Composition for purifying blue-green algae and green algae in a reservoir

Abstract

The present invention relates to the technical field of disinfecting and purifying water reservoirs of blue and green algae. The composition for purifying blue and green algae from water, according to the present invention, comprises copper sulfate powder and a binder, i.e. a hydrophobic agent, including a hydrophobic agent melt as a binder, in the form of a high melting point triglyceride fraction, by adding the hydrophobic agent melt to the copper sulfate powder heated to a temperature of 60-70° to form a superhydrophobic coating with a contact angle of 155-165°, the composition ratio of the components being as follows: copper sulfate: 85-97 wt%, the hydrophobic agent melt in the form of a high melting point triglyceride fraction - the balance, then homogenized, incubated at a temperature of 65°C for no more than 5 minutes, cooled to room temperature, and the resulting mixture is ground to a dispersed state with a particle size of 50-250 microns.

Description

[0001] This invention relates to the technical field of disinfection and purification of cyanobacteria and green algae in reservoirs.

[0002] Compositions for purifying water storage tanks are known, including copper sulfate and excipients (CN104556477(A), cl.C02F1 / 28, 2015).

[0003] Compositions for sterilizing water storage tanks are also known (CN107473344(A), cl.C02F43 / 36, 2017), comprising copper sulfate and excipients.

[0004] The common drawbacks of known technical solutions are that the composition preparation process is complex, costly, and difficult, and the efficiency of purifying blue-green algae and green algae in large reservoirs is insufficient because the active substances do not remain on the water surface for a sufficient time to completely dissolve.

[0005] Known technical solutions include embodiments of compositions for the buoyancy diffusion of cyanobacteria and green algae in water purification (Russian Patent No. 2687929, cl.C02F 103 / 04, 2019), one embodiment of which is closest in technical essence to the subject of the present invention comprises an active substance in the form of copper sulfate powder, a flotation agent derived from saturated hydrocarbons, resin materials, waxes, natural or synthetic latexes and combinations thereof, such as sawdust or rosin, and an adhesive, i.e. hydrophobic agent To form a coating of active substances and swelling agents.

[0006] The method for preparing the composition includes the following steps:

[0007] - Mix all ingredients thoroughly;

[0008] -The mixture is then fed into a granulator with a diameter of 12 mm, which produces beads with a thickness of about 7 mm and a mass of about 500 mg.

[0009] Then, the beads are incubated in an oven at 115°C for 3 minutes, removed from the oven, cooled, and ground.

[0010] The advantage of the known technical solution is that all embodiments of the composition are buoyancy preparations of various bleaching agents, which reduce the number of cyanobacteria in the treated water.

[0011] However, the known technical solutions have the following drawbacks:

[0012] -Using chlorine-containing agents as active substances can lead to toxicity when applied in large quantities due to their short dissolution time;

[0013] - Use saturated hydrocarbons, resin materials, waxes, natural or synthetic latexes and combinations thereof that are partially or completely insoluble in water to pollute the reservoir after the active substances have lost their activity.

[0014] - Using a small amount of active substance, it dissolves within 15 hours, so the water must be treated multiple times, and the trace toxicity of blue-green algae cannot be eliminated;

[0015] - The complexity increases the cost of the composition.

[0016] The purpose of this invention is to provide a composition with an active substance content of at least 70%, which can remain on the water surface for a long time while maintaining solubility, and has minimal toxicity and pollution.

[0017] The technical advantage of the claimed solution is that it can remain on the water surface for a long time while maintaining solubility, with minimal toxicity and pollution, and reduced costs, thereby expanding the range of applications for compositions used to purify blue-green algae and green algae in water, and thus achieving a synergistic effect when cleaning large reservoirs.

[0018] The achieved technical effect is that the composition for purifying blue-green algae and green algae in water, comprising copper sulfate powder and a binder, i.e., a hydrophobic agent, according to the present invention, includes a hydrophobic agent melt as a binder, which is in the form of a high-melting-point triglyceride fraction. The hydrophobic agent melt is added to copper sulfate powder heated to 60-70°C to form a superhydrophobic coating with a contact angle of 155-165°C. The composition has the following component ratios (wt%):

[0019] Copper sulfate: 85-97

[0020] Hydrophobic agent melt in the form of high-melting-point triglyceride fraction - balance

[0021] Then mix them evenly, incubate at 65°C for no more than 5 minutes, cool to room temperature, and grind the resulting mixture into a dispersion with a particle size of 50-250 micrometers.

[0022] The novelty of this composition lies in the fact that, in order to achieve this technical effect, a hydrophobic agent melt in the form of a high-melting-point triglyceride fraction is used as a binder, and the surface is crystallized under certain thermal conditions and in the qualitative state of the components of the composition, thereby forming a superhydrophobic coating with a contact angle of 155-165°.

[0023] Scientific, technical, and patent literature does not offer a set of features to solve problems that previously known technical solutions could not. The fact that the prior art does not provide an invention with the same distinguishing technical features as the subject composition of this invention indicates that the composition meets the patentability criterion of "inventive step".

[0024] The required industrial applicability stems from the fact that the preparation of the composition is technically feasible and that it can be used to purify cyanobacteria and green algae in water.

[0025] The essence of this invention is illustrated by the accompanying drawings, wherein... Figure 1 (a) schematically shows the arrangement of copper sulfate powder treated with a hydrophobic melt relative to the fluid; (b) is view A; Figure 2 A drop of water is shown on the surface of copper sulfate powder after it has been treated with a hydrophobic melt. Figures 3.1-3.2 These are micrographs of copper sulfate powder particles after being treated with a hydrophobic agent melt (sample No. 4); Figure 4 This is the test result of sample number 4 in water; Figure 5 This is a photomicrograph of the pulverized sample No. 4; Figures 6.1-6.2 The image shows water on day 12 after treatment with the composition.

[0026] The provisional name for the composition used to purify cyanobacteria and green algae in a reservoir is "Vodagrad C".

[0027] The following components were used to obtain this composition:

[0028] 1. As an active substance (As): Copper sulfate (copper sulfate pentahydrate), is an inorganic compound, a copper sulfate salt with the chemical formula CuSO4. It is a non-volatile, odorless substance. It exists as a white powder, and in its anhydrous form, it is a highly hygroscopic substance. It also exists as transparent, non-hygroscopic blue crystals of various shades, in its hydrated form. Copper sulfate (II) is extremely soluble in water. The blue pentahydrate CuSO4·5H2O, i.e., copper sulfate pentahydrate, is obtained by crystallization from aqueous solution.

[0029] It has disinfecting, sterilizing and astringent properties.

[0030] 2. Use a hydrophobic melt in the form of a high-melting-point triglyceride fraction as a binder. A hydrophobic melt refers to its liquid state at a temperature between its critical melting point and boiling point.

[0031] The following criteria should be considered when selecting a hydrophobic agent for preparing the composition:

[0032] - The selected hydrophobic agent, or more specifically, the hydrophobic agent-based coating, must have a contact angle of not less than 90°;

[0033] - Hydrophobic agents must have a melting point of at least 25°C, because many solid fats (triglycerides) exhibit good hydrophobicity at such temperatures;

[0034] - Hydrophobic agents are low in cost;

[0035] - Hydrophobic agents must be safe.

[0036] A study shows that The palm oil-based emulsifiers for the food industry produced by (https: / / www.palsgaard.ru / sustainable-emulsifiers / emulsifier-overview / ) meet these requirements.

[0037] These emulsifiers are high-melting-point triglyceride fractions.

[0038] The preparation method of the composition for purifying cyanobacteria and green algae in a water storage tank is as follows.

[0039] When copper sulfate powder is added to water, it will settle to the bottom slowly or quickly, depending on the particle size, and then dissolve. To allow the powder to remain on the water surface, it is necessary to create a contact angle θ. e A superhydrophobic coating with a range of >150°. Due to this coating, an air layer 1 is formed between the surface of powder 2 and liquid 3, which effectively pushes the material to the surface of the water-air interface. Figure 1 Therefore, it can remain on the water surface for a long time.

[0040] Two main conditions need to be met to prepare a superhydrophobic coating:

[0041] 1. By crystallizing a coating from a melt, a dispersed (rough) surface structure, including nanoscale structures, is formed.

[0042] 2. Make the surface hydrophobic so that the contact angle value is greater than 90°.

[0043] To prepare the superhydrophobic coating, 85-97 grams of copper sulfate (copper sulfate pentahydrate) powder are added to every 100 grams of the composition. The mixture is heated uniformly to 60-70°C, and then a suitable amount of hydrophobic agent melt (palm oil-based food emulsifier) ​​is added to bring the composition to 100g. The temperature of the hydrophobic agent melt does not exceed 65°C, which is the midpoint between the critical melting point and boiling point. The heated hydrophobic agent melt powder is uniformly sprayed onto the surface of the copper sulfate using a spraying device, while being uniformly mixed and incubated for no more than 5 minutes, allowing the surface to crystallize at a temperature not lower than the melting point (55°C) of the palm oil-based food emulsifier (hydrophobic agent). The mixture is then cooled to room temperature. The resulting mixture is then ground to a particle size of 50-250 micrometers. The combination of copper sulfate powder (60-70°C), hydrophobic agent melt (65°C), and stirring and aging at a temperature lower than the melting point (55°C) of the palm oil-based food emulsifier for no more than 5 minutes is designed to provide uniform crystallization on the surface of the active agent powder.

[0044] The composition was prepared using the following equipment: a vertical mechanical stirrer (https: / / www.ika.com / ru / Products-Lab-Eq / Overhead-Stirrers-Agitator-Blender-Lab-mixer-csp-187 / ), an induction cooker, a stainless steel tank (10L capacity), and a temperature sensor. A hammer crusher was selected as the dispersing device. https: / / infelko.ru / drobilki / drobilki-molotkovye-molot-200-400.html The grinding parameters are selected (motor power: 1.5kW, feed rate of the pulverized material: not exceeding 200g / min, internal grid aperture: 2mm) so that the output powder particle size is 50-250 micrometers. The composition obtained in this way exhibits a superhydrophobic effect, characterized by a water contact angle of 155-165°, determined by the sliding of droplets on the resulting coating. Figure 2 If a water droplet rolls on the surface of a copper sulfate powder coating without being absorbed, the coating formation process is considered uniform.

[0045] To determine the optimal dosage of components in the composition, five melts with different contents of active material and hydrophobic agent were prepared. The water contact angle of the superhydrophobic coating and the dissolution time of the composition were determined by directly immersing the composition in water. The results are shown in Table 1.

[0046] Table 1. Experimental results for determining the water contact angle and dissolution time of the superhydrophobic coating.

[0047]

[0048] According to the data in the table, sample No. 4, with a copper sulfate content of 97% and a hydrophobic agent melt content of 3%, was observed to have the longest dissolution and retention time on the water surface. Since sample No. 4 was the most effective, only this sample is shown in the attached figure. Figure 4 The results showed that, due to gravity exceeding the Archimedes force, a small portion of the material in sample 4 (which clearly had a larger particle size) settled to the bottom. Furthermore, the solubility in water was not very high; the sample completely dissolved within 7 days.

[0049] Furthermore, analysis of the micrographs of sample 4 particles showed that a discrete coating had formed, with a thickness of 100 to 200 nanometers. Figures 3.1-3.2 ).

[0050] After analyzing the dispersibility of the initial copper sulfate pentahydrate and sample No. 4, the particle size was determined to be between 200 and 3000 micrometers. According to the inventors, such a particle size negatively impacts the buoyancy and solubility of the material; therefore, pulverizing sample No. 4 to a dispersibility range of 50 to 250 micrometers was deemed most effective. Particle size was controlled using a Klin fineness analyzer. http: / / www.defectoscop.ru / product84.htmlOptical images of sample No. 4 after pulverization are shown below. Figure 5 As shown.

[0051] To demonstrate the effectiveness of the subject composition, a pilot-scale test was conducted.

[0052] These experiments were conducted at the tomato gene collection laboratory of the All-Russian Institute of Nature Conservation (Krasnodar), a federally funded research institution.

[0053] Following the workflow, water samples from Lake Abrau were collected using a planktonic net (Cloth No. 78) in a body of water abundant with cyanobacteria (both blue-green and green algae). The top 1 meter of the biomass was filtered out. Over two weeks after incubation, the water containing the cyanobacteria was poured into 20-liter analytical cups, and the composition was added at the consumption rate according to Table 2 to assess its impact on the cyanobacteria.

[0054] The experiment lasted for 4 to 8 weeks.

[0055] After application of the composition, algal cells formed colonies on the water surface and settled after a period of time. The water itself was a bright blue, fading as the product settled. It was further noted that at high doses, some product precipitated, while some remained on the surface. The algae color changed from bright green to grayish-brown. Within 12 days of applying the composition at the highest dose (20 kg / ha), no new colonies were observed forming on the bottom and walls of the container; the water became clear but remained pale yellow. Figures 6.1-6.2 ).

[0056] Table 2. Dosage of the composition in a reservoir model using biomaterials from Lake Abrau

[0057]

[0058] To assess the toxicity of the treated water, a bioassay using Lepidium sativum L. was employed.

[0059] Bioassays were performed three times for each sample in petri dishes. A filter paper tray was placed at the bottom of the petri dish. In each dish, 30 *Ligustrum lucidum* seeds were placed on the surface of the substrate. An identical filter paper tray was placed on top. Depending on the experimental variable, the filter paper in all petri dishes was moistened with water from the test samples. One sample containing distilled water served as a control for comparative analysis of plant parameters with other relevant samples. Seeds were germinated in a constant temperature incubator at 20–25°C for 7–10 days. At the end of the experiment, plant parameters were measured: seedling length, average dry weight, germination rate, and germination potential. The results are shown in Table 3.

[0060] Table 3. Measurement parameters of *Gnaphalium affine* formed under the influence of samples from Lake Ablau.

[0061]

[0062]

[0063] The studies conducted showed that, in the composition with the minimum variable, the sample containing residual cyanobacteria had severe sample toxicity, and the toxicity of the sample decreased as the composition dosage increased.

[0064] To confirm that the required technical solution meets the patentability criteria, a comparative analysis was conducted to determine the features that are novel relative to the prototype (Table 4) and the necessary technical features of the composition that can achieve the technical result (Table 5).

[0065] Table 4. Examining features to find novelty

[0066]

[0067] Table 5. Necessary technical features for examining the subject technical solution

[0068]

[0069] Therefore, based on the results obtained from the pilot-scale test (Tables 1, 2, and 3) and the examination of the characteristics (Tables 4 and 5), it can be concluded that the subject composition exhibits high efficiency in purifying cyanobacteria and green algae in the reservoir.

Claims

1. A composition for purifying cyanobacteria and green algae in water, comprising copper sulfate powder and a binder, characterized in that, The composition includes a hydrophobic melt as a binder, in the form of a high-melting-point triglyceride fraction, which is added to copper sulfate powder heated to 60-70°C to form a superhydrophobic coating with a contact angle of 155-165°. The composition has the following component ratio: copper sulfate: 85-97 wt%, hydrophobic melt in the form of a high-melting-point triglyceride fraction: balance, then uniformly mixed, incubated at 65°C for no more than 5 minutes, cooled to room temperature, and the resulting mixture is ground to a dispersion with a particle size of 50-250 micrometers.

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