Composition of particulate and liquid phosphate fertilizer

Abstract

The present invention relates to agrochemistry, in particular to phosphorus-containing fertilizers in particulate and liquid form, which can be suitable for planting various crop species on any type of soil. The composition according to the invention comprises: a particulate phosphorus-containing fertilizer prepared by introducing a functional additive into an ammonium phosphate slurry prior to feeding the slurry into a drum granulation dryer (DGD); or a liquid phosphorus-containing fertilizer prepared by introducing a functional additive into the liquid phosphorus-containing fertilizer under conditions that the resulting mixture is stirred to form a homogeneous composition, in both cases the contents (wt%) of the components being 50.0-99.9% of a particulate or liquid phosphorus-containing fertilizer, 0.05-25.0% of polymaleic acid, 0.05-25.0% of polyaminopolyether methylene phosphoric acid. This makes it possible to prevent phosphorus from binding into slightly soluble metal salts, thereby increasing the effective phosphorus concentration, due to the synergistic effect of the inhibitor composition wherein the effect of one component is increased in the presence of the other component.

Description

Technical Field

[0001] The present invention relates to the field of agricultural chemistry and in particular to phosphate fertilizers in granular and liquid form suitable for growing a variety of crop species on any type of soil. Background Art

[0002] Phosphorus is one of the main sources of plant nutrition, and its content in the soil determines the growth and development of plants, as well as the yield and quality of the resulting agricultural products. Agricultural chemistry reveals the exact amount of phosphorus that plants consume from the soil during growth (for example, the average consumption of wheat is 10 to 12 kg per ton of grain) [VG Hernenok, "Scientific principles and practical methods for managing soil fertility and crop productivity in Northern Kazakhstan", Astana, 2009]. To replenish the phosphorus consumed in the soil, phosphate fertilizers are applied in the necessary amount. The concentration of active phosphorus in the soil is usually low, because when it is applied to the soil, it quickly reacts with calcium (Ca), magnesium (Mg), iron (Fe) and aluminum (Al) to form sparingly soluble (and therefore unavailable for nutrition) salts, which are metal phosphates.

[0003] Since the formation of sparingly soluble salts leads to a high binding rate of phosphorus in the soil, it is imperative to prolong the presence of fertilizer phosphorus in active form in the soil without forming sparingly soluble salts and to convert the total phosphorus bound in sparingly soluble salts into available form, that is, to convert part of the phosphorus bound in sparingly soluble salts into active phosphorus available to plants.

[0004] There are many types of phosphate fertilizers known for use in agriculture [MEPozin, "Technology of mineralfertilizers", Moscow: Chemistry, 1989]. The main types of phosphate granules currently in use include superphosphate, double superphosphate, ammonium phosphate, diammonium phosphate, orthophosphate and potassium metaphosphate. Rock phosphate is also used.

[0005] Phosphate fertilizers of these types are characterized by a low percentage of phosphorus uptake by the plant, which is caused by the formation of sparingly soluble phosphates. This process is described in detail [AE Vozbutskaya, "Soil chemistry", Moscow: Vysshaya Shkola, 1968] as "fertilizer degradation" (Latin retrogrades means return), which is the conversion of nutrients in a mobile form that is easily absorbed by the plant into unusable or almost unusable compounds. The degradation of phosphorus-containing fertilizers is even greater, especially in acidic soils. When they are introduced into the soil, water-soluble and citrate-soluble calcium phosphates are converted into tricalcium phosphate, iron phosphate and aluminum phosphate, or into organic phosphates. Fertilizer nutrient degradation can have a long-term negative impact on plant yield.

[0006] When applied before sowing and tilled after spreading, the utilization coefficient of phosphorus in superphosphate in the year of application is only 10-15% of the applied amount ["Agrochemistry", 2nd edition, revised and supplemented, editors PMSmimov and EAMuravin].

[0007] Liquid phosphate fertilizers (liquid complex fertilizers or LCF) based on soluble phosphates and ammonium polyphosphate are known (for example, LCF NP 11:37 produced by PhosAgro PJSC, whose P 2 O 5 The phosphorus content is 37%). Fertilizers such as LCF have certain agrochemical advantages over other types of phosphorus-containing fertilizers because they contain ammonium polyphosphate that does not form sparingly soluble salts.

[0008] However, a disadvantage of LCF fertilizers is that they can only be produced in the form of aqueous solutions. LCS solutions contain water, which is inert and results in additional costs for transportation and storage.

[0009] In addition, LCF phosphates contain 20% orthophosphates, which, like ordinary phosphates, immediately bind to the soil after application to form sparingly soluble salts. Since plants absorb phosphorus precisely in the form of phosphates, the remaining 80% of LCF phosphorus in the form of polyphosphates hydrolyzes into orthophosphates in the soil over a long period of time, which negatively affects the nutrition of the plants during the growing season, i.e. during the development period, the plants will not be able to obtain the necessary phosphorus nutrients. At the same time, after the polyphosphates are hydrolyzed into orthophosphates, the phosphorus binds to sparingly soluble unavailable salts consisting of metal phosphates.

[0010] At the same time, the preparation of liquid mineral fertilizers from granular ammonium phosphate (diammonium hydrogen phosphate) is difficult due to the very slow and incomplete solubility of the phosphate raw materials. In addition, the production and use of liquid phosphate fertilizers do not solve the problem of phosphate binding by soil-forming elements.

[0011] A reasonable approach to solve the above problems is to find additives that inhibit the negative process of soil combining with phosphate to form slightly soluble salts.

[0012] The patent application discloses the following technical solution to the problem of phosphorus binding and sparingly soluble salt formation.

[0013] Patent No. RU 2675822 of December 25, 2018 "Fertilizer with polyanionic polymers and method for applying polyanionic polymers on plants" discloses anionic polymers with four types of repeating units, which are used as stand-alone products or fertilizer products and have many valuable properties in agriculture, including improving the ability of plants to absorb nutrients from fertilizers (especially phosphorus, nitrogen, potassium and trace elements), acting as a synergist for pesticides such as glyphosate herbicides, and when an organic desiccant is added, it dries very quickly when applied to solid fertilizers, thereby facilitating the preparation of finished products in the form of coated solid fertilizers.

[0014] In addition, the preferred polymers have been shown to have increased activity when using fertilizer compositions containing different types of partial polymer salts (US Patent Publication No. 2009 / 0217723, September 3, 2009). This technology is also disclosed in US Patent Nos. 6515090; 7655597; 7736412 and 8043995. For example, the phosphate activation effect when using the polymers showed an 18% increase in the concentration of active phosphate in plant tissue and a 20% increase in yield compared to the control (tests were conducted on cotton).

[0015] Patent No. RU 2267499 of October 1, 2006 "Anionic polymers formed from dicarboxylic acids and their use" discloses anionic polymers formed from dicarboxylic acid monomers such as maleic anhydride, itaconic anhydride or citraconic anhydride. Free radical polymerization is used for the synthesis of the polymers. The polymers can form complexes with ions and / or mixtures with fertilizers or seeds to prepare agriculturally suitable compositions. Preferred products of the invention can be applied to leaves or the ground near growing plants to improve the absorption of nutrients by the plants. For example, the phosphate activation effect when using carboxylate polymers compared to the efficacy of the control showed that the dry weight of corn increased by 41.9% in acidic soils and by 15.9% in alkaline soils.

[0016] However, the disadvantages of the compositions disclosed in said patent are the complex combination of said polymers, the complex synthesis, the lack of these polymers in the free market, the limited solubility of said polymers in concentrated solutions of phosphate fertilizers and the impossibility of adding these polymers to granular products.

[0017] Furthermore, the inhibitors mentioned have the disadvantage that it is proposed to apply them to the surface of the granules or to add them directly to the soil, which makes their efficacy doubtful, since the inhibitors are washed away from the granules by atmospheric precipitation, while their addition to the soil can lead to the depletion of the soil from phosphorus nutrients.

[0018] Problem solved by the invention. It is necessary to develop a composition for phosphate fertilizers capable of preventing the binding of phosphates to sparingly soluble salts and introducing inhibitors directly into the fertilizer composition. Another positive effect of the use of this composition is manifested in the ability to dissolve sparingly soluble phosphates previously formed in the soil, thereby converting the bound phosphorus into an active (available) form, as well as the enhanced mobility of other ions bound to sparingly soluble phosphates. Summary of the invention

[0019] Technical effects of the present invention:

[0020] Preventing phosphorus from binding to sparingly soluble metal salts by supplementing a phosphorus-containing fertilizer composition with an inhibitor of sparingly soluble salt formation to increase the concentration of available phosphorus; and

[0021] Synergistic effect of inhibitor combinations, wherein the effect of one component is enhanced in the presence of another component.

[0022] These technical effects are achieved by using a composition based on a polycarboxylic acid and a biodegradable polyanionic polymer of an organic phosphorus in an optimal ratio as a functional additive. This mixture prevents the fertilizer phosphorus from binding to sparingly soluble phosphates, thereby increasing the concentration of active phosphorus in the soil when applying phosphate fertilizers. The use of the composition according to the invention makes it possible to significantly reduce the loss of phosphorus due to binding to sparingly soluble salts when using phosphorus-containing fertilizers.

[0023] Specific embodiments of the present invention are given below.

[0024] A phosphate fertilizer composition (first embodiment) comprises a granular phosphate fertilizer and a functional additive, the composition comprising (wt.%):

[0025] Granular phosphorus fertilizers* 50.0-99.9％ Polymaleic acid 0.05-25.0％ Polyaminopolyether methylene phosphate 0.05-25.0％

[0026] * Granular phosphorus fertilizers are ammonium phosphate or diammonium phosphate.

[0027] A composition of a phosphorus-containing fertilizer (second embodiment), comprising a liquid phosphorus-containing fertilizer and a functional additive, the composition comprising (wt.%):

[0028] Liquid phosphorus fertilizers* 50.0-99.9％ Polymaleic acid 0.05-25.0％ Polyaminopolyether methylene phosphate 0.05-25.0％

[0029] *Liquid phosphorus fertilizer is LCF NP 11:37. DETAILED DESCRIPTION

[0030] Phosphorus-containing granular fertilizers and liquid fertilizers at recommended rates are used as the main source of phosphorus nutrients for plants.

[0031] The mixture of polymaleic acid and polyaminopolyether methylene phosphoric acid in the prescribed proportions in the recommended amounts is used to prevent phosphorus from binding to sparingly soluble metal salts, thereby increasing the concentration of available phosphorus by supplementing the phosphorus fertilizer composition with an inhibitor of the formation of sparingly soluble salts.

[0032] From experience, the applicant has determined that the best quality of the composition for preventing phosphorus from binding to sparingly soluble metal salts is obtained by using a mixture of anionic polymers based on polycarboxylic acids and organic phosphorus compounds. In the course of experiments carried out by the applicant, it was determined that in order to achieve these technical effects, the use of the following substances is most ideal:

[0033] Polymaleic acid with international CAS number 26099-09-2; and

[0034] The registration number is polyaminopolyether methylene phosphoric acid with international CAS number 130668-24-5.

[0035] When preparing the formulation, the chemical substances contained in its composition react with each other to provide a composition of granular fertilizer and liquid fertilizer, and allow solving the problems arising from the synergistic effect, in which the effect of one component is enhanced in the presence of another component. That is, due to the synergistic effect of the components used in the composition of granular fertilizer and liquid fertilizer at the claimed quantitative ratio, the above problems are solved and the above technical effects are achieved as confirmed by experiments.

[0036] The concentrations and ratios of phosphate fertilizers and inhibitors of sparingly soluble phosphate formation were selected based on the studies shown in Tables 2-10.

[0037] The technology for preparing the granular phosphate fertilizer composition can be implemented with well-known equipment used under industrial conditions, for example, utilizing existing granular phosphate fertilizer (ammonium phosphate and diammonium phosphate) production lines, introducing a solution of the proposed inhibitor composition at the stage of preparing the ammonium phosphate slurry before feeding the slurry to a rotary drum granulation dryer (DGD).

[0038] The equipment used for the production of granular phosphate fertilizers is described in the technical literature; see, for example, AA Sokolovskiy and EV Yashke, "Technology of mineral fertilizers and acids. Manual for technical schools", 2nd edition, revised and supplemented, Moscow: Chemistry, 1979, p. 384.

[0039] The technology for preparing the liquid phosphorus-containing fertilizer composition can be implemented by directly adding the inhibitor that forms sparingly soluble salts in a recommended proportion together with the liquid phosphorus-containing fertilizer to the liquid phosphorus-containing fertilizer under the condition of stirring the resulting mixture to form a uniform composition.

[0040] Example

[0041] The essence of the invention is illustrated by examples of the preparation of the compositions.

[0042] The composition of the granular fertilizer was prepared as described above, but under laboratory conditions (Table 1 gives a specific example illustrating the invention).

[0043] The compositions (first and second embodiments) are prepared from calculated amounts of ammonium phosphate or diammonium hydrogen phosphate, polymaleic acid, and polyamino polyether methylene phosphoric acid. The starting components are weighed on a balance. A slurry is prepared from the calculated amount of ammonium phosphate by adding a solution containing the calculated amounts of polymaleic acid and polyamino polyether methylene phosphoric acid in a 25-liter glass-lined reactor equipped with an agitator. The resulting mixture of ammonium phosphate, polymaleic acid, and polyamino polyether methylene phosphoric acid is then dried and granulated using a laboratory granulator.

[0044] The composition of the present invention (third embodiment) is made of calculated amounts of LCF NP 11:37, polymaleic acid and polyamino polyether methylene phosphoric acid. The starting components are weighed on a balance. LCF is filled in a 25-liter glass-lined reactor equipped with an agitator. Then, under stirring, polymaleic acid and polyamino polyether methylene phosphoric acid solutions are added. Stirring is continued until the components are fully mixed to form a uniform composition.

[0045] Table 1

[0046]

[0047] The efficacy of the composition in inhibiting the formation of sparingly soluble phosphates was determined based on measuring and comparing the amount of phosphate ions (not combined into sparingly soluble phosphates) in aqueous extracts of soil fertilized with a phosphorus-containing fertilizer with and without an added inhibitor of the formation of sparingly soluble salts.

[0048] The analysis of phosphate ions in aqueous soil extracts was carried out in accordance with EPR (Environmental Protection Regulation) F14.1:2:4.112-97 “Quantitative chemical analysis of water, determination of the weight concentration of phosphate ions in drinking water, surface water and wastewater by the ammonium molybdate photometric method”.

[0049] 1 g of soil (dried Rostov chernozem) sample, 10 ml of tap water, 1 ml of a solution of ammonium phosphate, diammonium hydrogen phosphate or LCF NP 11:37 (30 g / 100 ml of water diluted in 1000 ml of water) and the calculated concentrations of polymaleic acid and polyaminopolyether methylenephosphoric acid were placed in a centrifuge tube with a lid, stored for 1 hour, and then centrifuged to separate the precipitate. The concentration of phosphate ions in the aqueous extract was then determined.

[0050] Similar measurements were carried out without the addition of polymaleic acid, without the addition of polyaminopolyether methylenephosphonic acid, and without the addition of inhibitors for the formation of sparingly soluble phosphates.

[0051] The test results are shown in Tables 2 to 10.

[0052] The tests also included the effect of inhibitors of the formation of sparingly soluble phosphates on the release of available phosphorus from the soil by dissolving previously formed phosphates in the soil in the absence of phosphate fertilizers.

[0053] The test results are shown in Tables 11 to 13.

[0054] Since the primary purpose of the present invention is to maintain a maximum amount of available phosphorus (not bound as insoluble salts) in the soil during the plant growing season, a practical benefit of the present invention is increased crop yields in the field.

[0055] Scientific literature reveals exact values ​​of chemical elements removed from the soil in terms of the amount of agricultural product produced; see, for example, L.Yu.Ryzhikh and A.I.Lipatnikov, “Methodological Guide for Practical Exercises in Fertilizer system in crop rotations”, Kazan Federal University, Institute of Ecology and Nature Management, Department of Soil Science, Kazan, 2018.

[0056] According to the studies presented in this application, when using the proposed composition, the concentration of available phosphate ions in the soil increases to 1225.36% when using LCF, to 807.87% when using ammonium phosphate and to 793.93% when using diammonium phosphate. This is ensured by the action of a mixture of inhibitors forming sparingly soluble phosphates, and by the synergistic effect due to the dissolution of salts consisting of metal phosphates previously formed in the soil.

[0057] Therefore, under the same tillage and planting cultivation conditions, the actual yield is significantly increased in practice according to the element removal table per unit yield.

[0058] The most important factors determining the selection of additional components are their availability, relatively low cost, efficiency of use and environmental safety. According to the applicant, in addition to expanding the range of fertilizers, the claimed composition will currently be in great demand because it will significantly increase the efficiency of use of phosphorus-containing granular and liquid fertilizers, which will lead to an increase in crop yield and quality, and will also improve the efficiency of agricultural production. In the applicant's opinion, the composition of the present invention can meet the long-standing need for a tool for this purpose.

[0059] Table 2 Results of efficiency determination of granular fertilizers based on ammonium phosphate

[0060]

[0061] Table 3 Results of efficiency determination of granular fertilizers based on ammonium phosphate

[0062]

[0063] Table 4 Results of efficiency determination of granular fertilizers based on ammonium phosphate

[0064]

[0065] Table 5 Efficiency determination results of granular fertilizers based on diammonium phosphate

[0066]

[0067] Table 6 Results of efficiency determination of granular fertilizers based on diammonium phosphate

[0068]

[0069] Table 7 Results of efficiency determination of granular fertilizers based on diammonium phosphate

[0070]

[0071] Table 8 Efficiency measurement results of liquid compound fertilizer

[0072]

[0073] Table 9 Efficiency measurement results of liquid compound fertilizer

[0074]

[0075] Table 10 Efficiency measurement results of liquid compound fertilizer

[0076]

[0077] Table 11 Results of determination of the efficiency of inhibitors in soil without phosphate fertilizer application

[0078]

[0079]

[0080] Table 12 Results of determination of the efficiency of inhibitors in soil without phosphate fertilizer application

[0081]

[0082] Table 13 Results of determination of the efficiency of inhibitors in soil without phosphate fertilizer application

[0083]

Claims

1. A composition of a phosphorus-containing fertilizer in granular form, comprising a phosphorus-containing fertilizer and a functional additive, the composition comprising, in wt. %: 。 2. The composition according to claim 1, characterized in that Phosphorus-containing granular fertilizers are ammonium phosphate or diammonium phosphate.

3. A composition of a phosphorus-containing fertilizer in the form of a homogeneous mixture, comprising a liquid phosphorus-containing fertilizer and a functional additive, the composition comprising, in wt. %: 。 4. The composition according to claim 3, characterized in that The liquid phosphorus-containing fertilizer is a liquid compound fertilizer.

Images