonium sulfate is produced in amounts up to 30 wt. % of the UCS product and amounts up to 50 wt. % can be added.

(46) TABLE-US-00002 TABLE 2 (Removal of Water by Production of Ammonium Sulfate) Ammonium Sulfate Produced (wt. % of slurry) 10 9 8 7 6 5 4 3 2 1 0 Water Evaporated 78.4 70.6 62.8 54.9 47.1 39.2 31.4 23.5 15.7 7.8 0.0 (kg/metric ton of UCS product)

Example 4

(47) (Increasing Crush Strength)

(48) It is desirable to have fertilizer granules that are sufficiently hard to avoid or eliminate crushing during handling, shipping, storage, and application of the granules. Dust created from the crushing of fertilizer granules can be an irritant and dangerous if inhaled or ingested. The crushing of fertilizer granules can also lead to the loss of product. Hardness of granules containing UCS and 2 wt. % or more MgO were tested by the same assays described above in Example 2 and it was determined that MgO substantially improved crush strength. In some instances, MgO content is effected by addition of MgSO.sub.4 in the granule. As non-limiting examples, 2 wt. % of MgO in granules containing UCS provided a granule hardness of 12.8 N/granule, a 19.6% increase of hardness over a granule containing UCS without MgO (10.7 N/granule). As another non-limiting example, 4 wt. % of MgO in granules containing UCS provided a granule hardness of 41.6 N/granule, a 288.8% increase of hardness over a granule containing UCS without MgO.

(49) It was found that 2 wt. % of MgO was obtained in the UCS product of the current invention by adding 125.0 kg of MgSO.sub.4 heptahydrate per metric ton of the UCS product. MgSO.sub.4 anhydrate, MgSO.sub.4 monohydrate, or MgSO.sub.4 heptahydrate can also or alternatively be used to add the MgO into the granules.

Example 5

(50) (Compatibility)

(51) The stable UCS adduct granules of the present invention contain higher amounts of elemental nitrogen than other stable UCS adduct granules. The increased stability over urea, decreased production costs, and higher nitrogen content than other UCS adduct granules make the UCS adduct granules of the present invention an attractive fertilizer product alone and in blended or compounded fertilizers. It has been determined that the UCS adduct granules were compatible with a wide range of typical fertilizer raw materials such as DAP, MAP, urea, MOP, and SOP and more compatible than urea. Accordingly, the UCS adduct granules can be used to provide a range of nitrogen-phosphorus-sulfur (NPS), nitrogen-sulfur (NS), nitrogen-potassium-sulfur (NKS), and nitrogen-phosphorous-potassium (NPK) grades. Non-limiting examples of formulations for multiple grades and the nutrient concentration and nutrient ratios in each are shown in Tables 3-11 below (shown in wt. % of the final blend unless otherwise indicated).

(52) TABLE-US-00003 TABLE 3 (UCS adduct granule + DAP blend) Blend or Nutrient Nutrient Compounding (%) Concentrations (%) Ratios UCS DAP N P.sub.2O.sub.5 S N:P N:S 0 100 18 46 0 0.39 5 95 18.75 43.7 0.25 0.43 75.00 10 90 19.5 41.4 0.5 0.47 39.00 15 85 20.25 39.1 0.75 0.52 27.00 20 80 21 36.8 1 0.57 21.00 25 75 21.75 34.5 1.25 0.63 17.40 30 70 22.5 32.2 1.5 0.70 15.00 35 65 23.25 29.9 1.75 0.78 13.29 40 60 24 27.6 2 0.87 12.00 45 55 24.75 25.3 2.25 0.98 11.00 50 50 25.5 23 2.5 1.11 10.20 55 45 26.25 20.7 2.75 1.27 9.55 60 40 27 18.4 3 1.47 9.00 65 35 27.75 16.1 3.25 1.72 8.54 70 30 28.5 13.8 3.5 2.07 8.14 75 25 29.25 11.5 3.75 2.54 7.80 80 20 30 9.2 4 3.26 7.50 85 15 30.75 6.9 4.25 4.46 7.24 90 10 31.5 4.6 4.5 6.85 7.00 95 5 32.25 2.3 4.75 14.02 6.79 100 0 33 0 5 6.60

(53) TABLE-US-00004 TABLE 4 (UCS adduct granule + MAP blend) Blend or Nutrient Nutrient Compounding (%) Concentrations (%) Ratios UCS MAP N P.sub.2O.sub.5 S N:P N:S 0 100 11 52 0 0.21 5 95 12.1 49.4 0.25 0.24 48.40 10 90 13.2 46.8 0.5 0.28 26.40 15 85 14.3 44.2 0.75 0.32 19.07 20 80 15.4 41.6 1 0.37 15.40 25 75 16.5 39 1.25 0.42 13.20 30 70 17.6 36.4 1.5 0.48 11.73 35 65 18.7 33.8 1.75 0.55 10.69 40 60 19.8 31.2 2 0.63 9.90 45 55 20.9 28.6 2.25 0.73 9.29 50 50 22 26 2.5 0.85 8.80 55 45 23.1 23.4 2.75 0.99 8.40 60 40 24.2 20.8 3 1.16 8.07 65 35 25.3 18.2 3.25 1.39 7.78 70 30 26.4 15.6 3.5 1.69 7.54 75 25 27.5 13 3.75 2.12 7.33 80 20 28.6 10.4 4 2.75 7.15 85 15 29.7 7.8 4.25 3.81 6.99 90 10 30.8 5.2 4.5 5.92 6.84 95 5 31.9 2.6 4.75 12.27 6.72 100 0 33 0 5 6.60

(54) TABLE-US-00005 TABLE 5 (UCS adduct granule + urea blend) Blend or Nutrient Nutrient Compounding (%) Concentrations (%) Ratios UCS Urea N S N:S 0 100 46 0 5 95 45.35 0.25 181.40 10 90 44.7 0.5 89.40 15 85 44.05 0.75 58.73 20 80 43.4 1 43.40 25 75 42.75 1.25 34.20 30 70 42.1 1.5 28.07 35 65 41.45 1.75 23.69 40 60 40.8 2 20.40 45 55 40.15 2.25 17.84 50 50 39.5 2.5 15.80 55 45 38.85 2.75 14.13 60 40 38.2 3 12.73 65 35 37.55 3.25 11.55 70 30 36.9 3.5 10.54 75 25 36.25 3.75 9.67 80 20 35.6 4 8.90 85 15 34.95 4.25 8.22 90 10 34.3 4.5 7.62 95 5 33.65 4.75 7.08 100 0 33 5 6.60

(55) TABLE-US-00006 TABLE 6 (UCS adduct granule + potash blend (SOP)) Blend or Nutrient Nutrient Compounding (%) Concentrations (%) Ratios UCS SOP N K.sub.2O S Ca N:K.sub.2O 60 40 19.8 20 10.2 3 1.0 65 35 21.45 17.5 9.55 3.25 1.2 70 30 23.1 15 8.9 3.5 1.5 75 25 24.75 12.5 8.25 3.75 2.0 80 20 26.4 10 7.6 4 2.6 85 15 28.05 7.5 6.95 4.25 3.7 90 10 29.7 5 6.3 4.5 5.9 95 5 31.35 2.5 5.65 4.75 12.5 100 0 33 0 5 5

(56) TABLE-US-00007 TABLE 7 (UCS adduct granule + MOP blend) Blend or Nutrient Nutrient Compounding (%) Concentrations (%) Ratios UCS MOP N K.sub.2O S Ca N:K.sub.2O 50 50 16.5 30 2.5 2.5 0.6 55 45 18.15 27 2.75 2.75 0.7 60 40 19.8 24 10.2 3 0.8 65 35 21.45 21 9.55 3.25 1.0 70 30 23.1 18 8.9 3.5 1.3 75 25 24.75 15 8.25 3.75 1.7 80 20 26.4 12 7.6 4 2.2 85 15 28.05 9 6.95 4.25 3.1 90 10 29.7 6 6.3 4.5 5.0 95 5 31.35 3 5.65 4.75 10.5 100 0 33 0 5 5

(57) TABLE-US-00008 TABLE 8 (UCS adduct granule + DAP + MOP blend) Blend or Compounding Nutrient Nutrient (kg/metric ton) Concentrations (%) Ratios UCS MOP DAP N P.sub.2O.sub.5 K.sub.2O S N:P.sub.2O.sub.5 437 50 513 23.7 23.6 3 2.2 1.0 425.5 75 499.5 23.0 23.0 4.5 2.1 1.0 414 100 486 22.4 22.4 6 2.1 1.0 404.8 120 475.2 21.9 21.9 7.2 2.0 1.0 395.6 140 464.4 21.4 21.4 8.4 2.0 1.0 386.4 160 453.6 20.9 20.9 9.6 1.9 1.0 377.2 180 442.8 20.4 20.4 10.8 1.9 1.0 368 200 432 19.9 19.9 12 1.8 1.0 358.8 220 421.2 19.4 19.4 13.2 1.8 1.0 349.6 240 410.4 18.9 18.9 14.4 1.7 1.0 340.4 260 399.6 18.4 18.4 15.6 1.7 1.0 331.2 280 388.8 17.9 17.9 16.8 1.7 1.0 322 300 378 17.4 17.4 18 1.6 1.0 312.8 320 367.2 16.9 16.9 19.2 1.6 1.0 303.6 340 356.4 16.4 16.4 20.4 1.5 1.0 294.4 360 345.6 15.9 15.9 21.6 1.5 1.0 285.2 380 334.8 15.4 15.4 22.8 1.4 1.0 276 400 324 14.9 14.9 24 1.4 1.0 540 100 360 24.3 16.6 6 2.7 1.5 528 120 352 23.8 16.2 7.2 2.64 1.5 516 140 344 23.2 15.8 8.4 2.58 1.5 504 160 336 22.7 15.5 9.6 2.52 1.5 492 180 328 22.1 15.1 10.8 2.46 1.5 480 200 320 21.6 14.7 12 2.4 1.5 468 220 312 21.1 14.4 13.2 2.34 1.5 456 240 304 20.5 14.0 14.4 2.28 1.5 444 260 296 20.0 13.6 15.6 2.22 1.5 432 280 288 19.4 13.2 16.8 2.16 1.5 420 300 280 18.9 12.9 18 2.1 1.5 621 100 279 25.5 12.8 6 3.105 2.0 607.2 120 272.8 24.9 12.5 7.2 3.036 2.0 593.4 140 266.6 24.4 12.3 8.4 2.967 2.0 579.6 160 260.4 23.8 12.0 9.6 2.898 2.0 565.8 180 254.2 23.2 11.7 10.8 2.829 2.0 552 200 248 22.7 11.4 12 2.76 2.0 538.2 220 241.8 22.1 11.1 13.2 2.691 2.0 524.4 240 235.6 21.5 10.8 14.4 2.622 2.0 510.6 260 229.4 21.0 10.6 15.6 2.553 2.0 496.8 280 223.2 20.4 10.3 16.8 2.484 2.0 483 300 217 19.8 10.0 18 2.415 2.0 117 100 783 18.0 36.0 6 0.585 0.5 114.4 120 765.6 17.6 35.2 7.2 0.572 0.5 111.8 140 748.2 17.2 34.4 8.4 0.559 0.5 109.2 160 730.8 16.8 33.6 9.6 0.546 0.5 106.6 180 713.4 16.4 32.8 10.8 0.533 0.5 104 200 696 16.0 32.0 12 0.52 0.5 101.4 220 678.6 15.6 31.2 13.2 0.507 0.5 98.8 240 661.2 15.2 30.4 14.4 0.494 0.5 96.2 260 643.8 14.8 29.6 15.6 0.481 0.5 93.6 280 626.4 14.4 28.8 16.8 0.468 0.5 91 300 609 14.0 28.0 18 0.455 0.5 88.4 320 591.6 13.6 27.2 19.2 0.442 0.5 85.8 340 574.2 13.2 26.4 20.4 0.429 0.5 83.2 360 556.8 12.8 25.6 21.6 0.416 0.5 80.6 380 539.4 12.4 24.8 22.8 0.403 0.5 78 400 522 12.0 24.0 24 0.39 0.5

(58) TABLE-US-00009 TABLE 9 (UCS adduct granule + DAP + SOP blend) Blend or Compounding Nutrient Nutrient (kg/metric ton) Concentrations (%) Ratios UCS SOP DAP N P.sub.2O.sub.5 K.sub.2O S N:P.sub.2O.sub.5 437 50 513 23.7 23.6 2.5 3.085 1.0 425.5 75 499.5 23.0 23.0 3.75 3.4775 1.0 414 100 486 22.4 22.4 5 3.87 1.0 404.8 120 475.2 21.9 21.9 6 4.184 1.0 395.6 140 464.4 21.4 21.4 7 4.498 1.0 386.4 160 453.6 20.9 20.9 8 4.812 1.0 377.2 180 442.8 20.4 20.4 9 5.126 1.0 368 200 432 19.9 19.9 10 5.44 1.0 358.8 220 421.2 19.4 19.4 11 5.754 1.0 349.6 240 410.4 18.9 18.9 12 6.068 1.0 340.4 260 399.6 18.4 18.4 13 6.382 1.0 331.2 280 388.8 17.9 17.9 14 6.696 1.0 322 300 378 17.4 17.4 15 7.01 1.0 540 100 360 24.3 16.6 5 4.5 1.5 528 120 352 23.8 16.2 6 4.8 1.5 516 140 344 23.2 15.8 7 5.1 1.5 504 160 336 22.7 15.5 8 5.4 1.5 492 180 328 22.1 15.1 9 5.7 1.5 480 200 320 21.6 14.7 10 6 1.5 468 220 312 21.1 14.4 11 6.3 1.5 456 240 304 20.5 14.0 12 6.6 1.5 444 260 296 20.0 13.6 13 6.9 1.5 432 280 288 19.4 13.2 14 7.2 1.5 420 300 280 18.9 12.9 15 7.5 1.5 621 100 279 25.5 12.8 5 4.905 2.0 607.2 120 272.8 24.9 12.5 6 5.196 2.0 593.4 140 266.6 24.4 12.3 7 5.487 2.0 579.6 160 260.4 23.8 12.0 8 5.778 2.0 565.8 180 254.2 23.2 11.7 9 6.069 2.0 552 200 248 22.7 11.4 10 6.36 2.0 538.2 220 241.8 22.1 11.1 11 6.651 2.0 524.4 240 235.6 21.5 10.8 12 6.942 2.0 510.6 260 229.4 21.0 10.6 13 7.233 2.0 496.8 280 223.2 20.4 10.3 14 7.524 2.0 483 300 217 19.8 10.0 15 7.815 2.0 117 100 783 18.0 36.0 5 2.385 0.5 114.4 120 765.6 17.6 35.2 6 2.732 0.5 111.8 140 748.2 17.2 34.4 7 3.079 0.5 109.2 160 730.8 16.8 33.6 8 3.426 0.5 106.6 180 713.4 16.4 32.8 9 3.773 0.5 104 200 696 16.0 32.0 10 4.12 0.5 101.4 220 678.6 15.6 31.2 11 4.467 0.5 98.8 240 661.2 15.2 30.4 12 4.814 0.5 96.2 260 643.8 14.8 29.6 13 5.161 0.5 93.6 280 626.4 14.4 28.8 14 5.508 0.5 91 300 609 14.0 28.0 15 5.855 0.5 88.4 320 591.6 13.6 27.2 16 6.202 0.5 85.8 340 574.2 13.2 26.4 17 6.549 0.5 83.2 360 556.8 12.8 25.6 18 6.896 0.5 80.6 380 539.4 12.4 24.8 19 7.243 0.5 78 400 522 12.0 24.0 20 7.59 0.5 75.4 420 504.6 11.6 23.2 21 7.937 0.5 72.8 440 487.2 11.2 22.4 22 8.284 0.5 70.2 460 469.8 10.8 21.6 23 8.631 0.5 67.6 480 452.4 10.4 20.8 24 8.978 0.5 65 500 435 10.0 20.0 25 9.325 0.5 62.4 520 417.6 9.6 19.2 26 9.672 0.5 59.8 540 400.2 9.2 18.4 27 10.019 0.5 57.2 560 382.8 8.8 17.6 28 10.366 0.5 54.6 580 365.4 8.4 16.8 29 10.713 0.5 52 600 348 8.0 16.0 30 11.06 0.5

(59) TABLE-US-00010 TABLE 10 (UCS adduct granule + MAP + MOP blend) Blend or Compounding Nutrient Nutrient (kg/metric ton) Concentrations (%) Ratios UCS MOP MAP N P.sub.2O.sub.5 K.sub.2O S N:P.sub.2O.sub.5 522.5 50 427.5 21.9 22.2 3 2.6125 1.0 508.75 75 416.25 21.4 21.6 4.5 2.54375 1.0 495 100 405 20.8 21.1 6 2.475 1.0 484 120 396 20.3 20.6 7.2 2.42 1.0 473 140 387 19.9 20.1 8.4 2.365 1.0 462 160 378 19.4 19.7 9.6 2.31 1.0 451 180 369 18.9 19.2 10.8 2.255 1.0 440 200 360 18.5 18.7 12 2.2 1.0 429 220 351 18.0 18.3 13.2 2.145 1.0 418 240 342 17.6 17.8 14.4 2.09 1.0 407 260 333 17.1 17.3 15.6 2.035 1.0 396 280 324 16.6 16.8 16.8 1.98 1.0 385 300 315 16.2 16.4 18 1.925 1.0 374 320 306 15.7 15.9 19.2 1.87 1.0 363 340 297 15.2 15.4 20.4 1.815 1.0 352 360 288 14.8 15.0 21.6 1.76 1.0 341 380 279 14.3 14.5 22.8 1.705 1.0 330 400 270 13.9 14.0 24 1.65 1.0 594 100 306 23.0 15.9 6 2.97 1.4 580.8 120 299.2 22.5 15.6 7.2 2.904 1.4 567.6 140 292.4 21.9 15.2 8.4 2.838 1.4 554.4 160 285.6 21.4 14.9 9.6 2.772 1.4 541.2 180 278.8 20.9 14.5 10.8 2.706 1.4 528 200 272 20.4 14.1 12 2.64 1.4 514.8 220 265.2 19.9 13.8 13.2 2.574 1.4 501.6 240 258.4 19.4 13.4 14.4 2.508 1.4 488.4 260 251.6 18.9 13.1 15.6 2.442 1.4 475.2 280 244.8 18.4 12.7 16.8 2.376 1.4 462 300 238 17.9 12.4 18 2.31 1.4 666 100 234 24.6 12.2 6 3.33 2.0 651.2 120 228.8 24.0 11.9 7.2 3.256 2.0 636.4 140 223.6 23.5 11.6 8.4 3.182 2.0 621.6 160 218.4 22.9 11.4 9.6 3.108 2.0 606.8 180 213.2 22.4 11.1 10.8 3.034 2.0 592 200 208 21.8 10.8 12 2.96 2.0 577.2 220 202.8 21.3 10.5 13.2 2.886 2.0 562.4 240 197.6 20.7 10.3 14.4 2.812 2.0 547.6 260 192.4 20.2 10.0 15.6 2.738 2.0 532.8 280 187.2 19.6 9.7 16.8 2.664 2.0 518 300 182 19.1 9.5 18 2.59 2.0 279 100 621 16.0 32.3 6 1.395 0.5 272.8 120 607.2 15.7 31.6 7.2 1.364 0.5 266.6 140 593.4 15.3 30.9 8.4 1.333 0.5 260.4 160 579.6 15.0 30.1 9.6 1.302 0.5 254.2 180 565.8 14.6 29.4 10.8 1.271 0.5 248 200 552 14.3 28.7 12 1.24 0.5 241.8 220 538.2 13.9 28.0 13.2 1.209 0.5 235.6 240 524.4 13.5 27.3 14.4 1.178 0.5 229.4 260 510.6 13.2 26.6 15.6 1.147 0.5 223.2 280 496.8 12.8 25.8 16.8 1.116 0.5 217 300 483 12.5 25.1 18 1.085 0.5 210.8 320 469.2 12.1 24.4 19.2 1.054 0.5 204.6 340 455.4 11.8 23.7 20.4 1.023 0.5 198.4 360 441.6 11.4 23.0 21.6 0.992 0.5 192.2 380 427.8 11.0 22.2 22.8 0.961 0.5 186 400 414 10.7 21.5 24 0.93 0.5

(60) TABLE-US-00011 TABLE 11 (UCS adduct granule + MAP + SOP blend) Blend or Compounding Nutrient Nutrient (kg/metric ton) Concentrations (%) Ratios UCS SOP MAP N P.sub.2O.sub.5 K.sub.2O S N:P.sub.2O.sub.5 495 100 405 20.8 21.1 5 4.275 1.0 484 120 396 20.3 20.6 6 4.58 1.0 473 140 387 19.9 20.1 7 4.885 1.0 462 160 378 19.4 19.7 8 5.19 1.0 451 180 369 18.9 19.2 9 5.495 1.0 440 200 360 18.5 18.7 10 5.8 1.0 429 220 351 18.0 18.3 11 6.105 1.0 418 240 342 17.6 17.8 12 6.41 1.0 407 260 333 17.1 17.3 13 6.715 1.0 396 280 324 16.6 16.8 14 7.02 1.0 385 300 315 16.2 16.4 15 7.325 1.0 374 320 306 15.7 15.9 16 7.63 1.0 363 340 297 15.2 15.4 17 7.935 1.0 352 360 288 14.8 15.0 18 8.24 1.0 341 380 279 14.3 14.5 19 8.545 1.0 330 400 270 13.9 14.0 20 8.85 1.0 594 100 306 23.0 15.9 5 4.77 1.4 580.8 120 299.2 22.5 15.6 6 5.064 1.4 567.6 140 292.4 21.9 15.2 7 5.358 1.4 554.4 160 285.6 21.4 14.9 8 5.652 1.4 541.2 180 278.8 20.9 14.5 9 5.946 1.4 528 200 272 20.4 14.1 10 6.24 1.4 514.8 220 265.2 19.9 13.8 11 6.534 1.4 501.6 240 258.4 19.4 13.4 12 6.828 1.4 488.4 260 251.6 18.9 13.1 13 7.122 1.4 475.2 280 244.8 18.4 12.7 14 7.416 1.4 462 300 238 17.9 12.4 15 7.71 1.4 666 100 234 24.6 12.2 5 5.13 2.0 651.2 120 228.8 24.0 11.9 6 5.416 2.0 636.4 140 223.6 23.5 11.6 7 5.702 2.0 621.6 160 218.4 22.9 11.4 8 5.988 2.0 606.8 180 213.2 22.4 11.1 9 6.274 2.0 592 200 208 21.8 10.8 10 6.56 2.0 577.2 220 202.8 21.3 10.5 11 6.846 2.0 562.4 240 197.6 20.7 10.3 12 7.132 2.0 547.6 260 192.4 20.2 10.0 13 7.418 2.0 532.8 280 187.2 19.6 9.7 14 7.704 2.0 518 300 182 19.1 9.5 15 7.99 2.0 503.2 320 176.8 18.6 9.2 16 8.276 2.0 488.4 340 171.6 18.0 8.9 17 8.562 2.0 473.6 360 166.4 17.5 8.7 18 8.848 2.0 279 100 621 16.0 32.3 5 3.195 0.5 272.8 120 607.2 15.7 31.6 6 3.524 0.5 266.6 140 593.4 15.3 30.9 7 3.853 0.5 260.4 160 579.6 15.0 30.1 8 4.182 0.5 254.2 180 565.8 14.6 29.4 9 4.511 0.5 248 200 552 14.3 28.7 10 4.84 0.5 241.8 220 538.2 13.9 28.0 11 5.169 0.5 235.6 240 524.4 13.5 27.3 12 5.498 0.5 229.4 260 510.6 13.2 26.6 13 5.827 0.5 223.2 280 496.8 12.8 25.8 14 6.156 0.5 217 300 483 12.5 25.1 15 6.485 0.5 210.8 320 469.2 12.1 24.4 16 6.814 0.5 204.6 340 455.4 11.8 23.7 17 7.143 0.5 198.4 360 441.6 11.4 23.0 18 7.472 0.5 192.2 380 427.8 11.0 22.2 19 7.801 0.5 186 400 414 10.7 21.5 20 8.13 0.5