Stabilizer for organic water-soluble fertilizer and application thereof

Abstract

The invention discloses a stabilizer for an organic water-soluble fertilizer and application of the stabilizer, and belongs to the field of auxiliaries. The stabilizer comprises water and a solvent addition material, the water and the solvent addition material can be mutually dissolved to form hydrogen bonds, and the ratio of the refractive index of the stabilizer to the refractive index of the organic addition material in the organic water-soluble fertilizer is 0.9-1.1. According to a Van der Waals force formula, the influence of the Van der Waals force on the stability of the organic liquid fertilizer is reduced by utilizing the mechanism that the refractive indexes of the solute and the solvent are equal or approximately equal to enable the Van der Waals force to be equal to or approximately zero, so that the stability of the organic liquid fertilizer is realized.

Description

Technical Field

[0001] The invention belongs to the field of adjuvants, and in particular relates to a stabilizer for organic water-soluble fertilizers and application thereof. Background Art

[0002] The information disclosed in this background technology section is only intended to enhance the understanding of the overall background of the invention, and should not necessarily be regarded as an admission or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art.

[0003] Organic water-soluble fertilizers are widely used and have obvious effects. They can not only provide inorganic nutrients required by crops, but also provide organic nutrients required by crops. Organic additives in organic water-soluble fertilizers, such as amino acids, humic acid, alginic acid, etc., are effective in promoting nutrient absorption, increasing fruit quality, and crop resistance. However, due to the wide variety of organic additives, large differences in hydrophilicity, isoelectric points, and pH tolerance ranges, especially when the liquid fertilizer has a high salt content, not only is the workload large in the process of screening and configuring liquid fertilizers, but after being placed for a period of time, the organic additives in the liquid fertilizer are particularly prone to flocculation and sedimentation under the action of van der Waals gravity, which greatly affects the stability of the organic liquid fertilizer. Summary of the invention

[0004] In order to overcome the deficiencies in the prior art, the object of the present invention is to provide a stabilizer for organic water-soluble fertilizers and an application thereof. According to the van der Waals gravitational formula, the present invention reduces the influence of van der Waals force on the stability of organic liquid fertilizer by utilizing the mechanism that the refractive indexes of solute and solvent are equal or approximately equal so that the van der Waals force is equal to or approximately zero, thereby achieving the stability of the organic liquid fertilizer.

[0005] The principles used in the present invention are as follows:

[0006] The root cause of flocculation, stratification, sedimentation and other problems of organic additives is van der Waals gravity, and the formula of van der Waals gravity is as follows:

[0007]

[0008] The above formula 1 and formula 2 are mentioned in reference (Ninham, BW, and VA Parsegian. 1970. Van der Waals forces: special characteristics in lipid-water systems and a general method of calculation based on the Lifshitz theory. Biophys. J. 10: 646–674.) and Van der Waals Forces published by Cambridge University Press in 2005. vdw is the van der Waals force, d w represents the thickness of the hydration layer, d a represents the thickness of the water zone separating the hydrophobic layer, d h represents the thickness of the carbon-hydrogen core of the hydrophobic material. A represents the Hamark constant, which is composed of the zero-frequency contribution (A V＝0 ) and non-zero frequency contribution (A V>0 )(Formula 2). K is the Boltzmann constant, which is 1.380649×10 -23 J / K, T is the absolute temperature, ∈1 and ∈2 are the dielectric constants of the solute and solvent at zero frequency, respectively. h is Planck's constant, which is 6.63×10 -34 J×s,v e is the absorption frequency. For visible light, it is the frequency of dominant ultraviolet absorption (about 1.7-2.4×10 16 rad / s), n1 and n2 are the refractive indices of the solute and solvent respectively, a1 is the radius of the solute molecule, and r is the distance.

[0009] where hv e >>kT, so the present invention only considers the second part of formula 2. That is, when the refractive indexes of the solute and the solvent are close (n1≈n2), the Hammark constant A is close to zero, and the van der Waals force in formula 1 is also close to zero or even equal to zero. When the van der Waals force is close to zero or even equal to zero, the gravitational force is minimal, which will greatly reduce the flocculation, stratification, sedimentation and other problems of the organic additive materials caused by the van der Waals force.

[0010] The refractive index of water in organic water-soluble fertilizers is n2, which is equal to 1.333, while the refractive index of common pure organic additives such as glycine is about 1.42, the refractive index of sodium alginate of different molecular weights is 1.35-1.45, and the refractive index of potassium humate is about 1.73. The higher the refractive index of the organic additive, the greater the deviation of the refractive index of the solute and the solvent, the greater the van der Waals attraction, and the more unstable the fertilizer. Therefore, we need to change the refractive index of the solvent, add polyols, small molecule sugars, small molecule organic acid compounds, phenolic acid compounds, etc. to the water to form a mixed solvent as a stabilizer, increase the refractive index of the solvent, and reduce the deviation of the refractive index of the solute and the solvent. Solvent additives must meet two conditions: 1) high refractive index, which can increase the refractive index of the solvent, and the refractive index of the pure product is not less than 1.45; 2) can form hydrogen bonds with water molecules to become a stable mixed solvent. From the perspective of safety, carbohydrates are the best. At present, the best ones are glycerol (propylene glycol) and sorbitol, and glycerol is preferred.

[0011] In order to achieve the above object, the technical solution of the present invention is:

[0012] In a first aspect, the present invention provides a stabilizer for organic water-soluble fertilizers, the stabilizer comprising water and a solvent additive material, the water and the solvent additive material being mutually soluble to form hydrogen bonds, and the ratio of the refractive index of the stabilizer to the organic additive material in the organic water-soluble fertilizer is 0.9-1.1.

[0013] It should be noted that the refractive index of the above-mentioned organic additive is the refractive index of the pure organic additive, that is, the refractive index of the organic additive with 100% content.

[0014] Preferably, for low refractive index solutes (such as amino acids), the ratio range can be narrowed to 0.95-1.05.

[0015] In one or more embodiments, the refractive index of the solvent additive material is not less than 1.45, preferably between 1.45-1.8, and more preferably between 1.45-1.74. The higher the refractive index, the better, and the lower the amount, but the highest refractive index of existing materials does not exceed 1.8, so the upper limit is 1.74.

[0016] According to NYT3831-2021dz-General Requirements for Organic Water-soluble Fertilizers, organic water-soluble fertilizers are liquid or solid water-soluble fertilizers containing biostimulant ingredients, which are made from organic resources such as free amino acids, humic acid, seaweed extracts, chitosan, polyglutamic acid, polyaspartic acid, molasses, low-value fish and fermentation degradation products as the main raw materials, and are processed through physical, chemical and (or) biological processes, and appropriate amounts of large, medium and (or) trace elements are added according to the requirements of plant growth.

[0017] Therefore, in the present invention, the organic water-soluble fertilizer includes organic additives and inorganic additives. The organic additives include amino acids, humic acid, seaweed extracts, polyaspartic acid, molasses, low-value fish and fermentation degradation products. The seaweed extract is alginate, such as sodium alginate; the humic acid includes fulvic acid, such as potassium fulvic acid.

[0018] The inorganic additives include macroelements, medium elements and / or trace elements. The macroelements include nitrogen, phosphorus, potassium and other elements; the medium elements include calcium, magnesium and other elements; the trace elements include iron, manganese, zinc, boron, molybdenum and the like. When the fertilizer inorganic salt nutrients are completely dissolved into ions in water, their refractive index is similar to that of water and can be ignored. Therefore, the present invention only considers the refractive index of the organic additive when calculating the refractive index of the solute.

[0019] In one or more embodiments, the solvent additive material includes one or more of polyol compounds, small molecule sugar compounds, small molecule organic acid compounds, phenolic acid compounds and glycolipid compounds.

[0020] Preferably, the polyol compound includes one or more of propylene glycol, glycerol (glycerin), 1,3-butylene glycol, sorbitol, and polyethylene glycol 400; preferably one or more of glycerol (glycerin) and sorbitol; further preferably glycerol (glycerin).

[0021] Preferably, the small molecule carbohydrate compound includes one or more of glucose, galactomannan, D-mannitol and iota-carrageenan.

[0022] Preferably, the small molecule organic acid compound includes one or more of citric acid, malic acid, tartaric acid, oxalic acid, succinic acid, ascorbic acid and lactic acid.

[0023] Preferably, the phenolic acid compounds include one or more of caffeic acid, ferulic acid, gallic acid and tannic acid.

[0024] Preferably, the glycolipid compound comprises one or more of sophorolipids, rhamnolipids and mannolipids.

[0025] In one or more embodiments, the screening method for the stabilizer is:

[0026] (1) Measure or calculate the refractive index n2 of the mixed solvent (mixed solvent composed of water and solvent additive material) at different proportions using Formula 3;

[0027] (2) measuring the refractive index n1 of the organic additive in the organic water-soluble fertilizer, and calculating the refractive index range of the mixed solvent according to the mechanism that the refractive indexes of the solvent and the solute are equal or approximately equal in the van der Waals force formula, thereby calculating the concentration range of the organic additive according to formula 3;

[0028] (3) Select a mixed solvent composition having a refractive index similar to that in step (2) from the mixed solvent.

[0029] Among them, n 2混合 =n 水 *wt% (水) +n 甘油 *wt% (有机添加材料) (Formula 3).

[0030] In a second aspect, the present invention provides use of the above stabilizer in the preparation of organic water-soluble fertilizers.

[0031] In a third aspect, the present invention provides an organic water-soluble fertilizer, comprising the above-mentioned stabilizer, organic additives, inorganic additives and other chemically acceptable components.

[0032] One or some of the above technical solutions have the following advantages or beneficial effects:

[0033] The present invention is based on the van der Waals gravity formula and utilizes the mechanism that the solute and the solvent are equal or approximately equal to make the van der Waals gravity 0 or approximately 0, thereby avoiding the influence of the van der Waals gravity on the stability of the organic water-soluble fertilizer and achieving the stability of the organic water-soluble fertilizer. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] The accompanying drawings in the specification, which constitute a part of the present invention, are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations on the present invention.

[0035] Figure 1 This is a picture of the stabilizer obtained when adding materials using glycerol as a solvent in Example 1 of the present invention;

[0036] Figure 2 This is a picture of the stabilizer obtained when tannic acid is used as a solvent and materials are added in Example 5 of the present invention;

[0037] Figure 3 A comparison diagram of the stability effect of the glycerol-water stabilizer prepared by the present invention on the amino acid-containing liquid water-soluble fertilizer; wherein (a) is the effect of not adding a stabilizer (pure water) to the amino acid-containing liquid water-soluble fertilizer, and (b) is the effect of adding a stabilizer to the amino acid-containing liquid water-soluble fertilizer;

[0038] Figure 4The figure is a comparison of the stabilizing effect of the tannic acid-water stabilizer prepared by the present invention on the liquid water-soluble fertilizer containing humic acid; wherein (a) is the effect of not adding a stabilizer (pure water) to the liquid water-soluble fertilizer containing humic acid, and (b) is the effect of adding a stabilizer to the liquid water-soluble fertilizer containing humic acid;

[0039] Figure 5 This is a comparison chart of the stabilizing effect of the glycerol-water stabilizer prepared by the present invention on liquid water-soluble fertilizer containing alginate. DETAILED DESCRIPTION

[0040] In order to enable those skilled in the art to more clearly understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below in conjunction with specific embodiments.

[0041] Example 1

[0042] (1) Use an Abbe refractometer to measure or directly find out the refractive index of the additive material from the industrial product manual. It is miscible with water molecules. Since the refractive index is proportional to the concentration, the refractive index n2 of different mixed solvents can be directly calculated. Take glycerol as an example for solvent additives:

[0043] At 20°C, the refractive index of 100% water is 1.333, and the refractive index of 100% glycerol is 1.474. The refractive index of mixed solvents with different mass ratios of water and glycerol can be calculated by the following formula.

[0044] n 2混合 =n 水 *wt% (水) +n 甘油 *wt% (甘油)

[0045] For example, at 20°C, the refractive index of a mixed solvent of 90% water and 10% glycerol is n2 = 1.333*90% + 1.474*10% = 1.347

[0046] Table 1 Refractive index of mixed solvents with different mass ratios of water and glycerol (measured by Abbe refractometer at 20°C)

[0047] Glycerol mass fraction% Water mass fraction% Refractive Index 100 0 1.474 90 10 1.458 80 20 1.443 70 30 1.428 60 40 1.413 50 50 1.398 40 60 1.384 30 70 1.371 20 80 1.357 10 90 1.345 0 100 1.333

[0048] (2) Use Abbe refractometer to measure the refractive index of organic additives in organic water-soluble fertilizers. For example, the refractive index of a solution containing 10% glycine in amino acid water-soluble fertilizers is 1.342. The refractive index of 100% glycine can be adjusted according to the content of 1.42, n1 = 1.42. The refractive index range of the mixed solvent needs to be adjusted from 1.42*0.95 = 1.349 to 1.42*1.05 = 1.49. The refractive index of water is 1.333, and the refractive index of 100% glycerol is 1.474. If it cannot reach 1.49, the composition of the water and glycerol mixed solvent is: the concentration of added glycerol is 11.3-100%. The calculation is as follows:

[0049] n 2混合 =n 水 *wt% (水) +n 甘油 *wt% (甘油)

[0050] 1.349 = 1.333 * (1-wt% (甘油) )+1.474*wt% (甘油)

[0051] Wt% (甘油) =11.3

[0052] (3) Select a mixed solvent composition having a refractive index similar to that in step (2) from the mixed solvent.

[0053] Finally, when the organic additive material in the water-soluble organic fertilizer is amino acid, the main component of which is glycine, and the addition amount of free amino acid is 10%, the determined stabilizers are water and glycerol, and the content thereof cannot be less than 11.3%.

[0054] Figure 1 This is a picture of the stabilizer obtained when glycerol is used as the solvent to add materials in Example 1 of the present invention. The stabilizers of Examples 2-4 present the same effect as that of Example 1, and are all transparent solutions, so they are not shown again.

[0055] Example 2

[0056] The difference from Example 1 is that the solvent additive material is sorbitol. The refractive index of pure sorbitol is 1.46.

[0057] Table 2 Refractive index of mixed solvents with different mass ratios of water and sorbitol (measured by Abbe refractometer at 20°C)

[0058]

[0059]

[0060] Finally, when the organic additives in the water-soluble organic fertilizer are amino acids, mainly glycine, and the addition amount of free amino acids is 10%, the stabilizers determined are water and sorbitol, and the addition amount of sorbitol accounts for 14.6% and above of the mixed solvent.

[0061] Example 3

[0062] Different from Example 1, the solvent additive material is a small molecule sugar compound, mannose. The refractive index of pure mannose is 1.573. Note: Adding sugar to the amino acid-containing liquid water-soluble fertilizer is prone to Maillard reaction at high temperature. Therefore, the liquid fertilizer in this test cannot be heated.

[0063] Table 3 Refractive index of mixed solvents with different mass ratios of water and mannose (measured by Abbe refractometer at 20°C)

[0064] Mannose mass fraction% Water mass fraction% Refractive Index 70 30 1.497 60 40 1.473 50 50 1.449 40 60 1.425 30 70 1.401 20 80 1.377 10 90 1.353 0 100 1.333

[0065] Finally, when the organic additives in the water-soluble organic fertilizer are amino acids, mainly glycine, and the addition amount of free amino acids is 10%, the stabilizers are determined to be water and mannose, and the addition amount of mannose in the mixed solvent is 7.8%-65.8%.

[0066] Example 4

[0067] Different from Example 1, the solvent additive material is a small molecule organic acid compound, tartaric acid, for example, and the refractive index of pure tartaric acid is 1.586.

[0068] Table 4 Refractive index of mixed solvents with different mass ratios of water and tartaric acid (measured by Abbe refractometer at 20°C)

[0069] Tartaric acid mass fraction% Water mass fraction% Refractive Index 60 40 1.482 50 50 1.457 40 60 1.431 30 70 1.406 20 80 1.381 10 90 1.355 0 100 1.333

[0070] Finally, when the organic additive material in the water-soluble organic fertilizer is amino acid, mainly glycine, and the addition amount of free amino acid is 10%, the stabilizer is determined to be water and tartaric acid, and the addition amount of tartaric acid in the mixed solvent is 7.4%-62.5%.

[0071] Example 5

[0072] The difference from Example 1 is that the solvent additive material is phenolic acid compound-tannic acid. The refractive index of pure tannic acid is 1.704.

[0073] Table 5 Refractive index of mixed solvents with different mass ratios of water and tannic acid (measured by Abbe refractometer at 20°C)

[0074] Tannic acid mass fraction% Water mass fraction% Refractive Index 70 30 1.589 60 40 1.552 50 50 1.515 40 60 1.477 30 70 1.440 20 80 1.403 10 90 1.366 0 100 1.333

[0075] Finally, when the organic additive material in the water-soluble organic fertilizer is amino acid, the main component of which is glycine, and the addition amount of free amino acid is 10%, the determined stabilizer is water and tannic acid, and the content of tannic acid in the mixed solvent is 6.2%-43.1%.

[0076] Example 6

[0077] The difference from Example 1 is that the solvent additive material is a glycolipid compound, sophorolipid, for example. The refractive index of pure sophorolipid is 1.484.

[0078] Table 6 Refractive index of mixed solvents with different water and sophorolipid mass ratios (measured by Abbe refractometer at 20°C)

[0079] Sophorolipid mass fraction % Water mass fraction% Refractive Index 50 50 1.406 40 60 1.390 30 70 1.375 20 80 1.360 10 90 1.345 0 100 1.333

[0080] Finally, when the organic additive material in the water-soluble organic fertilizer is an amino acid whose main component is glycine, and the addition amount of free amino acids is 10%, the determined stabilizer is water and sophorolipids, and the sophorolipid content in the mixed solvent is 12.58%-55% (the solubility of sophorolipids in water is up to 55%).

[0081] Example 7

[0082] Different from Example 1, the organic additive in the organic water-soluble fertilizer is replaced with potassium humate, and the refractive index of potassium humate is 1.736. Potassium humate has a high refractive index, so the refractive index of the mixed solvent should be in the range of 1.561-1.907.

[0083] Finally, when the organic additive material in the water-soluble organic fertilizer is potassium humate, the addition amount of potassium humate is 3%. The stabilizer is determined to be water and tannic acid, and the content of tannic acid in the mixed solvent is 61.72% or more.

[0084] Example 8

[0085] The difference from Example 1 is that the organic additive amino acid in the organic water-soluble fertilizer is replaced by sodium alginate, the refractive index of sodium alginate is 1.45, and the refractive index of the mixed solvent should be in the range of 1.377-1.47.

[0086] Finally, when the organic additive material in the water-soluble organic fertilizer is alginic acid, the amount of alginic acid added is 2%. The stabilizers are determined to be water and glycerin, and the glycerin content in the mixed solvent is 31.2% or more.

[0087] Example 9

[0088] Different from Example 1, the organic additive amino acid in the organic water-soluble fertilizer is replaced by polyaspartic acid, the refractive index of which is 1.525. The refractive index of polyaspartic acid is relatively high, so the refractive index of the mixed solvent should be in the range of 1.373-1.677.

[0089] Finally, when the organic additive material in the water-soluble organic fertilizer is polyaspartic acid, the addition amount of polyaspartic acid is 10%, the stabilizer is determined to be water and glycerol, and the glycerol content in the mixed solvent is 28.4% or more.

[0090] When the refractive index of the solute and the mixed solvent is equal or approximately equal, the flocculation, precipitation or stratification of organic additives such as amino acids, humic acid and sodium alginate caused by van der Waals forces can be greatly avoided, thereby improving the stability of organic liquid fertilizers.

[0091] Comparative Example 1

[0092] The difference from Example 1 is that the solvent additive material is an amino acid compound. In pure water solvent, the solvent refractive index n2 = 1.333, amino acid liquid fertilizer-medium element type (containing amino acid powder 410g / L, calcium nitrate 150g / L), after being placed for 24 hours, flocculent precipitation appears, and its technical effect is as follows Figure 3 As shown in (a), the glycerol-water stabilizer in Example 1 is still a homogeneous solution after being placed for one month. Figure 3 As shown in (b).

[0093] Comparative Example 2

[0094] Unlike Example 8, no stabilizer was added, the solvent was pure water only, and the solvent refractive index n2 = 1.333. After the alginate liquid fertilizer (sodium alginate content 20g / L, urea content 200g / L) was placed for 12 hours, flocculent suspension was generated in the solution, and the solution became turbid. However, the alginate liquid fertilizer added with stabilizer in Example 8 was still clear and transparent after being placed for 30 days. Figure 5 shown.

[0095] Stability test:

[0096] Amino acid liquid fertilizer-medium element type (including amino acid powder 410g / L, calcium nitrate 150g / L), humic acid-containing macro-element liquid fertilizer (including potassium fulvic acid 80g / L, urea 200g / L, potassium dihydrogen phosphate 15g / L), alginic acid liquid fertilizer (sodium alginate content 20g / L, urea content 200g / L), after adding stabilizer (see Figure 3-Figure 5 ), at 20°C, it remains a uniform solution after 30 days, while flocculation, sedimentation and turbidity have already occurred in pure water solution.

[0097] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A stabilizer for organic water-soluble fertilizers, characterized in that: The stabilizer comprises water and solvent additives, the water and solvent additives are mutually soluble to form hydrogen bonds, and the refractive index ratio of the stabilizer to the organic additives in the organic water-soluble fertilizer is 0.9-1.

1.

2. The stabilizer according to claim 1, characterized in that The ratio of the refractive index of the stabilizer to that of the organic additive in the organic water-soluble fertilizer is 0.95-1.

05.

3. The stabilizer according to claim 1, characterized in that The refractive index of the solvent additive material is not less than 1.45, preferably between 1.45 and 1.

8.

4. The stabilizer according to claim 1, characterized in that The organic additives include amino acids, humic acid, seaweed extracts, polyaspartic acid, molasses, low-value fish and fermentation degradation products; Preferably, the seaweed extract is alginate; Preferably, the humic acid comprises fulvic acid.

5. The stabilizer according to claim 1, characterized in that The solvent additive material includes one or more of polyol compounds, small molecule sugar compounds, small molecule organic acid compounds, phenolic acid compounds and glycolipid compounds.

6. The stabilizer according to claim 5, characterized in that The polyol compound includes one or more of propylene glycol, glycerol, 1,3-butylene glycol, sorbitol, and polyethylene glycol 400; preferably one or more of glycerol and sorbitol; more preferably glycerol.

7. The stabilizer according to claim 5, characterized in that The small molecule carbohydrate compound includes one or more of glucose, galactomannan, D-mannitol and iota-carrageenan.

8. The stabilizer according to claim 5, characterized in that The small molecule organic acid compound includes one or more of citric acid, malic acid, tartaric acid, oxalic acid, succinic acid, ascorbic acid and lactic acid; Preferably, the phenolic acid compounds include one or more of caffeic acid, ferulic acid, gallic acid and tannic acid; Preferably, the glycolipid compound includes one or more of sophorolipids, rhamnolipids, and mannolipids.

9. Use of the stabilizer according to any one of claims 1 to 8 in the preparation of organic water-soluble fertilizers.

10. An organic water-soluble fertilizer, characterized in that: The invention comprises the stabilizer according to any one of claims 1 to 8, organic additives, inorganic additives and other chemically acceptable components.

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