Pesticides and fertilisers of mechanochemically micronised zeolitic sulphur for use in the treatment of plants

Abstract

The present invention relates to pesticides and fertilisers of controlled release zeolitic sulphur that are mechanochemically activated. For this purpose, 98% pure elemental sulphur with a particle size class up to 0.10 mm and a moisture content up to 10%, and processed zeolitic ore, or zeolitic ore processed and modified with nutrients for plants, with a particle size class up to 0.10 mm and a moisture content up to 10%, in a 2:1 or 1:1 or 1:2 ratio are introduced into a horizontal or vertical mixer and are mixed between 30 minutes and one hour. The mass obtained is introduced into a microniser mill that is suitable for sulphur work, processed zeolitic material, or zeolitic material processed and modified with nutrients, between 75 wt.-% and 95 wt.-% of the final product is introduced and said mixture is ground (micronised) between 30 minutes and 2 hours. As a result, a water-soluble pesticide or fertiliser of zeolitic sulphur with a particle size up to 0.05 mm is obtained comprising lower sulphur doses than those traditionally used in the treatment of plants with pesticidal activity for controlling the pests affecting the same, or as a leaf and soil fertiliser of the plants with pesticidal activity.

Description

[0001] Mechanochemically micronized zeolitic sulfur pesticides and fertilizers useful for plant treatment

[0002] DESCRIPTION

[0003] The present invention relates to the mining, metallurgical, chemical, and agricultural sectors and is based on the production of pesticide and fertilizer products from sulfur and natural zeolites using a mechanochemical micronization process. The sulfur present in the invention is obtained from mineral resources, associated with natural gas or crude oil, while the zeolite is selectively extracted from zeolitic rocks and mechanically prepared by crushing, grinding, and particle size classification. The zeolitic material can optionally be enriched with chemical fertilizers for agricultural use.The final products resulting from the process employed in the present invention contain sulfur in comparatively low, yet efficient, quantities, which solves the problems that are usually present in sulfur formulations applied in agriculture: damage due to excessive and repetitive use, resistance, stability, safety, uncontrolled release, and poor performance due to carryover and leaching during persistent precipitation.

[0004] The products proposed in the present invention possess pesticide characteristics, while functioning as fertilizers for plant development under extensive and intensive agricultural production conditions at different production scales, although they can also be used for domestic purposes.

[0005] Zeolite is an aluminosilicate mineral with beneficial properties for agriculture: it improves the quality of agricultural soils, absorbs pesticides, acts as a carrier for active ingredients, and controls soil acidity. Sulfur is used in agriculture to control pests in various crops, a very ancient practice.

[0006] Current processes for producing micronized sulfur powder are hazardous and energy-inefficient. Currently, micronized sulfur powder is typically produced by pulverizing sulfur lumps in mechanical grinding equipment. However, when very fine particles are desired, mechanical grinding processes involve significant energy consumption. Consequently, there is a need to develop methods for producing micronized sulfur powder that employ means other than mechanical grinding, or even that, by using mechanical grinding, would reduce energy consumption. (Micronized sulfur powder and method of production thereof, CA2657531A1). It is a fact that elemental sulfur is assimilable by plants as a nutrient in the form of its oxidized chemical species (SO4) 2 ' and SO3 2')- This process occurs naturally when microorganisms present in the soil carry out this transformation. However, this process is slow, and there is a risk that the sulfur particles will be washed away by rain and contaminate groundwater. The natural oxidation of elemental sulfur can be accelerated by reducing its particle size (particle size class) to make it more accessible to microorganisms. Another option is to obtain oxidized sulfur species without the sulfuric-hydrogen sulfide form. (Plantpesticides and uses thereof, W02004026033A1)

[0007] To solve the problem posed, the present invention proposes micronized zeolitic sulfur pesticide and fertilizer products obtained through the application of mechanochemistry.

[0008] The term "mechanochemistry" was formalized by IUPAC in 1997, and is defined as "a chemical reaction that is induced by the direct absorption of mechanical energy." (HORIE, K.; et al. “Definitions of Terms Relating to Reactions of Polymers and to Functional Polymeric Materials (IUPAC Recommendations 2003)”. Pure and Applied Chemistry. 2004, 76(4), 889-906. ISSN: 1365-30756). According to Cuban professor Fernández Beltrán, a renowned researcher in this field, mechanochemical reactions are very complex processes (Fernández-Bertran, JF "Mechanochemistry: an overview" Pure and Applied Chemistry, vol. 71, no. 4, 1999, pp. 581-586. https: / / doi.org / 10.1351 / pac199971040581). The technique is based on the concept that mechanical energy exerted on a material produces chemical transformations and involves the grinding of solid substances to form compounds.The industrial application of this technology offers advantages such as reduced environmental impact (it consumes less energy and emits less CO2), the elimination of solvent use (eliminating problems associated with solvent toxicity and reagent solubility), shorter reaction times (contributing to greater efficiency in chemical synthesis), and the possibility of stereochemical control in the synthesis of chemical products. These advantages make it an attractive technique for sustainable industry and chemical research.

[0009] Among the practical applications of this technology, the grinding of minerals to alter their properties for use in industry stands out. It is known that, for example, silica, alumina, and aluminosilicates can be activated to become valuable catalysts with the addition of small amounts of metals (G. Heinic et al., Tribochemistry. Akademic-Verlag, Berlin, 1984; and Tkacova, Mechanical Activation of Minerals. Elsevier, Amsterdam, 1989).

[0010] Although there are some reports related to zeolite and sulfur in different contexts, no specific studies were found on mechanochemical reactions between these materials for the production of fertilizers and pesticides. However, some examples related to zeolite and sulfur in different contexts can be mentioned: the use of improved zeolites to remove sulfur compounds from gas condensates, significantly reducing their total sulfur content (Ghasem Bakhtiari et al., High-performance desulfurization of gas condensates by the adsorption method of improved zeolites, Affinity: Journal of Theoretical and Applied Chemistry, ISSN 0001-9704, Vol. 73, No. 574, 2016, pp.148-155); zeolite has been used as a support for catalysts in chemical reactions, such as the desulfurization of sulfated compounds through their catalytic reaction in the presence of sulfur (Authors: Leonela Díaz Amado and AlbersonYanluis Muñoz Correa, Degree thesis presented as a requirement to obtain the title of Chemical Engineer, Analysis of the behavior of Ni-Mo catalysts supported on micro-mesoporous zeolites synthesized by a mechano-chemical route, in the hydrodesulfurization reaction of dibenzothiophene, 2022, available at: https: / / noesis.uis.edu.co / server / api / core / bitstreams / 3c7f3146-6c6c- 463b-93a7-8976a3d196e2 / content): and finally, mechanochemistry has been used in the synthesis of materials, such as zeolite ZSM-5, which has been used as a seed for the preparation of nickel and manganese catalysts (NiMo / ZSM-5) (Authors: Leonela Díaz Amado and Alberson Yanluis Muñoz Correa, Degree thesis submitted as a requirement for the degree of Chemical Engineer, Analysis of the behavior of Ni-Mo catalysts supported on micro-mesoporous zeolites synthesized by a mechanochemical route, in the hydrodesulfurization reaction of dibenzothiophene, 2022, available at: https: / / noesis.uis.edu.co / server / api / core / bitstreams / 3c7f3146-6c6c-463b-93a7-8976a3d196e2 / content).

[0011] In the field of patent information, some documents were found that describe compositions incorporating micronized sulfur. For example, in document W02004026033 A1 (Paul Agostino & Sam Papandrea, publication date: 04 / 01 / 2004), pesticides are disclosed, and in particular a plant pesticide comprising (a) avermectin, ivermectin, abamectin or emamectin and (b) sulfur (for example, Thivoit® (a micronized sulfur formulation) or a sulfur-containing compound (for example, captan, captafol or dimethyldithiocarbonic acid). The invention also relates to the uses of these pesticides in the treatment of diseases of ornamental and vegetable plants. The main active component Thiovit® is elemental sulfur. This invention starts from the problem caused by the excessive and repeated use of sulfur-based pesticides, which does not provide the degree of protection or crop yield.These types of products also face the problem of pesticide resistance. As a solution, the inventors propose a mixture comprising avermectin and micronized sulfur, and more preferably, wettable micronized sulfur. This invention does not employ zeolite or mechanochemical techniques.

[0012] The patent application published in document US20130230448 A1 (CCR Technologies Ltd, publication date: 05 / 09 / 2013) discloses a method for obtaining micronized sulfur that involves dissolving elemental sulfur in a solvent to produce a sulfur-solvent solution and controlling the precipitation of sulfur by pressure, temperature or water content. The solvent is selected from the group consisting of anhydrous ammonia, hydrated ammonia, liquid sulfur dioxide, liquid carbon dioxide, supercritical carbon dioxide, carbon disulfide, dimethyldisulfide and mixtures thereof. The micronized sulfur obtained by said process has an average particle size less than 1000 micrometers, although it is preferably 10 micrometers. The selected solvent is anhydrous or hydrated ammonia to facilitate the solubility of sulfur.

[0013] The invention described in document US20150230475 A1 (Deepak Pranjivandas Shah, publication date: 08 / 20 / 2015), relates to a pesticide composition comprising an effective amount of sulfur; an effective amount of at least one insecticide selected from the group consisting of cartapfipronil, pirimicarb, buprofezin, thiacloprid, acetamiprid, clothianidin, diafenthiuron, novaluron, flubendiamide, spirotetramate, thiamethoxam, imidacloprid or salts thereof, and at least one agrochemically acceptable excipient. This invention, according to its inventors, addresses the problem related to soil resistance and toxicity, such that reduced doses of sulfur can be used, among others, but does not use zeolite or the mechanochemical technique.

[0014] In EP2904903 B1 (UPL Ltd, publication date: 15 / 05 / 2019), it is stated that sulfur is one of the oldest known pesticides and is widely used today as a pesticide. However, it is stated that it is difficult to formulate, either alone or in combination. Problems associated with sulfur formulations include the formation of unsightly residues on ornamental plants and a tendency to settle when in liquid form (Olkowski, W. et al., Common Sense Pest Control, p. 109). Among the drawbacks of known sulfur compositions, it should be highlighted that some plants are sensitive to sulfur, and it can cause damage to plants when temperatures during application are above 30°C. Furthermore, the presence of a large amount of sulfur in a formulation imparts instability.Several drawbacks are associated with the known granular sulfur formulation, such as: high sulfur toxicity, residue formation, instability, difficulty in field use, and increased phytotoxicity. Sulfur particles also settle in the liquid formulation and therefore require a system to suspend them in the liquid. To solve these problems, the owners of this invention propose a suspension concentrate comprising particulate sulfur suspended in an aqueous medium that also includes a surfactant, a multisite fungicide, selected from copper oxychloride, copper sulfate, copper hydroxide, and tribasic copper sulfate, in which the sulfur particle size is 1.2 micrometers.

[0015] Document CA2657531 A1 (Sulphur Solutions Inc., publication date: 09 / 09 / 2010) discloses a process for obtaining a micronized sulfur powder product. This process prepares a sulfur emulsion from molten sulfur and a dispersant solution.The proposed method comprises: heating solid sulfur material to a temperature above the melting point of sulfur (115°C), melting the material to form liquid sulfur, preparing a dispersant solution by mixing a dispersing agent (naphthalene sulfonate, carboxymethylcellulose, and a surfactant) with solvent in selected proportions (between 1 and 100 parts per thousand by volume of the dispersant solution^; containing the dispersant solution under pressure and raising a temperature of the dispersant solution to a temperature approximately equal to the temperature of liquid sulfur; mixing together the liquid sulfur and the dispersant solution to produce an emulsified sulfur slurry; cooling the emulsified sulfur slurry to a temperature below the melting point of sulfur; removing the dispersant solution from the emulsified sulfur slurry to leave sulfur particles; and drying the sulfur particles.The inventors of this process claim that the problem with using particulate sulfur in fertilizer applications is that, when applied in the form of large particles (more than 100 micrometers), elemental sulfur is very slow to reach plant roots to deliver the required nutrients. This is because sulfur, in its original elemental form, is insoluble in water and therefore cannot be absorbed by plant roots. However, bacteria in the soil feed on elemental sulfur and convert it into water-soluble sulfate, which is then easily absorbed by plant roots. The problem with direct application of water-soluble sulfate fertilizers is that the method involves over-dissolution, uncontrolled release, and leaching during incessant rainfall, leading to insufficient returns on an agricultural investment.However, with smaller particulate sulfur, at a particle size of approximately 30 micrometers or less, the uptake and conversion of particulate sulfur is optimal and much more efficient. When applied to plants, finely divided micronized sulfur can provide plant nutrients in the same application season—as such, micronized sulfur (<30 micrometers) has great value and application in the fertilizer industry. The inventors also argue that current processes for producing micronized sulfur powder are hazardous and energy inefficient. Micronized sulfur powder is currently very often produced by pulverizing sulfur lumps in mechanical milling equipment. Particularly in circumstances where very finely sized particles are obtained, conventional milling results depend on considerable energy consumption.As such, it would be desirable from an economic perspective if it were possible to determine a method of producing micronized sulfur powder that used means other than mechanical milling or a mechanical milling process that significantly reduced energy requirements. There is a trend toward decreasing the size of sulfur particles to ensure their transformation into their effective species. The explanation for this trend is outlined in Micronized Sulfur Technology (MST®), https: / / smartnutritionmst.com / news-insiqhts / micronized-sulfur-technoloqv-explained / “Sulfur is widely recognized as an important component of a balanced crop nutrition program. Currently, growers have options to apply sulfur as liquid or solid fertilizers, either in the form of sulfate, which is mobile in the soil, or elemental sulfur, which remains immobile until oxidized.A newer option on the market for growers who apply sulfur is Smart Nutrition™ MAP+MST®, a homogeneous co-granulated fertilizer product from Nutrien Premium Fertilizer Technologies that utilizes Sulvaris’ micronized sulfur technology. The patented MST® process (US20130230448 A1, CCR Technologies Ltd, 05 / 09 / 2013; EP3902769 A1, Sulvaris Inc., 03 / 09 / 2021) transforms elemental sulfur, which is a byproduct of oil and natural gas processing, into ultra-fine elemental sulfur particles (average particle size <10 microns in diameter). The technology also encompasses co-granulation of these MST® particles with various NPK fertilizers to produce products like MAP+ MST®.

[0016] Uses of zeolites as pesticides

[0017] The first studies on possible applications of natural zeolites as pesticides were conducted in Japan in the 1970s, documented by Yoshinaga E., Takachasi Y., Kado M. in The Method of Making Granulated Preparation for Agricultural Application (SU336849 A3, 21 / 04 / 1972); Yoshinaga E. et al. Organophosphate-containing Agricultural and Horticultural Granule Formulation, (US3708573 A, Kumiai Chemical Industry Co Ltd.m 02 / 01 / 1973). In these studies, natural zeolites were used as carriers for fungicides and insecticides.

[0018] Frederick A. Mumpton in: Chapter VIII. “Using Zeolites in Agriculture “Zeo-Agriculture”: Use of Natural Zeolites in Agriculture & Aquaculture” (Westview, Boulder, CO, 1984) - Abstract: “Like their synthetic counterparts, the high dehydrated adsorption and ion exchange capacities of many natural zeolites make them effective carriers for herbicides, fungicides, and pesticides. Using natural zeolites as a base, Hayashizaki and Tsuneji (“Acaricidal Composition Containing Lime-Nitrogen,” Japan, Kokai 73,031,888) found clinoptilolite to be more than twice as effective as a carrier of the herbicide benthiocarb in suppressing weeds in rice fields than other commercial products. Torii (Utilization of Sedimentary Zeolites in Japan, “Seminar on the Occurrence, Origin, and Utilization of Sedimentary Zeolites in the Circum-Pacific Region, US -Japan Coop. Sci. Prof., Menlo Park, CA, July 1974) reported that over 100 tons of zeolite were used as a carrier in agriculture in Japan in 1973. There is a patent document (Aleshinet al, “Composition for creating a layer preventing groundwater contamination by herbicides in irrigation systems”, SU733595 A1 , 05 / 15 / 1980) disclosing a composition for creating a layer preventing groundwater contamination comprising herbicides in irrigation systems containing marl and water to increase the cumulative adsorption capacity and the possibility of regulating its filtration properties, the composition further containing substances containing lignin, bentonite clay, methyl silicone, carbon-alkali reagent and clinoptilolite at 3-4% (by weight).

[0019] A very comprehensive compilation of studies on the use of natural zeolites in pesticide formulations carried out in the territories of the former Soviet Union is published in Natural Zeolites as carriers (fillers) of pesticides and certain other chemicals used in plant-growing, by TG Andronikashvili, TF Urushadze, TN Kordzakhia, LG Eprikashvili, Ivane Javachishvili, Tbilisi State University, Petre Melikishvili, Institute of Physical and Organic Chemistry, published in Annals of Agrarian Science, vol. 9, no. 4, 2011. “The article is a review showing the advantage of granulated pesticide application using natural zeolites over traditional methods of soil and plant cultivation.This combination of pesticides with natural zeolites is characterized by increased activity, a prolonged effect, the ability to limit the migration of this toxic chemical in soil and plants, and also allows for lower dosages in plant cultivation. In most cases, natural zeolites used as pesticide carriers do not undergo chemical modifications. However, it is assumed that chemical modification of zeolites can increase the effectiveness of the preparation in the pesticide-vehicle variant. Overall, based on the critical analysis of the aforementioned material, it can be concluded that the use of chemical and biological plant protection agents, as well as growth and development stimulants, are more effective in combination with natural zeolites of sedimentary origin, both from a practical and ecological perspective."The reported studies do not show the development of a sulfur-zeolite pesticide.

[0020] The publication: A review: Insecticidal potential of Zeolite (Clinoptilolite), toxicity ratings and general properties of Turkish Zeolites, Eroglu, N. DOI: 10.14455 / DOA.res.2014.116 (11th International Working Conference on Stored Product Protection) states that the Codex Alimentarius Commission (1999) supports pest control in food products and lists zeolite as an authorized substance in organic food production and plant protection. The use of organic minerals in post-harvest treatment as an insecticide compared to synthetic insecticides results in no chemical residues, is affordable, and is practically more environmentally friendly for end-users. Inert powders used in stored product protection include zeolites, the group containing natural silica, and diatomaceous earth.The review of entomological and agricultural literature presents the insecticidal potential of zeolite formulations recently studied on Sitophilus zeamais Motschulsk, Rhyzopertha dominica (F.), Sitophilusoryzae (L.), Tribolium castaneum (Herbst), Lasiodermaserricorne (F), Tribolium confusum Jacquelin du Val, Meligethes spp., Aedes aegypti (L), Cimex lectularius Linnaeus progressively. The action of inert dust is carried out through five pathways; blockage and suffocation of spiracle, cuticle abrasion and water loss, cuticle water binding, ingestion of dust particles, epicuticular lipid absorption and desiccation (Subramanyum and Roesli, 2000, Kljajic et al., 2011). Here zeolite is used as an inert solid that acts on insects.

[0021] In Agricultural and agrochemical uses of natural zeolite of the clinoptilolite type. M. Rehakova', S. Cuvanova', M. Dziva'k, J. Rima'r, Z. Gavalova'. Current Opinion in Solid State and Materials Science 8 (2004) 397–404, the authors present the agricultural and agrochemical uses of natural clinoptilolite-type zeolite from the Niz”ny' Hrabovec deposit in eastern Slovakia. The structure of natural clinoptilolite is ideal for sorption and ion exchange processes. Due to its structure and properties, this natural, inert, and non-toxic material can be used as a carrier for slow-release fertilizers, as well as other agrochemical, pharmaceutical, and biochemical active compounds, including disinfectants. Natural zeolite can also be used to improve the physical properties of soils and for the treatment of contaminated soils. It is also suitable, in very small quantities, as an additive in animal feed.

[0022] In Nanoporous materials for pesticide formulation and delivery in the agricultural sector, https: / / doi.orq / 10.1016Zi.iconrel.2022.01 .036 by Gurwinder Singh et al., the authors state “One of the key approaches of the agricultural industry to prevent crop yield declines due to pests is to develop efficacious, safe, eco-friendly, and sustainable pesticide formulations. A key objective of the industry is to offer active ingredients (AIs) that have minimal off-site migration and non-target activity. Nanoporous materials have received much international attention for the efficient loading and controlled and targeted delivery of pesticides. This is largely possible due to their textural features, which include high surface area, large pore volume, and tunable pore size.In addition, advantages such as easier manipulation of their surface chemistry and stability in different environments are added. The unique characteristics of these materials allow them to address the solubility of active ingredients, their efficient loading into porous channels, and slow, time-controlled delivery. One of their main advantages is the wide range of materials that could be suitably designed using different approaches to adsorb, encapsulate, or entrap the active ingredient. This review is a timely presentation of recent advances made in nanoporous materials and analyzes critical aspects of pesticide formulation and delivery. Other zeolite-supported pesticide formulations have been found in patent and scientific article databases: KR20000058598 A (05 / 10 / 2000), Method for manufacturing zeolite-type pesticides.Kim Yong-Cheolet al, refers to a method for manufacturing a zeolite type pesticide capable of stabilizing the active ingredient of a pesticide, comprising the steps of spraying or adsorbing a liquid stabilizer while continuously stirring the zeolite; and separately from the above step, adding an extender to the active ingredient of the pesticide; and W02003105582 A2 (2003-12-24), Pursell Tet al. Pesticide carrier and products; About the inclusion of an insecticide in zeolitic materials, Sopkova' A, Mezes” P. J Therm Anal 1996; 46:471-8; and An insecticide stabilized by natural zeolite. Sopkova' A, Janokova' E. J Therm Anal 1998; 53: 477-85.

[0023] In Cuba, two scientific articles report the use of zeolites in the production of pesticides:

[0024] • “Pesticide dust products with zeolites” by A. Aguilera Castro, L.A. Brown Colás, R. Cruz Suárez, M. García Azcuy and R. Jiménez García. CENIC Chemical Sciences Journal, Vol. 40, No. 2, 2009. “This article summarizes research carried out to obtain pesticide dust products used against different pests in agriculture, human and animal health protection and environmental hygiene. The formulations were prepared using as inert diluents the so-called cyclone powders, considered as grinding residues from industrial plants processing Cuban natural zeolites from the Tasajeras and San Andrés deposits, by using the classic technology of impregnation with mixing-grinding-homogenization.Physical and chemical analyses corresponding to established international quality control indicators were first performed on the prepared formulations. They were subsequently stored at room temperature for one year, during which time they underwent periodic physical and chemical controls. The bioactive ingredient content of the insecticides was determined primarily using gas chromatography or high-performance liquid chromatography, and for the fungicide, using the international CIPAC MT 25 procedure. Quality indicators were checked using CIPAC and WHO procedures, as well as international standards. Satisfactory results were obtained using milling residues from Cuban natural zeolite processing plants from the aforementioned deposits, with nominal formulations of Cypermethrin 2.5 DP, Permethrin 0.4 DP, and Propoxur 2.0 DP.The use of zeolitic mineral processing waste as an inert support for three pesticides is described.

[0025] • “Evaluation of the effectiveness of zeolite on downy mildew (Pseudoperonospora cubensis) in cucumber (Cucumissativus L) crops under protected systems.” JE Almándoz Parrado, L. Armenio Rivero González, E. Rivero Robaina, JA Díaz Rodríguez, G. Orbeal López and D. Dominguez Valdivia. Phytohemeroteca 280 - June-July 2016. “Zeolite in agriculture shows encouraging results in improving the physical and chemical properties of the soil. However, its potential as a control of fungal diseases has not been sufficiently studied. The objective of this work was to evaluate the effectiveness of micronized natural zeolite and 75% zeolite + 15% bentonite + 10% copper oxychloride in controlling downy mildew (Pseudoperonospora cubensis) in cucumber crops under cover."Zeolite 75%+bentonite 15%+copper oxychloride 10% at a dose of 20 kg / ha, registered the lowest value of foliar damage from the disease (40.3%), with significant differences with respect to the treatment with natural zeolite and hydrated lime, used as a production standard. These treatments achieved the lowest values ​​of disease severity with 57.6% and 67.8% in relation to the control, which reflected 83%. This demonstrates that the treatments zeolite 75%+bentonite 15%+copper oxychloride 10% and natural zeolite can be included in the strategy for disease management in protected systems." Here, the fungicidal effects of two products are described: 1) micronized natural zeolite and 2) a mixture of micronized natural zeolite with bentonite (mineral) and copper oxychloride.

[0026] At least two products containing zeolite and sulfur have been identified in commercially available compositions, ZEOZOLFO® by FERTENENIA srl and ZEOVID by ZEOGROUP.

[0027] The ZEOZOLFO® product contains sulfur powder (50%) dispersible with “untreated” and “unchemically enriched” zeolitic inert in “very fine micronized particles.” According to its specifications, soil bacteria transform it into sulfuric acid, which acts to absorb pH by neutralizing bicarbonates. It is used by “foliar spraying.” Fertenia micronized zeolite containing chabazite retains and releases sulfur for a longer period. (Available at: https: / / www.fertenia.it / spa / fitofortificanti / zeozolfo.pdf; accessed 26 / 12 / 2023). As stated by the manufacturer, natural zeolite is used as “untreated inert.”

[0028] ZEOVID is a product containing micronized clinoptilolite-type zeolite supplemented with mineral sulfur and copper oxychloride. (Available at: https: / / www.zeoqroup.net / Q / es / products / , consulted on 26 / 12 / 2023). This product is described as a mechanical mixture - without a reaction occurring - of zeolite with mineral sulfur and copper oxychloride. The three parts contribute their own properties and effects on plant pests.

[0029] In WO2013043626A1, Sulfur containing silica particle, 28 / 03 / 2013, the development of a material based on supporting sulfur or its compounds on solids, specifically silicon materials, is reported, to achieve better disposition of sulfur on plants and control pests. The material obtained is a compound with the following formula: (SiO2) x (OH)yM z S aFB: wherein M is at least one cation of the following metals or metalloids: boron, magnesium, aluminum, calcium, titanium, vanadium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, molybdenum, palladium, silver, cadmium, tin, platinum, gold, and bismuth; and S is a selected sulfur-based species. The invention relates generally to a silica-containing composition, and more specifically to a silica-containing composition that includes a sulfur moiety. The invention is of particular relevance to silica-containing compositions that dry to a hygroscopic solid and that further include a metal or metalloid cation and an optional organosilane moiety.

[0030] Regarding the use of zeolite in agriculture, a very important document worth mentioning is patent CU20210017 A7 (Rodríguez Fuentes G. et al, University of Havana, publication date: 10 / 11 / 2022; also published as: CA3138031 A1, publication date: 09 / 18 / 2022). Document CU20210017 A7 describes a process for obtaining controlled-release zeolitic substrates and fertilizers and the use of the resulting products in methods for treating plants. The invention disclosed in this document relates to a process for obtaining controlled-release zeolitic substrates and fertilizers. These products are known as NEREA® type substrates and fertilizers, which are produced by the Geominera Holguin UEB and registered in the Cuban Central Fertilizer Registry for marketing and use.Also by the Zeolita Tasajeras UEB in the province of Villa Clara, and on an industrial scale by the Cienfuegos Chemical Company (EQUIFA). In all cases, production is carried out through licensing and technology transfer of NEREA® from the University of Havana, which holds the intellectual property rights. It is estimated that, to date, the three companies have produced more than 2,000 tons of the three NEREA® products, acquired by the Cuban Ministry of Agriculture for marketing throughout the country. Validation tests at the agricultural production scale carried out by the Grain Research Institute (IIG) indicated that the NEREA® fertilizer and NEREA® Plus foliar fertilizer products benefited production yields in bean and rice crops, preserving soil quality and its water retention capacity (Available at: https: / / www.citma.qob.cu / comienza-en-cuba-fabricacion-de-zeoliticos-a-escala-industrial / ; consultation date: 12 / 26 / 2023). The IIG specialists from its Territorial Grain Research Station “Sur del Jíbaro”, who evaluated the NEREA®Plus product as the sole fertilizer in the cultivation of common beans Phaseolus vulgaris L. in the provinces of Villa Clara, Ciego de Ávila and Sancti Spíritus, on 90 hectares under production conditions. The authors concluded that, “Thrips Megalurothrips usitatus populations show a tendency to decrease in the treatment with the foliar fertilizer NEREA®Plus, with an impact on the reduction of damage”, while “The agricultural yield of the crop was higher with the application scheme of the foliar fertilizer NEREA®Plus, compared to the reference witness” (Report on the results of the study of the Nerea Plus foliar fertilizer in the common bean crop, P. Meneses et al., 2022).

[0031] In summary, pesticides developed using the effects of sulfur on fungi, insects, and bacteria, as well as a nutrient in plant fertilizers, in combination with zeolites, especially natural ones, are based on:

[0032] 1. Zeolites are only used as an inert support.

[0033] 2. They do not consider that zeolitic minerals are a natural part of soils.

[0034] 3. They only make partial use of the physical and chemical properties of the zeolitic raw material.

[0035] 4. They do not take advantage of the natural nutrients of the zeolitic raw material.

[0036] 5. Zeolitic minerals are modified with thermal treatments, acids, and surfactants to alter their physical and chemical properties, thereby increasing their capacity to absorb nutrients or the molecules that contain them. These procedures increase the cost of the resulting products, can emit polluting residues into the environment, and limit the potential regeneration of the product.

[0037] 6. The products that are commercially available are mechanical mixtures of micronized natural zeolitic mineral, with sulfur or sulfur compounds.

[0038] 7. In all cases, the doses of sulfur applied to plants are similar to the traditional uses of this element as a pesticide or crop fertilizer.

[0039] 8. The processes for modifying elemental sulfur to obtain its species effective as pesticides or plant nutrients are diverse. The use of mechanochemistry to obtain sulfur species effective as pesticides and nutrients has been demonstrated.

[0040] 9. No procedure has been reported for the modification of elemental sulfur by mechanochemistry in combination with zeolites, specifically zeolitic minerals, that allows obtaining the oxidized sulfur species SO3. 2 ' and S04 2 'supported by bonds to zeolite crystals, which allow the production of zeolitic sulfur products, pesticides and fertilizers, for the cultivation of plants as treatment methods for these, in the different stages of their development, under extensive, intensive, open-air and protected cultivation conditions, for the control of fungal, insect and bacterial pests.

[0041] A different development of new materials composed of sulfur and natural zeolites must consider: 1) The physical and chemical properties of mineral sulfur, and its effects on the control of pests that affect plants, and also as an essential nutrient for these.

[0042] 2) The physical and chemical properties of natural zeolites, and their modified forms with plant nutrients, and their use in plant fertilization

[0043] 3) The physical and chemical properties of natural zeolites, and their substance-modified forms, for the control of pests affecting plants.

[0044] 4) The modification of the properties of both minerals when they are subjected to mechanochemical reaction processes.

[0045] 5) The design of new sulfur-zeolite composite materials through mechanochemical reactions, containing sulfur species effective in pest control and plant nutrition,

[0046] 6) Optimization of sulfur contents in new zeolitic sulfur materials to reduce the risks of environmental pollution, explosion and deterioration of facilities,

[0047] 7) The greater effectiveness of new zeolitic sulfur materials in controlling and eliminating pests that affect plant crops,

[0048] 8) Achieve new materials with a combined effect of plant nutrition and pest resistance.

[0049] Unlike the prior art presented, the present invention is based on processes that optimize the incorporation of nutrients into zeolitic materials, and on the mechanochemical reaction between elemental sulfur and the components of the processed and modified zeolitic minerals to obtain controlled-release zeolitic sulfur pesticide and fertilizer products. The products obtained by the process described in the present invention comprise oxidized sulfur species with a low sulfur content, but without diminishing their effect on the control of insect, fungal, and bacterial pests that damage plant crops, while also contributing to their optimal nutrition. These products produced according to the proposed method, due to their composition and physicochemical properties, are capable of providing benefits in terms of fertility, moisture retention, and pest control.

[0050] Detailed description of the invention

[0051] All the processes of this invention, the products obtained, and their uses through plant treatment methods pose a low risk to the environment, people, plants, and animals, while preserving the physical and chemical properties of soils. These are environmentally friendly products that do not contribute to groundwater contamination, as they contain low levels of sulfur and also provide the nutrients necessary for plant development and preserve them until they are extracted by the plants.

[0052] Of the documented uses of sulfur and natural zeolites in agriculture, the present invention relates to methods for preparing sulfur for application to plants as a pesticide and nutrient, the processing and modification of zeolitic mineral, and the combination of both materials, with the objective of obtaining three types of products and their use: a) pesticides for plant protection; b) fertilizers to be incorporated into soils; c) foliar fertilizers with pesticidal action.

[0053] The present invention combines the individual properties of sulfur and natural zeolites as pesticides and nutrients, not as a simple mixture or addition of raw materials. The composition is made through mechanochemical reactions, which, when used individually with sulfur and zeolites, have been shown to obtain more efficient products. The new product, called zeolitic sulfur, solves the deficiencies of products based on individual properties and production processes. It is not a simple physical combination of both materials; it is a new material with properties that allow the control and elimination of insects, fungi, and bacteria that attack plants. It also provides essential nutrients, including silicon, considered a structural element that strengthens the cell wall, strengthening the physical support of plants and protecting them from attack by external pathogens such as bacteria, fungi, and insects.

[0054] The present invention considers:

[0055] 1. Selection of sulfur to be used as raw material with the established characteristics.

[0056] 2. Selective extraction of zeolitic mineral from the deposit as a fundamental raw material for the products.

[0057] 3. Metallurgical processing of zeolitic mineral.

[0058] 4. Modification of the processed zeolitic mineral using a solution containing all the essential macro and micronutrients for plants, in contact with the zeolitic raw material, until obtaining the established characteristics, following the methodology of patent CU20210017 A7.

[0059] 5. Premixture of the processed and conditioned sulfur and zeolitic mineral until a homogeneous mixture is obtained.

[0060] 6. Incorporation of the sulfur-zeolitic mineral mixture into the reactor (micronizing mill) to subject it to mechanochemical reactions and obtain the desired zeolitic sulfur product.

[0061] 7. Characterization of the zeolitic sulfur pesticide or fertilizer product, determine its physical and chemical properties.

[0062] 8. Product packaging and preservation. 9. Use of the zeolitic sulfur pesticide product according to the plant treatment method for that purpose.

[0063] 10. Use of the zeolitic sulfur fertilizer product according to the method of treating plants for that purpose.

[0064] The stages for the production of the new zeolitic sulfur material are summarized as follows:

[0065] 1. Selection of processed mineral sulfur.

[0066] 2. Selection of zeolitic mineral.

[0067] 3. Mechanical preparation of the mineral into defined particle size classes and moisture content.

[0068] 4. Modification of the zeolitic raw material.

[0069] 5. Premix of the processed minerals.

[0070] 6. Mechanochemical reaction of the minerals contained in the mixture.

[0071] 7. Product packaging.

[0072] 8. Product quality control. Product characterization.

[0073] 9. Use of the product as a method of treating plants for pest control or nutrition.

[0074] 1. Selection of processed mineral sulfur.

[0075] Purity: 80 - 98%

[0076] CAS Number: 7704-34-9

[0077] EC number: 231-722-6

[0078] Index number: 016-094-00-1

[0079] 2. Selection of zeolitic mineral

[0080] CAS Number: 1318-02-1

[0081] EC number: 215-283-8

[0082] The zeolitic mineral to be extracted from the deposit or orebody must meet the following characteristics:

[0083] • Zeolite type: clinoptilolite (CLI), heulandite (HEU) and mordenite (MOR).

[0084] • Minimum total zeolite content: 60%.

[0085] • Non-zeolitic mineral phases: calcite, clays, quartz, feldspar, iron oxides.

[0086] • Maximum total content of non-zeolitic phases: 40%.

[0087] • Minimum total ion exchange capacity: 120 milliequivalents per 100 grams of mineral.

[0088] • Water absorption capacity: 16.3 - 23.50% • Humidity: 5.0 - 16.5%

[0089] • Specific weight: 2.0 - 2.37g / cm 3

[0090] • Volumetric weight: 1.35 - 2.06 g / cm 3

[0091] • Porosity: 13.0 - 40.0%

[0092] • Chemical composition: Shown in tables I and II.

[0093] PPI - loss on ignition

[0094] 3. Mechanical preparation of the mineral into defined particle size classes and moisture content

[0095] Mineral processing involves crushing (or primary grinding) to reduce rock particle size, followed by grinding (secondary grinding) to obtain particles with sizes between 1.0 and 5.0 mm, and less than 0.8 mm. The processed mineral is called "zeolitic raw material"; it must be stored and protected from the elements, especially rain or other sources of moisture.

[0096] 4. Modification of the zeolitic raw material.

[0097] The modification of the processed zeolitic raw material is carried out following the unit operations described in patent CU20210017 A7, using a solution containing all the essential macro and micronutrients for plants, in contact with the zeolitic raw material, until the established characteristics are obtained, following the methodology. a) Determination of the humidity of the zeolitic raw material at room temperature expressed in milliliters of absorbed water / gram or liters of absorbed water / ton. b) Quantity of nutrients to be incorporated into the zeolitic raw material.Water-soluble NPK fertilizers, complete formulas with micronutrients (Triple 15, 16, 17, 18, 19, 20, 22), are used as a source of nutrients. Formulas can be made using raw fertilizer materials such as ammonium monophosphate (MAP), ammonium diphosphate (DAP), phosphoric acid, potassium chloride, urea, ammonium nitrate, and micronutrient salts, all of which are highly soluble in water. The total amount of nutrients to be incorporated into the zeolitic raw material depends on its nutrient content (K, Ca, Mg, Fe) and the product to be produced, ranging from 1.0 to 20.0% by weight of the final product. With the defined quantity of nutrients, a solution is prepared and added to the processed zeolitic raw material. c) Preparation of the nutrient solution.The solution is prepared by adding the mass of fertilizer or mixture of fertilizers and nutrient and micronutrient salts determined in the previous step to the volume of water that the raw material can absorb without runoff, which was established by determining its moisture content (step a). The fertilizer or nutrient salts must dissolve completely, leaving no solid residue. The process can be accelerated by raising the water temperature to 60°C. d) The modification of the raw material with the nutrient solution is carried out in a vertical or horizontal mixer, into which the mass of the zeolitic raw material to be modified is introduced, which can contain up to 100% of the solution, depending on its size. The raw material is introduced while the mixer is moving. The nutrient solution is then dosed, ensuring that the mass of zeolitic raw material is moistened evenly, without the solution running off.This process stops when the entire solution has been dosed and all the particles are moistened. The process is carried out at room temperature, but may be raised if it is below 24°C and must not exceed 60°C. The duration of the process is determined until the solution is completely absorbed homogeneously, without runoff, a process that occurs between 10 and 30 minutes. e) Curing and drying of the obtained product. This stage, called "curing," of the obtained product is characterized by the processes of adsorption, ion exchange, and insertion of nutrients into the raw material, mainly in the zeolitic phases contained therein. The process begins when the zeolitic raw material is moistened with the nutrient solution and proceeds slowly over several days, until its moisture balances with the ambient humidity, and the pH and electrical conductivity values ​​stabilize.f) Particle size class adjustment. The modified zeolitic mineral is reduced in size to particles smaller than 0.091 mm (particle size class -0.091 mm) by grinding again. The dry product (6-10% moisture) must be ground in micronizing mills.

[0098] 5. Premix of the processed minerals.

[0099] The processed sulfur ore with the described characteristics is mixed with the processed zeolitic ore with the defined characteristics, or with the processed and modified zeolitic ore to incorporate the required plant nutrients. The processed zeolitic ore or the processed and modified zeolitic ore with plant nutrients is introduced into a moving vertical or horizontal mixer. The processed sulfur is introduced into the mixer. The weight ratio of sulfur to zeolitic ore should be 1:2 or 1:1 or 2:1. The mixer is kept in operation for a period of between 30 minutes and 2 hours, until a homogeneous premix of the minerals is obtained. The homogeneous premix is ​​extracted to proceed to the next stage.

[0100] 6. Mechanochemical reaction of the minerals contained in the mixture.

[0101] The mechanochemical reaction of sulfur and zeolite is carried out in a tubular ball mill. The homogeneous premix of the processed minerals is introduced into the micronizer. The processed zeolitic mineral or processed and nutrient-modified zeolitic mineral is added in a proportion between 75 and 95% by weight of the final product (zeolitic sulfur, pesticide, or fertilizer), and the micronizing mill is set in motion. The mechanochemical reaction occurs during grinding over a period of time ranging from 30 minutes to 2 hours. Upon completion, the zeolitic sulfur product is extracted, sieved, and material with particle sizes up to 0.050 mm is selected.

[0102] 7. Product packaging.

[0103] The product must be packaged in polyethylene bags of different sizes according to commercial requirements: 1, 25, and 50 kg. The bags containing the product can be grouped together for storage at room temperature, off the floor, under a roof, and isolated from other zeolitic and chemical products.

[0104] 8. Product quality control. Product characterization.

[0105] The quality of the products obtained using the process of this invention is determined by analytically determining several parameters. The technical data sheet for one of the products obtained using this invention must report several parameters of interest to the customer.

[0106] The product Zeolitic Sulfur Pesticide must be described as follows:

[0107] • Product Trade Name: Zeolitic Sulfur Pesticide

[0108] • Formula: (S) mMQS¡29Al7O72* XH2O where m = 3.7 - 19; Q = 1 - 7; M = Ca, Na, K, Mg and Fe

[0109] • Presentation form: Powder

[0110] • Color: yellow - green.

[0111] • Sulfur concentration by weight: 5.0 - 25.0%

[0112] • Humidity: 5 - 10%

[0113] Solubility in water: No • pH (assured range): 5.6 - 8.6.

[0114] • Total soluble salts (TDS): 400 - 800 ppm

[0115] • Compatibility with other agricultural products: Yes

[0116] • Granulometry: < 0.05 mm

[0117] • Compaction risks: Yes

[0118] • Storage conditions: Indoors, off the ground, away from chemicals.

[0119] • Expiration period: 3 years.

[0120] • Crops that can receive the product: All.

[0121] • Recommended average dose per crop: 2-8 kq / ha (10-20 q / L of water)

[0122] • Application time: After planting: Yes; Anytime: Yes

[0123] • Application frequency per crop cycle: More than three times: X

[0124] • Application method: Foliar

[0125] • Analytical techniques: Cuban standards that regulate the quality of natural zeolites NC 625, NC 626, NC 627, NC 628, NC 629, NC 629, NC 630 and NC 631. The determination of Sulfur is carried out following the methods and analytical techniques for pesticides.

[0126] • Chemical and mineral composition appear in tables III and IV.

[0127] • Qualitative analysis using infrared spectroscopy to determine the molecules present in the product Zeolitic sulfur pesticide appears in Table V.

[0128] The product Zeolitic sulfur fertilizer made from processed and nutrient-modified zeolite must be described as follows:

[0129] • Product Trade Name: Zeolitic Sulfur Fertilizer

[0130] • Formula: (S) m N n PTKiM Q Yeah 29 AI7O72* XH2O where m = 3.9 -19; n = 1.2 - 17.3; T = 0.54 - 3.1; L= 0.44 - 2.5; Q = 1 - 7; M = Ca, Na, k, Mg and Fe

[0131] • Presentation form: Powder

[0132] • Color: yellow - green.

[0133] • Sulfur concentration by weight: 5.0 - 25.0%

[0134] • Humidity: 5 - 10%

[0135] • Solubility in water: No

[0136] • pH (guaranteed range): 5.6 - 8.6.

[0137] • Total soluble salts (TDS): 400 - 2000 ppm

[0138] • Compatibility with other agricultural products: Yes

[0139] • Granulometry: < 0.05 mm

[0140] • Compaction risks: Yes

[0141] • Storage conditions: Indoors, off the ground, away from chemicals.

[0142] • Expiration period: 3 years.

[0143] • Crops that can receive the product: All.

[0144] • Recommended average dose per crop: 2-8 kq / ha (10-20 q / L of water)

[0145] • Application time: After planting: Yes; Anytime: Yes

[0146] • Application frequency per crop cycle: More than three times: X

[0147] • Application method: Foliar and soil • Analytical techniques: Cuban standards that regulate the quality of natural zeolites NC 625, NC 626, NC 627, NC 628, NC 629, NC 629, NC 630 and NC 631. The determination of Sulfur is carried out following the methods and analytical techniques for pesticides.

[0148] • Chemical and mineral composition appear in tables VI and VII

[0149] • Qualitative analysis using infrared spectroscopy to determine the molecules present in the product Zeolitic sulfur fertilizer appears in table VIII. 10. Use of the product as a method of treating plants for pest control or plant nutrition. The zeolitic sulfur products obtained by the present invention are: pesticide zeolitic sulfur and fertilizer zeolitic sulfur.

[0150] Zeolitic sulfur pesticide is applied as an aqueous solution with a concentration of 0.5 to 20 grams per liter of water, which is sprayed onto the aerial parts of plants to eliminate insect, fungal, and bacterial pests.

[0151] Zeolitic sulfur fertilizer is used in foliar and soil treatment of plants. As a foliar fertilizer, it is applied in the form of an aqueous solution with a concentration between 0.5 and 20 grams per liter of water, which is sprayed on the aerial parts of the plants as a foliar fertilizer to nourish them. It also has a pesticidal effect to eliminate insect, fungal, and bacterial pests. As a soil fertilizer, it is incorporated into the soil in the form of an aqueous solution with a concentration between 0.5 and 50 grams per liter of water, at the bottom of the furrow, prior to sowing the seed or transplanting seedlings previously grown in seedbeds or germinators, in doses of 100 to 200 mL of the solution per meter of furrow, or after the plant has developed around it in the area near the roots during hilling.

[0152] Examples of implementation

[0153] EXAMPLE 1. Zeolitic mineral from the San Ignacio deposit in the province of Mayabeque, processed at the UEB Roberto “Coco” Peredo plant of Minera de Occidente, by crushing, drying and secondary grinding, was classified by particle size classes using a mechanical screen. The product with a particle size class less than 1 mm and a physical and chemical composition that complies with the Cuban standard NC 625:2019 was chosen and used as zeolitic raw material for the production of the pesticide zeolitic sulfur product. A mass of 100 kg of raw material with a humidity of 10.0% was used, which was introduced into an industrial rotary drum mixer with a capacity of 500 kg. A 100 kg mass of domestically produced sulfur extracted from natural gas in the Varadero deposits in the province of Matanzas by the company ENERGAS, with a humidity of 10.0%, was introduced into the moving mixer, which contained the zeolitic mineral mass.The masses were mixed for 50 minutes, obtaining a homogeneous mass of sulfur-zeolitic mineral. The mass was discharged from the mixer and introduced into a micronizing ball mill, which was operated for 1 hour. 800 kg of zeolitic mineral with a particle size less than 0.091 mm and a moisture content of 10.0% were added. The grinding process continued for 1 hour. The resulting pesticide zeolitic sulfur product was packaged in polyethylene bags, which were then placed in raffia sacks for preservation. The product had a particle size class less than 0.040 mm and was characterized by Fourier transform infrared spectroscopy. The spectrum obtained showed the characteristic bands of natural clinoptilolite and the oxidized sulfur compounds of the zeolitic sulfur product. Chemical analysis showed the presence of the elements Si, Al, Ca, Mg, K, Fe, and S.

[0154] EXAMPLE 2. The zeolitic mineral from the San Ignacio deposit in the province of Mayabeque, processed at the UEB Roberto “Coco” Peredo plant of Minera de Occidente, by crushing, drying and secondary grinding, was classified by particle size classes using a mechanical screen. The product with a particle size class less than 1 mm and a physical and chemical composition that complies with the Cuban standard NC 625:2019 was chosen, modified with nutrients contained in the complete fertilizer Triple 18, and used for the production of the zeolitic sulfur fertilizer product. A mass of 100 kg of raw material with a moisture content of 10.0% was used, which was introduced into an industrial rotary drum mixer with a capacity of 500 kg.A 100 kg mass of domestically produced sulfur extracted from natural gas in the Varadero deposits in Matanzas province by the company ENERGAS, with a moisture content of 10.0%, was introduced into a moving mixer containing the zeolitic mineral mass. The masses were mixed for 50 minutes, obtaining a homogeneous sulfur-zeolitic mineral mass. The mass was discharged from the mixer and introduced into a micronizing ball mill, where the mill was operated for 1 hour. 800 kg of zeolitic mineral with a particle size less than 0.091 mm and a moisture content of 10.0% were added. The grinding process continued for 1 hour. The resulting zeolitic sulfur fertilizer product was packaged in polyethylene bags, which were then placed in raffia sacks for preservation.The product had a particle size class less than 0.040 mm and was characterized by Fourier transform infrared spectroscopy. The spectrum obtained showed the characteristic bands of natural clinoptilolite and oxidized sulfur compounds of the zeolitic sulfur fertilizer product. Chemical analysis showed the presence of the macronutrients N, P, K, Si, Al, Ca, Mg, Fe, and S, and the micronutrients Cu, Zn, Mn, and B.

[0155] Employment examples

[0156] EXAMPLE 1. The zeolitic sulfur pesticide product obtained in embodiment example 1 described was used to control the white mite (Polyphagotarsonemus latus) in chili pepper crops in a cultivation house module of the Horquita company in the province of Cienfuegos. It was applied at a dose of 3.0 kg per hectare in an aqueous solution that was sprayed, achieving an effectiveness in pest control of 87%, meeting the standards required for its proposal for pesticide registration.

[0157] EXAMPLE 2. The zeolitic sulfur pesticide product obtained in embodiment example 1 described was used to control powdery mildew (Erysiphe polygoni) in cucumber crops in a grow house module of the Horquita company in the province of Cienfuegos. It was applied at a dose of 3.5 kg per hectare in an aqueous sprayed solution, achieving 75% effectiveness in pest control.

[0158] EXAMPLE 3. The zeolitic sulfur pesticide product obtained in embodiment example 1 described was used to control the white mite (Polyphagotarsonemus latus) in tomato crops in the cultivation house of Farm No. 14 in the Boyeros municipality, Havana province. It was applied at a dose of 3.5 kg per hectare, in an aqueous solution that was sprayed, achieving 84% control of the pest.

[0159] EXAMPLE 4. The zeolitic sulfur pesticide product obtained in the described embodiment example 1 was used in the control of T rips sp. in pepper, garlic and onion crops on the Güines Coast, Mayabeque province, achieving control of the pest.

[0160] EXAMPLE 5. The zeolitic sulfur fertilizer product obtained in embodiment example 2 described was used in the treatment of Persian lemon, Creole lemon and orange plants affected by the citrus HLB (Huanglongbing) disease, caused by the bacterium Candidatus liberibacter asiaticus, in the Roberto Negrín cooperative in Punta Brava, Havana province. The product was applied at a dose of 2.0 kg per hectare in aqueous solution sprayed every 15 to 20 days. The pest was controlled and the affected plants recovered.

Claims

Mechanochemically micronized zeolitic sulfur pesticides and fertilizers useful for plant treatment CLAIMS Zeolitic sulfur pesticides and fertilizers obtained by mechanochemistry useful for the treatment of plants characterized in that it is obtained by a process comprising the following steps: (A) crushing or grinding and sieving elemental sulfur of purity between 98-100% and then selecting the material with a particle class size up to 0.10 mm and a humidity up to 10%; (B) introducing a processed zeolitic mineral, or a processed and modified zeolitic mineral with plant nutrients, into a vertical or horizontal moving mixer with particle class size up to 0.10 mm and a humidity up to 10%; (C) introducing the sulfur obtained in stage A to the mixer in a sulfur:zeolitic mineral weight ratio of 1:2 or 1:1 or 2:1; (D) premixing the mixer contents for a time between 30 minutes and 2 hours; (E) extracting the premixed mass and introducing it into a micronizing mill; (F) adding the processed zeolitic mineral, or processed and modified with nutrients with characteristics according to stage B to the micronizer in a proportion between 20 and 80% by weight of the final product (G) grinding in a period of time between 30 minutes and 4 hours, sifting and selecting the material with particle class size up to 0.040 mm. Zeolitic sulfur pesticides and fertilizers obtained by mechanochemistry according to claim 1, characterized in that the processed zeolitic mineral comprises up to 60% of zeolitic phases (clinoptilolite, heulandite and mordenite), up to 40% of non-zeolitic phases (calcite, clay,quartz, feldspar, iron oxides^ Zeolitic sulfur pesticides and fertilizers obtained by mechanochemistry according to claim 1, characterized in that the processed modified zeolite material comprises essential nutrients. Zeolitic sulfur pesticides and fertilizers obtained by mechanochemistry according to claim 3, characterized in that the essential nutrients are selected from ammonium monophosphate, ammonium diphosphate, phosphoric acid, potassium chloride, urea, ammonium nitrate, salts of the, micronutrients [ZnS04, CuS04, MnS04, MoS04, Na2B407], or complete NPK triple formulas 15, 17, 18 and 20.

5. Zeolitic sulfur pesticides and fertilizers obtained by mechanochemistry according to claim 1, characterized in that the horizontal or vertical mixer and the micronizing mill must be resistant to corrosion caused by sulfur products. 6 Zeolitic sulfur pesticides and fertilizers obtained by mechanochemistry according to claim 1, characterized by the pesticide product formula (S^MaS^gAlyC^* XH2O where m = 3.7 - 19; Q = 1 - 7; M = Ca, Na, K, Mg and Fe, and the FT-IR spectra of the final product show characteristic bands of oxidized sulfur species 1575, 1519, 1272, 827, 750 and 675 cor 1 supported on zeolite crystals, and characteristic bands of zeolite 3614, 3556, 3510, 3454, 1637, 1045, 789, 710 and 622 cm' 1 . 7 Zeolitic sulfur pesticides and fertilizers obtained by mechanochemistry according to claims 1, 3 and 4, characterized by the formula of the fertilizer product (S) m NnPiKiMQ Yes 29 AI7O 72» XH2O where m = 3.9 -19; n = 1,2 - 17.3; T = 0.54 - 3.1; L= 0.44 - 2.5; Q = 1 - 7; M = Ca, Na, K, Mg and Fe, and the FT-IR spectra of the final product show characteristic bands of oxidized sulfur species 1575, 1519, 1272, 827, 750 and 675 cm -1 supported on the zeolite crystals, the characteristic bands of zeolite 3614, 3556, 3510, 3454, 1637, 1045, 789, 710 and 622 cnr 1 , the characteristic bands of nitrogen compounds 3500, 3406, 3241, 1670, 1624, 1528, 1452, 1403, 1460 and 1403 cm _1 , and the characteristic bands of phosphorus compounds 1185, 1133, 887, 868 and 640 cm' 1 . 8 Zeolitic sulfur pesticides and fertilizers obtained by mechanochemistry according to claim 1, characterized in that the final product has a total sulfur content in a range between 5.0 to 25.0% by weight. 9 Plant treatment method, characterized in that an aqueous solution with a concentration between 0.5 to 20.0 g / L of the pesticide prepared according to the procedure described in claims 1, 2, 5 and 6 is applied by spraying to the aerial parts of the plants to eliminate insect, fungal and bacterial pests, between 7 to 15 days until the pest is eliminated. 10 Method of plant treatment, characterized in that an aqueous solution of concentration between 0.5 to 20.0 g / L of one of the fertilizers prepared according to the procedures described in claims 1 - 7 is applied by spraying (i) to the aerial parts of plants, as a foliar fertilizer to nourish them, or (ii) as a pesticide to eliminate insect, fungal and bacterial pests.

11. Method of plant treatment, characterized in that an aqueous solution of concentration between 0.5 to 50.0 g / L of one of the fertilizers obtained according to the procedures described in claims 1 - 7, is incorporated (i) at the bottom of the furrow, prior to the time of sowing the seed or transplanting seedlings, previously grown in seedbeds or germinators, of the solution per meter of furrow, or (ii) after the plant has developed around it in the area close to the roots when hilling, in doses of 100 to 200 mL.

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