Method for obtaining mixture of complexing agents for water softening

Abstract

FIELD: water softening agents.SUBSTANCE: method for obtaining a mixture of complexing agents for water softening involves the sequential introduction of acidic components to prepare a mixed-ligand mixture of organic acids. In this case, while stirring, citric acid, aminoacetic acid and succinic acid are added to water at a temperature of 40-60 °C sequentially until completely dissolved, obtaining a homogeneous solution. The homogeneity of the solution is controlled visually by the absence of sediment and stratification for at least 24 hours after preparation. The resulting concentrate is used for subsequent dilution with water to obtain working solutions.EFFECT: ensures the production of an environmentally friendly mixture of biologically active organic acids with complexing properties for water softening.4 cl, 1 dwg, 5 ex

Description

[0001] The present invention can be used for water softening. Organic acids such as succinic, citric, and aminoacetic (glycine) acids are bioactive ligands and have a broad spectrum of activity. The use of these acids makes the production of mixed-ligand complex compounds based on them a pressing issue.

[0002] In the work [1], research was conducted to study the effect of organic acids (succinic, malic, citric and oxalic) on the productivity and grain quality of spring soft wheat in the conditions of the Omsk Irtysh region. It was found that seed treatment with oxalic acid solutions (10 -3 M; 10 -5 M) and malic acid (10 -3 M) did not have a significant effect on the productivity of spring soft wheat. When pre-sowing seed treatment with malic acid (10 -5 M) an increase of 0.18 t / ha of grain was obtained. An increase of 0.21-0.22 t / ha was noted in the variants of seed treatment with citric acid (10 -3 M; 10 -7M) and succinic acid (10 -7 M). The maximum yield in the experiment was obtained in the variant of treating seeds with succinic acid at a concentration of 10 -3 M yielded 3.56 t / ha of grain, with an increase of 0.29 t / ha compared to the control. The increase from pre-sowing seed treatment in this variant, combined with fertilizer application, was 0.59 t / ha, which is 20% higher than in the control variant.

[0003] Amino acids activate growth mechanisms after salt stress and low temperatures, increase pollen fertility and fruit set, enhance nutrient absorption and resistance to pests and diseases [1, 2], etc. It has been found that plants and animals absorb natural α-acids, including citric, succinic, and aminoacetic acids, faster and better. These acids can be used to construct proteins with an optically active L-configuration. L-α-amino acids (e.g., aminoacetic acid) are easily absorbed by plants and are quickly incorporated into their own metabolism. "D-forms of amino acids are relatively rare in nature," "as metabolic products of lower organisms" [3].

[0004] The benefit of citric acid for vegetable crops stems from the fact that phosphorus fertilizers are citrate-soluble. Consequently, phosphorus salts, which are difficult for seedling roots to access, are easily dissolved in citric acid, a tribasic carboxylic acid, converting them into forms bioavailable to the absorptive roots. Furthermore, it has been scientifically proven that adding a citric acid solution to the soil stimulates all energy processes occurring in plants. Thus, ordinary food-grade citric acid dissolves phosphates, effectively energizing tomatoes.

[0005] Simultaneously with the conversion of phosphorus salts, the nutrient solution also mobilizes other chemical elements necessary for active tomato fruiting: calcium, iron, copper, manganese, zinc, and other micronutrients previously added to the soil but inactivated due to various chemical processes. Thus, even a single irrigation of tomatoes at the roots with a citric acid solution significantly improves the mineral nutrition of the bushes and leads to an increase in the yield of nightshade crops by up to 25%.

[0006] Succinic acid is one of the most common plant growth stimulants [4]. This acid is a universal intermediate metabolite of the tricarboxylic and dicarboxylic acid cycle (the Krebs cycle), formed by oxidative decarboxylation from α-ketoglutaric (oxaloacetic) acid. It has two main effects on plants. The first is stimulating (increasing yield), the second is a protective effect on plants that have been exposed to various stressors [5, 6]. When succinic acid is added, there is an increase in the biomass growth of wheat, potato, cucumber, and valerian seedlings, the growth of the root system is stimulated, and germination and yield are improved. The use of relatively small doses (10 mg / l) of succinic acid transfers the energy metabolism in plants to a new steady state, in which metabolic processes proceed more intensively [6-8].

[0007] In terms of price and quality, succinic acid and its salts are affordable growth regulators that can be used for pre-sowing seed treatment and for treating vegetative plants. Since excess succinic acid is used by plants and microorganisms as a nutrient, overdosing on this substance is not dangerous. This product helps stabilize the natural microflora of the soil, which is especially important for restoring fertility and cleaning up areas contaminated with toxic organic matter [9].

[0008] Currently, glycine occupies a leading position among amino acids widely used in plant growing. It is often used to create a variety of amino chelate fertilizers, which are a combination of amino acids and chelated nutrients. The use of amino acids, including glycine, represents a more sustainable approach to safe production compared to the use of chemical fertilizers.

[10] . Exogenous application of amino acids in many crops has been shown to improve plant growth and productivity compared to unfertilized controls. Glycine can stimulate plant growth and development, and the formation of their storage organs. Treatment with an aqueous glycine solution increases productivity, improves stress resistance, and enhances the adaptive capacity of plants [10-12].

[0009] Methods for using the above-mentioned acids in various combinations in the medical field are known. The patent application (RU 2011150901, A61K 9 / 10, published September 20, 2013) describes an antifungal composition for topical application to the nail, containing approximately 1%-20% of a diol component and approximately 0.1%-4% of an organic acid-based component. Citric and / or lactic acid are used as organic acids.

[0010] The patent (RU patent 2748698, A61K 8 / 362, published on 05 / 28 / 2021) provides compositions containing combinations of organic acids and methods for using them in the field of medicine, namely a method for increased destruction of a biofilm, which includes applying a composition containing succinic acid, aconitic acid and a carrier to a surface having a biofilm, wherein said succinic acid and aconitic acid are present in the composition in a ratio of succinic acid to aconitic acid from 0.9:1 to 40:1 by weight, where the surface is an oral surface selected from the surfaces of one or more teeth, gum surfaces, combinations of two or more of them.

[0011] A disadvantage of the well-known analogue is the use of expensive aconitic acid, which is an intermediate product in the Krebs cycle during citrate dehydration. It is likely possible to replace this acid with citric acid, which is equally potent and half the cost.

[0012] It is possible to use mixtures based on organic acids in obtaining a flushing liquid for combating deposits and extending the service life of heating system pipelines (patent RU 2518094, C11D 1 / 83, published on 10.06.2014). The proposed flushing liquids for heating systems contain either a solution of 1-3 wt.% citric acid, 0.03-0.05 wt.% hydrochloric acid and 0.05-0.5 wt.% chitosan modified with isobutyric acid containing a methylpyrazole group, or 1-3 wt.% citric acid, 0.1-0.15 wt.% sulfuric acid solution and 0.05-0.5 wt.% chitosan modified with isobutyric acid containing a methylpyrazole group.

[0013] A variant of flushing liquid for internal water pipes is known, which increases the solubility of iron oxides, zinc oxides and ensures sterilization. The flushing liquid for the internal water pipe contains 5-10 wt.% citric acid, 1-10 wt.% oxalic acid, 1-10 wt.% malic acid, 0.1-1 wt.% phosphoric acid, 5-15 wt.% hydrochloric acid, 1-2 wt.% hydrogen peroxide, and 0.01-0.1 wt.% ascorbic acid. The solution is obtained by mixing the components with water at room temperature to a total weight of 100 wt.% (patent KR 100808373, C11D 3 / 3947, published on February 27, 2008).

[0014] The disadvantages of known patents are the complexity of the compositions of these compounds, their low durability and the destructive effect on the pipeline metal due to the presence of aggressive inorganic acids in the composition.

[0015] The patent (RU 2814330, C11D 7 / 08, published on 28.02.2024) describes an invention for washing equipment in the chemical, food, pharmaceutical and other industries. The acidic non-foaming technical detergent has the following composition, wt.%: citric acid - 50-55; oxalic acid - 0.5-1.0; oxyethylidene diphosphonic acid - 0.5-1.0; water - the rest. The invention provides for the simultaneous removal of inorganic and organic contaminants, eliminating the need to use a large volume of detergents, eliminating the effect of the hardness of the wash water, is environmentally friendly, and prevents the redeposition of washed deposits on the surface being cleaned. All components of the product are complexing in relation to mineral contaminants of felts and meshes of paper and cardboard machines.

[0016] From the listed examples of the production and use in science, technology, agriculture, and medicine of mixtures of compounds based on succinic, citric, and aminoacetic acids, it can be concluded that increasing the complexity of the complexing composition leads to a greater positive effect when applied compared to compounds based on a single acid. However, the patents do not describe a mixed-ligand complexing mixture based on three acids—succinic, citric, and aminoacetic.

[0017] The closest method to the claimed method for producing a mixture of organic acids is (patent RU 2041629, A01N 59 / 16, published August 20, 1995) the synthesis of a composition of transition metals with dissimilar ligands, characterized in that mixed-ligand complexes of transition metals are used as the biologically active base, in which one of the ligands has physiological functions (citric acid), and the other ligand is the starting product of porphyrin biosynthesis (glycine). The resulting composition is used as a plant fertilizer to enhance their vital functions. This patent also considers the complication of the composition with the additional introduction of a solution of a manganese(II) complex with pyridoxamine (vitamin B6) and succinic acid into the previously mentioned mixture of iron(III) and copper(II) complexes. An effective influence of the mixed-ligand complex of biogenic metals containing vitamins on the growth of vegetative organs of tomatoes and the depth of root penetration was observed.The height of the stems of the experimental plants, compared to the control, 28 days after emergence was 1.5 times greater, and the length of the root was 1.7 times greater.

[0018] The disadvantages of this method include the complexity of the microelement composition, which increases the cost of the target product, and the labor-intensive nature of the process. The patent does not provide an example of the production and use of a mixture of the above organic acids without microelements, but it does provide a detailed, evidence-based explanation of their growth-promoting properties when used individually.

[0019] The objective of the present invention is to create and use a method for obtaining an environmentally safe mixture of biologically active organic acids with complexing (chelating) properties for softening water.

[0020] The technical result of the invention consists in developing the use of a method for obtaining a stable chelating composition based on organic acids that is non-toxic to plants and animals, with the possibility of its individual use and as a basis for softening water.

[0021] To achieve the technical result of the application, the method for obtaining a mixture of complexing agents for softening water includes the sequential introduction of acidic components to prepare a mixed-ligand mixture of organic acids, characterized in that an aqueous concentrate is first prepared, for which citric acid, aminoacetic acid and succinic acid are sequentially introduced into water at a temperature of 40-60 °C with stirring until complete dissolution, obtaining a homogeneous solution with the following ratio of components in the concentrate, mass%:

[0022] citric acid - 37.5-60.0

[0023] Aminoacetic acid - 0.1-2.8

[0024] Succinic acid - 0.1-2.8

[0025] water - the rest,

[0026] The homogeneity of the solution is visually controlled for the absence of sediment and stratification for at least 24 hours after preparation, and the resulting concentrate is used for subsequent dilution with water to obtain working solutions used to soften water by neutralizing hardness, stabilizing the pH of the treated water in the range of 5.0-6.5 and preventing the binding of glyphosate with calcium and magnesium ions.

[0027] In the claimed method, the concentrate is prepared at a pH of 2.0-3.5.

[0028] The prepared concentrate is stored at a temperature of 0-25 °C for at least 30 days before use without sediment or change in transparency.

[0029] To soften water, the prepared concentrate is added to the treated water in an amount of 0.5-1.0 l per 1000 l of treated water, ensuring the binding of hardness ions and establishing the pH of the treated water in the range of 5.0-6.5.

[0030] The use of a ready-made chelating (complexing) concentrate of a mixture of organic acids in the production of various preparations can reduce the labor intensity of their production and improve their technological effectiveness.

[0031] Mixtures of organic acids proposed in the claimed method have passed an expert commission at the Siberian State Medical University of the Ministry of Health of the Russian Federation to assess acute toxicity after a single intragastric administration to mice.

[0032] The declared mixture does not exhibit acute toxicity at a dose of 5000 mg / kg and belongs to the 4th class of toxicity and hazard (low-toxic substances) (GOST 12.1.007-76).

[0033] Confirmation of the complexing properties of the declared acid mixture is possible by the spectrophotometric method due to the differences in the intensity of the absorption bands when mixing the test composition with a d-metal

[13] . For spectrophotometric studies, three solutions were prepared: 1 - ferrous sulfate; 2 - ferrous sulfate and 10% citric acid solution; 3 - ferrous sulfate and a mixture of citric: aminoacetic: succinic acids in a ratio of 13.4%: 1%: 1%. The mixture of organic acids was prepared by dilution from the declared concentrate. The concentration of ferrous sulfate in all solutions was 0.54 mol / l. The analysis was carried out on an EKROS PE 54400-UV spectrophotometer using a 12 mm thick quartz cuvette in the wavelength range of 310-800 nm relative to distilled water. The obtained spectra are shown in Figure 1.(Absorption spectra of solutions: 1 - ferrous sulfate; 2 - ferrous sulfate and 10% citric acid solution; 3 - ferrous sulfate and a mixture of citric: aminoacetic: succinic acids in the ratio 13.4%: 1%: 1%).

[0034] The claimed method for obtaining a mixture of complexing agents for softening water is illustrated by the following examples.

[0035] Example 1.

[0036] To prepare Composition 1 of the organic acid mixture, add 100 ml of water at room temperature (at least 15°C) to a measuring cup. Then, while stirring, add 65 g of citric acid, 4.85 g of glycine, and 4.85 g of succinic acid, pre-weighed on an analytical balance. The order of addition corresponds to the listed sequence. Stir until completely dissolved after each addition. Visual inspection is performed after each reagent addition. This solution is a concentrated mixture of organic acids.

[0037] The result was a composition with the following characteristics:

[0038] citric acid, % - 37.5

[0039] Aminoacetic acid, % - 2.8

[0040] succinic acid, % - 2.8

[0041] water - the rest.

[0042] Example 2.

[0043] To prepare Composition 2 of the organic acid mixture, add 100 ml of water at room temperature (at least 15°C) to a measuring cup. Then, while stirring, add 100 g of citric acid, 2.46 g of glycine, and 2.46 g of succinic acid, pre-weighed on an analytical balance. The order of addition corresponds to the listed sequence. Stir until completely dissolved after each addition. Visually inspect after each reagent addition. This solution is a concentrated mixture of organic acids.

[0044] The result was a composition with the following characteristics:

[0045] citric acid, % - 48.8

[0046] Aminoacetic acid, % - 1.2

[0047] succinic acid, % - 1.2

[0048] water - the rest.

[0049] Example 3.

[0050] To prepare Composition 3 of the organic acid mixture, add 100 ml of water at room temperature (at least 15°C) to a measuring cup. Then, sequentially add 130 g of citric acid, 1 g of glycine, and 1 g of succinic acid, pre-weighed on an analytical balance, while stirring. The order of addition corresponds to the listed sequence. Stir until completely dissolved after each addition. Visually inspect the solution after each reagent addition. This solution is a concentrated mixture of organic acids.

[0051] The result was a composition with the following characteristics:

[0052] Citric acid, % - 56.030

[0053] Aminoacetic acid, % - 0.431

[0054] succinic acid, % - 0.431

[0055] water - the rest.

[0056] Example 4.

[0057] To prepare Composition 4 of the organic acid mixture, add 100 ml of water, preheated to 60°C on a hotplate or in a water bath, to a heat-resistant measuring cup. Then, while stirring, add 300 g of citric acid, 0.08 g of glycine, and 0.08 g of succinic acid, pre-weighed on an analytical balance. The order of addition corresponds to the listed sequence. Stir until completely dissolved after each addition. Visually inspect after each reagent addition. This solution is a concentrated mixture of organic acids.

[0058] The result was a composition with the following characteristics:

[0059] Citric acid, % - 75

[0060] Aminoacetic acid, % - 0.02

[0061] succinic acid, % - 0.02

[0062] water - the rest.

[0063] Example 5.

[0064] To prepare Composition 5 of the organic acid mixture, add 100 ml of water, preheated to 60°C on a hotplate or in a water bath, to a heat-resistant measuring cup. Then, while stirring, add 300 g of citric acid, 0.08 g of glycine, and 0.08 g of succinic acid, pre-weighed on an analytical balance. The order of addition corresponds to the listed sequence. Stir until completely dissolved after each addition. Visually inspect after each reagent addition. This solution is a concentrated mixture of organic acids.

[0065] The result was a composition with the following characteristics:

[0066] Citric acid, % - 75

[0067] Aminoacetic acid, % - 0.02

[0068] succinic acid, % - 0.02

[0069] water - the rest.

[0070] The obtained spectra are shown in Figure 1.

[0071] Bibliography:

[0072] 1. Tsyganova N.A. Efficiency of using organic acids as growth stimulants in the cultivation of spring soft wheat in the forest-steppe zone of Western Siberia. Abstract. Moscow, 2022. - 18 p.

[0073] 2. Mladenova YI, Rotcheva S., Vinarova K. 1989. Changes of growth and metabolism of maize seedlings under NaCl stress and interfering effect of Siapton leaf organic fertilizer on the stress responses. In: 20th Ann. ESNA Meeting, Lunteren (NL), Oct. (poster).

[0074] 3. V.L. Kretovich, Biochemistry of Plants. Moscow: Higher School, 1986, p. 27

[0075] 4. G.N. Chupakhina, A.A. Romanchuk. Possible mechanism of stimulation of growth processes by succinic acid. Theoretical and applied aspects of biology. Kaliningrad, 1999, pp. 46-51.

[0076] 5. Shmalko, N.A. Biochemical processes during germination of amaranth grain / N. A. Shmalko / / Vestn. Kub. state technological University. - 1997. - No. 2. - P. 42-56.

[0077] 6. Nikitina, E.V. Succinic acid and its salts as individual antioxidants and genoprotectors / E.V. Nikitina, N.K. Romanova / / Vestn. Kazan technological University. - 2010. - No. 10. - P. 375-381.

[0078] 7. Succinic acid in medicine, food industry, agriculture: collection of scientific articles / Pushchino Scientific Center of the Russian Academy of Sciences [et al.]; scientific editors M.N. Kondrashova [et al.]. - Pushchino, 1997. - P. 219-231.

[0079] 8. The influence of succinic acid on the yield and quality of agricultural crops / Yu.E. Andrianova [et al.] / / Agrochemistry. - 1996. - No. 8 / 9. - P. 117-122.

[0080] 9. Effect of ultra-low doses of Krebs cycle intermediates on the growth and development of some dicotyledonous plants / A.L. Vereshchagin, V.V. Kropotkina / / Federal Education Agency, Biysk Technological Institute, Altai State Technical University named after I.I. Polzunov. - Biysk, 2010. - Chapter 1, § 2. - P. 11-22.

[0081] 10. Souri MK, Hatamian M. Aminochelates in plant nutrition: a review. J PlantNutr. 2019;42(1):67-78.

[0082] 11. Mohammadipour N, Souri MK. Beneficial effects of glycine on growth and leaf nutrient concentrations of coriander (Coriandrumsativum) plants. J Plant Nutr. 2019;42:1-8.

[0083] 12. Xiaochuang C, Chu Z, Lianfeng Z, Junhua Z, Hussain S, Lianghuan W, Qianyu J. Glycine increases cold tolerance in rice via the regulation of N uptake, physiological characteristics, and photosynthesis. PlantPhysiolBiochem. 2017;112:251-60.

[0084] 13. Skorik N.A., Korotchenko N.M., Study of the stability of violate complexes of some d- and f-metals / N.A. Skorik, N.M. Korotchenko / / Journal of Inorganic Chemistry. - 2012. - V. 57, No. 1 - P. 141-147.

Claims

1. A method for producing a mixture of complexing agents for softening water, comprising the sequential introduction of acidic components to prepare a mixed-ligand mixture of organic acids, characterized in that an aqueous concentrate is first prepared by sequentially introducing citric acid, aminoacetic acid, and succinic acid into water at a temperature of 40-60°C with stirring until complete dissolution, resulting in a homogeneous solution with the following ratio of components in the concentrate, mass %: citric acid - 37.5-60.0 aminoacetic acid - 0.1-2.8 succinic acid - 0.1-2.8 water is the rest, In this case, the homogeneity of the solution is visually monitored for the absence of sediment and stratification for at least 24 hours after preparation, and the resulting concentrate is used for subsequent dilution with water to obtain working solutions used to soften water by neutralizing hardness, stabilizing the pH of the treated water in the range of 5.0-6.5 and preventing the binding of glyphosate with calcium and magnesium ions.

2. The method according to paragraph 1, characterized in that the concentrate is prepared at a pH of 2.0-3.

5.

3. The method according to paragraphs 1, 2, characterized in that the prepared concentrate is stored before use at a temperature of 0-25°C for at least 30 days without precipitation or change in transparency.

4. The method according to paragraphs 1-3, characterized in that, to soften water, the prepared concentrate is introduced into the treated water in an amount of 0.5-1.0 l per 1000 l of treated water, ensuring the binding of hardness ions and establishing the pH of the treated water in the range of 5.0-6.5.

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