Organic water-soluble fertilizer and preparation process thereof
Organic water-soluble fertilizer was prepared by mixing modified potassium humate with surfactants, and modified molybdenum carbide nanoporous particles were used to catalyze and activate humic acid, which solved the problem of poor water solubility of humic acid and achieved efficient and environmentally friendly fertilizer utilization and soil improvement effects.
Patent Information
- Application Number
- CN202411236463.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-04
- Publication Date
- 2026-01-27
- Estimated Expiration
- 2044-09-04
AI Technical Summary
Humic acid readily reacts with metal ions to form insoluble bound states, resulting in poor water solubility. Furthermore, existing activation methods are energy-intensive and pollute the environment, making it difficult to effectively improve fertilizer utilization and soil quality.
Organic water-soluble fertilizer was prepared by mixing modified potassium humate with surfactants, urea, phosphates, sulfates, etc. Humic acid was activated by modified molybdenum carbide nanoporous particles to increase water solubility, and solubility was further enhanced by alkaline extraction and sulfonation reaction.
It improves the water solubility and utilization rate of fertilizers, reduces the binding state of metal ions, achieves slow-release effect and efficient fertilization, and reduces environmental pollution.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of fertilizer technology, specifically to an organic water-soluble fertilizer and its preparation process. Background Technology
[0002] Humic acid fertilizer is a new type of fertilizer, mainly made from resources such as peat, weathered coal, lignite, and organic waste through specific technologies to extract humic acid. my country has relatively abundant reserves of humic acid resources such as peat, lignite, and weathered coal. According to incomplete statistics, peat reserves are approximately 12.5 billion tons, lignite reserves are approximately 130 billion tons, and weathered coal reserves are also relatively abundant. Although my country has a large total coal resource volume, it lacks high-quality coal resources, therefore, the development and utilization of low-rank coal is receiving increasing attention.
[0003] Agriculture is the primary application area for humic acid resources. In agriculture, humic acid is mainly used as fertilizer, potting soil / pots, animal feed, and as a growth regulator to stimulate plant development. Compared to chemical fertilizers and farmyard manure, humic acid fertilizers have a better effect on improving crop yield and quality, can alleviate pests and diseases to a certain extent, and also have a synergistic effect on chemical fertilizers.
[0004] The long-term excessive and unscientific application of chemical fertilizers not only reduces fertilizer utilization and increases costs, but also causes a series of problems such as resource waste and environmental pollution. Humic acid's unique physicochemical properties and diverse functional groups make it play an important role in stimulating plant growth, repairing and improving soil, increasing fertilizer utilization, enhancing plant stress resistance and disease resistance, and improving crop quality. However, humic acid easily reacts with metal ions such as calcium, magnesium, aluminum, and iron to form insoluble metal ion-bound humic acid, resulting in poor water solubility. Therefore, humic acid must undergo certain activation treatments to convert the bound humic acid, which is difficult for crops to absorb and utilize, into water-soluble humic acid, in order to improve its application effect in agriculture. Activated humic acid fertilizers can improve fertilizer utilization, improve soil quality, and promote crop growth, and are widely used in agricultural production. However, the activation methods for humic acid mainly use strong acid and strong alkali activation in a liquid state, which is not only energy-intensive and time-consuming, but also easily produces harmful gases that pollute the environment.
[0005] Water-soluble fertilizers are multi-element compound fertilizers that can completely dissolve in water. Compared to traditional non-water-soluble fertilizers such as superphosphate and granulated compound fertilizers, as well as slow-release varieties, they have experienced rapid development due to their significant advantages, including rapid dissolution, high absorption rate, quick effect, no residue, and convenient application. Especially in the face of increasingly severe environmental protection and water scarcity caused by the greenhouse effect, new fertilization methods with significant water-saving and fertilizer-saving functions, such as drip irrigation systems and sprinkler irrigation, have begun to be promoted and applied, fundamentally changing agricultural fertilizer users' understanding of fertilizers. Water-soluble compound fertilizers, as the current mainstream of irrigation fertilization, can save water, fertilizer, and labor time. Summary of the Invention
[0006] The purpose of this invention is to provide an organic water-soluble fertilizer and its preparation process to solve the problems existing in the prior art.
[0007] To solve the above-mentioned technical problems, the present invention provides the following technical solution:
[0008] An organic water-soluble fertilizer is prepared by mixing modified potassium humate with surfactants, urea, monoammonium phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, zinc sulfate, manganese sulfate, and modified molybdenum carbide nanoporous particles.
[0009] The modified potassium humate is prepared by first mixing mineral-source humic acid with potassium hydroxide and modified molybdenum carbide nanoporous particles, then activating it by solid-phase ball milling, and finally extracting and neutralizing it with alkaline solution to obtain potassium humate. Then, the potassium humate is reacted with formaldehyde and sodium sulfite to obtain the modified potassium humate.
[0010] The modified molybdenum carbide nanoporous particles are prepared by first reacting melamine with ammonium molybdate under oxalic acid induction to obtain a molybdenum precursor, and then mixing and calcining the molybdenum precursor with ammonium dihydrogen phosphate.
[0011] As an optimization, the mineral-sourced humic acid is one or more of lignite, weathered coal, and peat.
[0012] As an optimization, the surfactant is sodium methylene dinaphthalene sulfonate and sodium dodecylbenzene sulfonate.
[0013] A method for preparing an organic water-soluble fertilizer includes the following preparation steps:
[0014] (1) Weigh 1.1 to 1.3 parts of melamine and 40 to 50 parts of ethylene glycol by mass, mix them evenly, stir at 300 to 400 r / min at room temperature until dissolved, keep stirring, add 15 to 16 parts of ammonium molybdate solution at 3 to 5 drops per second, stir at 400 to 500 r / min at room temperature for 10 to 14 hours, centrifuge at 6000 to 8000 rpm for 8 to 12 minutes, take the solid, wash with ethanol, repeat centrifugation and washing 3 to 4 times, and vacuum dry at 60 to 70°C for 6 to 8 hours to obtain the molybdenum precursor;
[0015] (2) Mix molybdenum precursor and ammonium dihydrogen phosphate at a mass ratio of 1:(8~9), grind in a mortar for 30~40 min, place in a porcelain crucible, heat at 750~800℃ for 2~3 h in a hydrogen-argon mixed gas atmosphere, cool naturally to room temperature after heating, grind in a mortar for 30~40 min, and obtain modified molybdenum carbide nanoporous particles.
[0016] (3) Mix mineral-derived humic acid, potassium hydroxide, and modified molybdenum carbide nanoporous particles in a mass ratio of 1:(0.04~0.06):(0.0008~0.0012), add them to a ball mill, and ball mill at 50~60 r / s for 1~1.5 h to obtain activated humic acid;
[0017] (4) Mix activated humic acid and pure water at a ratio of 1:(6~7) evenly, add potassium hydroxide to adjust the pH to 10~11, react at 85~95℃ and 300~400r / min for 60~80min, cool naturally to room temperature, centrifuge at 3000~4000r / min for 15~20min, take the supernatant, and vacuum dry at 80~90℃ for 6~8h to obtain potassium humate;
[0018] (5) Potassium humate, 37% formaldehyde aqueous solution, sodium sulfite and deionized water are mixed evenly in a mass ratio of 1:(0.3~0.4):(0.44~0.6):(15~20), refluxed at 85~90℃ and 300~500r / min for 2~3h, then distilled under reduced pressure and dried under vacuum at 60~65℃ for 8~10h to obtain modified potassium humate;
[0019] (6) Weigh 40-50 parts of modified potassium humate, 3-5 parts of sodium methylene dinaphthalene sulfonate, 3-5 parts of sodium dodecylbenzene sulfonate, 30-40 parts of urea, 25-30 parts of monoammonium phosphate, 30-40 parts of ammonium dihydrogen phosphate, 20-25 parts of potassium dihydrogen phosphate, 10-15 parts of zinc sulfate, 10-15 parts of manganese sulfate, and 5-6 parts of modified molybdenum carbide nanoporous particles, mix them evenly, crush them with a pulverizer and pass them through a 100-mesh sieve to obtain organic water-soluble fertilizer.
[0020] As an optimization, the preparation method of the ammonium molybdate solution in step (1) is as follows:
[0021] Ammonium molybdate tetrahydrate and pure water are mixed evenly at a mass ratio of 1:(16~18). The mixture is stirred at 300~400 r / min at room temperature until completely dissolved. Then, 8~9 times the mass of ammonium molybdate tetrahydrate in 0.5 mol / L oxalic acid aqueous solution is added. The mixture is stirred at 300~400 r / min at room temperature for 30~40 min to obtain ammonium molybdate solution.
[0022] As an optimization, the hydrogen-argon mixture in step (2) is 10% hydrogen and 90% argon.
[0023] As an optimization, the heating rate in step (2) is 3~4℃ / min.
[0024] As an optimization, the mineral-source humic acid in step (3) is pretreated by drying and grinding the mineral-source humic acid through a 60-mesh sieve.
[0025] Compared with the prior art, the beneficial effects achieved by the present invention are:
[0026] In preparing organic water-soluble fertilizer, this invention first reacts melamine with ammonium molybdate under oxalic acid induction to obtain a molybdenum precursor; the molybdenum precursor is mixed with ammonium dihydrogen phosphate and calcined to obtain modified molybdenum carbide nanoporous particles; mineral-derived coal humic acid is mixed with potassium hydroxide and modified molybdenum carbide nanoporous particles and then activated by solid-phase ball milling to obtain activated humic acid; the activated humic acid is extracted and neutralized with alkaline solution to obtain potassium humate; potassium humate is reacted with formaldehyde and sodium sulfite to obtain modified potassium humate; the modified potassium humate is mixed with surfactant, urea, monoammonium phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, zinc sulfate, manganese sulfate, and modified molybdenum carbide nanoporous particles to obtain organic water-soluble fertilizer.
[0027] First, melamine was reacted with ammonium molybdate under oxalic acid induction to prepare a molybdenum precursor. Then, the molybdenum precursor was mixed with ammonium dihydrogen phosphate and calcined to obtain modified molybdenum carbide nanoporous particles. Melamine molecules can undergo self-assembly with the assistance of oxalic acid. Oxalic acid protonates the amino groups of melamine, which then coordinate with molybdate ions to form the molybdenum precursor. Subsequently, the precursor was mixed with ammonium dihydrogen phosphate and calcined at high temperature in a hydrogen-argon mixed gas atmosphere to form a nanoporous structure. The resulting modified molybdenum carbide nanoporous particles contain carbon, molybdenum, nitrogen, and phosphorus, all essential elements for plant growth. The nanoporous structure gives it a high specific surface area, more active sites, and improved catalytic efficiency. Phosphorus doping modification enhances electron transfer capacity and catalytic activity, while also exhibiting good adsorption effects. It can adsorb nutrients after being incorporated into water-soluble fertilizers. After fertilization, these nutrients are released as the modified molybdenum carbide nanoporous particles biodegrade, resulting in a slow-release effect.
[0028] Secondly, mineral-derived humic acid was mixed with potassium hydroxide and modified molybdenum carbide nanoporous particles and then activated using solid-phase ball milling to obtain activated humic acid. Solid-phase ball milling was used to activate and break down the large molecules in the mineral-derived humic acid into smaller molecules, increasing the content of water-soluble humic acid and reducing the formation of insoluble metal ion-bound humic acid with substances such as calcium, magnesium, aluminum, and iron. The aforementioned synthesized modified molybdenum carbide nanoporous particles were used as a catalyst, further enhancing the activation effect and increasing the content of soluble small-molecule humic acid. The amount further increases; potassium humate is prepared by extracting and neutralizing activated humic acid with alkaline solution, and water-soluble components in activated humic acid are extracted using alkaline solution. Potassium hydroxide is selected as the alkaline solution to generate potassium humate, which can be added as potassium fertilizer to reduce the amount of subsequent potassium fertilizer added; modified humic acid is prepared by reacting potassium humate with formaldehyde and sodium sulfite, and sulfonation reaction is carried out with potassium humate using formaldehyde and sodium sulfite to introduce sulfonic acid groups onto potassium humate, improve its hydrophilicity, accelerate its dissolution rate, and introduce sulfur nutrients at the same time.
[0029] Finally, modified potassium humate was mixed with surfactants, urea, monoammonium phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, zinc sulfate, manganese sulfate, and modified molybdenum carbide nanoporous particles to prepare an organic water-soluble fertilizer. Sodium methylene dinaphthalene sulfonate and sodium dodecylbenzene sulfonate were added as surfactants. Their high surface activity can promote the dissolution of water-soluble fertilizer particles in water and prevent fertilizer particles from caking during storage. The addition of modified molybdenum carbide nanoporous particles can utilize their nanoporous structure to adsorb nutrients, forming a slow-release effect, reducing fertilizer application amount, and improving fertilizer utilization rate. Detailed Implementation
[0030] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. 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 of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0031] The mineral-derived humic acid used in all the following examples and comparative examples is weathered coal humic acid, from Shanxi, China, with C: 39.10%, H: 2.59%, O: 24.63%, N: 0.95%, S: 0.99%, and ash content: 30.29%.
[0032] The commercially available palladium-on-carbon catalyst used in Comparative Example 4 was Yunbang YB54681.
[0033] All the weathered coal humic acid used in the following examples and comparative examples was pretreated by drying, grinding and passing the weathered coal humic acid through a 60-mesh sieve.
[0034] The preparation methods of the ammonium molybdate solution used in all the following examples and comparative examples are as follows:
[0035] Ammonium molybdate tetrahydrate and pure water were mixed evenly at a mass ratio of 1:16. The mixture was stirred at 350 r / min at room temperature until completely dissolved. Then, 0.5 mol / L oxalic acid aqueous solution with a mass of 8 times that of ammonium molybdate tetrahydrate was added. The mixture was stirred at 350 r / min at room temperature for 35 min to obtain an ammonium molybdate solution.
[0036] Example 1
[0037] A method for preparing an organic water-soluble fertilizer, the method comprising the following preparation steps:
[0038] (1) Weigh 1.1 parts of melamine and 40 parts of ethylene glycol by mass, mix them evenly, stir at 300 r / min at room temperature until dissolved, keep stirring, add 15 parts of ammonium molybdate solution at 3 drops per second, stir at 400 r / min for 10 h at room temperature, centrifuge at 6000 rpm for 12 min, take the solid, wash with ethanol, repeat centrifugation and washing 3 times, and vacuum dry at 60℃ for 8 h to obtain the molybdenum precursor;
[0039] (2) The molybdenum precursor and ammonium dihydrogen phosphate were mixed evenly at a mass ratio of 1:8, ground in a mortar for 30 min, placed in a porcelain crucible, heated at 750℃ for 3 h in a hydrogen-argon mixed gas atmosphere, with a heating rate of 3℃ / min, and after heating, naturally cooled to room temperature, ground in a mortar for 30 min to obtain modified molybdenum carbide nanoporous particles.
[0040] (3) Weathered coal humic acid, potassium hydroxide and modified molybdenum carbide nanoporous particles are mixed evenly at a mass ratio of 1:0.04:0.0008, added to a ball mill, and ball milled at 50 r / s for 1.5 h to obtain activated humic acid;
[0041] (4) Mix activated humic acid and pure water at a ratio of 1:6, add potassium hydroxide to adjust the pH to 10, react at 85℃ and 300r / min for 80min, cool naturally to room temperature, centrifuge at 3000r / min for 20min, take the supernatant, and vacuum dry at 80℃ for 8h to obtain potassium humate.
[0042] (5) Potassium humate, 37% formaldehyde aqueous solution, sodium sulfite and deionized water were mixed evenly in a mass ratio of 1:0.3:0.44:15, refluxed at 85℃ and 300r / min for 3h, then distilled under reduced pressure and dried under vacuum at 60℃ for 10h to obtain modified potassium humate.
[0043] (6) Weigh 40 parts of modified potassium humate, 3 parts of sodium methylene dinaphthalene sulfonate, 3 parts of sodium dodecylbenzene sulfonate, 30 parts of urea, 25 parts of monoammonium phosphate, 30 parts of ammonium dihydrogen phosphate, 20 parts of potassium dihydrogen phosphate, 10 parts of zinc sulfate, 10 parts of manganese sulfate, and 5 parts of modified molybdenum carbide nanoporous particles, mix them evenly, crush them with a pulverizer and pass them through a 100-mesh sieve to obtain organic water-soluble fertilizer.
[0044] Example 2
[0045] A method for preparing an organic water-soluble fertilizer, the method comprising the following preparation steps:
[0046] (1) Weigh 1.2 parts of melamine and 45 parts of ethylene glycol by mass, mix them evenly, stir at 350 r / min at room temperature until dissolved, keep stirring, add 15.5 parts of ammonium molybdate solution at 4 drops per second, stir at 450 r / min for 12 h at room temperature, centrifuge at 7000 rpm for 10 min, take the solid, wash with ethanol, repeat centrifugation and washing 3 times, and vacuum dry at 65℃ for 7 h to obtain the molybdenum precursor;
[0047] (2) The molybdenum precursor and ammonium dihydrogen phosphate were mixed evenly at a mass ratio of 1:8.5, ground in a mortar for 35 min, placed in a porcelain crucible, heated at 780℃ for 2.5 h in a hydrogen-argon mixed gas atmosphere at a heating rate of 4℃ / min, and then naturally cooled to room temperature after heating. The mixture was then ground in a mortar for 35 min to obtain modified molybdenum carbide nanoporous particles.
[0048] (3) Weathered coal humic acid, potassium hydroxide and modified molybdenum carbide nanoporous particles are mixed evenly at a mass ratio of 1:0.05:0.001, added to a ball mill, and ball milled at 55 r / s for 1.2 h to obtain activated humic acid;
[0049] (4) Mix activated humic acid and pure water at a ratio of 1:6.5, add potassium hydroxide to adjust the pH to 10.5, react at 90℃ and 350r / min for 70min, cool naturally to room temperature, centrifuge at 3500r / min for 18min, take the supernatant, and vacuum dry at 85℃ for 7h to obtain potassium humate.
[0050] (5) Potassium humate, 37% formaldehyde aqueous solution, sodium sulfite and deionized water were mixed evenly in a mass ratio of 1:0.35:0.52:18, refluxed at 90℃ and 400r / min for 2.5h, distilled under reduced pressure, and dried under vacuum at 65℃ for 9h to obtain modified potassium humate.
[0051] (6) Weigh 45 parts of modified potassium humate, 4 parts of sodium methylene dinaphthalene sulfonate, 4 parts of sodium dodecylbenzene sulfonate, 35 parts of urea, 28 parts of monoammonium phosphate, 35 parts of ammonium dihydrogen phosphate, 22 parts of potassium dihydrogen phosphate, 13 parts of zinc sulfate, 12 parts of manganese sulfate, and 5.5 parts of modified molybdenum carbide nanoporous particles, mix them evenly, crush them with a pulverizer and pass them through a 100-mesh sieve to obtain organic water-soluble fertilizer.
[0052] Example 3
[0053] A method for preparing an organic water-soluble fertilizer, the method comprising the following preparation steps:
[0054] (1) Weigh 1.3 parts of melamine and 50 parts of ethylene glycol by mass, mix them evenly, stir at 400 r / min at room temperature until dissolved, keep stirring, add 16 parts of ammonium molybdate solution at 5 drops per second, stir at 500 r / min for 14 h at room temperature, centrifuge at 8000 rpm for 8 min, take the solid, wash with ethanol, repeat centrifugation and washing 4 times, and vacuum dry at 70℃ for 6 h to obtain the molybdenum precursor;
[0055] (2) The molybdenum precursor and ammonium dihydrogen phosphate were mixed evenly at a mass ratio of 1:9, ground in a mortar for 40 min, placed in a porcelain crucible, heated at 800℃ for 2 h in a hydrogen-argon mixed gas atmosphere at a heating rate of 4℃ / min, and then naturally cooled to room temperature after heating. The mixture was then ground in a mortar for 40 min to obtain modified molybdenum carbide nanoporous particles.
[0056] (3) Weathered coal humic acid, potassium hydroxide and modified molybdenum carbide nanoporous particles are mixed evenly at a mass ratio of 1:0.06:0.0012, added to a ball mill, and ball milled at 60 r / s for 1 h to obtain activated humic acid.
[0057] (4) Mix activated humic acid and pure water at a ratio of 1:7, add potassium hydroxide to adjust the pH to 11, react at 95℃ and 400r / min for 60min, cool naturally to room temperature, centrifuge at 4000r / min for 15min, take the supernatant, and vacuum dry at 90℃ for 6h to obtain potassium humate.
[0058] (5) Potassium humate, 37% formaldehyde aqueous solution, sodium sulfite and deionized water were mixed evenly in a mass ratio of 1:0.4:0.6:20, refluxed at 90℃ and 500r / min for 2h, then distilled under reduced pressure and dried under vacuum at 65℃ for 8h to obtain modified potassium humate.
[0059] (6) Weigh out 50 parts of modified potassium humate, 5 parts of sodium methylene dinaphthalene sulfonate, 5 parts of sodium dodecylbenzene sulfonate, 40 parts of urea, 30 parts of monoammonium phosphate, 40 parts of ammonium dihydrogen phosphate, 25 parts of potassium dihydrogen phosphate, 15 parts of zinc sulfate, 15 parts of manganese sulfate, and 6 parts of modified molybdenum carbide nanoporous particles by weight, mix them evenly, crush them with a pulverizer and pass them through a 100-mesh sieve to obtain organic water-soluble fertilizer.
[0060] Comparative Example 1
[0061] A method for preparing an organic water-soluble fertilizer, the method comprising the following preparation steps:
[0062] (1) Weigh 1.2 parts of melamine and 45 parts of ethylene glycol by mass, mix them evenly, stir at 350 r / min at room temperature until dissolved, keep stirring, add 15.5 parts of ammonium molybdate solution at 4 drops per second, stir at 450 r / min for 12 h at room temperature, centrifuge at 7000 rpm for 10 min, take the solid, wash with ethanol, repeat centrifugation and washing 3 times, and vacuum dry at 65℃ for 7 h to obtain the molybdenum precursor;
[0063] (2) The molybdenum precursor and ammonium dihydrogen phosphate were mixed evenly at a mass ratio of 1:8.5, ground in a mortar for 35 min, placed in a porcelain crucible, heated at 780℃ for 2.5 h in a hydrogen-argon mixed gas atmosphere at a heating rate of 4℃ / min, and then naturally cooled to room temperature after heating. The mixture was then ground in a mortar for 35 min to obtain modified molybdenum carbide nanoporous particles.
[0064] (3) Mix the weathered coal humic acid and potassium hydroxide at a mass ratio of 1:0.05, add them to a ball mill, and ball mill at 55 r / s for 1.2 h to obtain activated humic acid;
[0065] (4) Mix activated humic acid and pure water at a ratio of 1:6.5, add potassium hydroxide to adjust the pH to 10.5, react at 90℃ and 350r / min for 70min, cool naturally to room temperature, centrifuge at 3500r / min for 18min, take the supernatant, and vacuum dry at 85℃ for 7h to obtain potassium humate.
[0066] (5) Potassium humate, 37% formaldehyde aqueous solution, sodium sulfite and deionized water were mixed evenly in a mass ratio of 1:0.35:0.52:18, refluxed at 90℃ and 400r / min for 2.5h, distilled under reduced pressure, and dried under vacuum at 65℃ for 9h to obtain modified potassium humate.
[0067] (6) Weigh 45 parts of modified potassium humate, 4 parts of sodium methylene dinaphthalene sulfonate, 4 parts of sodium dodecylbenzene sulfonate, 35 parts of urea, 28 parts of monoammonium phosphate, 35 parts of ammonium dihydrogen phosphate, 22 parts of potassium dihydrogen phosphate, 13 parts of zinc sulfate, 12 parts of manganese sulfate, and 5.5 parts of modified molybdenum carbide nanoporous particles, mix them evenly, crush them with a pulverizer and pass them through a 100-mesh sieve to obtain organic water-soluble fertilizer.
[0068] Comparative Example 2
[0069] A method for preparing an organic water-soluble fertilizer, the method comprising the following preparation steps:
[0070] (1) Weigh 1.2 parts of melamine and 45 parts of ethylene glycol by mass, mix them evenly, stir at 350 r / min at room temperature until dissolved, keep stirring, add 15.5 parts of ammonium molybdate solution at 4 drops per second, stir at 450 r / min for 12 h at room temperature, centrifuge at 7000 rpm for 10 min, take the solid, wash with ethanol, repeat centrifugation and washing 3 times, and vacuum dry at 65℃ for 7 h to obtain the molybdenum precursor;
[0071] (2) The molybdenum precursor and ammonium dihydrogen phosphate were mixed evenly at a mass ratio of 1:8.5, ground in a mortar for 35 min, placed in a porcelain crucible, heated at 780℃ for 2.5 h in a hydrogen-argon mixed gas atmosphere at a heating rate of 4℃ / min, and then naturally cooled to room temperature after heating. The mixture was then ground in a mortar for 35 min to obtain modified molybdenum carbide nanoporous particles.
[0072] (3) Weathered coal humic acid, potassium hydroxide and modified molybdenum carbide nanoporous particles are mixed evenly at a mass ratio of 1:0.05:0.001, added to a ball mill, and ball milled at 55 r / s for 1.2 h to obtain activated humic acid;
[0073] (4) Mix activated humic acid and pure water at a ratio of 1:6.5, add potassium hydroxide to adjust the pH to 10.5, react at 90℃ and 350r / min for 70min, cool naturally to room temperature, centrifuge at 3500r / min for 18min, take the supernatant, and vacuum dry at 85℃ for 7h to obtain potassium humate.
[0074] (5) Weigh out 45 parts of potassium humate, 4 parts of sodium methylene dinaphthalene sulfonate, 4 parts of sodium dodecylbenzene sulfonate, 35 parts of urea, 28 parts of monoammonium phosphate, 35 parts of ammonium dihydrogen phosphate, 22 parts of potassium dihydrogen phosphate, 13 parts of zinc sulfate, 12 parts of manganese sulfate, and 5.5 parts of modified molybdenum carbide nanoporous particles by weight, mix them evenly, crush them with a pulverizer and pass them through a 100-mesh sieve to obtain organic water-soluble fertilizer.
[0075] Comparative Example 3
[0076] A method for preparing an organic water-soluble fertilizer, the method comprising the following preparation steps:
[0077] (1) Mix weathered coal humic acid and potassium hydroxide at a mass ratio of 1:0.05, add them to a ball mill, and ball mill at 55 r / s for 1.2 h to obtain activated humic acid;
[0078] (2) Mix activated humic acid and pure water at a ratio of 1:6.5, add potassium hydroxide to adjust the pH to 10.5, react at 90℃ and 350r / min for 70min, cool naturally to room temperature, centrifuge at 3500r / min for 18min, take the supernatant, and vacuum dry at 85℃ for 7h to obtain potassium humate.
[0079] (3) Potassium humate, 37% formaldehyde aqueous solution, sodium sulfite and deionized water were mixed evenly in a mass ratio of 1:0.35:0.52:18, refluxed at 90℃ and 400r / min for 2.5h, distilled under reduced pressure, and dried under vacuum at 65℃ for 9h to obtain modified potassium humate.
[0080] (4) Weigh 45 parts of modified potassium humate, 4 parts of sodium methylene dinaphthalene sulfonate, 4 parts of sodium dodecylbenzene sulfonate, 35 parts of urea, 28 parts of monoammonium phosphate, 35 parts of ammonium dihydrogen phosphate, 22 parts of potassium dihydrogen phosphate, 13 parts of zinc sulfate, and 12 parts of manganese sulfate by mass, mix them evenly, crush them with a pulverizer and pass them through a 100-mesh sieve to obtain organic water-soluble fertilizer.
[0081] Comparative Example 4
[0082] A method for preparing an organic water-soluble fertilizer, the method comprising the following preparation steps:
[0083] (1) Weigh 1.2 parts of melamine and 45 parts of ethylene glycol by mass, mix them evenly, stir at 350 r / min at room temperature until dissolved, keep stirring, add 15.5 parts of ammonium molybdate solution at 4 drops per second, stir at 450 r / min for 12 h at room temperature, centrifuge at 7000 rpm for 10 min, take the solid, wash with ethanol, repeat centrifugation and washing 3 times, and vacuum dry at 65℃ for 7 h to obtain the molybdenum precursor;
[0084] (2) The molybdenum precursor and ammonium dihydrogen phosphate were mixed evenly at a mass ratio of 1:8.5, ground in a mortar for 35 min, placed in a porcelain crucible, heated at 780℃ for 2.5 h in a hydrogen-argon mixed gas atmosphere at a heating rate of 4℃ / min, and then naturally cooled to room temperature after heating. The mixture was then ground in a mortar for 35 min to obtain modified molybdenum carbide nanoporous particles.
[0085] (3) The weathered coal humic acid, potassium hydroxide and commercial palladium on carbon catalyst were mixed evenly in a mass ratio of 1:0.05:0.001, added to a ball mill, and ball milled at 55 r / s for 1.2 h to obtain activated humic acid;
[0086] (4) Mix activated humic acid and pure water at a ratio of 1:6.5, add potassium hydroxide to adjust the pH to 10.5, react at 90℃ and 350r / min for 70min, cool naturally to room temperature, centrifuge at 3500r / min for 18min, take the supernatant, and vacuum dry at 85℃ for 7h to obtain potassium humate.
[0087] (5) Potassium humate, 37% formaldehyde aqueous solution, sodium sulfite and deionized water were mixed evenly in a mass ratio of 1:0.35:0.52:18, refluxed at 90℃ and 400r / min for 2.5h, distilled under reduced pressure, and dried under vacuum at 65℃ for 9h to obtain modified potassium humate.
[0088] (6) Weigh 45 parts of modified potassium humate, 4 parts of sodium methylene dinaphthalene sulfonate, 4 parts of sodium dodecylbenzene sulfonate, 35 parts of urea, 28 parts of monoammonium phosphate, 35 parts of ammonium dihydrogen phosphate, 22 parts of potassium dihydrogen phosphate, 13 parts of zinc sulfate, 12 parts of manganese sulfate, and 5.5 parts of modified molybdenum carbide nanoporous particles, mix them evenly, crush them with a pulverizer and pass them through a 100-mesh sieve to obtain organic water-soluble fertilizer.
[0089] Comparative Example 5
[0090] A method for preparing an organic water-soluble fertilizer, the method comprising the following preparation steps:
[0091] (1) Weigh 1.2 parts of melamine and 45 parts of ethylene glycol by mass, mix them evenly, stir at 350 r / min at room temperature until dissolved, keep stirring, add 15.5 parts of ammonium molybdate solution at 4 drops per second, stir at 450 r / min for 12 h at room temperature, centrifuge at 7000 rpm for 10 min, take the solid, wash with ethanol, repeat centrifugation and washing 3 times, and vacuum dry at 65℃ for 7 h to obtain the molybdenum precursor;
[0092] (2) Grind the molybdenum precursor in a mortar for 35 min, place it in a porcelain crucible, heat it at 780°C for 2.5 h in a hydrogen-argon mixed gas atmosphere, with a heating rate of 4°C / min, and allow it to cool naturally to room temperature after heating. Grind it in a mortar for 35 min to obtain molybdenum carbide nanoporous particles.
[0093] (3) Weathered coal humic acid, potassium hydroxide and molybdenum carbide nanoporous particles are mixed evenly in a mass ratio of 1:0.05:0.001, added to a ball mill, and ball milled at 55 r / s for 1.2 h to obtain activated humic acid;
[0094] (4) Mix activated humic acid and pure water at a ratio of 1:6.5, add potassium hydroxide to adjust the pH to 10.5, react at 90℃ and 350r / min for 70min, cool naturally to room temperature, centrifuge at 3500r / min for 18min, take the supernatant, and vacuum dry at 85℃ for 7h to obtain potassium humate.
[0095] (5) Potassium humate, 37% formaldehyde aqueous solution, sodium sulfite and deionized water were mixed evenly in a mass ratio of 1:0.35:0.52:18, refluxed at 90℃ and 400r / min for 2.5h, distilled under reduced pressure, and dried under vacuum at 65℃ for 9h to obtain modified potassium humate.
[0096] (6) Weigh 45 parts of modified potassium humate, 4 parts of sodium methylene dinaphthalene sulfonate, 4 parts of sodium dodecylbenzene sulfonate, 35 parts of urea, 28 parts of monoammonium phosphate, 35 parts of ammonium dihydrogen phosphate, 22 parts of potassium dihydrogen phosphate, 13 parts of zinc sulfate, 12 parts of manganese sulfate, and 5.5 parts of molybdenum carbide nanoporous particles, mix them evenly, crush them with a pulverizer and pass them through a 100-mesh sieve to obtain organic water-soluble fertilizer.
[0097] Test Example 1
[0098] Humic acid activation effect test: The activation effect of humic acid is evaluated by measuring the content of water-soluble humic acid, water-soluble calcium ions, and water-soluble magnesium ions in the prepared activated humic acid. The specific test method is as follows:
[0099] Water-soluble humic acid content: The water-soluble humic acid content in the prepared activated humic acid was determined according to the residue method in GB / T 11957-2001. Sodium hydroxide solution was used for extraction. Unactivated weathered coal was used as a control group. Each group was tested three times and the average value was taken.
[0100] Water-soluble calcium and magnesium ion content: The content of free water-soluble calcium and magnesium ions in the prepared activated humic acid was determined by atomic absorption spectrometry. Unactivated weathered coal was used as a control group. Each group was tested three times and the average value was taken.
[0101] The results are shown in Table 1.
[0102] Table 1
[0103]
[0104] A comparison of the experimental data from Examples 1-3, Comparative Examples 1-5, and the control group in Table 1 reveals that the activated humic acid prepared by this invention has a higher content of water-soluble humic acid and water-soluble calcium and magnesium ions.
[0105] By comparison, the contents of water-soluble humic acid and water-soluble calcium and magnesium ions in Examples 1-3 are greater than those in Comparative Examples 1 and 3, indicating that the modified molybdenum carbide nanoporous particles have a good activation and catalytic effect, effectively increasing the content of active substances in humic acid.
[0106] By comparison, the contents of water-soluble humic acid and water-soluble calcium and magnesium ions in Examples 1-3 are greater than those in Comparative Example 4, indicating that the modified molybdenum carbide nanoporous particles have better catalytic activity than commercially available palladium on carbon catalysts.
[0107] By comparison, the contents of water-soluble humic acid and water-soluble calcium and magnesium ions in Examples 1-3 are greater than those in Comparative Example 5, indicating that the modification of molybdenum carbide nanoporous particles effectively improves their catalytic activity and enhances the catalytic activation effect on humic acid, thus effectively improving the utilization of unactivated humic acid.
[0108] Test Example 2
[0109] Dissolution test: The dissolution rate of the prepared organic water-soluble fertilizer is tested to evaluate its dissolution performance. The specific test method is as follows:
[0110] Dissolution rate: Under room temperature and without stirring, the time it takes for 4g of the prepared organic water-soluble fertilizer to be completely dissolved in 1L of water is measured. Each group is tested three times and the average value is taken.
[0111] The results are shown in Table 2.
[0112] Table 2
[0113]
[0114] A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-5 in Table 2 reveals that the organic water-soluble fertilizer prepared by this invention has good water solubility and dissolution rate.
[0115] By comparison, the dissolution time of Examples 1-3 was shorter than that of Comparative Example 2, indicating that the sulfonic acid groups introduced by the reaction of activated humic acid with formaldehyde and sodium sulfite improved the hydrophilicity and increased the dissolution rate.
[0116] Test Example 3
[0117] Field planting experiment: The prepared organic water-soluble fertilizer was used to plant cucumbers of the Ningfeng Chunqiu variety. The basic properties of the experimental soil were: pH 6.28, organic matter 37.42 g / kg, available nitrogen 218.46 mg / kg, available phosphorus 144.95 mg / kg, and available potassium 260.88 mg / kg. Fertilization methods included normal fertilization and reduced fertilization. A control group was set up with no fertilization. Each experimental group was planted with 2000 cucumber plants using conventional methods, arranged in a randomized block design with three replicates. The organic water-soluble fertilizer was applied via drip irrigation: 8 kg / mu (approximately 0.067 hectares) for the normal fertilization group, applied every 15 days; and 6 kg / mu (approximately 0.067 hectares) for the reduced fertilization group, applied every 20 days. After 60 days, the cucumber yield per mu (approximately 0.067 hectares) for each group was calculated.
[0118] The results are shown in Table 3.
[0119] Table 3
[0120]
[0121] A comparison of the experimental data from Examples 1-3, Comparative Examples 1-4, and the control group in Table 3 shows that the organic water-soluble fertilizer prepared by this invention has a good slow-release effect and fertilizer utilization rate.
[0122] By comparison, the cucumber yield per mu in Examples 1-3 was greater than that in Comparative Example 1, indicating that the modified molybdenum carbide nanoporous particles had a better catalytic activation effect on weathered coal humic acid. The catalytically activated humic acid had more easily absorbed active nutrients than that obtained by normal activation.
[0123] By comparison, the cucumber yield per mu in Examples 1-3 was greater than that in Comparative Example 2, indicating that the sulfonation modification of potassium humate improved its hydrophilicity, and the enhanced hydrophilicity also improved the efficiency of absorption and utilization.
[0124] By comparison, the cucumber yield per mu in Examples 1-3 was greater than that in Comparative Example 3, indicating that the addition of modified molybdenum carbide nanoporous particles effectively improved the fertilizer utilization rate of organic water-soluble fertilizer. At the same time, the yield only decreased slightly under the condition of reduced fertilizer application, and the decrease was less than that in Comparative Example 3, indicating that molybdenum carbide nanoporous particles also provided a slow-release effect, reducing the amount of fertilizer used.
[0125] By comparison, the cucumber yield per mu in Examples 1-3 was greater than that in Comparative Example 4, indicating that the modified molybdenum carbide nanoporous particles have a greater catalytic activation effect on weathered coal humic acid than commercially available palladium carbon catalysts, and the activated humic acid contains more easily absorbed active substances.
[0126] By comparison, the cucumber yield per mu in Examples 1-3 was greater than that in Comparative Example 5, indicating that the modification of molybdenum carbide nanoporous particles has a good effect, effectively improving its catalytic activity, and the active humic acid obtained by catalytic activation contains more easily absorbed active substances.
[0127] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.
Claims
1. A method for preparing an organic water-soluble fertilizer, characterized in that, The preparation steps include the following: (1) Weigh 1.1 to 1.3 parts of melamine and 40 to 50 parts of ethylene glycol by mass, mix them evenly, stir at 300 to 400 r / min at room temperature until dissolved, keep stirring, add 15 to 16 parts of ammonium molybdate solution at 3 to 5 drops per second, stir at 400 to 500 r / min at room temperature for 10 to 14 hours, centrifuge at 6000 to 8000 rpm for 8 to 12 minutes, take the solid, wash with ethanol, repeat centrifugation and washing 3 to 4 times, and vacuum dry at 60 to 70°C for 6 to 8 hours to obtain the molybdenum precursor; (2) Mix molybdenum precursor and ammonium dihydrogen phosphate at a mass ratio of 1:(8~9), grind in a mortar for 30~40 min, place in a porcelain crucible, heat at 750~800℃ for 2~3 h in a hydrogen-argon mixed gas atmosphere, cool naturally to room temperature after heating, grind in a mortar for 30~40 min, and obtain modified molybdenum carbide nanoporous particles. (3) Mix mineral-derived humic acid, potassium hydroxide, and modified molybdenum carbide nanoporous particles in a mass ratio of 1:(0.04~0.06):(0.0008~0.0012), add them to a ball mill, and ball mill at 50~60 r / s for 1~1.5 h to obtain activated humic acid; (4) Mix activated humic acid and pure water at a ratio of 1:(6~7) evenly, add potassium hydroxide to adjust the pH to 10~11, react at 85~95℃ and 300~400r / min for 60~80min, cool naturally to room temperature, centrifuge at 3000~4000r / min for 15~20min, take the supernatant, and vacuum dry at 80~90℃ for 6~8h to obtain potassium humate; (5) Potassium humate, 37% formaldehyde aqueous solution, sodium sulfite and deionized water are mixed evenly in a mass ratio of 1:(0.3~0.4):(0.44~0.6):(15~20), refluxed at 85~90℃ and 300~500r / min for 2~3h, then distilled under reduced pressure and dried under vacuum at 60~65℃ for 8~10h to obtain modified potassium humate; (6) Weigh 40-50 parts of modified potassium humate, 3-5 parts of sodium methylene dinaphthalene sulfonate, 3-5 parts of sodium dodecylbenzene sulfonate, 30-40 parts of urea, 25-30 parts of monoammonium phosphate, 30-40 parts of ammonium dihydrogen phosphate, 20-25 parts of potassium dihydrogen phosphate, 10-15 parts of zinc sulfate, 10-15 parts of manganese sulfate, and 5-6 parts of modified molybdenum carbide nanoporous particles, mix them evenly, crush them with a pulverizer and pass them through a 100-mesh sieve to obtain organic water-soluble fertilizer; The preparation method of the ammonium molybdate solution in step (1) is as follows: Ammonium molybdate tetrahydrate and pure water are mixed evenly at a mass ratio of 1:(16~18). The mixture is stirred at 300~400 r / min at room temperature until completely dissolved. Then, 8~9 times the mass of ammonium molybdate tetrahydrate in 0.5 mol / L oxalic acid aqueous solution is added. The mixture is stirred at 300~400 r / min at room temperature for 30~40 min to obtain ammonium molybdate solution.
2. The method for preparing an organic water-soluble fertilizer according to claim 1, characterized in that, The hydrogen-argon mixture in step (2) is 10% hydrogen and 90% argon.
3. The method for preparing an organic water-soluble fertilizer according to claim 1, characterized in that, The heating rate in step (2) is 3~4℃ / min.
4. The method for preparing an organic water-soluble fertilizer according to claim 1, characterized in that, The mineral-source humic acid mentioned in step (3) has been pretreated by drying and grinding the mineral-source humic acid through a 60-mesh sieve.
5. An organic water-soluble fertilizer, characterized in that, It is prepared by the preparation method described in any one of claims 1-4.
6. An organic water-soluble fertilizer according to claim 5, characterized in that, The mineral-derived humic acid is one or more of lignite, weathered coal, and peat.
Citation Information
Patent Citations
Long-acting stable humic acid water-soluble fertilizer and preparation method thereof
CN116082095A