WO2024082041A1 - Process for aggregating elemental sulfur in solid fertilizers - Google Patents

Process for aggregating elemental sulfur in solid fertilizers Download PDF

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Publication number
WO2024082041A1
WO2024082041A1 PCT/BR2023/050239 BR2023050239W WO2024082041A1 WO 2024082041 A1 WO2024082041 A1 WO 2024082041A1 BR 2023050239 W BR2023050239 W BR 2023050239W WO 2024082041 A1 WO2024082041 A1 WO 2024082041A1
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WO
WIPO (PCT)
Prior art keywords
fertilizer
disintegrant
fertilizers
elemental sulfur
sulfur
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PCT/BR2023/050239
Other languages
French (fr)
Inventor
Ubaldo SIMONE BARUFFI
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Ocp Fertilizantes Ltda.
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Publication date
Priority claimed from BR102022021114A external-priority patent/BR102022021114A2/en
Priority claimed from BR102023009669-7A external-priority patent/BR102023009669A2/en
Application filed by Ocp Fertilizantes Ltda. filed Critical Ocp Fertilizantes Ltda.
Publication of WO2024082041A1 publication Critical patent/WO2024082041A1/en

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    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G1/00—Mixtures of fertilisers belonging individually to different subclasses of C05
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/30—Layered or coated, e.g. dust-preventing coatings
    • C05G5/36—Layered or coated, e.g. dust-preventing coatings layered or coated with sulfur

Definitions

  • Elemental Sulfur is insoluble in water and its root absorption is very slow reducing its use in agriculture, especially in shorter cycle crops.
  • Granulated Sulfur has high density, and therefore, causes unwanted segregation when mixed with other fertilizers of different densities, with consequently nutritional imbalance during its application along the cultivation line;
  • Granulated Sulfur has a granulometric difference, that is, in the size of the grains, which are smaller than most fertilizers, also causing unwanted segregation when mixed with other fertilizers with larger granules, with consequently nutritional imbalance during their application along the cultivation line;
  • This product has a high concentration of Sulfur, because it is based on the elemental form of this nutrient; for this reason, it is used in low doses in mixtures with other raw materials, making appropriate homogenization at the time of industrial mixing difficult, or even impossible, a fact that causes an uneven distribution of this nutrient in the soil, which can lead to high concentrations in certain areas while causing deficiencies in others, resulting in significant losses in agricultural productivity.
  • the proposed new technology adds Sulfur to all fertilizer granules, ensuring perfect homogenization and nutritional distribution in the soil.
  • Sulfur will be part of a small fraction of the applied fertilizer, which makes homogeneous fertilization along the cultivation line difficult;
  • the existing process only allows the production of isolated granulated Sulfur without other nutrients, serving as a raw material to be added to mixtures.
  • the new process allows for the production of complex fertilizers, where the added Sulfur can be combined with each primary macronutrient, other secondary macronutrients, and/or micronutrients, resulting in a compound that is not only nutritionally complete but also has a completely homogeneous distribution. This compound increases agricultural productivity and reduces operational costs for both the industry and farmers;
  • One of the objectives of the present invention is to provide a new process of production of fertilizers enriched with Elemental Sulfur.
  • Elemental Sulfur in granulated fertilizers, in appropriate doses, with particle size that would promote faster oxidation to soluble form (SO4) , in addition to practically extinguishing the risks of explosion in the industrial, operational and handling phase, at the time of application in crops, we found the solution of melting this product and coating the fertilizer grains homogeneously .
  • a disintegrant/deaggregating agent has been added to the molten Sulfur, where this disintegrant/deaggregating agent may be Citric Acid, Ammonium Bicarbonate, Sodium Bicarbonate, Starches, Bentonite, Attapulgite, Expanding Clay or a mixture of these, or similar substances, preferably Bentonite Clay.
  • the disintegrant/deaggregating agent in contact with water has a high expansion coefficient, increasing its volume by approximately 35 times.
  • One of the objectives of the present invention is to homogeneously aggregate Elemental Sulfur to the coat of all types of granular fertilizers, together with a disintegrant/deaggregating agent, enabling the homogeneous addition of high doses of this nutrient, in addition to ensuring its oxidation and release for plant root absorption.
  • this disintegrant/deaggregating agent can be Citric Acid, Ammonium Bicarbonate, Sodium Bicarbonate, Starches, Bentonite, Attapulgite, Expanding Clay or a mixture of these, or similar substances, preferably Bentonite Clay.
  • the process of the present invention consists of spraying molten Sulfur together with a disintegrant/deaggregating agent in primary and/or secondary macronutrient fertilizers, with or without micronutrients, in a Pelletizing and Coating Drum which can be a continuous rotary drum or batch, fixed die, ribbon or paddle mixer, or continuous belt.
  • the fertilizers to be pelleted by the molten Sulfur may be mononutrients, binary or ternary, with or without micronutrients or secondary macronutrients, and also micronutrients isolated or added together with the fertilizers.
  • the disintegrant/deaggregating agent can be added in the process, directly into the heating drum, or into the pelletizing drum, or mixed into the molten Sulfur .
  • Elemental Sulfur in solid form is transfered to the Melt Storage Tank and melted at a temperature between 140 and 200 degrees Celsius, its preferred point being between 140 to 150 degrees Celsius, filtered if necessary and subsequently sent to the Storage Tank or Mixer and maintained at these temperatures. We can also receive the already molten Sulfur .
  • the disintegrant/deaggregating agent can be added in a ratio between 5% to 95% w/w, preferably between 9.5 to 30% w/w in relation to the Elemental Sulfur, depending on each product.
  • the disintegrant/deaggregating agent ratio will also be the same in relation to Elemental Sulfur if it is added either to the heating drum, or to the pelletizing drum.
  • the mononutrient, binary, or ternary fertilizers with or without micronutrients or secondary macronutrients, as well as isolated micronutrients, are added to a continuous or batch dosing process where they are weighed and can be directed to the Mixer depending on each case, and then directed to a Heating Drum or directly to the Pelletizing System depending on specific conditions of each situation and product to be manufactured.
  • the fertilizer or fertilizers dosed are heated to a temperature that varies between 50 to 140 degrees Celsius, depending on each type of fertilizer.
  • the preferred range is 80 to 100 degrees Celsius, and for the other fertilizers, between 100 and 120 degrees Celsius.
  • this heating favors the homogeneous addition of molten Sulfur .
  • Aft er heating, the dosed fertilizer or fertilizers are directed to the Pelletizing System, where the mixture of molten Sulfur with the disintegrant/deaggregating agent is sprayed, or only the molten Sulfur is sprayed if the disintegrant/deaggregating agent is added directly to the heating drum or the pelletizing drum.
  • the product will go through a cooling equipment, or if the temperature is not high, it will not be necessary to cool it, and in this case, the Sulfur incorporation stage will already be completed.
  • the final product contains the established and required amount of Sulfur for each type of product and culture incorporated in all grains homogeneously.
  • the amount (% w/w) of Sulfur in the final product depends on the needs of each customer, and the minimum amount required by the legislation of the Ministry of Agriculture, Livestock and Supply can be added, which is 1.0% w/w, and can reach values greater than 40% w/w.
  • the Sulfur content in the formulation depends on the requirements of each soil and culture being defined by the company customers or agronomists, according to some examples below: Example of some products manufactured in this stage, always expressed as % w/w:
  • Zinc (Zn) 0.40%
  • This Mixing System may occur in continuous rotary drum or batch, with fixed die, or ribbon or paddle mixers, and also continuous belts, and v or w mixers.
  • each micronutrient that can be added is quite varied and can reach high concentrations per element, and can exceed 60% w/w, preferably 5% of each of the following nutrients: Zinc, Boron, Copper, Molybdenum, Manganese, Iron, Cobalt, Selenium, Silicon, Nickel, Cobalt, Chlorine.
  • Zinc ( Zn) 0.60%
  • Zinc (Zn) 0.55%
  • the product resulting from the process of the present invention is a pellet-shaped fertilizer characterized in that it is coated by a mixed layer of Elemental Sulfur and a disintegrant/deaggregating agent in which the concentration of the disintegrant/deaggregating agent is from 5.0% w/w to 95% w/w, preferably from 9.5% w/w to 30% w/w of the amount of Elemental Sulfur, and the concentration of Elemental Sulfur in the referred fertilizer is at least 1% w/w, where the fertilizer to be coated is of the following types: Organic fertilizers, Organomineral fertilizers, Simple mineral fertilizers, Mixed mineral fertilizers and or Complexes containing NPK, NP, NK or PK with or without secondary macronutrients or micronutrients.
  • the amount of Sulfur to be added in the process may be less than 1% w/w, in case the legislation of the Ministry of Agriculture, Livestock and Supply changes and allows for values lower than 1% w/w.
  • Figure 01 illustrates the process flowchart of the present invention where the following components are described :
  • - Heat Generator (1) that can be supplied by a Furnace or Boiler with energy from coal, wood, liquid fuel, gas, electricity, or any other type of fuel;
  • - Storage Tank (2) for receiving solid or molten liquid Sulfur.
  • Elemental Sulfur is heated between 140 and 200 degrees Celsius so that it melts, with the preferred melting point being between 140 and 150 degrees Celsius. If received in solid form it may be filtered before use.
  • the disintegrant/deaggregating agent can be added and mixed;
  • Pelletizing System (6) implemented by drum for the coating of fertilizers with the mixture of Elemental Sulfur with disintegrant/deaggregating agent continuously or by batch, where temperatures are maintained between 50°C and 140°C, depending on the type of fertilizer. For Nitrogen fertilizers the preferred range is 80 to 100 degrees Celsius, and for the other fertilizers, between 100 and 120 degrees Celsius.
  • This Pelletizing System (6) can be implemented with continuous rotary drum or batch, fixed die pelletizer and ribbon or paddle mixers and also continuous belts; it may receive the molten Sulfur already mixed with the disintegrant/deaggregating agent, or these may added separately .
  • Cooler (7) which can be rotary, fluidized bed or other similar system
  • Disintegrant/deaggregating agent dosing system (8) which can include a continuous or batch system;
  • Fertilizer Dosage System Micronutrients and disintegrant/deaggregating agent (9) , which can include a continuous or batch system, in the Dosage System (9) fertilizers such as organic fertilizers, organomineral fertilizers, simple mineral fertilizers, mixed mineral fertilizers and or Complexes containing NPK, NP, NK or PK with or without secondary macronutrients or micronutrients are introduced, all isolated and disintegrant/disaggregating Micronutrients all approved by the fertilizer legislation regulated by the Ministry of Agriculture, Livestock and Supply, depending on room temperature conditions, the product and/or quantity produced it is not necessary to use heating, as well as depending on the amount of product manufactured it will not be necessary to use the Mixer;
  • fertilizers such as organic fertilizers, organomineral fertilizers, simple mineral fertilizers, mixed mineral fertilizers and or Complexes containing NPK, NP, NK or PK with or without secondary macronutrients or micronutrients are introduced, all isolated and disintegrant/disaggregating Micronutrients all
  • Micronutrient Dosage System (10) , which can be installed with a continuous or batch system;
  • Micronutrient Mixing System (11) for the coating of micronutrients which can be implemented by continuous rotary drum or batch, fixed die mixer and ribbon or paddle mixers, also continuous belts and v or w mixers; and
  • - Raw Material Mixing System (12) can be implemented by continuous rotary drum or batch, fixed die mixer and ribbon or paddle mixers, also continuous belts and v or w mixers.
  • each part of the process flow is represented by a color.
  • the dark blue color represents the flow of the Fertilizing Raw Materials
  • the purple color represents the flow of the disintegrant/deaggregating agent
  • the mustard color represents the flow of the molten Sulfur
  • the brown color represents the flow of the molten Sulfur plus the disintegrant/deaggregating agent
  • the pink color represents the flow of the micronutrients
  • the turquoise color represents the dosed raw materials
  • the light green color represents the flow of the adhesive additives
  • the light blue color represents the flow of the finished product
  • the red color represents the flow of the steam
  • the green color represents the flow of cold air at room temperature
  • the black color represents the equipment .
  • Figure 02 illustrates samples of the product manufactured by the process of the present invention.
  • the illustrated pellets are from a fertilizing product of type 00-40-00 + 13% w/w Calcium + 10% w/w Sulfur + 0.18% w/w Boron + 0.50% w/w Zinc.
  • Figure 3 illustrates how sowing was performed on 04/21/2022, where three furrows were made in each vessel.
  • the corn seeds were placed in the central furrow, and in the lateral furrows, the fertilizer Triple Superphosphate coated with the mixture of Elemental Sulfur and disintegrant/deaggregating agent from the present invention, identified as TSP+S+Be, was applied.
  • Figure 4 illustrates the development of corn plants on 05/04/22.
  • Figure 5 illustrates the development of corn plants on 06/13/22.
  • Figure 6 illustrates the development of corn plants on 07/20/22.
  • Figure 7 illustrates the development of corn plants on 08/03/22.
  • Figure 8 illustrates in an enlarged view the development of the corn ear resulting from the applied treatment .
  • Figure 9 illustrates a graph with the results of the dry mass of the aboveground part of the corn plants and the grain yield per plant, treated at 30, 60, and 137 days.
  • the results clearly demonstrate the excellent performance of the product produced by the process of the present invention, identified in the graph as TSP+S+Be, when compared to other products currently on the market identified as SSP, TSP, TSP+S, and Superactiv, as well as the Control vessel without the addition of fertilizers.
  • Figure 10 illustrates photos of the evolution of corn plants according to the treatments used. We can verify that the size of the plant generated with the use of the product manufactured by the process of the present invention is greater than the other plants fertilized with the market products and the control vessel.
  • FIG. 11 illustrates the difference between a pellet with and without the disintegrant/deaggregating agent, namely Bentonite Clay, with 3 days of moisture presence. It is clear from this image that, with the addition of the disintegrant/deaggregating agent, the coating disintegrates and initiates fragmentation of the Elemental Sulfur which is the technical foundation of the objective of this invention. In other words, disintegrant/deaggregating agent within this new process fragments the Elemental Sulfur, facilitating its solubilization and oxidation in the soil, which is corroborated by the agronomic result indicated in figure 09.
  • Figure 12 illustrates an enlargement of the pellets of figure 11.
  • Figure 13 illustrates a comparison between a dry pellet and a pellet with 3 days of moisture, being both pellets produced by the process of the present invention, i.e. coated by the mixture of Elemental Sulfur and a disintegrant/deaggregating agent.
  • Figure 14 illustrates the triple Superphosphate fertilizer coated with 12% w/w elemental Sulfur and 10% w/w disintegrant/deaggregating agent in relation to elemental Sulfur.
  • the figure shows the thickness of the coating. In general this coating thickness is from 20 pm to 60 pm, its preferred range being between from 30 pm to 50 pm.
  • the process for aggregating Elemental Sulfur in fertilizers of the present invention is characterized by consisting of the following stages: a. In the initial phase of the process, Elemental Sulfur is placed in the Storage Tank (2) in solid form or already melted, where it is heated between 140°C and 200°C to be melted or maintained in a molten state, with apreferred melting point between 140 to 150 degrees Celsius; the disintegrant/deaggregating agent is weighed and dosed in the disintegrant/deaggregating agent Dosing System (8) or (9) ; one or several types of granulated fertilizers and micronutrients are weighed and dosed in batches or continuously in the Fertilizer Dosing System (9) ; if necessary, additional micronutrients are weighed and dosed in the Micronutrient Dosing System (10) ; b.
  • the dosed products are directed to the mixer where the adhesive additive can be used ( 12 ) ; c.
  • the fertilizers are transfered to the Fertilizer Heating System (5) , and are heated to a temperature between 50 to 140 degrees, depending on the type of fertilizer.
  • the preferred range is 80 to 100 degrees Celsius, and for the other fertilizers, between 100 and 120 degrees Celsius. This facilitates the homogeneous aggregation of pure molten Elemental Sulfur or Elemental Sulfur with the disintegrant/deaggregating agent, where the Fertilizer Heating System (5) can be rotary, fluidized bed, or a similar system; d.
  • the Elemental Sulfur of the Storage Tank (2) and the disintegrant/deaggregating agent of the Dosing System (8) are transfered to the Mixing Tank (3) and are mixed until homogenized, where the disintegrant/deaggregating agent is in a ratio between 5.0% to 95% w/w, preferably 9.5% to 30% w/w of the mixture with Elemental Sulfur, depending on each product ; e.
  • the mixture of Elemental Sulfur and disintegrant/deaggregating agent is transfered to the Application Tank (4) ; f.
  • the dosed Raw Materials are transfered to the
  • the molten Elemental Sulfur can be added to the Pelletizer in two ways: (e.l) pure, coming from the Storage Tank (2) , in this option the disintegrant/deaggregating agent is also added to the Pelletizer simultaneously with the Cast Elemental Sulfur, and the simultaneous mixing is performed during the Fertilizer Pelletization, or (e.2) already mixed with the disintegrant/deaggregating agent, from the Application Tank (4) where it is sprayed in the Pelletizing System (6) ; the percentage of disintegrant/deaggregating agent in relation to the cast Elemental Sulfur depends on each product being within the range of 5.0% to 95% w/w , preferably 9.5% to 30% w/w being its most preferred range from 9.5% to 15% w/w; in these two application methods, the percentage of Final Sulfur in the product is previously defined to reach the necessary content for each type of product.
  • the coating phase is completed; h. Then the product may follow 02 different routes:
  • - Manufacturing completed and the product can be either stored in bulk in boxes/warehouses , or loaded and directly dispatched in bulk in trucks, or directly bagged in Big Bag packaging of 250 to 1500 kg or bags of 10 to 50 kg for storage and subsequent dispatch, or directly bagged in Big Bag packaging of 250 to 1500 kg or bags of 10 to 50 kg for direct dispatch, or directed for the production of other types of fertilizers; or It will proceed to the incorporation or supplementation of additional micronutrients in a micronutrient mixing system (11) ; at this stage, various types of micronutrients that were weighed and dosed in batches or continuously in the micronutrient dosing system (10) are added to the product along with a specific adhesive additive in the micronutrient mixing system (11) ; The regulated adhesive additive approved by the Ministry of Agriculture, Livestock, and Supply, categorized as an Adhesive Additive, will be used.
  • It can be of vegetable origin such as Starches, Flaxseed Oil, Glucose Syrup, or mineral origin such as Silicones, Waxes, and Paraffins, with the function of binding bind all the micronutrients to the fertilizer, and its quantity can vary from 0.1% to 30% w/w, preferably from 0.2% to 1.5% w/w , depending on the amount of micronutrients to be aggregated; the amount (% w/w) of micronutrients to be added varies greatly and can reach high concentrations of each element, exceeding 60% w/w, preferably 5% w/w of each of the following nutrients: Zinc, Boron, Copper, Molybdenum, Manganese, Iron, Cobalt, Selenium, Silicon, Nickel, Cobalt, Chlorine.
  • the product can be directed to bulk storage in boxes/warehouses , or loaded and shipped directly in bulk on trucks, or directly bagged in Big Bag packaging ranging from 250 to 1500 kg or in bags ranging from 10 to 50 kg, for storage and subsequent shipment, or directly bagged in Big Bag packaging ranging from 250 to 1500 kg or in bags ranging from 10 to 50 kg, for direct shipment, or directed towards the production of other types of fertilizers.
  • the disintegrant/deaggregating agent of the process of the present invention may be Citric Acid, Ammonium Bicarbonate, Sodium Bicarbonate, Starches, Bentonite, Attapulgite, Expanding Clay or a mixture of these, or similar substances, preferably Bentonite Clay, and all disintegrant/deaggregating agents areauthorized by regulatory agencies.
  • the products manufactured by the process of the present invention are Granulated Fertilizers, subsequently Pelletized, coated with a layer of the mixture of Elemental Sulfur and disintegrant/deaggregating agent, which can receive a coating of micronutrients.
  • NPK The sum of NPK will be equal to or greater than 18% w/ w - The sum of NP, NK or PK will be equal to or greater than 15% w/w
  • Copper (Cu) 0.02%, Iron (Fe) : 0.02%, Manganese (Mn) : 0.02%, Molybdenum (Mo) : 0.005%, Nickel (Ni) : 0.005%, Selenium (Se) : 0.003%, Silicon (Si) : 0.05%, Zinc (Zn) : 0.1%
  • Hardness 1.5 kgf minimum Establishes the mechanical strength of the grain that is important to support transport, storage and handling during application.
  • Humidity (H2O) 5.0% w/w maximum Defines the maximum amount of Water present in the product above which it impairs handling, manipulation, application, in addition to favoring grain breakage. Acidity (H3PO4) : 5.0% w/w maximum.
  • Table 1 below illustrates the work plan and operational schedule of the test.
  • Table 2 below illustrates the characteristics of the soil used in the experiment.
  • Figure 11 illustrates the difference between a pellet without Bentonite Clay and with Bentonite Clay with 3 days of moisture presence. It is possible to clearly see the fragmentation of the Elemental Sulfur coating in the sample with Bentonite Clay compared to the sample without Bentonite.
  • Figure 12 illustrates an enlargement of the pellets of figure 11.
  • Figure 13 illustrates a comparison between a dry pellet and a pellet with 3 days of moisture, being both pellets produced by the process of the present invention, i.e. coated by the mixture of Elemental Sulfur and Bentonite Clay.
  • Figure 14 illustrates the triple Superphosphate fertilizer coated with 12% w/w elemental Sulfur and 10% w/w Bentonite Clay in relation to elemental Sulfur.
  • the figure shows the thickness of the coating. In general this coating thickness is from 20 pm to 60 pm, its preferred range being between from 30 pm to 50 pm.

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Abstract

The present invention describes a process to incorporate Elemental Sulfur into any type of solid fertilizers that are already prepared or in the manufacturing process by coating them with a layer of Elemental Sulfur and a disintegrant/deaggregating agent in order to optimize their nutritional performance, particularly in terms of sulfur solubilization, oxidation, and availability for root absorption.

Description

PROCESS FOR AGGREGATING ELEMENTAL SULFUR IN SOLID FERTILIZERS
FIELD OF APPLICATION:
[0001] The process described in this patent application applies to the field of agricultural fertilizers, specifically a process for incorporating Elemental Sulfur into any type of solid fertilizers that are already prepared or in the manufacturing process, in order to optimize their nutritional performance, particularly in the availability of Sulfur for root absorption .
STATE OF THE ART
[0002] Elemental Sulfur is insoluble in water and its root absorption is very slow reducing its use in agriculture, especially in shorter cycle crops.
[0003] To increase the efficiency in the absorption of this type of Sulfur it is necessary to grind it into particles smaller than 0.15 mm, which is an industrial challenge due to the risks of explosion, requiring the grinding to be carried out in an inert environment, enclosed with the use of nitrogen gas, thus avoiding explosions, but elevating the operating costs.
[0004] Another aspect that hinders the use of Sulfur in particles smaller than 0.15 mm, ideal for plant absorption, is how to perform this application due to the fact that these fine particles are incompatible with most mixtures of granulated fertilizers, causing in addition to serious occupational and handling health risks, great unevenness in the the product application to soil leading to deficient agricultural production.
[0005] Currently, the market already offers granulated Elemental Sulfur with Bentonite Clay, but for its application, it must be added in blends with other granulated fertilizers to meet the nutritional demand of nutrients since this technology only provides the nutrient Sulfur.
[0006] Some problems that can be identified during the use of this currently used form are the following:
Granulated Sulfur has high density, and therefore, causes unwanted segregation when mixed with other fertilizers of different densities, with consequently nutritional imbalance during its application along the cultivation line;
Granulated Sulfur has a granulometric difference, that is, in the size of the grains, which are smaller than most fertilizers, also causing unwanted segregation when mixed with other fertilizers with larger granules, with consequently nutritional imbalance during their application along the cultivation line; and
This product has a high concentration of Sulfur, because it is based on the elemental form of this nutrient; for this reason, it is used in low doses in mixtures with other raw materials, making appropriate homogenization at the time of industrial mixing difficult, or even impossible, a fact that causes an uneven distribution of this nutrient in the soil, which can lead to high concentrations in certain areas while causing deficiencies in others, resulting in significant losses in agricultural productivity. [0007] The process, the subject of the present invention, presents the following differences and advantages compared to the prior art:
The proposed new technology adds Sulfur to all fertilizer granules, ensuring perfect homogenization and nutritional distribution in the soil. In the currently used process, when it is added as granulated isolated Sulfur with Bentonite Clay, Sulfur will be part of a small fraction of the applied fertilizer, which makes homogeneous fertilization along the cultivation line difficult;
The existing process only allows the production of isolated granulated Sulfur without other nutrients, serving as a raw material to be added to mixtures. The new process allows for the production of complex fertilizers, where the added Sulfur can be combined with each primary macronutrient, other secondary macronutrients, and/or micronutrients, resulting in a compound that is not only nutritionally complete but also has a completely homogeneous distribution. This compound increases agricultural productivity and reduces operational costs for both the industry and farmers;
The presence of Sulfur in all grains, unlike what normally occurs today, provides a significant increase in the specific surface area of contact of the same with the soil solution, ensuring oxidation to the form of Sulfate in a significantly shorter time, meeting the demands of crops more efficiently;
Comparing this new process to the existing Sulfur melting process, it guarantees a much faster fragmentation of the Sulfur coating due to the thin layer of Sulfur and the effects of the added Bentonite Clay in the process, which is not present in the current state- of-the-art technology.
SUMMARY OF THE INVENTION
[0008] One of the objectives of the present invention is to provide a new process of production of fertilizers enriched with Elemental Sulfur. With the intention of finding an alternative that would allow the addition of Elemental Sulfur in granulated fertilizers, in appropriate doses, with particle size that would promote faster oxidation to soluble form (SO4) , in addition to practically extinguishing the risks of explosion in the industrial, operational and handling phase, at the time of application in crops, we found the solution of melting this product and coating the fertilizer grains homogeneously .
[0009] However, it would be necessary to ensure that this coat formed would fragment into small particles, meeting the requirement for a more accelerated oxidation in the soil, supplying plants with soluble Sulfur. To assist in this process, a disintegrant/deaggregating agent has been added to the molten Sulfur, where this disintegrant/deaggregating agent may be Citric Acid, Ammonium Bicarbonate, Sodium Bicarbonate, Starches, Bentonite, Attapulgite, Expanding Clay or a mixture of these, or similar substances, preferably Bentonite Clay. [0010] The disintegrant/deaggregating agent in contact with water has a high expansion coefficient, increasing its volume by approximately 35 times. [0011] When we add the disintegrant/deaggregating agent to Elemental Sulfur, which will form the coat that will cover all fertilizer granules, the coating formed in contact with the water of the soil solution will cause the disintegrant/deaggregating agent to expand, fragmenting this Sulfur coating into particles smaller than 0.15 mm, enabling greater oxidation and consequent root absorption by the plants.
[0012] One of the objectives of the present invention is to homogeneously aggregate Elemental Sulfur to the coat of all types of granular fertilizers, together with a disintegrant/deaggregating agent, enabling the homogeneous addition of high doses of this nutrient, in addition to ensuring its oxidation and release for plant root absorption. Where this disintegrant/deaggregating agent can be Citric Acid, Ammonium Bicarbonate, Sodium Bicarbonate, Starches, Bentonite, Attapulgite, Expanding Clay or a mixture of these, or similar substances, preferably Bentonite Clay.
[0013] The process of the present invention consists of spraying molten Sulfur together with a disintegrant/deaggregating agent in primary and/or secondary macronutrient fertilizers, with or without micronutrients, in a Pelletizing and Coating Drum which can be a continuous rotary drum or batch, fixed die, ribbon or paddle mixer, or continuous belt. The fertilizers to be pelleted by the molten Sulfur may be mononutrients, binary or ternary, with or without micronutrients or secondary macronutrients, and also micronutrients isolated or added together with the fertilizers. The disintegrant/deaggregating agent can be added in the process, directly into the heating drum, or into the pelletizing drum, or mixed into the molten Sulfur .
[0014] The Elemental Sulfur in solid form is transfered to the Melt Storage Tank and melted at a temperature between 140 and 200 degrees Celsius, its preferred point being between 140 to 150 degrees Celsius, filtered if necessary and subsequently sent to the Storage Tank or Mixer and maintained at these temperatures. We can also receive the already molten Sulfur .
[0015] In this same Storage Tank or Mixer the disintegrant/deaggregating agent can be added in a ratio between 5% to 95% w/w, preferably between 9.5 to 30% w/w in relation to the Elemental Sulfur, depending on each product. The disintegrant/deaggregating agent ratio will also be the same in relation to Elemental Sulfur if it is added either to the heating drum, or to the pelletizing drum.
[0016] At the same time, the mononutrient, binary, or ternary fertilizers, with or without micronutrients or secondary macronutrients, as well as isolated micronutrients, are added to a continuous or batch dosing process where they are weighed and can be directed to the Mixer depending on each case, and then directed to a Heating Drum or directly to the Pelletizing System depending on specific conditions of each situation and product to be manufactured.
[0017] If the use a Heating Drum is required, the fertilizer or fertilizers dosed are heated to a temperature that varies between 50 to 140 degrees Celsius, depending on each type of fertilizer. For Nitrogen fertilizers the preferred range is 80 to 100 degrees Celsius, and for the other fertilizers, between 100 and 120 degrees Celsius. For some products this heating favors the homogeneous addition of molten Sulfur .
[0018] Aft er heating, the dosed fertilizer or fertilizers are directed to the Pelletizing System, where the mixture of molten Sulfur with the disintegrant/deaggregating agent is sprayed, or only the molten Sulfur is sprayed if the disintegrant/deaggregating agent is added directly to the heating drum or the pelletizing drum.
[0019] Depending on the temperature of the pelleted fertilizer, the product will go through a cooling equipment, or if the temperature is not high, it will not be necessary to cool it, and in this case, the Sulfur incorporation stage will already be completed.
[0020] The final product contains the established and required amount of Sulfur for each type of product and culture incorporated in all grains homogeneously.
[0021] The amount (% w/w) of Sulfur in the final product depends on the needs of each customer, and the minimum amount required by the legislation of the Ministry of Agriculture, Livestock and Supply can be added, which is 1.0% w/w, and can reach values greater than 40% w/w. The Sulfur content in the formulation depends on the requirements of each soil and culture being defined by the company customers or agronomists, according to some examples below: Example of some products manufactured in this stage, always expressed as % w/w:
Product: 00 - 40 - 00 + 13%Ca + 11.5%S
Phosphorus (P2O5) CNA+H20 = 40.0%
Calcium (Ca) = 13.0%
Sulfur (S) = 11.5%
Composition :
Triple Superphosphate - 870.0 kg/ ton
Elemental Sulfur - 115.0 Kg/ ton
Bentonite Clay - 15.0 Kg/ ton
Product: 06 - 31 - 15 + 2%Ca + 10%S
Nitrogen (N) = 6.0%
Phosphorus (P2O5) CNA+H2O = 31.0%
Potassium (K2O) = 15.0%
Calcium (Ca) = 2.0%
Sulfur (S) = 10.0%
Composition :
Triple Superphosphate - 146.6 Kg/ ton
12-46+6%S - 335.0 Kg/ ton
Monoammonium Phosphate - 180.0 Kg/ ton
Potassium Chloride - 250.0 Kg/ ton
Elemental Sulfur - 80.0 Kg/ ton
Bentonite Clay - 8.4 Kg/ ton
Product: 10-43 + 10%S + l%Ca + 10%S + 0.40%Zn + 0.10%B
+ 0.10%Cu
Nitrogen (N) = 10.0%
Phosphorus (P2O5) CNA+H2O = 43.0%
Calcium (Ca) = 1.0%
Sulfur (S) = 10.0%
Zinc (Zn) = 0.40%
Boron (B) = 0.10%
Copper (Cu) = 0.10%
Composition :
Triple Superphosphate - 79.9 Kg/ ton
12 - 46 + 5.5%S + 0.6%Zn +0.15B + 0.15Cu - 667.0 Kg/ ton
Monoammonium Phosphate - 183.0 Kg/ ton
Elemental Sulfur - 63.4 Kg/ ton
Bentonite Clay - 6.7 Kg/ ton
Product: 40 - 00 - 00 + 11.5%S
Nitrogen (N) = 40% Sulfur (S) = 11.5%
Composition :
Urea - 870.0 kg/ ton
Elemental Sulfur - 115.0 Kg/ ton
Bentonite Clay - 15.0 Kg/ ton
[0022] The incorporation of more micronutrients is part of this new process, if desired, and therefore, after the end of the previously described stage, the product will be ready for shipment and use by customers or will proceed to the incorporation of additional micronutrients .
[0023] At this stage, the product will go to a Mixer for the addition of any type of micronutrients approved by the fertilizer legislation regulated by the Ministry of Agriculture, Livestock and Supply. This Mixing System may occur in continuous rotary drum or batch, with fixed die, or ribbon or paddle mixers, and also continuous belts, and v or w mixers.
[0024] The amount (% w/w) of each micronutrient that can be added is quite varied and can reach high concentrations per element, and can exceed 60% w/w, preferably 5% of each of the following nutrients: Zinc, Boron, Copper, Molybdenum, Manganese, Iron, Cobalt, Selenium, Silicon, Nickel, Cobalt, Chlorine.
Some examples of products manufactured in this stage, always expressed as % w/w:
Product: 00 - 40 - 00 + 13%Ca + 10%S + 0.50%Zn + 0.15%B
Phosphorus (P2O5) CNA+H20 = 40.0% Calcium (Ca) = 13.0% Sulfur (S) = 10.0% Zinc (Zn) = 0.50% Boron (B) = 0.15%
Composition : Triple Superphosphate - 870.0 Kg/ ton
Elemental Sulfur - 100.0 Kg/ ton
Bentonite Clay - 10.5 Kg/ ton
Zinc Oxide (ZnO) - 7.0 Kg/ ton
Ulexite - 10.0 Kg/ ton
Adhesive Additive - 2.5 Kg/ ton
Product: 04 - 40 - 00 + 7%Ca + 12%S + 0.60%Zn + 0.20%B
Nitrogen (N) = 4.0%
Phosphorus (P2O5) CNA+H2O = 40.0%
Calcium (Ca) = 7.0%
Sulfur (S) = 12.0%
Zinc ( Zn) = 0.60%
Boron (B) = 0.20%
Composition :
Triple Superphosphate - 476.6 Kg/ ton
Monoammonium Phosphate - 364.0 Kg/ ton
Elemental Sulfur - 120.0 Kg/ ton
Bentonite Clay - 12.6 Kg/ ton
Zinc Oxide (ZnO) - 8.4 Kg/ ton
Ulexite - 13.4 Kg/ ton
Adhesive Additive - 5.0 Kg/ ton
Product: 05 - 30 - 10 + 3.5%Ca + 17%S + 0.55%Zn + 0.13%B
+ 0.13%Cu
Nitrogen (N) = 5.0%
Phosphorus (P2O5) CNA+H2O = 30.0%
Potassium (K2O) = 10.0%
Calcium (Ca) = 3.5%
Sulfur (S) = 17.0%
Zinc (Zn) = 0.55%
Boron (B) = 0.13%
Copper (Cu) = 0.13%
Composition :
Triple Superphosphate - 235.4 Kg/ ton
12 + 46 + 6%S - 416.8 Kg/ ton
Potassium Chloride - 166.7 Kg/ ton
Elemental Sulfur - 145.0 Kg/ ton
Bentonite Clay - 15.3 Kg/ ton
Zinc Oxide (ZnO) - 7.7 Kg/ ton
Ulexite - 8.7 Kg/ ton
Copper Oxide (CuO) - 1.9 Kg/ ton
Adhesive Additive - 2.5 Kg/ ton
Product: 40 00 00 + 10%S + 0.50%Zn + 0.14%B Nitrogen (N) = 40.0% Sulfur (S) = 10.0% Zinc (Zn) = 0.50% Boron (B) = 0.14%
Composition :
Urea - 870.0 kg/ ton
Elemental Sulfur - 100.0 Kg/ ton
Bentonite Clay - 10.6 Kg/ ton
Zinc Oxide (ZnO) - 7.0 Kg/ ton
Ulexite - 9.4 Kg/ ton
Adhesive Additive - 3.0 Kg/ ton
[0025] At the end of the process, the final product goes through the following routes:
Bulk storage box\warehouse, or;
Direct bulk loading and shipping on trucks; or
Direct bagging in Big Bag packages of 250 to 1500 kg or bags of 10 to 50 kg, for storage and subsequent shipment, or;
Direct bagging in Big Bag packages of 250 to 1500 kg or bags of 10 to 50 kg, for direct shipment, or;
Directed to the production of other types of fertilizers .
[0026] It is important to note that all products manufactured in this new process are approved by the Ministry of Agriculture, Livestock and Supply (MAPA) .
[0027] Several fertilizer raw materials are used in the manufacturing process:
- Monoammonium Phosphate, Diammonium Phosphate, Ammonium Chloride, Single Superphosphate, Triple Superphosphate, Double Superphosphate, Partially Acidulated Phosphate, Sulphuric Acid Phosphate, Phosphuric Acid Phosphate, Ammonium Single Superphosphate, Triple Ammonium Superphosphate, Urea, Ammonium Sulphate, Potassium Chloride, Magnesian Multiphosphate, Calcium Oxide, Calcium Hydroxide, Ammonium Phosphate, Potassium Phosphite, Potassium Carbonate, Calcium Carbonate, Ammonium Phosphite, Precipitated Phosphate, Ammonium Phosphosulfate, Calcium Oxide, Calcium Oxide, Magnesium Phosphosulfate, Magnesium Polyphate, Silicon Phosphate, Calcium Magnesium Silicate, Magnesium Silicate, Potassium Silicate, Calcium Sulfate, Potassium Sulfate, Potassium Magnesium Sulfate, chelating and complexing agents for mineral fertilizers, organic and organomineral fertilizers, adhesive additives for mineral fertilizers, organic and organomineral fertilizers, Approved fillers for mineral fertilizers, Organic and organomineral fertilizers, Simple mineral fertilizers, Mixed and or Complex mineral fertilizers containing NPK, NP, NK or PK with or without secondary macronutrients or micronutrients, Organic fertilizers, Organomineral fertilizers, all authorized sources of micronutrients, all authorized sources of secondary macronutrients, Elemental Sulfur, and a disintegrant/deaggregating agent such as Citric Acid, Ammonium Bicarbonate, Sodium Bicarbonate, Starches, Bentonite, Attapulgite, Expanding Clay or a mixture of these, or similar substances, preferably Bentonite Clay and all disintegrant/deaggregating agents authorized by regulatory agencies.
[0028] It is important to note that all raw materials indicated are approved by the Ministry of Agriculture, Livestock and Supply (MAPA) .
[0029] The product resulting from the process of the present invention is a pellet-shaped fertilizer characterized in that it is coated by a mixed layer of Elemental Sulfur and a disintegrant/deaggregating agent in which the concentration of the disintegrant/deaggregating agent is from 5.0% w/w to 95% w/w, preferably from 9.5% w/w to 30% w/w of the amount of Elemental Sulfur, and the concentration of Elemental Sulfur in the referred fertilizer is at least 1% w/w, where the fertilizer to be coated is of the following types: Organic fertilizers, Organomineral fertilizers, Simple mineral fertilizers, Mixed mineral fertilizers and or Complexes containing NPK, NP, NK or PK with or without secondary macronutrients or micronutrients. The amount of Sulfur to be added in the process may be less than 1% w/w, in case the legislation of the Ministry of Agriculture, Livestock and Supply changes and allows for values lower than 1% w/w.
BRIEF DESCRIPTION OF THE DRAWINGS
[0030] Figure 01 illustrates the process flowchart of the present invention where the following components are described :
- Heat Generator (1) that can be supplied by a Furnace or Boiler with energy from coal, wood, liquid fuel, gas, electricity, or any other type of fuel;
- Storage Tank (2) for receiving solid or molten liquid Sulfur. In this tank Elemental Sulfur is heated between 140 and 200 degrees Celsius so that it melts, with the preferred melting point being between 140 and 150 degrees Celsius. If received in solid form it may be filtered before use. In this same tank, the disintegrant/deaggregating agent can be added and mixed; Mixing Tank (3) for Elemental Sulfur with a disintegrant/deaggregating agent, from where the mixture of elemental Sulfur with disintegrant/deaggregating agent is pumped to the Application Tank (4) ;
Application Tank (4) of elemental Sulfur with disintegrant/deaggregating agent, from where the mixture of elemental Sulfur with disintegrant/deaggregating agent is pumped to the Pelletizing System (6) ;
- Fertilizer Heating System (5) , which can be rotary, fluidized bed or other similar system;
- Pelletizing System (6) implemented by drum for the coating of fertilizers with the mixture of Elemental Sulfur with disintegrant/deaggregating agent continuously or by batch, where temperatures are maintained between 50°C and 140°C, depending on the type of fertilizer. For Nitrogen fertilizers the preferred range is 80 to 100 degrees Celsius, and for the other fertilizers, between 100 and 120 degrees Celsius. This Pelletizing System (6) can be implemented with continuous rotary drum or batch, fixed die pelletizer and ribbon or paddle mixers and also continuous belts; it may receive the molten Sulfur already mixed with the disintegrant/deaggregating agent, or these may added separately .
- Cooler (7) , which can be rotary, fluidized bed or other similar system;
- Disintegrant/deaggregating agent dosing system (8) , which can include a continuous or batch system;
Fertilizer Dosage System, Micronutrients and disintegrant/deaggregating agent (9) , which can include a continuous or batch system, in the Dosage System (9) fertilizers such as organic fertilizers, organomineral fertilizers, simple mineral fertilizers, mixed mineral fertilizers and or Complexes containing NPK, NP, NK or PK with or without secondary macronutrients or micronutrients are introduced, all isolated and disintegrant/disaggregating Micronutrients all approved by the fertilizer legislation regulated by the Ministry of Agriculture, Livestock and Supply, depending on room temperature conditions, the product and/or quantity produced it is not necessary to use heating, as well as depending on the amount of product manufactured it will not be necessary to use the Mixer;
Micronutrient Dosage System (10) , which can be installed with a continuous or batch system;
- Micronutrient Mixing System (11) for the coating of micronutrients, which can be implemented by continuous rotary drum or batch, fixed die mixer and ribbon or paddle mixers, also continuous belts and v or w mixers; and
- Raw Material Mixing System (12) , can be implemented by continuous rotary drum or batch, fixed die mixer and ribbon or paddle mixers, also continuous belts and v or w mixers.
[0031] In the flowchart of figure 1 each part of the process flow is represented by a color. The dark blue color represents the flow of the Fertilizing Raw Materials, the purple color represents the flow of the disintegrant/deaggregating agent, the mustard color represents the flow of the molten Sulfur, the brown color represents the flow of the molten Sulfur plus the disintegrant/deaggregating agent, the pink color represents the flow of the micronutrients, the turquoise color represents the dosed raw materials, the light green color represents the flow of the adhesive additives, the light blue color represents the flow of the finished product, the red color represents the flow of the steam, the green color represents the flow of cold air at room temperature, and the black color represents the equipment .
[0032] Figure 02 illustrates samples of the product manufactured by the process of the present invention. The illustrated pellets are from a fertilizing product of type 00-40-00 + 13% w/w Calcium + 10% w/w Sulfur + 0.18% w/w Boron + 0.50% w/w Zinc.
[0033] Figure 3 illustrates how sowing was performed on 04/21/2022, where three furrows were made in each vessel. The corn seeds were placed in the central furrow, and in the lateral furrows, the fertilizer Triple Superphosphate coated with the mixture of Elemental Sulfur and disintegrant/deaggregating agent from the present invention, identified as TSP+S+Be, was applied. [0034] Figure 4 illustrates the development of corn plants on 05/04/22.
[0035] Figure 5 illustrates the development of corn plants on 06/13/22.
[0036] Figure 6 illustrates the development of corn plants on 07/20/22.
[0037] Figure 7 illustrates the development of corn plants on 08/03/22. [0038] Figure 8 illustrates in an enlarged view the development of the corn ear resulting from the applied treatment .
[0039] Figure 9 illustrates a graph with the results of the dry mass of the aboveground part of the corn plants and the grain yield per plant, treated at 30, 60, and 137 days. The results clearly demonstrate the excellent performance of the product produced by the process of the present invention, identified in the graph as TSP+S+Be, when compared to other products currently on the market identified as SSP, TSP, TSP+S, and Superactiv, as well as the Control vessel without the addition of fertilizers. Also in figure 9, we can see that the grain production per plant in the product manufactured by the process of the present invention, identified in the graph as TSP+S+Be, was much grater than with other fertilizers, reaching 150.2 g/plant, 12.17% w/w above TSP+S and 26% w/w above SSP.
[0040] Figure 10 illustrates photos of the evolution of corn plants according to the treatments used. We can verify that the size of the plant generated with the use of the product manufactured by the process of the present invention is greater than the other plants fertilized with the market products and the control vessel.
[0041] The images of figures 11 to 13 clearly show that the presence of the disintegrant/deaggregating agent, namely Bentonite Clay, with Elemental Sulfur exhibits a very different behavior when compared to Elemental Sulfur without the disintegrant/deaggregating agent . [0042] Figure 11 illustrates the difference between a pellet with and without the disintegrant/deaggregating agent, namely Bentonite Clay, with 3 days of moisture presence. It is clear from this image that, with the addition of the disintegrant/deaggregating agent, the coating disintegrates and initiates fragmentation of the Elemental Sulfur which is the technical foundation of the objective of this invention. In other words, disintegrant/deaggregating agent within this new process fragments the Elemental Sulfur, facilitating its solubilization and oxidation in the soil, which is corroborated by the agronomic result indicated in figure 09.
[0043] Figure 12 illustrates an enlargement of the pellets of figure 11.
[0044] Figure 13 illustrates a comparison between a dry pellet and a pellet with 3 days of moisture, being both pellets produced by the process of the present invention, i.e. coated by the mixture of Elemental Sulfur and a disintegrant/deaggregating agent.
[0045] Figure 14 illustrates the triple Superphosphate fertilizer coated with 12% w/w elemental Sulfur and 10% w/w disintegrant/deaggregating agent in relation to elemental Sulfur. The figure shows the thickness of the coating. In general this coating thickness is from 20 pm to 60 pm, its preferred range being between from 30 pm to 50 pm.
[0046] It is clear from the images that the presence of the disintegrant/deaggregating agent quickly disintegrates the Elemental Sulfur, which favors its solubilization in the soil and its absorption by the root of the plant to be fertilized, which was proven in the actual in-vessel tests in the cultivation of Corn presented in figures 09 and 10.
DETAILED DESCRIPTION OF THE INVENTION
[0047] The process for aggregating Elemental Sulfur in fertilizers of the present invention is characterized by consisting of the following stages: a. In the initial phase of the process, Elemental Sulfur is placed in the Storage Tank (2) in solid form or already melted, where it is heated between 140°C and 200°C to be melted or maintained in a molten state, with apreferred melting point between 140 to 150 degrees Celsius; the disintegrant/deaggregating agent is weighed and dosed in the disintegrant/deaggregating agent Dosing System (8) or (9) ; one or several types of granulated fertilizers and micronutrients are weighed and dosed in batches or continuously in the Fertilizer Dosing System (9) ; if necessary, additional micronutrients are weighed and dosed in the Micronutrient Dosing System (10) ; b. If pre-mixing is required, the dosed products are directed to the mixer where the adhesive additive can be used ( 12 ) ; c. If heating is necessary, the fertilizers are transfered to the Fertilizer Heating System (5) , and are heated to a temperature between 50 to 140 degrees, depending on the type of fertilizer. For Nitrogen fertilizers the preferred range is 80 to 100 degrees Celsius, and for the other fertilizers, between 100 and 120 degrees Celsius. This facilitates the homogeneous aggregation of pure molten Elemental Sulfur or Elemental Sulfur with the disintegrant/deaggregating agent, where the Fertilizer Heating System (5) can be rotary, fluidized bed, or a similar system; d. The Elemental Sulfur of the Storage Tank (2) and the disintegrant/deaggregating agent of the Dosing System (8) are transfered to the Mixing Tank (3) and are mixed until homogenized, where the disintegrant/deaggregating agent is in a ratio between 5.0% to 95% w/w, preferably 9.5% to 30% w/w of the mixture with Elemental Sulfur, depending on each product ; e. The mixture of Elemental Sulfur and disintegrant/deaggregating agent is transfered to the Application Tank (4) ; f. The dosed Raw Materials are transfered to the
Pelletizing System (See) (6) ; the molten Elemental Sulfur can be added to the Pelletizer in two ways: (e.l) pure, coming from the Storage Tank (2) , in this option the disintegrant/deaggregating agent is also added to the Pelletizer simultaneously with the Cast Elemental Sulfur, and the simultaneous mixing is performed during the Fertilizer Pelletization, or (e.2) already mixed with the disintegrant/deaggregating agent, from the Application Tank (4) where it is sprayed in the Pelletizing System (6) ; the percentage of disintegrant/deaggregating agent in relation to the cast Elemental Sulfur depends on each product being within the range of 5.0% to 95% w/w , preferably 9.5% to 30% w/w being its most preferred range from 9.5% to 15% w/w; in these two application methods, the percentage of Final Sulfur in the product is previously defined to reach the necessary content for each type of product. Mixing and Pelletizing are carried out until the final product is fully coated with the layer of Elemental Sulfur and disintegrant/deaggregating agent. The minimum amount of Sulfur is 1.0% w/w and can reach values greater than 40% w/w depending on the needs of each customer and product . g. After coating the fertilizer with the mixture of Elemental Sulfur and disintegrant/deaggregating agent the product may follow 02 different routes:
If it has been heated, due to the specific conditions of each product, it follows the route to the Cooler ( 7 ) ;
- If it has not been heated, due to the specific conditions of each product, the coating phase is completed; h. Then the product may follow 02 different routes:
- Manufacturing completed and the product can be either stored in bulk in boxes/warehouses , or loaded and directly dispatched in bulk in trucks, or directly bagged in Big Bag packaging of 250 to 1500 kg or bags of 10 to 50 kg for storage and subsequent dispatch, or directly bagged in Big Bag packaging of 250 to 1500 kg or bags of 10 to 50 kg for direct dispatch, or directed for the production of other types of fertilizers; or It will proceed to the incorporation or supplementation of additional micronutrients in a micronutrient mixing system (11) ; at this stage, various types of micronutrients that were weighed and dosed in batches or continuously in the micronutrient dosing system (10) are added to the product along with a specific adhesive additive in the micronutrient mixing system (11) ; The regulated adhesive additive approved by the Ministry of Agriculture, Livestock, and Supply, categorized as an Adhesive Additive, will be used. It can be of vegetable origin such as Starches, Flaxseed Oil, Glucose Syrup, or mineral origin such as Silicones, Waxes, and Paraffins, with the function of binding bind all the micronutrients to the fertilizer, and its quantity can vary from 0.1% to 30% w/w, preferably from 0.2% to 1.5% w/w , depending on the amount of micronutrients to be aggregated; the amount (% w/w) of micronutrients to be added varies greatly and can reach high concentrations of each element, exceeding 60% w/w, preferably 5% w/w of each of the following nutrients: Zinc, Boron, Copper, Molybdenum, Manganese, Iron, Cobalt, Selenium, Silicon, Nickel, Cobalt, Chlorine. After this stage, the product can be directed to bulk storage in boxes/warehouses , or loaded and shipped directly in bulk on trucks, or directly bagged in Big Bag packaging ranging from 250 to 1500 kg or in bags ranging from 10 to 50 kg, for storage and subsequent shipment, or directly bagged in Big Bag packaging ranging from 250 to 1500 kg or in bags ranging from 10 to 50 kg, for direct shipment, or directed towards the production of other types of fertilizers.
[0048] The disintegrant/deaggregating agent of the process of the present invention may be Citric Acid, Ammonium Bicarbonate, Sodium Bicarbonate, Starches, Bentonite, Attapulgite, Expanding Clay or a mixture of these, or similar substances, preferably Bentonite Clay, and all disintegrant/deaggregating agents areauthorized by regulatory agencies.
[0049] As illustrated in figure 02, the products manufactured by the process of the present invention are Granulated Fertilizers, subsequently Pelletized, coated with a layer of the mixture of Elemental Sulfur and disintegrant/deaggregating agent, which can receive a coating of micronutrients.
Technical Specifications of the Products resulting from the process of the present invention
[0050] The technical specifications of the products resulting from this process must comply with the legal parameters established by the Ministry of Agriculture, Livestock and Supply with regard to the contents of Primary and Secondary Macronutrients and Micronutrients, as well as their particle size specification, so these products will strictly follow these specifications, namely :
Primary Macronutrients : N , P , K
- The sum of NPK will be equal to or greater than 18% w/ w - The sum of NP, NK or PK will be equal to or greater than 15% w/w
Secondary Macronutrients : Ca , S , Mg
- The contents of each element will not be less than 1% w/ w
Micronutrients:
- The % w/w content of each element shall not be less than :
Boron (B) : 0.01%, Chlorine (Cl) : 0.1%, Cobalt (Co) :
0.005%
Copper (Cu) : 0.02%, Iron (Fe) : 0.02%, Manganese (Mn) : 0.02%, Molybdenum (Mo) : 0.005%, Nickel (Ni) : 0.005%, Selenium (Se) : 0.003%, Silicon (Si) : 0.05%, Zinc (Zn) : 0.1%
GRANULOMETRY
Granules retained in the 4.80 mm mesh - 5% w/w maximum Granules passing through the 2.00 mm mesh - 40% w/w maximum
Granules passing through the 1.00 mm mesh - 5% w/w maximum
Other specifications:
In addition to the specifications established by the Ministry of Agriculture, Livestock and Supply, the products will also have other specific parameters, being : Hardness: 1.5 kgf minimum Establishes the mechanical strength of the grain that is important to support transport, storage and handling during application.
Humidity (H2O) : 5.0% w/w maximum Defines the maximum amount of Water present in the product above which it impairs handling, manipulation, application, in addition to favoring grain breakage. Acidity (H3PO4) : 5.0% w/w maximum.
Defines the maximum free Phosphoric Acid present in the product above which it impairs handling, manipulation, application, in addition to favoring grain breakage and corrosion in the fertilization system.
SGN: 200 to 380
This parameter defines the maximum and minimum range of the average grain size for the product. It is important to ensure granulometric homogeneity during application. IU: 30 minimum
Defines the Uniformity of the grains, below which the product will have uneven sizes of grains.
Scientific proof of the efficiency of the new product and process
I. Agronomic Efficiency
[0051] A test to evaluate the agronomic efficiency of the product on maize crop was conducted by UNESP - Universidade Estadual Paulista "Julio de Mesquita Filho" for 127 days.
[0052] The agronomic results found allowed us to observe that the Bentonite Clay added to molten Elemental Sulfur was effective in ensuring oxidation that meets the demands of the crop.
[0053] Table 1 below illustrates the work plan and operational schedule of the test.
Table 1. Work Plan and Operational Schedule
Figure imgf000027_0001
[0054] Table 2 below illustrates the characteristics of the soil used in the experiment.
Table 2. Experimental Soil
Figure imgf000027_0002
[0055] Table 3 below illustrates the treatments performed in the test.
Dose* P2O5 S
T D i i
Kg . ha1
Figure imgf000028_0001
1 Control (without fertilization)
2 Simple superphosphate (SS) 555 100 62
3 Triple superphosphate (TS) 217 100 0
4 TS + S 250 100 62
5 TS + S + Bentonite (Be) 250 100 62
6 Superactiv 476 100 62
Electron Microscopy Study
[0056] A microscopy study of the coated fertilizer products of the mixture of Fertilizing Sulfur and Bentonite Clay was carried out according to the process of the present invention and the efficiency of Bentonite Clay acting on the fragmentation of the coated Elemental Sulfur in the granulated fertilizers when in contact with water was evaluated, simulating soil conditions.
[0057] The images in figures 11 to 13 clearly show that the presence of Bentonite Clay with Elemental Sulfur leads to a quite different behavior when compared to Elemental Sulfur without Bentonite Clay.
[0058] Figure 11 illustrates the difference between a pellet without Bentonite Clay and with Bentonite Clay with 3 days of moisture presence. It is possible to clearly see the fragmentation of the Elemental Sulfur coating in the sample with Bentonite Clay compared to the sample without Bentonite.
[0059] Figure 12 illustrates an enlargement of the pellets of figure 11.
[0060] Figure 13 illustrates a comparison between a dry pellet and a pellet with 3 days of moisture, being both pellets produced by the process of the present invention, i.e. coated by the mixture of Elemental Sulfur and Bentonite Clay.
[0061] Figure 14 illustrates the triple Superphosphate fertilizer coated with 12% w/w elemental Sulfur and 10% w/w Bentonite Clay in relation to elemental Sulfur. The figure shows the thickness of the coating. In general this coating thickness is from 20 pm to 60 pm, its preferred range being between from 30 pm to 50 pm.

Claims

1. Process for aggregating Elemental Sulfur in solid fertilizers characterized by consisting of the following steps : a. In the initial phase of the process, Elemental Sulfur is placed in the Storage Tank (2) in solid form or already melted, where it is heated between 140°C and 200°C to be melted or maintained in a molten state; The disintegrant /deaggregating agent is weighed and dosed in the disintegrant/deaggregating agent Dosing System (8) or (9) ; one or several types of granulated fertilizers and micronutrients are weighed and dosed in batches or continuously in the Fertilizer Dosing System (9) ; if necessary, additional micronutrients are weighed and dosed in the Micronutrient Dosing System (10) ; b. If pre-mixing is required, the dosed products are directed to the mixer where the adhesive additive can be used ( 12 ) ; c. If heating is required, the fertilizers are directed to the Fertilizer Heating System (5) and heated to a temperature between 50 to 140 degrees, where the Fertilizer Heating System (5) can be rotary, fluidized bed, or another similar system; d. The Elemental Sulfur from the Storage Tank (2) and the disintegrant/deaggregating agent of the Dosing System (8) are directed to the Mixing Tank, (3) and are mixed until homogenized, where the disintegrant/deaggregating agent is in the ratio between 5.0% to 95% w/w, preferably 9.5% to 30% w/w of the mixture with Elemental Sulfur, depending on each product; e. The mixture of Elemental Sulfur and disintegrant/deaggregating agent is transfered to the Application Tank (4) ; f. The dosed Raw Materials are transfered to the
Pelletizing System (6) ; the molten Elemental Sulfur can be added to the Pelletizer in two ways: (e.l) pure, coming from the Storage Tank (2) , in this option the disintegrant/deaggregating agent is also added to the Pelletizer simultaneously with the molten Elemental Sulfur, and the simultaneous mixing is performed during the Fertilizer Pelletization, or (e.2) already mixed with the disintegrant/deaggregating agent, coming from the Application Tank (4) where it is sprayed in the Pelletization System (6) ; the percentage of the disintegrant/deaggregating agent in relation to the molten Elemental Sulfur depends on each product being within the range of 5.0% to 95% w/w, preferably 9.5% to 30% w/w being its most preferred range of 9.5% to 15% w/w; mixing and pelletization are carried out until the final product is fully coated with the layer of Elemental Sulfur and disintegrant/deaggregating agent; where the minimum amount of Sulfur is 1.0% w/w and can reach values higher than 40% w/w; g. After coating the fertilizer with the mixture of Elemental Sulfur and disintegrant/deaggregating agent the product may follow 02 different routes: If it has been heated, due to the specific conditions of each product, it follows the route to the Cooler ( 7 ) ;
- If it has not been heated, due to the specific conditions of each product, the coating phase is completed; h. Then the product may follow 02 different routes:
- Manufacturing completed and the product can be either stored in bulk in boxes/warehouses , or loaded and directly dispatched in bulk in trucks, or directly bagged in Big Bag packaging of 250 to 1500 kg or bags of 10 to 50 kg for storage and subsequent dispatch, or directly bagged in Big Bag packaging of 250 to 1500 kg or bags of 10 to 50 kg for direct dispatch, or directed for the production of other types of fertilizers; or
It will proceed to the incorporation or supplementation of additional micronutrients in a micronutrient mixing system (11) ; at this stage, various types of micronutrients that were weighed and dosed in batches or continuously in the micronutrient dosing system (10) are added to the product along with a specific adhesive additive in the micronutrient mixing system (11) ; The regulated adhesive additive approved by the Ministry of Agriculture, Livestock, and Supply, categorized as an Adhesive Additive, will be used. It can be of vegetable origin such as Starches, Flaxseed Oil, Glucose Syrup, or mineral origin such as Silicones, Waxes, and Paraffins, with the function of binding bind all the micronutrients to the fertilizer, and its quantity can vary from 0.1% to 30% w/w, preferably from 0.2% to 1.5% w/w, depending on the amount of micronutrients to be aggregated; the amount (% w/w) of micronutrients to be added varies greatly and can reach high concentrations of each element, exceeding 60% w/w, preferably 5% of each nutrient Zinc, Boron, Copper, Molybdenum, Manganese, Iron, Cobalt, Selenium, Silicon, Nickel, Cobalt, Chlorine. After this stage, the product can be directed to bulk storage in boxes/warehouses , or loaded and shipped directly in bulk on trucks, or directly bagged in Big Bag packaging ranging from 250 to 1500 kg or in bags ranging from 10 to 50 kg, for storage and subsequent shipment, or directly bagged in Big Bag packaging ranging from 250 to 1500 kg or in bags ranging from 10 to 50 kg, for direct shipment, or directed towards the production of other types of fertilizers.
2. Process, according to claim 1, characterized in that the disintegrant/deaggregating agent is Citric Acid, Ammonium Bicarbonate, Sodium Bicarbonate, Starches, Bentonite, Attapulgite, Expansive Clay, or a mixture thereof, or other similar substances, Bentonite Clay, and all disintegrant/deaggregating agents are authorized by regulatory agencies.
3. Process, according to claim 1, characterized in that the disintegrant/deaggregating agent is Bentonite Clay.
4. Process, according to claim 1, characterized in that the granulated solid fertilizers, macronutrients, and powdered or granulated micronutrients used as starting material in the process comprise simple mineral fertilizers, Monoammonium Phosphate, Diamonic Phosphate, Ammonium Chloride, Single Superphosphate, Triple Superphosphate, Double Superphosphate, Partially Acidulated Phosphate, Sulfuric Acidulated Phosphate, Phosphoric Acidulated Phosphate, Ammoniated Single Superphosphate, Double Ammoniated Superphate, Urea, Ammonium Sulfate, Potassium Chloride, Magnesian Multiphosphate, Calcium Oxide, Calcium Hydroxide, Ammonium Phosphosulfate, Potassium Phosphate, Potassium Carbonate Potassium, Calcium Carbonate, Ammonium Phosphite, Precipitated Phosphate, Ammonium Phosphate, Calcium Oxide, Calcium Magnesium Oxide, Ammonium Polyphosphate, Calcium Silicate, Calcium Magnesium Silicate, Magnesium Silicate, Potassium Silicate, Calcium Sulfate, Potassium Sulfate, Potassium Sulfate, Potassium Magnesium Sulfate, chelating and complexing agents for mineral fertilizers, adherent additives for mineral fertilizers, fillers for mineral fertilizers, organomineral fertilizers, all authorized sources of micronutrients, all authorized sources of secondary macronutrients, NPK/NP/NK/PK fertilizers with or without micronutrients or secondary macronutrients, Elemental Sulfur, Bentonite Clay, Additivated Bentonite Clay and dis integrant/ de aggregating agents .
5. Process, according to claim 1, characterized
Figure imgf000034_0001
that the Elemental Sulfur placed in the Storage Tank (2) is preferably heated between 140°C to 150°C.
6. Process, according to claim 1, characterized in that the Nitrogenated fertilizers directed to the Fertilizer Heating System (5) are heated within the range of 90°C to 100°C and the other fertilizers within the range of 100°C to 120°C.
7. Process, according to claim 1, characterized in that the percentage of disintegrant/deaggregating agent relative to molten Elemental Sulfur is within the range of 9.5% to 15% w/w.
8. Process, according to claim 1, characterized in that the Pelletizing System (6) is implemented by continuous rotary drum or batch, fixed die pelletizer, ribbon or paddle mixers and/or continuous belts.
9. Process, according to claim 1, characterized in that the Micronutrient Mixing System (11) is implemented by continuous rotary drum or batch, fixed die mixer, ribbon or paddle mixers, continuous belts, and/or V or W mixers.
10. Pellet-shaped fertilizer, produced by the process of claim 1, characterized in that it is coated by a mixture layer of Elemental Sulfur and a disintegrant/deaggregating agent wherein the disintegrant/deaggregating agent concentration is from 5.0% to 95%, preferably from 9.5% w/w to 15% w/ w of the amount of Elemental Sulfur and the concentration of the Elemental Sulfur in the referred fertilizer is at least 1% w/w.
11. Fertilizer, according to claim 10, characterized in that the disintegrant/deaggregating agent is Citric Acid, Ammonium Bicarbonate, Sodium Bicarbonate, Starches, Bentonite, Attapulgite, Expansive Clay or a mixture of these, or similar substances, Bentonite Clay and all disintegrant/deaggregating agents authorized by regulatory agencies.
12. Fertilizer, according to claim 10, characterized in that the disintegrant/deaggregating agent is Bentonite Clay .
13. Fertilizer, according to claim 10, characterized in that the fertilizer used as starting material to be coated is of the following type: organic fertilizers, organomineral fertilizers, simple mineral fertilizers, mixed mineral fertilizers and or Complexes containing NPK, NP, NK or PK with or without secondary macronutrients or micronutrients and all isolated micronutrients .
14. Fertilizer, according to claim 10, characterized in that the sum of the NPK is equal to or greater than 18% w/ w .
15. Fertilizer, according to claim 10, characterized in thatthe sum of the NP, NK, or PK is equal to or greater than 15% w/w.
16. Fertilizer, according to claim 10, characterized in that the Ca, S and Mg contents are at least 1% w/w.
17. Fertilizer, according to claim 10, characterized in that the contents of: Boron (B) be at least 0.01% w/w; Chlorine (Cl) be at least 0.1% w/w; Cobalt (Co) be at least 0.005% w/w; Copper (Cu) be at least 0.02% w/w; Iron (Fe) be at least 0.02% w/w; Manganese (Mn) be at least 0.02% w/w; Molybdenum (Mo) be at least 0.005% w/w; Nickel (Ni) be at least 0.005% w/w; Selenium (Se) be at least 0.003% w/w; Silicon (Si) be at least 0.05% w/w; and/or Zinc (Zn) be at least 0.1% w/w
18. Fertilizer, according to claim 10, characterized in that its granules, produced according to the process of claim 1, have a maximum of 5% w/w of 4.80 mm mesh retained granules, have a maximum of 40% w/w of 2.00 mm mesh passing granules and have a maximum of 5% w/w of 1.00 mm mesh passing granules per batch produced.
19. Fertilizer, according to claim 10, characterized in that its granules, produced according to the process of claim 1, have a minimum hardness of 1.5 Kgf; maximum humidity (H2O) of 5.0% w/w; acidity (H3PO4) of at most 5.0% w/w; average grain size (SGN) of 200 to 380; and grain uniformity (IU) of at least 30.
20. Fertilizer, according to claim 10, characterized in thatthe percentage of disintegrant/deaggregating agent relative to molten elemental sulfur is within the range of 9.5 to 15% w/w.
21. Fertilizer, according to claim 10, characterized by containing 40% Phosphorus (P2O5) CNA+H2O, 13% Calcium (Ca) , 11.5% Sulfur (S) .
22. Fertilizer, according to claim 10, characterized by containing 4% Nitrogen (N) , 40% Phosphorus (P2O5)
CNA+H2O, 7% Calcium (Ca) , 12% Sulfur (S) , 0.60% Zinc (Zn) , and 0.20% Boron (B) .
23. Fertilizer, according to claim 10, characterized by containing 5% Nitrogen (N) , 30% Phosphorus (P2O5)
CNA+H2O, 10% Potassium (K2O) , 3.5% Calcium (Ca) , 17% Sulfur (S) , 0.55% Zinc (Zn) , 0.13% Boron (B) , and 0.13% Copper (Cu) .
24. Fertilizer, according to claim 10, characterized by containing 40% Nitrogen (N) , 10% Sulfur (S) , 0.50% Zinc (Zn) , 0.14% Boron (B) .
PCT/BR2023/050239 2022-10-18 2023-07-19 Process for aggregating elemental sulfur in solid fertilizers WO2024082041A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
BR1020220211140 2022-10-18
BR102022021114A BR102022021114A2 (en) 2022-10-18 2022-10-18 Process to add elemental sulfur to solid root fertilizers
BR1020230096697 2023-05-18
BR102023009669-7A BR102023009669A2 (en) 2023-05-18 2023-05-18 PROCESS FOR ADDING ELEMENTAL SULFUR INTO SOLID ROOT FERRILIZERS

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020151621A1 (en) * 2001-04-11 2002-10-17 Bohden Zakiewicz Matrix of meltable minerals and fertilizers
US20040050127A1 (en) * 2002-09-17 2004-03-18 Franco Ambri Fertilizer based on elemental sulfur
BR0215750A (en) * 2002-06-17 2005-03-15 Yara Int Asa Method for the production of an elemental sulfur urea fertilizer and urea sulfur fertilizer
US20180148384A1 (en) * 2013-02-07 2018-05-31 Tiger-Sul (Canada) Co. Sulphur-based fertilizer composition with low rock phosphate content
US11180424B1 (en) * 2018-12-07 2021-11-23 Fertile Peat Products, Llc Phosphate fertilizer with finely ground elemental sulfur, swelling agent and rock phosphate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020151621A1 (en) * 2001-04-11 2002-10-17 Bohden Zakiewicz Matrix of meltable minerals and fertilizers
BR0215750A (en) * 2002-06-17 2005-03-15 Yara Int Asa Method for the production of an elemental sulfur urea fertilizer and urea sulfur fertilizer
US20040050127A1 (en) * 2002-09-17 2004-03-18 Franco Ambri Fertilizer based on elemental sulfur
US20180148384A1 (en) * 2013-02-07 2018-05-31 Tiger-Sul (Canada) Co. Sulphur-based fertilizer composition with low rock phosphate content
US11180424B1 (en) * 2018-12-07 2021-11-23 Fertile Peat Products, Llc Phosphate fertilizer with finely ground elemental sulfur, swelling agent and rock phosphate

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