CA3138031A1 - Procedure for obtaining substrates and controlled release zeolitic fertilizers and plant treatment methods - Google Patents

Abstract

The present invention relates to a process for obtaining controlled release zeolitic substrates and fertilizers. The procedure comprises the selective extraction of the zeolite mineral from its mineral and chemical composition, ion exchange capacities and adsorption. The selected mineral is modified with aqueous solutions that contain all the nutrients required by the plants, which allows its incorporation into its particles. This procedure, as claimed, allows the incorporation of all the nutrients in a single step and the obtaining of substrates, fertilizers for soil treatment and foliar fertilizer, without generating residual environmental pollutants. The products obtained by this procedure: substrates, fertilizers and foliar fertilizers, all with controlled nutrient release, first allow the treatment of the plants for the assimilation of all the incorporated nutrients, including silicon, which are extracted only by the plants, and second, they avoid the generation of polluting waste in the environment. The substrates are used for the germination of seeds, the obtaining of seeds by biotechnological procedures, the development of plants by means of the technology of crops without soils known as zeoponic, and they use only water for the irrigation of the plants. All the products obtained are classified as end-use, but the substrates for zeoponic cultures can be reactivated after the nutrients are partially or totally depleted.

Description

PROCEDURE FOR OBTAINING SUBSTRATES AND CONTROLLED RELEASE ZEOLITIC FERTILIZERS
AND PLANT
TREATMENT METHODS
The present invention is related to the mining-metallurgical, chemical and agriculture sectors, as it deals with the selective extraction of zeolitic rocks, their mechanical preparation by crushing, grinding, particle size classification, drying, and chemical modification that allows the incorporation of chemical species which constitute essential plant nutrients, obtaining products with characteristics of substrates, fertilizers and foliar fertilizers for the optimal development of plants in conditions of extensive and intensive agricultural production at different scales. All the processes of this invention, the obtained products and their uses by means of plant treatment methods, do not represent a risk to the environment, people, plants and animals, but the recovery and preservation of the physical and chemical properties of soils. They are environmentally friendly products, which do not contribute to groundwater contamination by containing only the nutrients necessary for the development of plants and preserving them until their extraction by the plants.
Of the documented uses on the utilization of natural zeolites in agriculture, the present invention is related to the procedures for the modification of the zeolitic mineral in order to obtain three types of products and their use: a) substrates for plant cultivation; b) fertilizers to be incorporated into the soils; c) foliar application fertilizers, foliar-fertilizers.
The procedure for obtaining substrates and fertilizers of the present invention takes as its starting point the procedures for obtaining NEREA substrates described in "The Commercial Zeoponic in Cuba: Handbook for Zeoponic Engineers", by the authors Lorenzo Rivero, Jose Emilio Perez and Gerardo Rodriguez-Fuentes, limited publication of the Development and Technical Services Area of the Ministry of Agriculture, Republic of Cuba, (1990). Although the present invention is based on the detailed study of the physical and chemical properties of zeolite rocks, in particular ion exchange and adsorption, it is the result of a process of technological innovation that optimizes the incorporation of nutrients into zeolites contained in the mineral, and allows to obtain not only substrates for the cultivation of plants without soil, also controlled release fertilizers and foliar fertilizers;
and it solves the deficiencies observed throughout more than 30 years of study, development, industrial production, product registration, use and commercialization in Cuba and other countries. The procedure has not been disclosed in publications or scientific events, but it has been protected as an Industrial and Commercial Secret of the Institute of Materials Science and Technology (IMRE) of the University of Havana (UH). In turn, NEREA is the acronym for Nutrients In Rock and Water Use (in Spanish), it is a trademark intellectual property of IMRE-UH (0CPICertificate No. 0096/2014 Resolution:
1251/2015).

Date regue / Date received 2021-11-05 The NEREA-Chinobampo products were registered, produced and marketed in Mexico, through the "License Agreement for the use of know-how for production No. 107/06", signed on March 22, 2006 by Grupo Bampoahi S.A. de C.V. and COMERCIAL MERCADU S.A. that "acts on behalf of the University of Havana, which is the owner of the technologies and know-how for the industrial production of technical zeolitic products, protected by the Industrial and Commercial Secret, with the corresponding Certificates of Trademark Registration". The technology transferred was one of those described in the Manual for Zeoponic Engineers under the confidentiality clause "THE LICENSEE is obliged to maintain the Confidentiality agreements referred to in the previous section even after the TERM of this Contract has been concluded, until the aforementioned Know How of obtaining THE PRODUCTS is not public knowledge."
Since 1988, when the work "Cuban experience with the use of natural zeolite substrates in soilless culture"
was presented by the authors L.A. Rivero Gonzalez and G. Rodriguez-Fuentes, at the Seventh International Congress on Soilless Culture, in Flevohof, The Netherlands, sponsored by the International Society for Soilless Culture (Proceedings pp. 405-416, 1988), only the results of the use of NEREA
zeolitic products, never the process of obtaining. In 2018, the work "NEREA Zeoponic Substrates: Positive and Negative Facts after 30 years of Development" was presented at ZEOLITE 2018 10th International Conference on the Occurrence, Properties and Utilization of Natural Zeolites, Krakow, Poland, summary of the works of research, development and innovation carried out during 3 decades by the authors G. Rodriguez-Fuentes and L.A. Rivero Gonzalez (ZEOLITE 2018, Book of Abstracts, pp 129-130, 2018).
NEREA zeolitic products are currently produced at the NEREA Experimental Plant of the UEB Geominera Holguin company, through a joint production contract between the University of Havana and EES Geominera Oriente, under strict confidentiality clause. The products have been registered in the Central Registry of Fertilizers of the Republic of Cuba for their production, commercialization and use in the territory of Cuba as:
= NEREA PLUS fertilizante foliar: No RCF 017/20. Libro primero, Tomo I, Folio 65.
= NEREA Fertilizante: No RCF 018/20. Libro primero, Tomo I, Folio 62.
= NEREA Sustrato: No. RCF 019/20. Libro primero, Tomo I, Folio 64.
In this invention, the fundamental raw material is the zeolitic mineral or zeolitic rock, which is usually called natural zeolite, ignoring the fact that 50 types of natural zeolites have been described in nature, with different crystalline structures, and different physical and chemical properties.
Natural zeolites are part of the mineral composition of the soils close to zeolite occurrence and deposits, or due to the transformation of volcanic materials into zeolites. Soils contain a wide variety of zeolites, and their occurrence in them has been documented by D.W. Ming and J.L: Boettinger in "Zeolites in Soil Environments",

2 Date recue / Date received 2021-11-05 chapter 11 of Natural Zeolites: Occurrence, Properties, Applications (Mineralogical Society of America, Geochemical Society ISSN 1529-6466, 2001). The types of zeolites that formed in soils include analcima, phillipsite, clinoptilolite, chabasite, and natrolite. In Cuba, where 106 occurrences of zeolitic rocks have been documented, distributed in all the provinces, 31 of them studied geologically as deposits, their natural presence in the soils has also been demonstrated by A. Brito and D. Coutin in "Las zeolititas de Cuba: results of 45 years dedicated to its study "(Inst. Geol. Paleont., Geological Survey of Cuba, 2017). Studies carried out by the Ministry of the Sugar Industry (MINAZ) of Cuba in the 1990s showed that the soils with the best yields in the production of sugarcane without irrigation or "dry land", were those close to the occurrences of natural zeolites and that in its mineral composition were zeolites. This observation allowed MINAZ the natural use of Cuban zeolitic rocks, incorporating them into the soils in doses of up to 15 tons per hectare, to significantly increase crop yields without the addition of fertilizers (Crespo, Ramon, Revista Canaveral, Vol. 4, No. 1, January-March 1998, MINAZ, p. 27).
Professor Frederick A. Mumpton first documented in "Zeo-Agriculture: Use of Natural Zeolites in Agriculture &
Aquaculture" (Westview, Boulder, CO, 1984); and then in "The magic rock: Uses of natural zeolites in agriculture and industry" in the colloquium "Geology, Mineralogy and Human Wellbeing"
organized by the National Academy of Sciences of the United States of America on November 8-9, 1998, (Proc. Nat. Science Academy of USA, Vol. 96, Issue 7, 3463-3470, 1999) that the oldest use of zeolites in agriculture is in Japan, as a soil improver and additive to fertilizers, dating back several centuries (Minato, H. Koatsu Gasu 5, 536-547, 1968).
While in other countries its use was reported during the second half of the 20th century, with similar objectives of improving the properties of soils, increasing the efficiency of fertilizers, and consequently increases crop yields. Mumpton in his compilation established that the uses of natural zeolites in agriculture were:
1. Soil improver.
2. Additive to chemical fertilizers.

3. Treatment of animal excreta for use as compost.

4. Obtaining artificial soils or substrates for growing plants, zeoponic crops.
The term zeoponic arose to indicate that a natural zeolite was used as a substrate in hydroponic soilless cultivation technology, which requires an inert support for plants that are systematically irrigated with nutrient solutions. However, quickly the farmers were able to know that the replacement of nutrients in the solutions was lower despite the fact that the plants grew optimally, because the nutrients not used by them were preserved by the zeolitic mineral particles. Expression of ion exchange and absorption properties of zeolites.

Date recue / Date received 2021-11-05 In 2001, D.W. Ming and E.R. Allen in "Use of Natural Zeolites in Agronomy, Horticulture and Environmental Soil Remediation", (chapter 18. Nat. Zeol. Occur. Prop., Appl., Mineralogical Society of America. Geochemical Society ISSN 1529-6466, 2001) established that the correctly documented uses of natural zeolites in agriculture were:
1. As substrates for plants in greenhouses.
2. As substrates for potting plants in the houses.
3. As fertilizers and soil conditioners on golf courses.
4. As slow release fertilizers in agricultural applications.

5. As fertilizers, insecticides and slow release herbicides in areas where environmental problems are important (sandy soils near surface waters or aquifers).

6. As remedial agents for soils with environmental problems of contamination by heavy metals and radionuclides.
From the review carried out by Ming and Allen in 2001 to 2020, numerous works have been reported that use zeolitic rocks or zeolitic minerals directly in agricultural technologies or in the elaboration of products for that purpose. The zeolitic mineral modification procedures are aimed at the highest possible incorporation of the macronutrients N, P and K to the mineral, for their subsequent slow or controlled release in the soil and plant nutrition, for the preparation of substrates and rooting agents for the development of plants without soil in intensive and protected crops. These procedures and uses can be grouped into:
1. Mixture with chemical fertilizers that can contain up to 50% of the zeolitic mineral with particle size classes similar to those of chemical fertilizers.
2. Mixture with organic matter, usually zeolitic mineral with particle size class between 1.0 and 4.0 mm is used. This practice extends to the treatment of the excreta of production animals such as poultry, pigs and cattle, and of human waste in garbage dumps, with zeolitic mineral. The obtained material is used as a fertilizer.
3. Mix with minerals that provide nutrients such as apatite, calcium phosphate carbonate, etc.
4. Modification of the previously ground zeolitic mineral with different particle sizes, to obtain fertilizers with slow or controlled release of a nutrient: ammonium, potassium or phosphorus. Here the concept is to incorporate as much of the nutrient as possible into the zeolitic mineral particles by prior modification of the mineral by applying heat, treatments with acids or surfactants, or a combination of these treatments, and the subsequent incorporation of the nutrient by ion exchange or adsorption of the fertilizer that contains the nutrient.

Date recue / Date received 2021-11-05 5. The combination of the above procedures to obtain a fertilizer material that provides nutrients and organic matter.
6. In the elaboration of substrates for the cultivation of plants without soils called zeoponic, which is the most complex of the procedures for the use of natural zeolites in agriculture, since its objective is to obtain an artificial soil.
Directly related to the present invention are the modification of the zeolitic mineral for the elaboration of substrates and fertilizers for the cultivation of plants. The three primary procedures for obtaining substrates using natural zeolitic rocks, recognized by specialists in natural zeolites and agriculture are:
BALKANIN substrate: In 1982, the invention patent US 4337078 - Substrate for cultivation of agricultural crops and rooting of green cuttings in greenhouses and in open air, was granted to Georgi S. Petrov et al., On a substrate called BALKANIN for the cultivation of plants in greenhouses or outdoors containing clinoptilolite zeolite dried at a temperature between 250 and 350 C, with particle fractions of sizes 0.8 to 2.0 mm, 2.0 to 5.0 mm and 5.0 to 8.0 mm, in proportions of 1: 1: 0.01 to 2: 3: 1, enriched with nitrogen and phosphorus in the amount of 0.1 to 0.5%, fractionated vermiculite with particles smaller than 1.0 mm and expanded vermiculite with particles of size 5.0 to 15.0mm in a ratio of 1: 9 to 2: 8; and an organic mass of peat, the ratio of zeolite:
vermiculite: peat from 10: 0.01: 0.01 to 5: 2: 3. In the description of the invention, the authors describe that the zeolite-vermiculite-peat mixture was treated with ammonium nitrate fertilizer such as ammonium sulfate and superphosphate that contributed 0.1 to 0.5% nitrogen and the same amount of phosphorus. This procedure for obtaining a substrate is based on a mixture of three solid components, zeolite, vermiculite and peat, with different kinds of particle sizes and densities that, after mixing, are treated with solid-state ammonium and phosphorus fertilizers. It only uses water to irrigate the plants that grow in it. The three basic components have particles with different sizes, densities and nutrient absorption capacities, which gives the substrate little homogeneity, and limits the uptake of nutrients in the same way by plants. In the same way, from the industrial production of the substrate with an optimal mixture, during its transportation to the agricultural facility where it will be used, the particles different in size and density are separated, affecting its homogeneity and changing the quality of the mixture. It is not described what to do when the nutrients are depleted in the substrate. The Balkanin substrate was successfully tested on one of the MIR manned cosmic flights.
Substrate NASA. Since the late 1980s, the United States National Aeronautics Administration (NASA) developed Project Biosphere 2 to support the life of astronauts in space. The project comprised the development of a zeoponic substrate for plant growth that was developed by DW
Ming and ER Allen et al.
(Zeoponic Substrates for Space Applications: Advances in the Use of Natural Zeolites for Plant Growth. Natural Date recue / Date received 2021-11-05 Microporous Materials in Environmental Technology pp 157-176 and NATO Science Series book series (NSSE, volume 362). The substrate is composed of a mixture of clinoptilolite zeolite exchanged with NH4, zeolite exchanged with K and natural and synthetic apatite as sources of P. A
fertilization of slow release due to the dissolution of natural apatite that contributes Ca and PO4; synthetic apatite is hydroxyapatite and contributes Mg, S and micronutrients previously inserted in its structure; and the cation exchange reactions of the exchanged clinoptilolite that contributes K and NH4. Substrate only requires water for the irrigation of the plants that grow in it. It is not described what to do when the nutrients they are depleted in the substrate. The zeolite-based substrate or product is marketed in the United States by a company as a slow-release fertilizer for golf courses with the ZeoProTM brand, no other industrial uses are reported, even though the authors advance applications in horticulture, agriculture and agriculture, grass industry for sports fields, as efficient fertilizers and environmental protectors. This invention is an inhomogeneous mixture of several solid components that separately provide the nutrients to the plants that grow in it. Seeking a maximum incorporation of ammonium and potassium, they use clinoptilolite exchanged with ammonium and clinoptilolite exchanged with potassium, natural apatite as a source of phosphorus and calcium, and synthetic apatite as a source of micronutrients. Its production includes several slow and costly production processes, which contribute residual pollutants. The invention does not refer to how to replenish the nutrients when they are depleted in the substrate, which must be complex due to the heterogeneity of its phase composition.
NEREA substrates. During the years 1984 to 1989, G. Rodriguez Fuentes and L.A.
Rivero Gonzalez developed five procedures for the modification of the zeolitic mineral containing zeolites type clinoptilolite, heulandite and mordenite. The procedures to modify the zeolitic mineral with the appropriate particle size directly in the hydroponic cultivation facilities of Cuba, using their irrigation systems, made possible the incorporation of the nutrients not contained in the zeolitic mineral and the balance of those present; all the macro and micro nutrients contained in the "loading" solution were taken completely during the successive irrigations over several hours, days or weeks, without generating residual pollutants in the facilities with closed or recirculation irrigation. The described formulas differed in the loading time and the fertilizers and salts used in the preparation of the loading solution. The zeolitic substrate obtained was called NEREA, acronym for Nutrients In Rock and Water Use (in Spanish). The procedures are described in "The Commercial Zeoponic in Cuba:
Handbook for Engineers" limited publication only for the personnel of the zeoponic facilities of the Ministry of Agriculture of Cuba (MINAG) (1990). During their use they only require water for the irrigation of the plants, when the nutrients are depleted when they are taken by the plants, they can reincorporate formulating a new nutrient solution balancing their contents with the rest in the substrate; the solution is brought into contact Date recue / Date received 2021-11-05 with the substrate using the irrigation system. These substrates are distinguished from Balkanin and the one developed by NASA, in:
1) They only contain zeolitic mineral as basic raw material.
2) All the macro and micro nutrients necessary for the development of the plants are incorporated into the mineral particles through the irrigation system.
3) They are homogeneous substrates, each particle contains all the nutrients.
4) Plants grown on these substrates are only irrigated with water.
5) The substrates preserve the nutrients until the plants extract them, thus minimizing losses due to leaching, dragging or volatilization.
6) They can be recharged when nutrients are depleted.

7) They can be subjected to the cultural work of the crops including disinfection at the end of the harvests.

8) To know its properties, the same analytical studies are used for the study of soils.

9) They were produced industrially in the zeoponic facilities of Cuba from 1988 to 1994.
Between 1988 and 1990, NEREA substrates were positively validated for their use in plant cultivation by the National Institute for Tropical Flora and Agriculture Research (INIFAT) of Cuba. The specialists of that institution developed the analytical methods and the corresponding standards to study the zeoponic substrates and their use by MINAG. (IE. Perez, L. Rivero, N. Arozarena. Memories 3rd Conf. Int.
Zeol. Nat. Part 2, pp 3-7, La Habana, 1991). The main deficiencies of these substrates are:
1) The volumes of nutrient dissolution necessary to obtain them in the zeoponic facilities.
2) The long treatment time of the zeolitic mineral.
3) The loss of nutrient dissolution in zeoponic facilities with an open irrigation system that do not reuse water, causing environmental pollution.
Variants of the elaboration of NEREA substrates for the cultivation of plants using Cuban zeolitic minerals are:
LITONITA: It is a zeolitic product that was made during the 1990s using as raw material the zeolitic mineral from the Tasajeras deposit, Villa Clara province, Cuba. It used the procedure developed by G. Rodriguez Fuentes and L. Rivero Gonzalez who transferred the technology for obtaining NEREA
products to the Center for Research and Projects of the Mining and Metallurgical Industry (CIPIMM) of the Ministry of Basic Industry of Cuba in 1988. The original procedure was modified by the CIPIMM researchers and was basically based on the immersion of the zeolitic mineral in a solution of complete NPK fertilizer for 24 - 48 hours. An industrial plant Date recue / Date received 2021-11-05 was built next to the zeolitic mineral processing plant in Tasajeras, San Juan de los Yeras, Remedios municipality, of the UEB Geominera Centro, for the production of the Litonite product. The liquid waste from the industrial process with a high load of nutrients not adsorbed by the mineral was deposited in a micro dam built for this purpose. The high environmental impact determined that the delegation of the Ministry of Science, Technology and Environment (CITMA) of the province of Villa Clara indicated the closure of the plant and conserve the waste until its treatment.
CELTONITA. It is a zeolitic product made using as raw material the zeolitic mineral from the San Andres deposit, in the province of Holguin, Cuba, enriched with macro and micro nutrients. Use the procedure for obtaining Litonite. Celtonita is a trademark, the production procedure is not patented and is protected by an industrial secret of the Celta Brasil Group, which buys the zeolitic raw material from the UEB Geominera Holguin, in Cuba. According to the technical sheet of the product, its use is recommended by incorporating 15%
Celtonita in the traditional substrate used in seedbeds and nurseries of all types of plants. As a fertilizer to be incorporated into the soil in doses of 500 to 1000 kg / ha, which replaces the bottom NPK fertilizer during sowing, but requires the application of the complementary nitrogen fertilizer recommended for the crop, which can be reduced by 20 to 25%. (J. A. Febles et al. Zeolite 2014 Book of Abstract - 9th Int. Conf. Natural Zeolites, Belgrade, Serbia, 8 - 13 June 2014 pp 67-68).
Variants of the elaboration of substrates for the cultivation of plants using zeolitic minerals and based on the three basic procedures are:
Procedures for obtaining substrates based on the modification of zeolitic rocks CN1017395 B (1989-05-06). Zeolite cultivating substrate for plant. The invention describes the obtaining of a substrate for the cultivation of plants without soils that uses natural clinoptilolite with a particle size class +
20-40 mesh, which is subjected to: a) acid activation with HCI, b) activation with a temperature of 70 -90 C, c) mixed with a solid fertilizer at a temperature of 40-60 C for 1-24 hours according to the needs of the plants. It is reported as a slow release substrate and fertilizer. In this invention acid treatments of the mineral are used that damage the crystalline structure of clinoptilolite; heat treatment for drying that increases the cost of the product; mix with a solid chemical fertilizer that does not directly incorporate the nutrients into the zeolite.
US20080116141 Al. (2008-01-29). Complete plant growth medium. This invention describes the coating of the zeolitic mineral with a special Fe oxide nanophase, to form a new zeolite material coated with iron nanophase, which is dosed with nutrients for plants and then mixed with other materials used in the preparation of substrates such as sand, peat, compost, vegetable and flower beds, native and manufactured soils, which provide beneficial properties to plants. This invention modifies the zeolitic mineral particles with an Date recue / Date received 2021-11-05 iron oxide compound to increase the nutrient adsorption capacity, the product is mixed with other materials to make substrates.
US5106405 A. (2009-09-13) priority to JP63-232589 (1989-09-13). Horticultural medium consisting essentially of natural zeolite particles. The invention describes the preparation of a substrate for plant development consisting essentially of natural zeolite particles, nitrifying bacteria, nitrogen fertilizer, phosphate fertilizer, compost, and sludge from a water purifying plant as a source of nitrifying bacteria. In this invention, the natural zeolite is the fundamental component or support of the substrate and it is not modified, it is mixed with the other components that provide the nutrients.
CN103553832 Al, CN1096994395 Al, CN107827568 Al, CN107827569 Al, CN107721659 Al, CN108147904 Al. They are some of the many inventions patented in China that describe substrates and fertilizers for growing plants, which are mixtures of natural zeolite with other natural organic materials, fertilizers, waste from agricultural, food and medicinal productions.
There are several works published in different scientific journals on the development of substrates for plant growth that use natural zeolites in their production. A comprehensive review of the topic was conducted by T.G.
Andronikashvili et al. Zeolite containing substrates - A new way from plant-growing in plant production.
(Annals of Agrarian Science Vol 7, No 4 14-45, 2009). The work analyzes numerous examples of the successful uses of the development and use of substrates containing natural zeolites that are essentially based on the three primary substrates. T.G. Andronikashvili et al. (Bull. Georg. Natl.
Acad. Sci. Vol. 5, no. 2, 2011) describe a substrate based on a mixture of three components brown carbon or lignite, natural zeolite type clinoptilolite-heulandite modified with ammonium, and with potassium. The bioproduction of the plants grown in the substrate was 2.9 times higher than that obtained in the soil.
The three primary product inventions describe the making of Balkanin, NASA and NEREA substrates, and the potential use of these as fertilizers. In the same way, the subsequent works that describe the elaboration of zeolitic substrates, do not cease to signify their potential use as fertilizers. Inventions of processes and products based on the modification of natural zeolites are found in the patent bases of several countries. The ways of modifying the zeolite mineral use thermal treatments, with acids, with organic and inorganic chemical compounds, a combination of these treatments, all with the aim of increasing the adsorption capacity of the zeolite to retain plant nutrients.
Procedures for obtaining fertilizers based on the modification of zeolitic rocks Date recue / Date received 2021-11-05 US5695542 A (1995-11-14) Method of preparing a slow release fertilizer. The method consists of several steps: I) Twenty parts of the inorganic fertilizer and one part of water are mixed; II) the mixture is heated to the temperature between 105 C -115 C with continuous stirring until the mixture passes to the liquid state; III) add a volume of zeolite to the liquid mixture, three times the volume of the fertilizer used in stage I, stir continuously while heating until the liquid mixture of the fertilizer is completely absorbed by the zeolite; IV) cooling the mixture with air to a temperature below 80 C, causing the mixture to return to the solid state; VI) cooling the solid mixture continuously with air to a temperature below 50 C, then adding a gelatinous substance to the mixture and mixing continuously; VII) air dry the mixture until the final product is obtained.
This procedure uses the zeolite in a physical mixture that needs to be preserved using a gelatinous substance.
The properties of zeolite are partially utilized. The product obtained is a fertilizer with high nutrient content and the product will be solubilized to the extent that rain or irrigation water acts on the gelatinous substance.
CA2998756 (2016-09-19). Synthetic agricultural product. The invention describes the process for obtaining a synthetic liquid fertilizer that uses various silicic materials with high cation exchange capacity; such as silica alumina, silicate, sodium aluminosilicate, hydrated calcium sodium aluminosilicate, and minerals such as montmorillonite, kaolinite, smectite, and zeolite. The mineral substance with a particle size between 1 and 1000 nanometers, suspended in double distilled and ultrapure water, is mixed with the solution of the agricultural product, fertilizers and organic compounds, to be incorporated into the solid material. Energy is applied to effectively achieve nutrient incorporation. The final product is classified as a synthetic agricultural product.
02013119108 Al (2012-02-06). Controlled release fertilizer composite comprising zeolite. The objective of the invention is to obtain and use a dry compound of modified clinoptilolite and mordenite type zeolites, activated carbon, molasses, nitrogen fertilizer, Fe, Mn, Zn nutrients and a binder, for the controlled release of water and nutrients for the cultivation of plants.
U53441400 A (1986-04-29). Porous mineral carrier impregnated with a nitrogen fertilizer. The invention describes the elaboration of a solid product for the development of plants that uses a clay mineral ¨ zeolite is not specified ¨ called a carrier, which after its extraction is ground to obtain particles between 0.1 and 3.4 mm.
that are calcined at temperatures between 480 C and 870 C, and then placed on a moving surface (rotary mixer) where they are impregnated, by spraying, with a solution containing 0.5 - 90.0% water, 0.5 to 90.0% by weight of an aqueous solution of 50% ammonium nitrate, 0.5 to 35% by weight of aqueous solution of phosphoric acid, and 0.5 to 65% of an aqueous solution of 45% of potassium hydroxide. The impregnation is carried out for a sufficient time to allow obtaining a product containing 60 to 99% by weight of the mineral carrier and the fertilizer solution. The description of the procedure and the example are presented carried out Date recue / Date received 2021-11-05 under laboratory conditions, in which distilled water is used to wash the calcined mineral and in the preparation of the fertilizer solutions. The process of incorporating the fertilizer into the carrier is described as absorption.
The studies carried out to determine the degree of retention of the nutrients in the mineral carrier showed that after 72 hours of contact with 100 grams of the product in contact with 1000 mL of distilled water, 50% of nitrogen remained in the product, 2 % phosphorus and 6% potassium, indicating that they are leached from the product by the water and not extracted by the plants.
US20040099027 Al (2004-05-27). Manufacturing method for zeolite-containing fertilizer. The invention relates to the method of producing a slow release fertilizer containing natural zeolite particles, residual from the refining of beet sugar, and calcium carbonate, mixed with water. The dry mix is called precursor and before being applied to the soil it must be loaded with commercial fertilizers for soils that contain the nutrients, to become a controlled release fertilizer. Loading is done by mixing the precursor with the fertilizer.
US20130327103 Al (2001-01-07). Use of zeolites in supplying micronutrients.
The invention describes the use of zeolites to supply micronutrients to plants that can be assimilated by them. The micronutrients copper, manganese, zinc, molybdenum, cobalt or iron, and the meso-elements calcium or magnesium, are incorporated into the natural or modified zeolite in the amount of 1.5 to 15% of the mass of the zeolite. The micronutrients and zeolite are mixed in a container that can be a glass bottle, a plastic tank, etc. using a paddle stirrer to mix.
The plant treatment method employs doses from 0.1 to 600,000 g/ha, preferably from 10 to 50,000 g/ha.
W02013110106 Al (2012-01-09). Method for producing mineral foliar fertilizer.
The invention describes a method for producing and using a mineral foliar fertilizer, characterized by a mixture of clinoptilolite, dolomite and calcite materials that are ground to obtain particles with sizes less than 40 microns and the product thus obtained is used as a foliar fertilizer.
Fabrication and characterization of nanoporous zeolite based N fertilizer. A.
Manikandan and K. S.
Subramanian. (African Journal of Agriculture Research Vol. 9 (2), pp. 276-284 January, 2014). A laboratory study to increase the efficient use of nitrogen using a natural zeolite (Z) or a zeolite with nanopores (NZ) as an adsorbent substrate to which urea is impregnated. The commercial urea and the adsorbent in the ratio were mixed or fused in the ratio of 1: 1 to 1:10 using simple liquid immersion with the hydrothermal technique. The 1:1 ratio registered the highest total N content of 18.5 zeourea (ZU) and 28%
nano-zeourea (NZU), respectively.
The study suggests that a fertilizer based on a zeolite with nanopores can be used as a strategy to improve the efficient use of nitrogen.
Other procedures described for obtaining fertilizers evaluate the use of surfactants to modify the surface of the crystals and zeolite particles, which increases the adsorption capacity of nitrates and phosphates. One of Date recue / Date received 2021-11-05 the surfactants used is hexadecyltrimethylammonium bromide, a cationic surfactant that modifies the surface of zeolite and increases its ability to retain anions such as phosphates and nitrates. Although the material obtained in addition to containing significant amounts of the nutrients N and P. and releasing them slowly, the cost of the procedure and the toxicity of the surfactant are discussed. Use of surfactant-modified zeolite as fertilizer carriers to control nitrate realease. Zhaohui Li. (Microporous and Mesoporous Materials 61 (1) 181-188, 2003) and Surfactant-Modified Zeolite as a Slow Release Fertilizer for Phosphorus. Amit Kumar Bansiwal et al. (J. Agric. Food Chem. 2006, 54, 13, 4773-4779).
The 2016 Australian Government IP Australia study, PATENT ANALYTICS REPORT:
AGRICULTURAL
NANOMATERIALS, analyzed the impact of nanomaterials on agriculture through the lens of intellectual property, assessing the scale and intensity of patent activity as a reflection of the innovation in this technology.
128 innovations related to nanomaterials for agriculture were identified. The main contributions to this field come from the United States, China and Germany. The study defines zeolites among the main raw materials for the development of nanomaterials for agriculture. It states that, when considering agriculture, nanomaterials and zeolites should be divided into two categories: soil improvers and protective agents. In turn, soil improvers are grouped into two categories: 1) physical soil improvers (PSEs) that improve the absorption capacity of water or available water for plants, which regenerate the soil and generally improve the soil conditions for plant growth. 2) chemical soil improvers (CSEs) that improve the chemical characteristics of soils, including fertilizer delivery and release; mineralization of soils to provide essential nutrients;
capture of undesirable components such as heavy metals, gases, toxins of a chemical or biological nature. The study considered plant protection agents (PPAs) that are defined as materials that fight pests that directly affect plant well-being, including herbicides, insecticides and fungicides.
According to the study, 40% of the inventions included in the CSE-type study were slow-release or sustained-release fertilizers. Between 2012 and 2021, the Chinese company Shikefeng Chemical Industry Co Ltd producer and distributor of fertilizers obtained the highest number of this type. The family of fertilizers patents for soybean (W02014 / 101266 Al), corn Al (W02014 / 101265 Al), rice (W02014 /
101269 Al) and tobacco (W02014 / 101267 Al), as well as patents W02014 / 101268 Al and W02014 /
101270 Al are characterized in the preparation of a solid and granulated compound of chloride or sulfate-based fertilizers, ammonium and potassium, which are coated first with stearic acid and then with modified zeolite powder. The products obtained are classified as slow release fertilizers.
The study considers that the inventions that describe the elaboration of inorganic fertilizers to increase the qualities of the soils through the addition of minerals are the most reported of the CSE type. The patent family Date recue / Date received 2021-11-05 W02005 / 117581 Al owned by Envirofocus of New Zealand, which describes a treatment agent containing a zeolite core coated with diatomite and an external coating, which are useful to control the release of fertilizers and nutrients to plants. The composition of the grain is particularly useful to control the release of fertilizers and nutrients to plants and as a soil improver. A physical soil improver is described in W02008 / 080616 A2 which contains zeolite and is used to aid in water retention. The improver is a mixture of cellulose fibers and zeolites.
In summary, the substrates and fertilizers made using modified zeolitic rocks:
1. They do not consider that zeolitic minerals are a natural part of soils.
2. They only make partial use of the physical and chemical properties of the zeolitic raw material.
3. They do not take advantage of the natural nutrients of the zeolitic raw material.
4. Inventions using modified natural zeolites incorporate one or two essential plant nutrients into the particles.
5. They are based on the concept of incorporating as much of the nutrient as possible into the product to maintain the agronomic principle that to achieve higher yields, more nutrients must be incorporated into the soil.
6. Modifications of the zeolitic mineral are carried out with heat treatments, acids and surfactants to modify its physical and chemical properties, in order to increase its capacity to absorb nutrients or the molecules that contain the nutrients. They are procedures that make the obtained products more expensive, can emit residual pollutants into the environment and limit the possible regeneration of the product.
7. The final products are mechanical mixtures of natural or modified zeolitic mineral, with other natural materials such as peat, phosphate rock, clays; and with chemical fertilizers, and as in the case of NASA
with synthetic materials.
8. In the process of adding the zeolitic mineral in a mixture with fertilizers, the natural dissolution of the fertilizer must occur so that the nutrients not taken by the plants migrate to the zeolite, but does not stop their loss or the contaminating migration to the groundwaters.
9. A modification procedure of the zeolitic mineral has not been reported, which allows the elaboration of three types of products, substrate, fertilizer and foliar fertilizer, with similar properties and different uses for the cultivation of plants as methods of treatment of these, in the different stages of its development, extensive, intensive, outdoor and protected cultivation conditions.
The objective of the present invention is the procedure that solves the deficiencies of the original procedures for obtaining the NEREA formulations, regulating the characteristics of the product obtained in relation to Date recue / Date received 2021-11-05 containing only the composition and amount necessary for the nutrition of the plants of the macronutrients N, P. K, also Ca, Mg, Fe and Si, and of the micronutrients Mn, Zn, Cu, B, optimizing the production time of the product, establishing quality control parameters: pH, conductivity, humidity, size of particles, storage conditions, specific rules for its use as a substrate, fertilizer to be incorporated into the soil and foliar fertilizer.
The new procedure for producing the products eliminates the emission of residues of aqueous solutions of the fertilizers used in the modification of the zeolitic raw material, which in the previous procedures were polluting the environment. The products thus obtained do not constitute a risk to the environment during their use since the chemical elements contained in their structure are only extracted by the plants, and their extraction by leaching during contact with irrigation water or rain is very low. The fertilizer product is incorporated into the mineral phase of the soil, increasing its storage capacity for nutrients and water, balancing the pH and the composition of particle sizes. The products obtained not only provide the macro and micro nutrients essential for the development of plants, they provide silicon in an assimilable and optimal way.
The present invention solves the deficiencies of the previous inventions to elaborate fertilizers and substrates for the cultivation of plants, which use the rocks or zeolitic minerals as fundamental raw materials, designing the process and the products considering:
1. The selective extraction of the zeolitic mineral in the deposit as a fundamental raw material of the products.
2. Produce them using a solution that contains all the essential macro and micronutrients for plants, in contact with the zeolitic raw material.
3. The contact of the nutrient solution and the processed zeolitic mineral is carried out using industrial mixers with low energy consumption, during optimized times and temperatures from 20 C to 60 C.
4. The incorporation of the cationic nutrients to the zeolitic rock particles occurs through multi-element ion exchange, while the adsorption of P and B is carried out with the formation of compounds with the cationic nutrients that are exchanged. These processes take place from the first minutes of contact until several days later. This stage is called "curing."
5. The final content of the nutrients in the products obtained, considered the content of natural nutrients of the zeolitic raw material, the needs of the plants for the development stage in which the product is used Substrate, Fertilizer to be incorporated into the soil, and Foliar fertilizer.
6. Homogeneity, each particle contains all the nutrients.
7. Adjustment of particle size after chemical modification and curing of the product. Each product obtained has particles with certain size classes.

Date recue / Date received 2021-11-05 8. The obtained fertilizer is incorporated into the soil as a natural or friendly supplement, so the nutrient content does not exceed the limits considered as pollutants.
9. The Fertilizer in doses of 1 ton/ha, is the minimum amount of the zeolitic mineral necessary for its incorporation as a mineral phase of the soil.

10. The nutrients necessary for the plants are incorporated into the Fertilizer, without waiting for the fertilizer dissolution process and its absorption by the zeolite. The agronomy concept of applying an excess of nutrients is modified to ensure that the plants take the necessary ones, estimating the losses.

11. In the Substrate, the nutrient contents allow the germination of the seeds, the development of the plants, their flowering and fruiting, optimally, only using water for irrigation.
Agricultural yields are comparable to those obtained in hydroponic crops that use fertilizer dissolution for irrigation and plant nutrition.

12. In the Substrate, the nutrients can be restored in the same amount extracted by the plants during their development, something that other inventions do not report.

13. In the Substrate and Fertilizer, the plants take in the nutrients in the amounts they need. What remains is preserved in the product particles. Nutrient leaching from zeolite particles is limited by their properties.

14. The foliar fertilizer allows the nutrition of the plants in their aerial parts, without the need to use other foliar fertilizers.

15. The foliar fertilizer protects the flowers, leaves and fruits from the attack of insects by creating a physical barrier with the particles smaller than 0.091 mm, and also protects the plants from the presence of fungi and bacteria.

16. Substrate, Soil Fertilizer and Foliar Fertilizer provide silicon as an essential nutrient for plant development.
The stages of the new procedure are summarized in:
1. Selection of the zeolitic mineral.
2. Mechanical ore preparation in defined size classes.
3. Modification of the zeolitic raw material.
4. Curing and drying of the obtained product.
5. Adjustment of particle size, if required.
6. Packaging of the product.
7. Product quality control.
8. Use of the product as a treatment method in the cultivation of plants.
Date recue / Date received 2021-11-05 1. Selection of the zeolitic mineral The zeolitic mineral to be extracted from the reservoir or deposit must meet the following characteristics:
= Type of zeolite: clinoptilolite (CLI), heulandite (HEU) and mordenite (MOR).
= Minimum total zeolite content: 60%.
= Non-zeolitic mineral phases: calcite, clays, quartz, feldspar, iron oxides.
= Maximum total content of non-zeolitic phases: 40%.
= Minimum total ion exchange capacity: 120 milliequivalent per 100 grams of mineral.
= Water absorption capacity: 16.3 - 23.50%
= Humidity: 5.0 - 16.5%
= Specific gravity: 2.0 - 2.37g/cm3 = Volumetric weight: 1.35 - 2.06 g/cm3 = Porosity: 13.0 - 40.0%
= Chemical composition: It is shown in tables I and II.
Table I. Chemical composition of zeolitic mineral [% weight]
5i02 A1203 Fe2O3 FeO MgO CaO Na2O K20 PPI
Max 72,4 13,7 5,3 2,7 7,2 7,5 3,5 1,7 12,1 Min 58,3 8,6 0.9 0.2 0.5 1,9 1,0 0,4 8,5 PPI ¨ lost by ignition Table II. Content of toxic elements [g/t]
F Pb As Cd Hg <200 <10 <3 <2 <5 2. Mineral processing and granulometric classification The processing of the mineral includes crushing (or primary grinding) to reduce the particle size of the rocks, to continue with the grinding (secondary grinding) that allows obtaining particles with sizes between 1.0 and 5.0 mm, with a content less than 10% of particles with sizes less than 0.8 mm. The processed mineral is called "zeolitic raw material"; it must be stored and preserved from inclement weather, especially rain or other source of moisture.
3. Modification of the zeolitic raw material.
The modification of the zeolitic raw material is carried out following the following unit operations:

Date recue / Date received 2021-11-05 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. This determination is made by weighing a mass of zeolitic raw material with a particle size of 1.0 to 5.0 mm, which can be 1, 10, 100 or 1000 grams at room temperature. Then moisten totally with the raw water that will be used in the preparation of the nutrient solution, until total saturation. Let the excess water drain, weigh again and subtract from the previously determined weight. The calculated weight expressed in 1kg = 1 L is the volume of water to be used to make the nutrient solution.
b) Amount of nutrients to be incorporated into the zeolitic raw material. As a source of nutrients, water-soluble NPK fertilizers in complete formulas with micronutrients (Triple 15, 16, 17, 18, 19, 20, 22) are used. The formulas can be formed using raw materials fertilizers like ammonium monophosphate (MAP), ammonium diphosphate (DAP), phosphoric acid, potassium chloride, urea, ammonium nitrate, salts of the micronutrients, in all cases highly soluble in water. The total sum of nutrients to be incorporated into the zeolitic raw material will depend on its nutrient content (K, Ca, Mg, Fe) and on the product to be elaborated in a range of 1.0 to 20.0% by weight of the final product. With the amount of nutrients defined, a solution is prepared that is added to the zeolitic raw material.
c) Preparation of the nutrient solution. The solution is prepared by adding the mass of fertilizer or mixture of fertilizers and salts of the nutrients and micronutrients determined in the previous step, to the volume of water that the raw material can absorb without runoff and that was established when determining its humidity (step a). The fertilizer or nutrient salts must be completely dissolved without leaving solid residues. The process can be accelerated by raising the water temperature up to 60 C.
d) The modification of the raw material with the dissolution of nutrients is carried out in a vertical or horizontal mixer, into which the mass of the zeolitic raw material to be modified is introduced and which it can contain according to its dimensions. The introduction of the raw material is carried out with the mixer in motion. Then the nutrient solution is dosed, taking care that the mass of zeolitic raw material is homogeneously humidified, without the solution running off. This process stops when all of the solution is dosed and the particles are all wetted. The process is carried out at room temperature, but it can rise if it is below 24 C and should not be higher than 60 C. The duration of the process will be determined until the total absorption of the solution is achieved in a homogeneous way, without dripping, a process that occurs between 10 and 30 minutes.
4. Curing and drying of the obtained product.

17 Date recue / Date received 2021-11-05 This stage called "curing" of the obtained product is characterized by the processes of adsorption, ion exchange and insertion of the nutrients in the raw material, mainly in the zeolitic phases contained in it. The process begins during the wetting of the zeolitic raw material with the dissolution of nutrients. Unlike the way in which it was carried out in the previous technologies for obtaining N EREA
products, which occurred as an ion exchange process in an exchange column, which required the continuous step of the dissolution of nutrients and their recirculation for hours until achieving the exchange of cationic nutrients (NH4., K.) and the adsorption of PO4-, in the current procedure the process is carried out slowly over days.
The wet product extracted from the mixer must remain unpackaged between 24 to 96 hours until its humidity balances with the ambient humidity, and the pH and electrical conductivity values stabilize. Drying can be done in an oven or drying chamber at a temperature of 35 to 80 C, reducing the process time.
During curing, the drying of the product occurs, characterized by reaching a constant mass. However, the curing does not end with the drying of the product, it continues effectively over time. Full nutrient insertion can be achieved in 100 days. The verification that the curing process has concluded and was effective is carried out when the pH and conductivity values of the product do not vary.
5. Particle size adjustment While the production of the substrate and soil fertilizer products may not require a particle size adjustment (particle size class + 1-5 mm) for use, the foliar fertilizer product requires the reduction of the size of its particles at dimensions less than 0.091 mm (particle size class -0.091 mm), carrying out a new grinding. This allows the foliar fertilizer obtained to be dispersed in water for application by manual or mechanical sprinkling equipment.
The dry product (6 - 10% humidity) must be ground in micronizing mills.
6. Packaging of the product obtained.
Once dry, the product must be packed in bags of different sizes according to commercial requirements: 1, 25, 50, 100 and 1000 kg. The bags with the product can be grouped for storage at room temperature, off the floor, indoors, isolated from other zeolitic and chemical products.
7. Product quality control.
The quality of the products obtained by the process of this invention is established by analytical determination of various parameters. The technical data sheet of one of the products obtained by the present invention must report several parameters of interest to the customer. As an example, the Foliar Fertilizer product should be described as follows:
= Commercial name of the product: Foliar fertilizer = Form of presentation: Powder

18 Date recue / Date received 2021-11-05 = Color: gray - green.
= Concentration of active principles: 9.0 - 18.0%.
= Humidity: 10 - 14%
= Solubility in water: No = PH (guaranteed range): 5.6 - 7.6.
= Compatibility with other products for agricultural use: Yes = Particle size: <0.091 mm = Compaction risks: No = Storage conditions: Under roof, off the floor, away from chemicals_.
= Expiration period: 3 years.
= Crops that can receive the product: All.
= Average recommended dose per crop: 2-8 kg/ha (10-20 g/L of water) = Time of application. After sowing: Yes; Anytime: Yes = Frequency of application per crop cycle: More than three times: X
= Form of application: Foliar = 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 Nitrogen, Phosphorus and Potassium is carried out following the analytical methods and techniques for the study in a soil.
= Chemical and mineral composition appear in tables III and IV.
Table III. Nutrient composition of the foliar fertilizer [% by weight]
N P K CaO Na2O MgO Fe2O3 0,7 ¨ 10,0 0,7 ¨ 4,0 0,7 ¨ 4,0 2,0 ¨ 3,0 0,7 - 1,0 0,4 2,5 Mn Zn Cu B 5i02 A1203 H20 0,02 0,02 0,02 0,02 64,0 - 66,2 10,0 -11,2 14,2 Table IV. Composition of mineral phases of the foliar fertilizer [% by weight]
Non-zeolitic minerals Zeolitic minerals Quartz + Feldspar + Calcite + Montmorillonite +
Clinoptilolite + Heulandite + Mordenite Iron oxides >80 <20 8. Use of the product as a treatment method in the cultivation of plants.
The products obtained by the present invention are described in Table V.

19 Date recue / Date received 2021-11-05 Table V. Macronutrient composition in the products [% by weight]
Kind of product Particle size [mm] N P K
Susbtrate 1,0 ¨ 4,0 0,7 ¨ 1,0 0,7 ¨ 1,0 0,7 ¨ 1,0 Fertilizer 1,0 ¨ 4,0 0,7 ¨ 2,5 0,7 ¨ 2,5 0,7 ¨ 2,5 Foliar fertilizer <0,074 5,0¨ 10,0 2,0 ¨ 4,0 2,0 ¨ 4,0 The use of each product in the treatment of plants is:
The Fertilizer = It can be used in all types of crops and soils, depending on the dose of nutrient demand in each case.
They are NOT soluble particles with a size between 1 and 4 mm.
= The content of nutrients in the Fertilizer product is low for the beneficial effects that are obtained. The Fertilizer contains all the nutrients necessary for the plants in a balanced way, which are not lost in the soil by leaching or volatilization as occurs with conventional fertilizers.
They are only taken by plants. By placing 2 grams of the product in 100 mL of water for 10 days and every 24 hours, aliquots of 10 mL
were taken, replacing the extracted volume, the contents of N, P and K in the aliquots were determined.
The values determined were less than 0.06 mg/L for N; at 0.003 mg/L for P; at 0.0005 mg/L for K; which shows the low leaching of nutrients from the product particles by water.
= The Fertilizer has a high content of silicon (60.0 to 68.0% SiO2 by weight of the product), an element that due to its importance is considered a major nutrient, which is extracted from the soil by plants in large quantities, depleting its nature reserves and is generally not applied to the ground. Its presence in the soil improves the availability of phosphorus for plant nutrition. Table VI
shows the silicon contents in corn leaves, a plant that requires silicon for its development, grown in a compacted red ferralitic soil to which different doses of Fertilizer were incorporated and it is compared with the contents determined in the plants grown in the soil with complete NPK fertilization and in the Substrate obtained by the process of this invention. It was observed that the content of silicon in the leaves increased with the content of the Fertilizer and that it was significantly higher when the plant was grown in the Substrate as soil.
Table VI. Silicon Content [% 5i02 Dry Base] in corn husks Soil with 25% Soil with 50%
Soil with NPK Susbtrate 100%
Fertilizer Fertilizer 0,04 0,15 0,25 0,33 = The Fertilizer can be used as a physical-chemical improver of all types of soil regardless of its pH, obtaining the best results in acidic soils.
Date recue / Date received 2021-11-05 = The Fertilizer has been applied for five years in doses equivalent to 100 ton/ha without determining damage to the physical and chemical properties of the soil.
= In all crops the application of the Fertilizer must be carried out at the bottom of the furrow, and in case of a second application the product must be placed close to the roots and covered in the hilling process. By being in contact with the active zone of the roots, the plants take the nutrients according to their needs, acting as a controlled release fertilizer. In general, the application rate should be between 1 - 2 ton/ha.
The Susbtrate = The Substrate for nurseries can be used alone or mixed with organic matter, compost, earthworm humus, coconut fiber, national peat, brown peat, rice husk charcoal, etc. Mixes can be from 10 to 50%, depending on the organic matter and the desired objective. After filling the tray or bag with the substrate, the seed is introduced to the required depth, covered and only watered with water.
= In transplants of fruit trees, coffee, coconut and forestry, the Substrate must be applied at the bottom of the planting hole and on the edges after placing the plants in doses of 0.5-10.0 kg per plant. It is recommended to mix the Substrate product with the soil extracted from the seed hole before application.
= The Substrate for in vitro cultures can be used directly or in mixtures with other substrates. The vitroplants will be placed and the necessary irrigation must be carried out taking into account the evapotranspiration of the culture beds.
= Substrate in protected crops can be applied in high doses, for example 5-10 kg/m', only water is applied in irrigation.
= The Substrate in the activation of organoponics is recommended to remove the existing substrate and open furrows in the sowing band, and the Substrate is applied in doses of 1-2 ton/ha. The plants are sown and the furrow is covered. The Substrate can also be mixed with the existing material and sowing or transplanting in the usual way.
= The use of The Substrate only requires water to irrigate the plants.
The Foliar Fertilizer Date recue / Date received 2021-11-05 = The applications of Foliar Fertilizer must be made with the same technical rigor as other foliar fertilizers or pesticide products; preferably in the early hours of the morning when the plants have more open stomata and the air speed is slower.
= The foliar fertilizer is applied as a suspension in water, using manual or mechanical spraying equipment, with a stirring system.
= It must be ensured that the equipment and nozzles are clean, without residues of other products or obstructions.
= It must make the total dispersion of the dose of The Foliar Fertilizer in a volume of water contained in a container outside the spraying equipment. This aqueous dispersion is incorporated into the tank of the equipment that must contain a volume of water, keeping the agitation working.
Fill with water until the tank is filled.
= The general dose of Foliar Fertilizer for all crops is 2 to 10 kg per hectare, in dispersions of 10 to 20 grams per liter of water. The volume of final solution will be 200 to 400 liters per hectare.
= During the application of the Foliar Fertilizer it must be ensured that the product covers all the foliage, flowers and fruits of the plants.
= When using Foliar Fertilizer, the use of other foliar fertilizers or nutrient solutions applied to the foliage of the plants is not required.
= Studies have shown that Foliar Fertilizer also acts as a plant protector against insect pests, and fungal, bacterial and viral infections.
Realization examples EXAMPLE I
The zeolitic mineral from the San Andres deposit in the province of Holguin, processed in the plant of the UEB Geominera Holguin company, by crushing, drying and secondary grinding, was classified by particle size classes using a mechanical sieve. The product with a particle size class of +1-3mm, and physical and chemical composition that complies with the Cuban standard NC 625: 2019, was used as zeolitic raw material for the production of the Fertilizer product. A raw material mass of 250 kg with a humidity of 14.0% was used, which was introduced into an industrial rotary drum mixer with a capacity of 500 kg.
A solution of 6.0 kg of NPK 9-13-17 fertilizer was prepared in 50 L of raw water, at a temperature of 30 C, stirring until completely dissolved. The solution was continuously added to the zeolite mineral while the mixer was rotating. Once the addition of the solution was completed, the mixer was kept in motion for 15 minutes until its total adsorption by the mineral Date recue / Date received 2021-11-05 was completed. During the process, the solution spillage was avoided. The mineral thus modified was extracted from the mixer and subjected to the curing-drying process in a drying chamber at 40 C for 48 hours. The product obtained was characterized by determining that it contained 2.4% of nutrients, a particle size class of +
1-3mm, humidity of 15.0%, pH 6.2 and electrical conductivity of 1700 ppm. The Fertilizer was used in the fertilization of the potato crop, at a dose of 2 ton/ha, incorporating it to the bottom of the furrow in a Compacted Red Ferralitic soil, before the introduction of the CIMEGA variety potato seed at sowing. The yield of the potato crop obtained was 29.95 ton/ha, while the yield observed in the same field and variety of potato using as a control the traditional fertilization with NPK 9-13-17 fertilizer with 25% zeolitic mineral, applied at doses of 1.34 ton/ha was 31.10 ton/ha. The costs of each fertilizer formula are very different. A significant saving was found in The Fertilizer compared to the 9-13-17 formula with a dose cost of 1675.0 USD. The cost of the 9-13-17 fertilizer used in the preparation of The Fertilizer represented 6% of the cost of the formula used as a control.
EXAMPLE II
The zeolitic mineral from the San Andres deposit in Holguin province, processed in the plant of the UEB
Geominera Holguin company by crushing, drying and secondary grinding, was classified by particle size using a mechanical screen. The product was chosen with a particle size class of +1-4mm, and physical and chemical composition that complies with the Cuban standard NC 625: 2019, it was used as zeolitic raw material for the preparation of the Substrate product. A raw material mass of 500 kg with a humidity of 15.0% was used, which was introduced into an industrial rotary drum mixer with a capacity of 500 kg.
A solution of 7.0 kg of triple 18 NPK fertilizer with micronutrients was prepared in 75 L of raw water, at a temperature of 30 C, stirring until completely dissolved. The solution was continuously added to the zeolite mineral while the mixer was rotating.
Once the addition of the solution was completed, the mixer was kept in motion for 20 minutes until its total adsorption by the mineral was completed. During the process, the solution spillage was avoided. The mineral thus modified was extracted from the mixer and subjected to the curing-drying process in a drying chamber at 40 C for 48 hours. The product obtained was characterized by determining that it contained 1.4% of nutrients, particle size class +1-4mm, humidity of 14.0%, pH 6.7 and electrical conductivity of 1700 ppm. The product obtained called Substrate was used as the sole substrate in the Floradel variety tomato crop using the soilless culture of crops zeoponic technology, in the open air, with a micro-sprinkler localized irrigation system. The yield obtained was 80 ton/ha, while in the control the tomato plants grown in the hydroponic system with irrigation using Steiner's universal formula nutrient solution was 60 ton/ha.
EXAMPLE III

Date recue / Date received 2021-11-05 The zeolitic mineral from the San Andres deposit in Holguin province, processed in the plant of the UEB
Geominera Holguin company by crushing, drying and secondary grinding, was classified by particle size using a mechanical screen. The product was chosen with a particle size of 1.0 to 4.0 mm, and a physical and chemical composition that complies with the Cuban standard NC 625: 2019, it was used as zeolitic raw material for the elaboration of the Foliar Fertilizer product. A raw material mass of 500 kg with a humidity of 15.0% was used, which was introduced into an industrial rotary drum mixer with a capacity of 500 kg. A solution of 20.0 kg of NPK 20-8-20 fertilizer with micronutrients was prepared in 100 L of raw water, at a temperature of 30 C, stirring until completely dissolved. The solution was continuously added to the zeolite mineral while the mixer was rotating. Once the addition of the solution was completed, the mixer was kept in motion for 20 minutes until its total adsorption by the mineral was completed. During the process, the solution spillage was avoided. The mineral thus modified was extracted from the mixer and subjected to the curing process in a drying chamber at 40 C for 72 hours. The final dried, cured product was introduced into a micronizing mill to reduce the size of the particles to dimensions less than 0.091mm. The product obtained called Foliar Fertilizer was characterized by determining that it contained 6.0% of nutrients, humidity of 10.0%, pH 5.7 and electrical conductivity of 2000 ppm. It was used as a foliar fertilizer and protector of the Bountifull and Liver varieties of green bean plants, against the attack of the Thrips Megalurothrips usitatus present in nearby areas, using untreated controls. The application rate was 4 kg/ha, in a water dispersion of 10 g/L, every 7 days. A
total of 8 applications were made.
The plants suffered a high infestation of the thrips, which did not affect the development of those treated with the foliar fertilizer. The yields obtained were equivalent to 9.89 ton/ha for fresh beans, and 2.45 ton/ha for grain. Control plants deteriorated significantly and did not produce.

Date recue / Date received 2021-11-05

Claims (18)

1. Procedure for obtaining substrates and controlled release zeolitic fertilizers that comprises the following stages: (A) crushing or grinding a zeolite mineral to reduce the size of the rocks until obtaining particle size classes between 1.0 and 5.0 mm and with a content of less than 10% of particles with a size less than 0.8 mm; (B) prepare a nutrient solution comprising water-soluble fertilizers selected from ammonium monophosphate [(NH4) H2PO4], ammonium diphosphate [(NH4) 2H2PO4], phosphoric acid [H3PO4], potassium chloride (KCI), urea [CH4N20], ammonium nitrate [NH4NO3], salts of the micronutrients [ZnSO4; CuSO4;
MnSO4; MoSO4; Na2B407], complete triple NPK formulas 15, 17, 18 and 20, so that the total sum must be in a range between 1.0 to 20% by weight of the final product; (C) introduce the zeolitic raw material obtained in stage (A) in a moving vertical or horizontal mixer, add the nutrient solution obtained in stage (B) and let it humidify homogeneously without draining the solution at room temperature for 5 to 60 minutes; (D) extracting the wet product from the mixer and drying the product in ovens or drying chambers at temperatures between 30 C and 80 C in a period of time ranging from 1 to 30 days; (E) curing of the product in which the nutrients are inserted into the product in a period of time ranging from 1 to 100 days.

2. Process for obtaining controlled release zeolitic substrates and fertilizers according to claim 1, characterized in that the zeolitic mineral to be crushed or ground in stage (A) is selected from the deposit among those that comprise a minimum content of 60% of zeolitic phases (clinoptilolite, heulandite and mordenite), a maximum content of 40% of non-zeolitic phases (calcite, clay, quartz, feldspar, iron oxides), a minimum total ion exchange capacity of 120 milliequivalent per 100 grams of the mineral and a water absorption capacity between 16.3 - 23.50%.

3. Procedure for obtaining substrates and controlled release zeolitic fertilizers according to claim 1, characterized in that to calculate the volume of the nutrient solution from step (B), between 1, 10, 100 or 1000 grams must be weighed of the material obtained in stage (A) at room temperature, moisten with raw water until total saturation of the weighed material, and drain the excess water, weigh again, subtract from the weight determined in the previous step and express the calculated weight in 1 kg = 1 L, which will correspond to the volume of water to be used in the preparation of the nutrient solution.
Date recue / Date received 2021-11-05

4. Procedure for obtaining substrates and zeolitic fertilizers of controlled release according to claim 1, characterized in that in stage (B) the dissolution of the contents of the nutrients and micronutrients must be prepared that take into account the contents of these in the zeolite from the untreated deposit to achieve concentrations of the nitrogen, phosphorus and potassium macronutrients between 1.0 and 20.0%, and of the manganese, zinc, copper, boron and molybdenum macronutrients in concentrations between 0.1 and 0.3%.

5. Process for obtaining substrates and controlled release zeolitic fertilizers according to claim 1, characterized in that the nutrient dissolution process of stage (B) can be accelerated by increasing the water temperature up to 60 C.

6. Process for obtaining substrates and controlled release zeolitic fertilizers according to claim 1, characterized in that in the wetting process in stage (C), the temperature in the mixer can rise if it is lower than 24 C, but must not be higher than 60 C; the duration of the process will be determined until the total absorption of the solution is achieved in a homogeneous way, without dripping, a process that occurs between 10 and 30 minutes.

7. Procedure for obtaining substrates and controlled release zeolitic fertilizers according to claim 1, characterized in that in stage (D) of the process, drying can be carried out at room temperature for 24 to 96 hours, or in an oven or Drying chamber at temperatures ranging from 35 C to 80 C from 10 to 30 minutes.

8. Procedure for obtaining substrates and zeolitic fertilizers with controlled release according to claim 1, characterized in that during stages (C) and (D) the product curing process (E) takes place, in which the insertion occurs of the nutrients in the product particles by ion exchange and adsorption processes.

9. Process for obtaining substrates and controlled release zeolitic fertilizers according to claim 1, characterized in that the curing stage (E) is concluded and is considered effective when the pH values between 5.6 - 8.6, and electrical conductivity between 1500 - 3000 ppm of the aqueous phase of the product do not vary.

Date recue / Date received 2021-11-05

10. Process for obtaining substrates and controlled release zeolitic fertilizers according to claim 1, characterized in that in the final product curing stage (E), the total insertion of the nutrients is reached in 100 days.

11. Process for obtaining substrates and controlled release zeolitic fertilizers according to claim 1, characterized in that to obtain substrates and fertilizers, the dry product (10 - 14%
humidity) with particle size classes between 1.0 and 5.0, preferably 1.0 and 4.0 mm, and more preferably 1.0 and 3.0 mm.

12. Procedure for obtaining substrates and controlled release zeolitic fertilizers according to claim 1, characterized in that to obtain a foliar fertilizer, the dry product (6-10%
humidity) obtained in stage (D) is subjected to a grinding process in micronizing mills until the particle size is adjusted to values lower than 0.091 mm.

13. Treatment method in the cultivation of plants in soils, characterized in that the fertilizer obtained according to the procedure described in claims 1 - 11, is incorporated in doses between 0.5 to 10.0 tons per hectare at the bottom of the furrow, prior to or at the time of sowing the seed or transplanting seedlings, previously grown in seedbeds or germinators using the substrate obtained by the procedure described in claims 1-11, or using other substrates.

14. Treatment method in the cultivation of plants in soils according to claim 13, characterized in that the fertilizer is also applied during the development of the plants, placing it near the roots and covering it with the soil.

15. Treatment method in the cultivation of plants, characterized in that the foliar fertilizer obtained according to the procedure described in claims 1 - 10, and 12, is applied dispersed in water, using dispensers or manual sprinklers and mechanized sprinklers that allow depositing the product in the leaves, flowers, fruits and all the aerial parts of the plants at a rate of 10.0 to 20.0 g/L of water, to achieve a final dosage of 1.0 to 10.0 kg per hectare.

Date recue / Date received 2021-11-05

16. Use of the substrate obtained according to claims 1 - 11 for the germination of seeds and the obtaining of seeds by biotechnological methods in 100% or in mixtures with other materials used in the preparation of substrates such as coconut fiber, rockwool, expanded clay, and organic matter such as peat, compost from animal excreta, and / or wastes from agricultural productions in proportions ranging between 1:1 - 1:5, using only water to irrigate the plants.

17. Use of the substrate obtained according to claims 1-11 as the sole component of an artificial soil in which only water is used for irrigation.

18. Treatment method in the cultivation of soilless plants whose leaves, flowers and fruits show a significant decrease in nutrients or that show signs of malnutrition characterized in that nutrients are incorporated up to the original levels to the substrate product obtained according to claims 1 - 10 and 17, by means of aqueous solutions of complete NPK fertilizers with water-soluble micronutrients that are put in contact with the substrate for 10 to 120 minutes using the water irrigation system.

Date recue / Date received 2021-11-05