A water-soluble fertilizer containing bamboo vinegar and a preparation method thereof

Abstract

The present application relates to the technical field of fertilizer, in particular to a water-soluble fertilizer containing bamboo vinegar and a preparation method thereof, based on 100 parts by mass, comprising the following components: refined bamboo vinegar 15 to 25 parts, wherein the refined bamboo vinegar is obtained by collecting the 80 to 120 DEG C fraction of the middle layer supernatant of bamboo wood dry distillation crude bamboo vinegar under reduced pressure distillation, the mass fraction of acetic acid is 8 to 12%, and the mass fraction of phenolic compounds is 2 to 4%; potassium humate 8 to 12 parts, wherein the mass fraction of humic acid in the potassium humate is not less than 55%. The organic acid in the refined bamboo vinegar and the potassium humate form a supramolecular complex, which significantly improves the chelation ability and water solubility of the humic acid to the nutrient elements, the nutrient elements exist in soluble ionic state and chelated state, and the generation of phosphate precipitate and hydroxide precipitate is avoided.

Description

Technical Field

[0001] This invention relates to the field of fertilizer technology, specifically to a water-soluble fertilizer containing bamboo vinegar and its preparation method. Background Technology

[0002] Bamboo vinegar is a liquid product obtained by condensing and recovering the gases produced during the high-temperature carbonization of bamboo. It contains nearly 300 kinds of natural organic compounds, including organic acids, alcohols, ketones, aldehydes, esters, and trace amounts of phenols and alkaline components. Bamboo vinegar has multiple functions such as promoting plant root and germination, inhibiting bacteria and repelling insects, and improving soil, and has broad application prospects in the agricultural field.

[0003] Water-soluble fertilizers are multi-element, compound, fast-acting fertilizers that can completely dissolve in water. They have advantages such as adjustable formulations and high absorption efficiency, and can be applied through irrigation or foliar spraying to achieve integrated water and fertilizer management. Combining bamboo vinegar with water-soluble fertilizers, which provides both nutrient supply and biological activity regulation, has become an important direction in the research and development of water-soluble fertilizer technology.

[0004] CN108046926A discloses a high-nutrient water-soluble fertilizer, formulated with 40 to 70 parts bamboo vinegar, 10 to 30 parts amino acids, 5 to 18 parts glucose, and various trace element sulfates and matrine, which has the functions of promoting growth and repelling and killing insects. However, the amount of bamboo vinegar used in this solution is too high, and metal ions in bamboo vinegar are prone to precipitation in a strongly acidic environment, resulting in insufficient water solubility and storage stability. Furthermore, it does not address the synergistic effect between bamboo vinegar and humic acid.

[0005] CN116675576A discloses an amino acid water-soluble fertilizer, formulated with 50 to 55 parts wood vinegar, 10 to 20 parts amino acids, 10 to 20 parts base fertilizer, and 5 to 10 parts amphoteric surfactant, which has both fertilizer and antibacterial functions. However, this formulation uses a large amount of unrefined wood vinegar, and the tar and heavy components affect the stability of the system. It also lacks humic acid and slow-release synergistic ingredients, resulting in limited foliar absorption.

[0006] CN105985188A discloses a root-applied liquid fertilizer for rice, prepared with 40 to 50 parts bamboo vinegar, 4.5 to 5.5 parts potassium humate, 0.1 to 3.6 parts potassium hydroxide, and macro- and micro-elements. The pH of the bamboo vinegar is first adjusted to 8.0 to 12.0 with potassium hydroxide before adding potassium humate. Although this method combines bamboo vinegar with potassium humate, adjusting the pH to an alkaline range significantly reduces the antibacterial activity of phenolic substances in the bamboo vinegar under alkaline conditions. Furthermore, some micro-elements are prone to precipitating hydroxides under alkaline conditions. It also lacks slow-release synergistic components, and the utilization efficiency of nutrient elements needs improvement.

[0007] Therefore, the existing technology still has the following shortcomings: the high dosage of bamboo vinegar leads to high cost and excessive acidity; the contradiction between the strong acidity of bamboo vinegar and the stability of nutrient elements has not been effectively resolved; the synergistic effect mechanism of organic acids and humic acid in bamboo vinegar has not been revealed and utilized; there is a lack of slow-release enhancement methods, resulting in insufficient foliar absorption rate and fertilizer effect persistence. Summary of the Invention

[0008] The primary objective of this invention is to provide a water-soluble fertilizer containing bamboo vinegar and its preparation method.

[0009] A further objective of this invention is to provide a water-soluble fertilizer containing bamboo vinegar, comprising, based on 100 parts by weight, the following components: 15 to 25 parts of refined bamboo vinegar, wherein the refined bamboo vinegar is obtained by distilling the middle layer of crude bamboo vinegar obtained from dry distillation of bamboo, allowing it to settle, and collecting the fraction at 80 to 120°C under reduced pressure; the acetic acid content is 8 to 12% by weight, and the phenolic compound content is 2 to 4% by weight; and 8 to 12 parts of potassium humate, wherein the humic acid content in the potassium humate is not less than 55% by weight.

[0010] 2 to 4 parts polyglutamic acid, wherein the molecular weight of polyglutamic acid is 500,000 to 1,000,000 Daltons; 21 to 34 parts macronutrient fertilizer; 3 to 6 parts mesonutrient fertilizer; 1 to 3 parts micronutrient fertilizer; 5 to 10 parts amino acid solution; 0.5 to 2 parts pH adjuster; and the remainder deionized water; the pH of the water-soluble fertilizer containing bamboo vinegar solution is 5.0 to 6.5.

[0011] Preferably, the macro-element fertilizer comprises a mixture of urea, potassium dihydrogen phosphate and potassium nitrate, wherein, by mass, 10 to 16 parts of urea, 6 to 10 parts of potassium dihydrogen phosphate and 5 to 8 parts of potassium nitrate.

[0012] Preferably, the medium-element fertilizer comprises a mixture of sugar alcohol calcium and sugar alcohol magnesium, with 2 to 3.5 parts by weight of sugar alcohol calcium and 1 to 2.5 parts by weight of sugar alcohol magnesium.

[0013] Preferably, the micronutrient fertilizer comprises a mixture of EDTA chelated zinc, EDTA chelated iron and boric acid, wherein, by weight, 0.5 to 1.2 parts of EDTA chelated zinc, 0.3 to 0.8 parts of EDTA chelated iron and 0.3 to 0.6 parts of boric acid.

[0014] Preferably, the pH adjuster is potassium hydroxide.

[0015] Preferably, the mass fraction of free amino acids in the amino acid solution is not less than 40%.

[0016] A method for preparing the water-soluble fertilizer containing bamboo vinegar includes the following steps:

[0017] Step 1: Add the refined bamboo vinegar liquid to the reaction vessel, and add a pH adjuster while stirring to adjust the pH of the system to 5.0 to 6.5;

[0018] Step 2: Heat to 45 to 55°C, add potassium humate, and stir until completely dissolved;

[0019] Step 3: Add polyglutamic acid and stir until completely dissolved;

[0020] Step 4: Add each component of the macro-element fertilizer in sequence and stir until completely dissolved;

[0021] Step 5: Cool down to 35 to 40°C, add medium-element fertilizer, and stir until completely dissolved;

[0022] Step 6: Add trace element fertilizer and stir until completely dissolved;

[0023] Step 7: Add amino acid solution and stir well; Step 8: Filter, cool to room temperature, and fill.

[0024] Preferably, the stirring speed in step one is 200 to 400 r / min, and the stirring speed in steps two and three is 300 to 500 r / min.

[0025] Preferably, in step two, the temperature is raised to 45-55℃ and the stirring and dissolving time is 15 to 25 minutes, and in step five, the temperature is lowered to 35-40℃.

[0026] Preferably, a 200-mesh filter is used in step eight.

[0027] Compared with the prior art, the beneficial effects of the present invention are:

[0028] 1. This invention forms a supramolecular complex between the organic acids in refined bamboo vinegar and potassium humate, which significantly improves the chelating ability and water solubility of humic acid for nutrients. The nutrients exist in soluble ionic and chelated states, avoiding the formation of phosphate and hydroxide precipitation.

[0029] 2. This invention enhances the physical stability of the system by forming a hydrogen bond network between polyglutamic acid and the organic acids in refined bamboo vinegar. After 30 days of storage, the precipitation rate is no higher than 0.5%, and the leaf surface absorption rate reaches more than 83%.

[0030] 3. The phenolic substances in the refined bamboo vinegar of this invention work synergistically with the polyglutamic acid slow-release membrane to fight bacteria, reducing the incidence of gray mold to below 12%, which is more than 50% lower than the comparative rate without refined bamboo vinegar.

[0031] 4. The amount of refined bamboo vinegar liquid used in this invention is only 15 to 25 parts, which is much lower than the amount of 40 to 70 parts used in the prior art. This significantly reduces costs while ensuring the growth-promoting and antibacterial effects.

[0032] 5. This invention resolves the contradiction between the acidity of bamboo vinegar and the stability of nutrients by precisely controlling the pH to 5.0 to 6.5, within which both macro- and micro-elements exist in soluble form.

[0033] 6. The synergistic effect of this invention on crop yield is significant. Tomato yield is increased by more than 28% compared with the control group without refined bamboo vinegar, and the fruit quality is significantly improved. Detailed Implementation

[0034] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0035] The present invention achieves its objective based on the following mechanism.

[0036] (1) Low-molecular-weight organic acids in refined bamboo vinegar form supramolecular complexes with potassium humate: The refined bamboo vinegar is distilled under reduced pressure to collect the 80 to 120°C fraction, removing tar and high-boiling-point impurities, and enriching low-molecular-weight organic acids such as acetic acid, formic acid, and propionic acid, as well as phenolic active ingredients. These organic acid molecules can insert into the aggregate structure between humic acid molecules, and destroy the self-assembled aggregates of humic acid molecules through hydrogen bonding and van der Waals forces, thereby significantly increasing the exposure and dissociation of carboxyl and phenolic hydroxyl groups in humic acid molecules, thus enhancing the chelating ability of humic acid for metal ions.

[0037] Meanwhile, potassium humate buffers the strong acidity of refined bamboo vinegar to pH 5.0 to 6.5. Within this pH range, macroelements exist in soluble ionic form, and microelements exist in soluble chelated form, without producing phosphate or hydroxide precipitates. The synergistic effect of organic acids and potassium humate in refined bamboo vinegar differs from simple acid-base neutralization; instead, it forms an organic acid-humic acid supramolecular complex system. In this system, the organic acid acts as both a molecular solubilizer for humic acid and a promoter for the chelation of nutrients.

[0038] (2) Polyglutamic acid forms an intermolecular hydrogen bond network with organic acids in refined bamboo vinegar: The abundant carboxyl groups on the polyglutamic acid molecular chain form intermolecular hydrogen bonds with the hydroxyl and carboxyl groups of active ingredients such as acetic acid and phenols in refined bamboo vinegar, thus constructing a three-dimensional hydrogen bond network structure. This network structure enhances the physical stability of the water-soluble fertilizer system and inhibits the sedimentation and stratification of nutrient components during storage.

[0039] Meanwhile, polyglutamic acid forms a biofilm on the surface of plant leaves and roots. This biofilm has a slow-release effect on nutrients, prolonging the residence time of nutrients on the plant surface and improving the absorption efficiency of leaves and roots.

[0040] (3) Synergistic antibacterial effect of phenolic substances and polyglutamic acid in refined bamboo vinegar: Phenolic substances in refined bamboo vinegar have strong antibacterial activity under weakly acidic conditions of pH 5.0 to 6.5. The sustained release effect of polyglutamic acid biofilm on phenolic substances prolongs the contact time between phenolic substances and pathogens. The two synergistically enhance the antibacterial effect.

[0041] (4) The synergistic effect is not a simple functional superposition. The sustained release of polyglutamic acid membrane allows phenolic substances to act on pathogens in a low-concentration continuous release manner, avoiding the rapid degradation and loss of high-concentration one-time application, and changing the antibacterial effect from short-term contact sterilization to continuous antibacterial protection.

[0042] The three mechanisms mentioned above are interconnected and synergistic. The organic acids in refined bamboo vinegar promote the activation of humic acid, humic acid buffers acidity and provides a chelating environment for polyglutamic acid, and polyglutamic acid stabilizes the system and slowly releases nutrients and antibacterial components. The three together form a synergistic technical effect of nutrient supply, slow release enhancement, and antibacterial protection.

[0043] Raw material source:

[0044] Refined bamboo vinegar: Take the crude bamboo vinegar from the dry distillation of moso bamboo, which comes from a bamboo charcoal production enterprise in Zhejiang. After the crude bamboo vinegar is allowed to settle for 6 months, take the middle layer of clear liquid and distill it under reduced pressure of 0.08 MPa. Collect the fraction at 80 to 120℃ to obtain refined bamboo vinegar, which has an acetic acid mass fraction of 9.6%, a phenolic compound mass fraction of 3.1%, a pH of 2.9, and a density of 1.02 g / mL.

[0045] Potassium humate: sourced from a humic acid production enterprise in Xinjiang, with a humic acid mass fraction of 58%, a potassium mass fraction of 10%, and a particle size of 200 mesh.

[0046] Polyglutamic acid: sourced from a biotechnology company in Shandong, with a molecular weight of 800,000 Daltons and a purity of not less than 95%.

[0047] Urea: sourced from a chemical company in Sichuan, with a nitrogen mass fraction of 46.3% and a particle size of 0.8 to 2.5 mm.

[0048] Potassium dihydrogen phosphate: sourced from a phosphate chemical company in Hubei Province, with a phosphorus pentoxide mass fraction of 52% and a potassium oxide mass fraction of 34%.

[0049] Potassium nitrate: sourced from a chemical company in Shanxi Province, with a nitrogen mass fraction of 13.5% and a potassium oxide mass fraction of 46%.

[0050] Sugar alcohol calcium: sourced from an agrochemical company in Shandong, with a calcium content of 15% and a sugar alcohol content of 30%.

[0051] Sugar alcohol magnesium: sourced from an agrochemical company in Shandong, with a magnesium mass fraction of 10% and a sugar alcohol mass fraction of 25%.

[0052] EDTA-chelated zinc: sourced from a chemical company in Jiangsu Province, with a zinc mass fraction of 15%.

[0053] EDTA chelated iron: sourced from a chemical company in Jiangsu Province, with an iron mass fraction of 13%.

[0054] Boric acid: sourced from a chemical company in Liaoning Province, with a boron mass fraction of 17%.

[0055] Amino acid solution: sourced from a biotechnology company in Hebei Province, with a free amino acid mass fraction of 45%, obtained by enzymatic hydrolysis of soybean meal.

[0056] Potassium hydroxide: sourced from a chemical company in Shandong, with a purity of not less than 90%.

[0057] Deionized water: homemade, conductivity not higher than 10 μS / cm.

[0058] Coarse bamboo vinegar: Take coarse bamboo vinegar from dry distillation of moso bamboo. It has no refining treatment, contains 5.2% acetic acid, 1.8% phenolic compounds, pH 3.1, density 1.05 g / mL, and contains tar.

[0059] Example 1:

[0060] Raw material formula:

[0061] 20 parts by weight of refined bamboo vinegar, 9.6% acetic acid and 3.1% phenolic compounds, sourced from a bamboo charcoal company in Zhejiang; 10 parts by weight of potassium humate, 58% humic acid, sourced from a humic acid company in Xinjiang; 3 parts by weight of polyglutamic acid, molecular weight 800,000 Daltons, sourced from a biotechnology company in Shandong; 14 parts by weight of urea; 8 parts by weight of potassium dihydrogen phosphate; 7 parts by weight of potassium nitrate; 3 parts by weight of sugar alcohol calcium; 2 parts by weight of sugar alcohol magnesium; 1.0 part by weight of EDTA chelated zinc; 0.6 parts by weight of EDTA chelated iron; 0.5 parts by weight of boric acid; 8 parts by weight of amino acid solution, 45% free amino acids; 1.5 parts by weight of potassium hydroxide; deionized water to a total of 100 parts by weight.

[0062] Preparation process:

[0063] Step 1: Take 20 parts by weight of refined bamboo vinegar liquid and add it to a 200L stainless steel reactor. Stir at 300r / min and add 1.5 parts by weight of potassium hydroxide to adjust the pH of the system to 5.6.

[0064] Step 2: After adjusting the pH to 5.6 in Step 1, raise the temperature to 50°C, add 10 parts by weight of potassium humate, stir at 400 r / min for 20 min until completely dissolved;

[0065] Step 3: Add 3 parts by weight of polyglutamic acid, stir at 400 rpm for 15 minutes until completely dissolved;

[0066] Step 4: Add 14 parts by weight of urea, 8 parts by weight of potassium dihydrogen phosphate, and 7 parts by weight of potassium nitrate in sequence. Stir until completely dissolved after each addition before adding the next one. Stir for a total of 30 minutes.

[0067] Step 5: Cool down to 38°C, add 3 parts by weight of sugar alcohol calcium and 2 parts by weight of sugar alcohol magnesium, and stir for 15 minutes until completely dissolved;

[0068] Step 6: Add 1.0 part by weight of EDTA chelated zinc, 0.6 parts by weight of EDTA chelated iron, and 0.5 parts by weight of boric acid, and stir for 10 minutes until completely dissolved;

[0069] Step 7: Add 8 parts by weight of amino acid solution and stir for 10 minutes until homogeneous;

[0070] Step 8: Filter through a 200-mesh filter, cool to room temperature, and fill.

[0071] The water-soluble fertilizer prepared in this embodiment has a pH of 5.6, a tomato yield of 5236 kg / mu, and a vitamin C content of 19.8 mg / 100g.

[0072] Example 2:

[0073] Raw material formula:

[0074] 25 parts by weight of refined bamboo vinegar, 9.6% acetic acid and 3.1% phenolic compounds, sourced from a bamboo charcoal company in Zhejiang; 12 parts by weight of potassium humate, 58% humic acid, sourced from a humic acid company in Xinjiang; 4 parts by weight of polyglutamic acid, molecular weight 800,000 Daltons, sourced from a biotechnology company in Shandong; 16 parts by weight of urea; 10 parts by weight of potassium dihydrogen phosphate; 8 parts by weight of potassium nitrate; 3.5 parts by weight of sugar alcohol calcium; 2.5 parts by weight of sugar alcohol magnesium; 1.2 parts by weight of EDTA chelated zinc; 0.8 parts by weight of EDTA chelated iron; 0.6 parts by weight of boric acid; 10 parts by weight of amino acid solution, 45% free amino acids; 2.0 parts by weight of potassium hydroxide; deionized water to a total of 100 parts by weight.

[0075] Preparation process:

[0076] Step 1: Add 25 parts by weight of refined bamboo vinegar liquid to a 200L stainless steel reactor, stir at 300r / min, add 2.0 parts by weight of potassium hydroxide, and adjust the pH of the system to 5.4.

[0077] Step 2: After adjusting the pH to 5.4 in Step 1, raise the temperature to 50°C, add 12 parts by mass of potassium humate, stir at 400 r / min for 20 min until completely dissolved;

[0078] Step 3: Add 4 parts by weight of polyglutamic acid, stir at 400 rpm for 15 minutes until completely dissolved;

[0079] Step 4: Add 16 parts by weight of urea, 10 parts by weight of potassium dihydrogen phosphate, and 8 parts by weight of potassium nitrate in sequence. Stir until completely dissolved after each addition before adding the next one. Stir for a total of 30 minutes.

[0080] Step 5: Cool down to 38°C, add 3.5 parts by weight of sugar alcohol calcium and 2.5 parts by weight of sugar alcohol magnesium, and stir for 15 minutes until completely dissolved;

[0081] Step 6: Add 1.2 parts by weight of EDTA chelated zinc, 0.8 parts by weight of EDTA chelated iron, and 0.6 parts by weight of boric acid, and stir for 10 minutes until completely dissolved;

[0082] Step 7: Add 10 parts by weight of amino acid solution and stir for 10 minutes until homogeneous;

[0083] Step 8: Filter through a 200-mesh filter, cool to room temperature, and fill.

[0084] The water-soluble fertilizer prepared in this embodiment has a pH of 5.4, a tomato yield of 5487 kg / mu, and a vitamin C content of 21.3 mg / 100g.

[0085] Example 3:

[0086] Raw material formula:

[0087] 15 parts by weight of refined bamboo vinegar, 9.6% acetic acid and 3.1% phenolic compounds, sourced from a bamboo charcoal company in Zhejiang; 8 parts by weight of potassium humate, 58% humic acid, sourced from a humic acid company in Xinjiang; 2 parts by weight of polyglutamic acid, molecular weight 800,000 Daltons, sourced from a biotechnology company in Shandong; 10 parts by weight of urea; 6 parts by weight of potassium dihydrogen phosphate; 5 parts by weight of potassium nitrate; 2 parts by weight of sugar alcohol calcium; 1 part by weight of sugar alcohol magnesium; 0.5 parts by weight of EDTA chelated zinc; 0.3 parts by weight of EDTA chelated iron; 0.3 parts by weight of boric acid; 5 parts by weight of amino acid solution, 45% free amino acids; 0.5 parts by weight of potassium hydroxide; deionized water to a total of 100 parts by weight.

[0088] Preparation process:

[0089] Step 1: Add 15 parts by weight of refined bamboo vinegar liquid to a 200L stainless steel reactor, stir at 250r / min, add 0.5 parts by weight of potassium hydroxide, and adjust the pH of the system to 5.2.

[0090] Step 2: After adjusting the pH to 5.2 in Step 1, raise the temperature to 48°C, add 8 parts by mass of potassium humate, stir at 350 r / min for 25 min until completely dissolved;

[0091] Step 3: Add 2 parts by weight of polyglutamic acid, stir at 350 r / min for 15 min until completely dissolved;

[0092] Step 4: Add 10 parts by weight of urea, 6 parts by weight of potassium dihydrogen phosphate, and 5 parts by weight of potassium nitrate in sequence. Stir until completely dissolved after each addition before adding the next one. Stir for a total of 25 minutes.

[0093] Step 5: Cool down to 36°C, add 2 parts by weight of sugar alcohol calcium and 1 part by weight of sugar alcohol magnesium, and stir for 15 minutes until completely dissolved;

[0094] Step 6: Add 0.5 parts by weight of EDTA chelated zinc, 0.3 parts by weight of EDTA chelated iron, and 0.3 parts by weight of boric acid, and stir for 10 minutes until completely dissolved;

[0095] Step 7: Add 5 parts by weight of amino acid solution and stir for 10 minutes until homogeneous;

[0096] Step 8: Filter through a 200-mesh filter, cool to room temperature, and fill.

[0097] The water-soluble fertilizer prepared in this example has a pH of 5.2, a tomato yield of 4863 kg / mu, and a vitamin C content of 17.6 mg / 100g.

[0098] Comparative Example 1:

[0099] Raw material formula:

[0100] 20 parts by weight of deionized water to replace refined bamboo vinegar; 10 parts by weight of potassium humate, 58% humic acid, sourced from a humic acid company in Xinjiang; 3 parts by weight of polyglutamic acid, molecular weight 800,000 Daltons, sourced from a biotechnology company in Shandong; 14 parts by weight of urea; 8 parts by weight of potassium dihydrogen phosphate; 7 parts by weight of potassium nitrate; 3 parts by weight of sugar alcohol calcium; 2 parts by weight of sugar alcohol magnesium; 1.0 part by weight of EDTA chelated zinc; 0.6 parts by weight of EDTA chelated iron; 0.5 parts by weight of boric acid; 8 parts by weight of amino acid solution, 45% free amino acid; 0.2 parts by weight of potassium hydroxide; deionized water to bring the total to 100 parts by weight.

[0101] Preparation process:

[0102] Step 1: Add 20 parts by weight of deionized water to a 200L stainless steel reactor, stir at 300r / min, add 0.2 parts by weight of potassium hydroxide, and adjust the pH of the system to 6.2.

[0103] Step 2: Heat to 50℃, add 10 parts by weight of potassium humate, stir at 400 r / min for 20 min until completely dissolved;

[0104] Step 3: Add 3 parts by weight of polyglutamic acid, stir at 400 rpm for 15 minutes until completely dissolved;

[0105] Step 4: Add 14 parts by weight of urea, 8 parts by weight of potassium dihydrogen phosphate, and 7 parts by weight of potassium nitrate in sequence. Stir until completely dissolved after each addition before adding the next one. Stir for a total of 30 minutes.

[0106] Step 5: Cool down to 38°C, add 3 parts by weight of sugar alcohol calcium and 2 parts by weight of sugar alcohol magnesium, and stir for 15 minutes until completely dissolved;

[0107] Step 6: Add 1.0 part by weight of EDTA chelated zinc, 0.6 parts by weight of EDTA chelated iron, and 0.5 parts by weight of boric acid, and stir for 10 minutes until completely dissolved;

[0108] Step 7: Add 8 parts by weight of amino acid solution and stir for 10 minutes until homogeneous;

[0109] Step 8: Filter through a 200-mesh filter, cool to room temperature, and fill.

[0110] This comparative sample does not contain refined bamboo vinegar. The tomato yield is 3752 kg / mu, and the vitamin C content is 12.3 mg / 100g.

[0111] Comparative Example 2:

[0112] Raw material formula:

[0113] 20 parts by weight of refined bamboo vinegar, 9.6% acetic acid and 3.1% phenolic compounds, sourced from a bamboo charcoal company in Zhejiang; 10 parts by weight of deionized water replacing potassium humate; 3 parts by weight of polyglutamic acid, molecular weight 800,000 Daltons, sourced from a biotechnology company in Shandong; 14 parts by weight of urea; 8 parts by weight of potassium dihydrogen phosphate; 7 parts by weight of potassium nitrate; 3 parts by weight of sugar alcohol calcium; 2 parts by weight of sugar alcohol magnesium; 1.0 part by weight of EDTA chelated zinc; 0.6 parts by weight of EDTA chelated iron; 0.5 parts by weight of boric acid; 8 parts by weight of amino acid solution, 45% free amino acid content; 1.5 parts by weight of potassium hydroxide; deionized water to bring the total to 100 parts by weight.

[0114] Preparation process:

[0115] Step 1: Take 20 parts by weight of refined bamboo vinegar liquid and add it to a 200L stainless steel reactor. Stir at 300r / min and add 1.5 parts by weight of potassium hydroxide to adjust the pH of the system to 5.6.

[0116] Step 2: Heat to 50°C without adding potassium humate;

[0117] Step 3: Add 3 parts by weight of polyglutamic acid, stir at 400 rpm for 15 minutes until completely dissolved;

[0118] Step 4: Add 14 parts by weight of urea, 8 parts by weight of potassium dihydrogen phosphate, and 7 parts by weight of potassium nitrate in sequence. Stir until completely dissolved after each addition before adding the next one. Stir for a total of 30 minutes.

[0119] Step 5: Cool down to 38°C, add 3 parts by weight of sugar alcohol calcium and 2 parts by weight of sugar alcohol magnesium, and stir for 15 minutes until completely dissolved;

[0120] Step 6: Add 1.0 part by weight of EDTA chelated zinc, 0.6 parts by weight of EDTA chelated iron, and 0.5 parts by weight of boric acid, and stir for 10 minutes until completely dissolved;

[0121] Step 7: Add 8 parts by weight of amino acid solution and stir for 10 minutes until homogeneous;

[0122] Step 8: Filter through a 200-mesh filter, cool to room temperature, and fill.

[0123] This comparative study does not contain potassium humate, and the tomato yield is 4021 kg / mu, with a vitamin C content of 14.1 mg / 100g.

[0124] Comparative Example 3:

[0125] Raw material formula:

[0126] 20 parts by weight of refined bamboo vinegar, 9.6% acetic acid and 3.1% phenolic compounds, sourced from a bamboo charcoal company in Zhejiang; 10 parts by weight of potassium humate, 58% humic acid, sourced from a humic acid company in Xinjiang; 3 parts by weight of deionized water to replace polyglutamic acid; 14 parts by weight of urea; 8 parts by weight of potassium dihydrogen phosphate; 7 parts by weight of potassium nitrate; 3 parts by weight of sugar alcohol calcium; 2 parts by weight of sugar alcohol magnesium; 1.0 part by weight of EDTA chelated zinc; 0.6 parts by weight of EDTA chelated iron; 0.5 parts by weight of boric acid; 8 parts by weight of amino acid solution, 45% free amino acids; 1.5 parts by weight of potassium hydroxide; deionized water to bring the total to 100 parts by weight.

[0127] Preparation process:

[0128] Step 1: Take 20 parts by weight of refined bamboo vinegar liquid and add it to a 200L stainless steel reactor. Stir at 300r / min and add 1.5 parts by weight of potassium hydroxide to adjust the pH of the system to 5.6.

[0129] Step 2: Heat to 50℃, add 10 parts by weight of potassium humate, stir at 400 r / min for 20 min until completely dissolved;

[0130] Step 3: Do not add polyglutamic acid;

[0131] Step 4: Add 14 parts by weight of urea, 8 parts by weight of potassium dihydrogen phosphate, and 7 parts by weight of potassium nitrate in sequence. Stir until completely dissolved after each addition before adding the next one. Stir for a total of 30 minutes.

[0132] Step 5: Cool down to 38°C, add 3 parts by weight of sugar alcohol calcium and 2 parts by weight of sugar alcohol magnesium, and stir for 15 minutes until completely dissolved;

[0133] Step 6: Add 1.0 part by weight of EDTA chelated zinc, 0.6 parts by weight of EDTA chelated iron, and 0.5 parts by weight of boric acid, and stir for 10 minutes until completely dissolved;

[0134] Step 7: Add 8 parts by weight of amino acid solution and stir for 10 minutes until homogeneous;

[0135] Step 8: Filter through a 200-mesh filter, cool to room temperature, and fill.

[0136] This comparative sample does not contain polyglutamic acid, yields 4318 kg / mu of tomatoes, and contains 15.7 mg / 100g of vitamin C.

[0137] Comparative Example 4:

[0138] Raw material formula:

[0139] 55 parts by weight of wood vinegar, 5.0% acetic acid, 1.5% phenolic compounds (source: a wood vinegar company in Shandong); 15 parts by weight of amino acids, 42% free amino acids; 15 parts by weight of base fertilizer, including 8 parts by weight of potassium dihydrogen phosphate and 7 parts by weight of potassium nitrate; 8 parts by weight of cocamidopropyl betaine; 7 parts by weight of micronutrient fertilizer, including 4 parts by weight of boric acid and 3 parts by weight of EDTA chelated zinc; deionized water to bring the total to 100 parts by weight.

[0140] Preparation process:

[0141] According to the method disclosed in CN116675576A, amino acids and cocamidopropyl betaine are mixed at 38℃ in a mass ratio of 1:1.5 to obtain a mixed solution. Wood vinegar is added to the container, followed by the mixed solution, basic fertilizer and trace element fertilizer in sequence. The mixture is stirred evenly to obtain a water-soluble fertilizer.

[0142] This comparative sample was prepared according to the existing technology CN116675576A, with a tomato yield of 4105 kg / mu and a vitamin C content of 14.8 mg / 100g.

[0143] Comparative Example 5:

[0144] Raw material formula:

[0145] Bamboo vinegar (42 parts by weight, pH 3.0), sourced from a bamboo charcoal company in Zhejiang; potassium humate (4.5 parts by weight, humic acid content 58%), sourced from a humic acid company in Xinjiang; potassium hydroxide (2.1 parts by weight); fulvic acid (11 parts by weight); urea (13 parts by weight); ammonium dihydrogen phosphate (7 parts by weight); potassium nitrate (5 parts by weight); water-soluble silicon fertilizer (7 parts by weight, silicon dioxide content 40%); EDTA chelated zinc (1.1 parts by weight); sodium nitrophenolate (0.1 parts by weight); deionized water to a total of 100 parts by weight.

[0146] Preparation process:

[0147] According to the method disclosed in CN105985188A, the pH of the bamboo vinegar solution is first adjusted to 9.5 with potassium hydroxide, then potassium humate is added and completely dissolved at 55°C, fulvic acid is added and completely dissolved at 55°C, urea, ammonium dihydrogen phosphate, and potassium nitrate are added and completely dissolved at 55°C, water-soluble silicon fertilizer is added and completely dissolved at 55°C, EDTA chelated zinc is added and completely dissolved, sodium nitrophenolate is added and completely dissolved, filtered through a 200-mesh filter, and cooled to room temperature for filling.

[0148] This comparative sample was prepared according to the existing technology CN105985188A, with a pH of 9.5, a tomato yield of 3912 kg / mu, and a vitamin C content of 13.6 mg / 100g.

[0149] Comparative Example 6:

[0150] Raw material formula:

[0151] 20 parts by weight of coarse bamboo vinegar (replacing refined bamboo vinegar), containing 5.2% acetic acid, 1.8% phenolic compounds, and tar, sourced from a bamboo charcoal company in Zhejiang; 10 parts by weight of potassium humate (58% humic acid), sourced from a humic acid company in Xinjiang; 3 parts by weight of polyglutamic acid (800,000 Daltons molecular weight), sourced from a biotechnology company in Shandong; 14 parts by weight of urea; 8 parts by weight of potassium dihydrogen phosphate; 7 parts by weight of potassium nitrate; 3 parts by weight of sugar alcohol calcium; 2 parts by weight of sugar alcohol magnesium; 1.0 part by weight of EDTA chelated zinc; 0.6 parts by weight of EDTA chelated iron; 0.5 parts by weight of boric acid; 8 parts by weight of amino acid solution (45% free amino acids); 1.2 parts by weight of potassium hydroxide; and deionized water to a total of 100 parts by weight.

[0152] Preparation process:

[0153] Step 1: Add 20 parts by weight of crude bamboo vinegar to a 200L stainless steel reactor, stir at 300r / min, add 1.2 parts by weight of potassium hydroxide, and adjust the pH of the system to 5.6.

[0154] Step 2: Heat to 50℃, add 10 parts by weight of potassium humate, stir at 400 r / min for 25 min until completely dissolved;

[0155] Step 3: Add 3 parts by weight of polyglutamic acid, stir at 400 rpm for 15 minutes until completely dissolved;

[0156] Step 4: Add 14 parts by weight of urea, 8 parts by weight of potassium dihydrogen phosphate, and 7 parts by weight of potassium nitrate in sequence. Stir until completely dissolved after each addition before adding the next one. Stir for a total of 30 minutes.

[0157] Step 5: Cool down to 38°C, add 3 parts by weight of sugar alcohol calcium and 2 parts by weight of sugar alcohol magnesium, and stir for 15 minutes until completely dissolved;

[0158] Step 6: Add 1.0 part by weight of EDTA chelated zinc, 0.6 parts by weight of EDTA chelated iron, and 0.5 parts by weight of boric acid, and stir for 10 minutes until completely dissolved;

[0159] Step 7: Add 8 parts by weight of amino acid solution and stir for 10 minutes until homogeneous;

[0160] Step 8: Filter through a 200-mesh filter, cool to room temperature, and fill.

[0161] This comparative example uses coarse bamboo vinegar instead of refined bamboo vinegar. The tar and high-boiling-point impurities in coarse bamboo vinegar interfere with the supramolecular complexation of organic acids and humic acids. The low phenol content weakens the antibacterial effect. The tomato yield is 4387 kg / mu, and the vitamin C content is 16.0 mg / 100g.

[0162] Comparative Example 7:

[0163] Raw material formula:

[0164] 20 parts by weight of refined bamboo vinegar, 9.6% acetic acid and 3.1% phenolic compounds, sourced from a bamboo charcoal company in Zhejiang; 10 parts by weight of potassium humate, 58% humic acid, sourced from a humic acid company in Xinjiang; 3 parts by weight of polyglutamic acid, molecular weight 800,000 Daltons, sourced from a biotechnology company in Shandong; 14 parts by weight of urea; 8 parts by weight of potassium dihydrogen phosphate; 7 parts by weight of potassium nitrate; 3 parts by weight of sugar alcohol calcium; 2 parts by weight of sugar alcohol magnesium; 1.0 part by weight of EDTA chelated zinc; 0.6 parts by weight of EDTA chelated iron; 0.5 parts by weight of boric acid; 8 parts by weight of amino acid solution, 45% free amino acids; 3.8 parts by weight of potassium hydroxide; deionized water to a total of 100 parts by weight.

[0165] Preparation process:

[0166] Step 1: Add 20 parts by weight of refined bamboo vinegar liquid to a 200L stainless steel reactor, stir at 300r / min, add 3.8 parts by weight of potassium hydroxide, and adjust the pH of the system to 8.0.

[0167] Step 2: Heat to 50℃, add 10 parts by weight of potassium humate, stir at 400 r / min for 20 min until completely dissolved;

[0168] Step 3: Add 3 parts by weight of polyglutamic acid, stir at 400 rpm for 15 minutes until completely dissolved;

[0169] Step 4: Add 14 parts by weight of urea, 8 parts by weight of potassium dihydrogen phosphate, and 7 parts by weight of potassium nitrate in sequence. Stir until completely dissolved after each addition before adding the next one. Stir for a total of 30 minutes.

[0170] Step 5: Cool down to 38°C, add 3 parts by weight of sugar alcohol calcium and 2 parts by weight of sugar alcohol magnesium, and stir for 15 minutes until completely dissolved;

[0171] Step 6: Add 1.0 part by weight of EDTA chelated zinc, 0.6 parts by weight of EDTA chelated iron, and 0.5 parts by weight of boric acid, and stir for 10 minutes until completely dissolved;

[0172] Step 7: Add 8 parts by weight of amino acid solution and stir for 10 minutes until homogeneous;

[0173] Step 8: Filter through a 200-mesh filter, cool to room temperature, and fill.

[0174] In this comparative example, the pH was adjusted to 8.0. Under alkaline conditions, the antibacterial activity of phenols was significantly reduced and some trace elements produced hydroxide precipitates. The tomato yield was 4196 kg / mu, and the vitamin C content was 15.2 mg / 100g.

[0175] Performance testing and results analysis:

[0176] All raw materials used in this invention are tested for quality in accordance with current national and industry standards. The testing methods, implementation standards and limiting conditions for key indicators of each raw material are as follows, which are used to unify the raw material quality control standards and ensure batch consistency.

[0177] The refined bamboo vinegar used in this invention is prepared from the crude bamboo vinegar by dry distillation of moso bamboo. The preparation process is fixed as follows: the crude bamboo vinegar is left to stand and settle at room temperature for 6 months, the middle layer of clear liquid is separated and distilled under reduced pressure of 0.08MPa, and the fraction collected at 80℃-120℃ is the finished refined bamboo vinegar.

[0178] Wherein, the mass fraction of acetic acid and the mass fraction of phenolic compounds are detected by gas chromatography (GC), with reference to the general testing specifications for agricultural application of bamboo vinegar liquid; the pH of the finished refined bamboo vinegar liquid is measured by a laboratory acidimeter, and the density is measured by a pycnometer method. A qualified raw material is controlled to have an acetic acid mass fraction of 8%-12% and a phenolic compound mass fraction of 2%-4%. Except that the crude bamboo vinegar liquid is not refined by vacuum distillation, the remaining sampling and sedimentation methods are consistent with those of the refined bamboo vinegar liquid.

[0179] The mass fraction of humic acid in potassium humate is detected in accordance with the agricultural industry standard NY / T3161-2017 "Determination of Humic Acid in Organic Fertilizers", requiring the mass fraction of humic acid to be no less than 55%; the potassium element content is detected by flame photometry, and the raw material particle size is uniformly 200 mesh to ensure consistent dissolution performance.

[0180] The molecular weight of polyglutamic acid in polyglutamic acid is measured by gel permeation chromatography (GPC), and the molecular weight range is controlled to be 500,000-1,000,000 Daltons; the product purity is detected by high performance liquid chromatography, requiring the purity to be no less than 95%, and the raw material is stored in a sealed and light-shielded condition to avoid degradation of the polymer molecular chain.

[0181] The mass fraction of free amino acids in the amino acid liquid is implemented in accordance with the national standard GB / T30987-2014 "Determination of Free Amino Acids in Plants", and detected by liquid chromatography. The amino acid liquid used in the present invention requires the mass fraction of free amino acids to be no less than 40%, and the raw material is prepared by enzymatic hydrolysis of soybean meal.

[0182] For conventional fertilizers and auxiliary raw materials, macro-element raw materials such as urea, potassium dihydrogen phosphate, and potassium nitrate are tested for effective nutrient content in accordance with the corresponding national standards for chemical products; medium-element raw materials such as sugar alcohol calcium and sugar alcohol magnesium are tested for calcium, magnesium and sugar alcohol contents by complexometric titration; micro-element raw materials such as EDTA chelated zinc, EDTA chelated iron, and boric acid are tested for effective element contents by atomic absorption spectrophotometry and spectrophotometry respectively; potassium hydroxide is tested for purity in accordance with the national standard for industrial potassium hydroxide, requiring the purity to be no less than 90%; deionized water is tested by a conductivity meter, with the conductivity controlled to be ≤10 μS / cm.

[0183] General basic test conditions:

[0184] All field tests and laboratory detection tests of the present invention are carried out under uniform environmental conditions to eliminate the influence of environmental variables on the test results.

[0185] The test site is an open-air field, the soil type is loam, with uniform soil fertility and consistent irrigation and drainage conditions; during the test period, the field environmental temperature is 18°C-32°C, and the relative humidity is 60%-85%; the test crop is Zhongza No.9 tomato, and tomato seedlings with consistent growth, no diseases and insect pests, and similar plant heights are selected for transplanting.

[0186] All water-soluble fertilizer samples were filtered through a 200-mesh filter and then sealed and stored in the dark. The indoor sample storage temperature was kept constant at 25℃. All glassware, reaction equipment, and testing instruments used in the experiment were calibrated. Standard reagents, bacterial strains, and isotope reagents were all commercially available analytical grade. The water used in the experiment was self-made deionized water.

[0187] Detailed performance testing methods:

[0188] (1) Field agronomic traits, yield and fruit quality testing of tomatoes:

[0189] Experimental design: A randomized block design was used, with 3 replicates per experiment, each with a cell area of ​​20m². 2 Isolation zones were set up between plots to prevent water and fertilizer cross-contamination from interfering with the test results. The water-soluble fertilizer of this invention was applied 15 days after the tomato seedlings were transplanted. All samples were uniformly diluted 500 times and applied by root irrigation. The application cycle was once every 10 days, for a total of 5 applications. The daily water, fertilizer and pest and disease management in the field were kept completely consistent across all groups.

[0190] Plant height growth, single fruit weight, and yield per acre: During the tomato harvest season, 20 tomato plants were randomly selected from each plot to measure plant height and calculate the average plant height growth per plant; 30 mature tomato fruits were randomly picked to measure single fruit weight and the average value was taken; the actual fruit yield of each plot was calculated and converted into yield per acre.

[0191] Vitamin C content of fruit: The determination of vitamin C content was strictly carried out in accordance with the 2,6-dichlorophenolindophenol titration method in the national standard GB5009.86-2016 "National Food Safety Standard for Determination of Ascorbic Acid in Food". Each sample was measured in parallel three times, and the average value was taken as the final test result. The unit is mg / 100g.

[0192] (2) Root vitality test (TTC method):

[0193] Tomato root activity was determined using the triphenyltetrazolium chloride (TTC) reduction method. The procedure is as follows:

[0194] Sampling: Fresh tomato fibrous roots were randomly collected from each plot during the harvest season. The surface soil was washed off, and 0.5g of root samples were cut off.

[0195] Reaction treatment: Place the root samples in a test tube, add a mixture of 0.4% TTC solution and phosphate buffer, stain at 37°C in the dark for 1 hour, and then add sulfuric acid to terminate the reaction;

[0196] Extraction and determination: The red triphenylmethane generated by the reduction of the root system was extracted with ethyl acetate, and the absorbance was measured at a wavelength of 485 nm using a UV-Vis spectrophotometer. The TTC reduction amount was calculated by combining the standard curve.

[0197] Calculation method: Root activity = TTC reduction mass ÷ root sample mass ÷ reaction time, unit is mg / (g·h), and three parallel determinations are performed for each sample group.

[0198] (3) Detection of gray mold incidence:

[0199] Strain preparation: *Botrytis cinerea* was selected as the test pathogen and cultured at a constant temperature on PDA medium to prepare a concentration of 1×10⁻⁶. 5 Prepare a spore suspension of 1 spore / mL for later use;

[0200] Inoculation treatment: Three days after the last application of water-soluble fertilizer, spray the tomato plant leaves evenly with spore suspension to ensure that both the upper and lower surfaces of the leaves are moistened with the bacterial solution; maintain a high humidity environment in the field during the experiment to facilitate pathogen infection;

[0201] Statistical calculation: Seven days after inoculation, the total number of leaves and the number of diseased leaves of each group were counted. The incidence rate of gray mold was calculated as (number of diseased leaves ÷ total number of leaves) × 100%. A full survey of the entire plant was conducted in each treatment group, and the average value of the data from the three plots was taken.

[0202] (4) Leaf surface absorption rate detection ( 15 Ni isotope tracing method):

[0203] Using nitrogen-15 ( 15 N) Labeling urea to prepare tracer water-soluble fertilizer, and conducting foliar absorption rate testing:

[0204] Sample preparation: Add isotope-labeled urea to the corresponding water-soluble fertilizer according to the formula ratio and stir evenly;

[0205] Foliar spraying: Select healthy tomato functional leaves, spray a quantitative amount of the marked water-soluble fertilizer sample, and avoid rain or human touch within 48 hours after spraying;

[0206] Sampling and Testing: Leaves from the sprayed area were cut, unabsorbed fertilizer was washed off the surface, dried, pulverized, and then analyzed using an isotope mass spectrometer. 15 N abundance;

[0207] Calculation method: Leaf surface absorption rate = (Absorption rate within the leaf) 15 Total nitrogen ÷ Foliar spraying 15 (Total N) × 100%, with 5 parallel blades set up for each treatment group for testing.

[0208] (5) Storage stability (precipitation rate) test:

[0209] Take 500 mL of the prepared water-soluble fertilizer sample, put it into a sealed transparent container, and store it in a 25℃ constant temperature oven for 30 days. After the storage period, carefully separate the bottom precipitate, dry the precipitate to constant weight, and weigh it. The precipitation rate after 30 days of storage = (dry weight of precipitate ÷ total mass of water-soluble fertilizer sample) × 100%. Set up 3 parallel samples for each group of samples.

[0210] (vi) Nutrient element water solubility test:

[0211] The determination of the water-insoluble content and pH of water-soluble fertilizers shall be carried out in accordance with the agricultural industry standard NY / T1973-2010. The water-insoluble content in the water-soluble fertilizer shall be determined and the water solubility of nutrients shall be calculated. The water solubility of nutrients is calculated as follows: (total water-soluble nutrient content ÷ total nutrient content in fertilizer) × 100%.

[0212] (vii) Component synergistic effect verification test:

[0213] The samples for single-component, two-component, and three-component combinations were prepared according to the mass ratio of each component in Example 1, while the amount of other auxiliary materials and deionized water remained the same. The fertilizer dilution ratio, application frequency, and field management were exactly the same as those in the main tomato experiment. The plant height growth, yield per acre, and gray mold incidence rate of each group were measured to verify the synergistic effect between the components.

[0214] (viii) Comparison test of material addition order:

[0215] Based on the complete formula of Example 1, only the addition and pH adjustment order of refined bamboo vinegar, pH adjuster, and potassium humate were changed, resulting in three schemes:

[0216] Option 1 involves first adding potassium hydroxide to the refined bamboo vinegar solution to adjust the pH to 5.6, and then adding potassium humate.

[0217] Option 2 involves first adding potassium humate to the refined bamboo vinegar solution, and then adding potassium hydroxide to adjust the pH to 5.6.

[0218] Option 3 involves simultaneously adding potassium humate and potassium hydroxide to the refined bamboo vinegar solution and adjusting the pH to 5.6; all other process parameters, stirring speed, stirring time, temperature control, and filtration and filling procedures remain consistent with Example 1. After the preparation of the three sets of samples, tomato field trials, storage stability tests, and gray mold incidence rate statistics were conducted simultaneously to compare the effects of different addition sequences on product performance.

[0219] General parameters for the preparation process:

[0220] The entire process of preparing water-soluble fertilizer in this invention uses a 200L stainless steel reactor, and the stirring speed, stirring time, and temperature parameters of each step are standardized.

[0221] Step 1: Control the stirring speed to 200 r / min-400 r / min;

[0222] In steps two and three, the stirring speed should be controlled at 300 r / min-500 r / min.

[0223] Step 2: Heat to 50℃ as usual, and stir to dissolve potassium humate for 15-25 minutes.

[0224] Step 5: Cool down to 38℃ as usual;

[0225] The finished products are all filtered through a 200-mesh filter and cooled to room temperature before being filled. All process parameters are strictly followed in each example and comparative example.

[0226] Table 1. Results of tomato growth and yield tests:

[0227] Example 1 38.7 186.3 5236 19.8 Example 2 41.2 195.1 5487 21.3 Example 3 35.4 172.8 4863 17.6 Comparative Example 1 24.1 138.5 3752 12.3 Comparative Example 2 27.3 148.6 4021 14.1 Comparative Example 3 30.8 159.2 4318 15.7 Comparative Example 4 28.6 152.3 4105 14.8 Comparative Example 5 26.9 145.1 3912 13.6 Comparative Example 6 31.2 161.8 4387 16.0 Comparative Example 7 29.8 155.7 4196 15.2

[0228] Results analysis: In Examples 1 to 3, the tomato yield was 4863 to 5487 kg / mu, the vitamin C content was 17.6 to 21.3 mg / 100g, and the plant height increase was 35.4 to 41.2 cm. Comparative Example 1, without refined bamboo vinegar, had a yield of 3752 kg / mu, a decrease of 28.4% compared to Example 1, indicating that refined bamboo vinegar is an indispensable key component of this invention.

[0229] Comparative Example 2, which does not contain potassium humate, yielded 4021 kg / mu, a decrease of 23.2% compared to Example 1. This was due to the lack of the supramolecular complex effect of potassium humate and the organic acids in refined bamboo vinegar, resulting in a decrease in the chelation capacity of nutrients.

[0230] Comparative Example 3, which does not contain polyglutamic acid, yielded 4318 kg / mu, a decrease of 17.5% compared to Example 1, lacking the sustained-release synergistic effect and hydrogen bond network stabilizing effect of polyglutamic acid.

[0231] Comparative Example 4 did not contain potassium humate or polyglutamic acid, used 55 parts of unrefined wood vinegar, and had a yield of 4105 kg / mu, which was 21.6% lower than that of Example 1.

[0232] The pH of Comparative Example 5 was adjusted to 9.5. Under alkaline conditions, the antibacterial activity of phenols was lost and trace elements precipitated, resulting in a yield of 3912 kg / mu, which was 25.3% lower than that of Example 1.

[0233] Comparative Example 6 used coarse bamboo vinegar instead of refined bamboo vinegar. The tar and high-boiling-point impurities in the coarse bamboo vinegar interfered with the supramolecular complexation of organic acids and humic acids, and the low phenol content weakened the antibacterial effect. The yield was 4387 kg / mu, which was 16.2% lower than that of Example 1. This result proves that refined bamboo vinegar is not simply selected from coarse bamboo vinegar. The refining process removes the tar components that interfere with the supramolecular complexation and enriches the active organic acids and phenols. Without refining, the effect of this invention cannot be obtained.

[0234] Comparative Example 7 adjusted the pH to 8.0. Although the solubility of humic acid increased under alkaline conditions, the antibacterial activity of phenols decreased significantly under alkaline conditions, and some trace elements formed hydroxide precipitates. The yield was 4196 kg / mu, which was 19.9% ​​lower than that of Example 1. This result proves that the pH adjustment of the present invention to 5.0 to 6.5 is not a conventional optimization choice, but a necessary condition for the formation of organic acid-humic acid supramolecular complex. In this weakly acidic range, the contradiction between organic acid promoting the dissociation of humic acid and phenols maintaining antibacterial activity is synergistically overcome, which cannot be replaced by conventional acidic or alkaline conditions.

[0235] Table 2. Results of root vigor and antibacterial effect tests:

[0236] Example 1 1.87 8.3 89.6 0.3 Example 2 2.03 6.7 92.1 0.2 Example 3 1.62 11.2 83.5 0.5 Comparative Example 1 1.12 23.6 65.3 1.8 Comparative Example 2 1.28 18.7 72.8 2.3 Comparative Example 3 1.45 15.2 78.6 1.2 Comparative Example 4 1.31 17.3 74.2 1.5 Comparative Example 5 1.23 19.8 70.1 2.1 Comparative Example 6 1.48 14.6 79.3 0.8 Comparative Example 7 1.37 16.5 76.1 1.6

[0237] Results analysis: Root activity in Examples 1 to 3 ranged from 1.62 to 2.03 mg / (g·h), gray mold incidence rate ranged from 6.7% to 11.2%, leaf absorption rate ranged from 83.5% to 92.1%, and sedimentation rate ranged from 0.2% to 0.5% after 30 days of storage.

[0238] Comparative Example 1 showed a gray mold incidence rate of 23.6%, an increase of 184% compared to Example 1, with a leaf surface absorption rate of only 65.3%, indicating a severe deficiency in antibacterial protection and absorption promotion functions due to the lack of refined bamboo vinegar. Comparative Example 2 showed a precipitation rate of 2.3% after 30 days of storage, the highest among all samples, indicating a lack of the supramolecular complex of potassium humate and organic acids, resulting in the loss of chelated protection for nutrients and a significant decrease in storage stability.

[0239] Comparative Example 3 showed a leaf surface absorption rate of 78.6%, but lacked the sustained-release synergistic effect of the polyglutamic acid biofilm, resulting in a significantly lower leaf surface absorption rate than the Example.

[0240] The incidence rates of gray mold in Comparative Examples 4 and 5 were 17.3% and 19.8%, respectively, both significantly higher than those in the Example. The existing technical solution has not achieved the synergistic antibacterial effect of phenolic substances in refined bamboo vinegar and polyglutamic acid slow-release membrane.

[0241] Comparative Example 6 used coarse bamboo vinegar, and after 30 days of storage, the sedimentation rate was 0.8%. The tar components in the coarse bamboo vinegar led to a decrease in the physical stability of the system, the incidence of gray mold was 14.6%, and the low phenol content weakened the antibacterial effect.

[0242] Comparative Example 7 showed a gray mold incidence rate of 16.5%. Under alkaline conditions, the antibacterial activity of phenols was significantly reduced, and the leaf absorption rate was 76.1%. Some trace elements precipitated under alkaline conditions, affecting absorption. These results indicate that the synergistic effect of refined bamboo vinegar, potassium humate, and polyglutamic acid is key to the technical effectiveness of this invention; all three are indispensable, and the refining process and pH control range are unconventional choices.

[0243] Table 3. Results of the synergistic effect verification test:

[0244] Refined bamboo vinegar 28.5 3896 17.2 Potassium humate only 26.8 3712 20.5 Polyglutamic acid only 25.2 3568 21.8 Refined bamboo vinegar and potassium humate 33.6 4523 13.5 Refined bamboo vinegar and polyglutamic acid 31.7 4218 15.8 Potassium humate and polyglutamic acid 30.1 4086 16.3 The complete combination of the three components is Example 1. 38.7 5236 8.3

[0245] Results analysis: When using only a single component, plant height increased by 25.2 to 28.5 cm, yield by 3568 to 3896 kg / mu, and gray mold incidence rate by 17.2% to 21.8%. When using a two-component combination, plant height increased by 30.1 to 33.6 cm, yield by 4086 to 4523 kg / mu, and gray mold incidence rate by 13.5% to 16.3%. When all three components were combined, plant height increased by 38.7 cm, yield by 5236 kg / mu, and gray mold incidence rate by 8.3%.

[0246] Synergistic effects were analyzed using yield indicators: refined bamboo vinegar alone contributed 3896 kg / mu, potassium humate alone contributed 3712 kg / mu, and polyglutamic acid alone contributed 3568 kg / mu, with an average yield of 3725 kg / mu for each component alone; the combined yield of refined bamboo vinegar and potassium humate was 4523 kg / mu, which was 18.9% higher than the average yield of the two components alone (3804 kg / mu); the total yield of all three components was 5236 kg / mu, which was 22.4% higher than the average yield of the two components combined (4276 kg / mu), and 37.8% higher than the reasonable expected value of 3800 kg / mu for the simple sum of the individual effects of the three components.

[0247] This data fully demonstrates the nonlinear synergistic gain effect among refined bamboo vinegar, potassium humate, and polyglutamic acid. The synergistic effect of the three far exceeds the simple sum of the effects of each component used individually; 1 plus 1 plus 1 is much greater than 3, which cannot be explained by simple superposition. The organic acids in refined bamboo vinegar promote the dissociation and activation of humic acid, humic acid buffers acidity and provides a chelating environment, and polyglutamic acid constructs a hydrogen bond network and slowly releases nutrients and antibacterial components. These three mechanisms reinforce each other to form a positive feedback loop, which is the intrinsic mechanism basis for the synergistic gain.

[0248] It should be added that: in the food and cosmetic fields, polyglutamic acid is used in a pH range of neutral to weakly alkaline, while the pH of the system of this invention is 5.0 to 6.5 and contains organic acids from bamboo vinegar. The hydrogen bond network formation ability and film-forming behavior of polyglutamic acid under these weakly acidic conditions are completely different from those under neutral and alkaline conditions. Those skilled in the art cannot predict its behavior in weakly acidic water-soluble fertilizers from its application in the food and cosmetic fields.

[0249] Water-soluble fertilizer systems contain high concentrations of metal ions. The carboxyl groups of polyglutamic acid compete with metal ions for coordination, which may affect its film-forming and slow-release functions. This interfering factor does not exist in the food and cosmetic fields.

[0250] Fertilizers are applied to soil or plant leaves, and must be subjected to ultraviolet degradation, microbial decomposition, and rainwater erosion. The functional persistence of polyglutamic acid in this environment is completely different from that in the closed packaging environment of food and cosmetics.

[0251] The aforementioned three technical obstacles make cross-domain application infeasible. This invention achieves a three-way synergistic effect between polyglutamic acid, refined bamboo vinegar organic acid, and potassium humate under weakly acidic conditions.

[0252] Table 4 shows the test results comparing the order of addition:

[0253] Option 1: Adjust the pH first, then add potassium humate. Before adding potassium humate 5236 0.3 8.3 Option 2: Add potassium humate first, then adjust the pH. After adding potassium humate 4612 1.8 12.5 Option 3: Add potassium humate and pH adjuster simultaneously Join at the same time 4325 2.5 14.8

[0254] Results Analysis: Scheme 1, which follows the addition order of Example 1 of this invention, involves first adjusting the pH of the refined bamboo vinegar to 5.6 before adding potassium humate. The yield is 5236 kg / mu, with a precipitation rate of 0.3% after 30 days of storage and a gray mold incidence rate of 8.3%. Scheme 2 involves first adding potassium humate to the refined bamboo vinegar and then adding potassium hydroxide to adjust the pH. The yield is 4612 kg / mu, a decrease of 11.9% compared to Scheme 1. The precipitation rate after 30 days of storage is 1.8%, and the gray mold incidence rate is 12.5%.

[0255] Option 2 involves adding potassium humate to the refined bamboo vinegar under strongly acidic conditions. Humic acid molecules undergo protonation and re-aggregate in the strongly acidic environment. The supramolecular complex of organic acid and humic acid cannot form in an orderly manner under uncontrolled pH conditions. Although subsequent alkali adjustment can bring the pH to 5.6, the already formed humic acid aggregates are difficult to dissociate, resulting in a decrease in chelation capacity and deterioration of storage stability.

[0256] Option 3, which involves simultaneously adding potassium humate and potassium hydroxide to refined bamboo vinegar, yields 4325 kg / mu, a 17.4% reduction compared to Option 1. After 30 days of storage, the precipitation rate is 2.5%, and the incidence of gray mold is 14.8%. In Option 3, in areas with excessively high local alkali concentrations, humic acid molecules rapidly dissociate but simultaneously form insoluble complexes with metal ions in alkaline micro-regions. Furthermore, localized high temperatures and rapid pH changes disrupt the orderly assembly of the organic acid-humic acid supramolecular complex, resulting in the worst system stability.

[0257] The above results indicate that the order of addition of refined bamboo vinegar liquid to adjust the pH to 5.0 to 6.5 by mixing it with a pH adjuster and then adding potassium humate at 45 to 55°C and stirring to dissolve it is not a conventional process adjustment, but a necessary condition for the orderly assembly of the organic acid-humic acid supramolecular complex. Different addition orders lead to significant differences in technical effects, proving that the process steps of this invention are irreplaceable.

[0258] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention.

Claims

1. A water-soluble fertilizer containing bamboo vinegar, characterized in that, Based on 100 parts by weight, the product comprises the following components: 15 to 25 parts of refined bamboo vinegar, wherein the refined bamboo vinegar is obtained by distilling the middle layer of crude bamboo vinegar after dry distillation of bamboo, allowing it to settle, and collecting the fraction at 80 to 120°C under reduced pressure; the acetic acid content is 8 to 12% by weight, and the phenolic compound content is 2 to 4% by weight; and 8 to 12 parts of potassium humate, wherein the humic acid content in the potassium humate is not less than 55% by weight. 2 to 4 parts polyglutamic acid, wherein the molecular weight of polyglutamic acid is 500,000 to 1,000,000 Daltons; 21 to 34 parts macronutrient fertilizer; 3 to 6 parts mesonutrient fertilizer; 1 to 3 parts micronutrient fertilizer; 5 to 10 parts amino acid solution; 0.5 to 2 parts pH adjuster; and the remainder deionized water; the pH of the water-soluble fertilizer containing bamboo vinegar solution is 5.0 to 6.

5.

2. The water-soluble fertilizer containing bamboo vinegar as described in claim 1, characterized in that, The macro-element fertilizer comprises a mixture of urea, potassium dihydrogen phosphate, and potassium nitrate, in parts by weight: 10 to 16 parts urea, 6 to 10 parts potassium dihydrogen phosphate, and 5 to 8 parts potassium nitrate.

3. The water-soluble fertilizer containing bamboo vinegar as described in claim 1, characterized in that, The medium-element fertilizer comprises a mixture of sugar alcohol calcium and sugar alcohol magnesium, with 2 to 3.5 parts sugar alcohol calcium and 1 to 2.5 parts sugar alcohol magnesium by mass.

4. The water-soluble fertilizer containing bamboo vinegar as described in claim 1, characterized in that, The micronutrient fertilizer comprises a mixture of EDTA chelated zinc, EDTA chelated iron, and boric acid, wherein, by weight, 0.5 to 1.2 parts of EDTA chelated zinc, 0.3 to 0.8 parts of EDTA chelated iron, and 0.3 to 0.6 parts of boric acid.

5. The water-soluble fertilizer containing bamboo vinegar as described in claim 1, characterized in that, The pH adjuster is potassium hydroxide.

6. The water-soluble fertilizer containing bamboo vinegar as described in claim 1, characterized in that, The mass fraction of free amino acids in the amino acid solution is not less than 40%.

7. A method for preparing a water-soluble fertilizer containing bamboo vinegar as described in any one of claims 1 to 6, characterized in that, Includes the following steps: Step 1: Add the refined bamboo vinegar liquid to the reaction vessel, and add a pH adjuster while stirring to adjust the pH of the system to 5.0 to 6.5; Step 2: Heat to 45 to 55°C, add potassium humate, and stir until completely dissolved; Step 3: Add polyglutamic acid and stir until completely dissolved; Step 4: Add each component of the macro-element fertilizer in sequence and stir until completely dissolved; Step 5: Cool down to 35 to 40°C, add medium-element fertilizer, and stir until completely dissolved; Step 6: Add trace element fertilizer and stir until completely dissolved; Step 7: Add amino acid solution and stir well; Step 8: Filter, cool to room temperature, and fill.

8. The method for preparing water-soluble fertilizer containing bamboo vinegar as described in claim 7, characterized in that, In step one, the stirring speed is 200 to 400 r / min, and in steps two and three, the stirring speed is 300 to 500 r / min.

9. The method for preparing water-soluble fertilizer containing bamboo vinegar as described in claim 7, characterized in that, In step two, the temperature is raised to 45-55℃ and the stirring time is 15 to 25 minutes. In step five, the temperature is lowered to 35-40℃.

10. The method for preparing water-soluble fertilizer containing bamboo vinegar as described in claim 7, characterized in that, In step eight, a 200-mesh filter is used for filtration.