Preparation method of anti-flocculation liquid humic acid water-soluble fertilizer based on subcritical technology

Abstract

The invention discloses a preparation method of an anti-flocculation liquid humic acid water-soluble fertilizer based on a subcritical technology, which comprises the following steps: carrying out preliminary subcritical water treatment on fertilizer raw materials, adding dipotassium phosphate and monopotassium phosphate, carrying out subcritical water treatment again, extracting a nutrient solution, and adding an additive to prepare the liquid humic acid water-soluble fertilizer. Through subcritical water treatment and combination of dipotassium phosphate and monopotassium phosphate, high-valence cations in the humic acid water-soluble fertilizer are removed, the attraction of the cations to negative charges on humic acid colloid can be reduced, and the charge balance of the humic acid water-soluble fertilizer is kept; the defect of flocculation phenomenon in the use process of the humic acid water-soluble fertilizer in the prior art is overcome; according to the humic acid water-soluble fertilizer, the fertilizer raw materials are subjected to subcritical water treatment and temperature adjustment, the fertilizer raw materials are subjected to sufficient micromolecularization and then subjected to passivation of metal ions, and the metal ions can be subjected to more sufficient passivation treatment, so that the flocculation phenomenon of the humic acid water-soluble fertilizer is avoided.

Description

Technical Field

[0001] The invention relates to the technical field of water-soluble fertilizer preparation, and in particular to a method for preparing anti-flocculation liquid humic acid water-soluble fertilizer based on subcritical technology. Background Art

[0002] The content of soil organic matter plays a decisive role in soil fertility, and humic acid is the core component of soil organic matter. Humic acid fertilizer can promote the growth of crops and control the expansion of crop pores. At the same time, humic acid can also improve soil structure, increase soil aeration and water retention, and improve soil microbial activity, thereby further enhancing soil fertility.

[0003] Liquid humic acid water-soluble fertilizer is a new type of high-efficiency fertilizer containing biostimulants. With the continuous maturity of water-fertilizer integration and drip irrigation technology, liquid humic acid water-soluble fertilizer has developed rapidly and has been widely used in economic crops such as fruits and vegetables. Humic acid solution is a colloid, which not only has the Tyndall effect, but also has the metastability of colloid. Humic acid is a polybasic organic weak acid, and its aqueous solution can ionize cations and negatively charged humic acid anions. Humic acid anions with the same charge repel each other to form a stable system.

[0004] Prior art CN 116675577 A discloses a humic acid water-soluble fertilizer. In terms of mass parts, the raw materials for preparing the humic acid water-soluble fertilizer include 50-55 parts of wood vinegar, 5-5.5 parts of humic acid and 32.5-41.5 parts of basic fertilizer. It can not only be used as a fertilizer, but also has the functions of resisting pathogens and insect pests. However, diluting the humic acid solution will change its concentration. When the concentration is reduced to a certain extent, the distance between the humic acid molecules in the solution increases, the interaction is weakened, and the cations in the solution are adsorbed on the surface of the negatively charged humic acid colloid, shielding the negative charge on the surface of the humic acid colloid, and the repulsive force between adjacent particles in the humic acid colloid is continuously reduced, breaking the original charge balance, and a flocculation state occurs. The product storage stability, drip irrigation, fertilizer efficiency and other aspects have a negative impact, which hinders the application of liquid humic acid water-soluble fertilizer to a certain extent.

[0005] Therefore, it is necessary to improve the humic acid water-soluble fertilizer in the prior art to solve the above problems. Summary of the invention

[0006] The invention overcomes the shortcomings of the prior art and provides a method for preparing a deflocculating liquid humic acid water-soluble fertilizer based on a subcritical technology, aiming to solve the defect of the prior art that humic acid water-soluble fertilizer flocculates during use.

[0007] To achieve the above object, the technical solution adopted by the present invention is: a method for preparing deflocculated liquid humic acid water-soluble fertilizer based on subcritical technology, comprising the following steps:

[0008] S1: putting one or more raw materials of chicken manure, rice bran, molasses, seawater, rapeseed cake, weathered lignite, potassium hydroxide, citric acid, and inorganic acid into a reactor, wherein at least chicken manure is included;

[0009] S2: subjecting the material in the S1 reactor to subcritical water treatment for 30-60 min under stirring;

[0010] S3: adding dipotassium hydrogen phosphate and potassium dihydrogen phosphate, and continuing the subcritical water treatment for 10-20 minutes;

[0011] S4: performing solid-liquid separation on the reactants in S3, collecting and concentrating the separated liquid to obtain a nutrient solution;

[0012] S5: Adding additives to the nutrient solution in S4, wherein the additives contain urea, potassium polyphosphate, ammonium polyphosphate, high potassium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium hydroxide, and mineral potassium humate to obtain liquid humic acid water-soluble fertilizer.

[0013] In a preferred embodiment of the present invention, the content of chicken manure in the raw material in S1 is at least 50%, and the moisture content in the raw material is 20%-40%.

[0014] In a preferred embodiment of the present invention, when the raw materials in S1 are selected, the mass ratio of chicken manure, rice bran, molasses, seawater, rapeseed cake, weathered lignite, potassium hydroxide, citric acid, and inorganic acid is 0.5-0.7:0.1-0.2:0.05-0.1:0.05-0.1:0.05-0.1:0.05-0.1:0.01-0.05:0.01-0.05:0.005-0.01:0.005-0.01.

[0015] In a preferred embodiment of the present invention, in the S2 reactor, the mass ratio of raw materials to water is 1:4.2-1:12.8.

[0016] In a preferred embodiment of the present invention, the temperature of the subcritical water treatment in S2 is 130°C-220°C.

[0017] In a preferred embodiment of the present invention, the ratio between the dipotassium hydrogen phosphate and the potassium dihydrogen phosphate in S3 is 1:3, and the ratio of the total mass of the added dipotassium hydrogen phosphate and the potassium dihydrogen phosphate to the raw material is 3%-5%.

[0018] In a preferred embodiment of the present invention, the temperature of the subcritical water treatment in S3 is 160°C-180°C.

[0019] In a preferred embodiment of the present invention, S4 concentrates the separated liquid to obtain a nutrient solution, wherein the organic matter content in the nutrient solution is ≥30 g / L, the sum of the nitrogen content, phosphorus content and potassium content is ≥15 g / L, the humic acid content is ≥8 g / L, and the amino acid content is ≥5 g / L.

[0020] In a preferred embodiment of the present invention, the ratio of urea, potassium polyphosphate, ammonium polyphosphate, potassium perphosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium hydroxide and mineral potassium humate added to S5 is 0.2-0.3:0.1-0.15:0.06-0.09:0.04-0.06:0.1-0.15:0.08-0.12:0.02-0.03:0.1-0.15.

[0021] In a preferred embodiment of the present invention, the ratio of the total mass of urea, potassium polyphosphate, ammonium polyphosphate, potassium perphosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium hydroxide and mineral potassium humate added in S5 to the nutrient solution is 1:40-1:70.

[0022] The present invention solves the defects existing in the background technology and has the following beneficial effects:

[0023] (1) The present invention provides a method for preparing a deflocculating liquid humic acid water-soluble fertilizer based on subcritical technology, wherein the fertilizer raw material is subjected to a preliminary subcritical water treatment, and then dipotassium hydrogen phosphate and potassium dihydrogen phosphate are added, and the fertilizer raw material is subjected to a subcritical water treatment again, and a nutrient solution is extracted and then an additive is added to prepare a liquid humic acid water-soluble fertilizer. The combination of subcritical water treatment and dipotassium hydrogen phosphate and potassium dihydrogen phosphate removes high-valent cations in the humic acid water-soluble fertilizer. Compared with the humic acid water-soluble fertilizer preparation method in the prior art, the method can reduce the attraction of cations to negative charges on humic acid colloids, maintain the charge balance of the humic acid water-soluble fertilizer, and solve the defect of the humic acid water-soluble fertilizer in the prior art that flocculation occurs during use.

[0024] (2) The fertilizer raw materials of the present invention include chicken manure, rice bran, molasses, seawater, rapeseed cake, weathered lignite, potassium hydroxide, citric acid, and inorganic acid, which can provide nutrients, enhance soil structure, and adjust pH value. Compared with the prior art, the fertilizer raw materials can provide nutrients required by plants and microorganisms, ensure the growth requirements of plants, promote the active transformation activities of microorganisms on the soil, increase soil aeration and water retention, and place plants in a suitable acid-base environment.

[0025] (3) In the present invention, the temperature is adjusted when the fertilizer raw materials are subjected to subcritical water treatment. When the subcritical water treatment is at an unadjusted temperature, the fertilizer raw materials can be decomposed to generate small molecules and dissolve metal ions. After the subcritical water treatment temperature is adjusted, the metal ions in the solution can be passivated by combining with dipotassium hydrogen phosphate and potassium dihydrogen phosphate. Compared with the prior art, the fertilizer raw materials are fully reduced to small molecules and then the metal ions are passivated, so that the fertilizer raw materials can be fully utilized, and the metal ions can be more fully passivated, thereby improving the passivation efficiency and rate of the metal ions and avoiding the flocculation of the humic acid water-soluble fertilizer. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art are briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative work.

[0027] Figure 1 It is a method step diagram of a preferred embodiment of the present invention. DETAILED DESCRIPTION

[0028] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0029] In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention may also be implemented in other ways different from those described herein. Therefore, the protection scope of the present invention is not limited to the specific embodiments disclosed below.

[0030] like Figure 1 As shown, a method for preparing anti-flocculation liquid humic acid water-soluble fertilizer based on subcritical technology comprises the following steps:

[0031] S1: One or more raw materials of chicken manure, rice bran, molasses, seawater, rapeseed cake, weathered lignite, potassium hydroxide, citric acid, and inorganic acid are put into a reactor, wherein at least chicken manure is included.

[0032] S2: The material in the S1 reactor is subjected to subcritical water treatment for 30-60 minutes under stirring.

[0033] S3: Add dipotassium hydrogen phosphate and potassium dihydrogen phosphate, and continue the subcritical water treatment for 10-20 minutes.

[0034] S4: separating the reactants in S3 into solid and liquid, collecting and concentrating the separated liquid to obtain a nutrient solution.

[0035] S5: Adding additives to the nutrient solution in S4, wherein the additives include urea, potassium polyphosphate, ammonium polyphosphate, high potassium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium hydroxide, and mineral potassium humate to obtain liquid humic acid water-soluble fertilizer.

[0036] The method comprises the following steps: performing preliminary subcritical water treatment on fertilizer raw materials, adding dipotassium hydrogen phosphate and potassium dihydrogen phosphate, performing subcritical water treatment again, extracting nutrient solution, and adding additives to prepare liquid humic acid water-soluble fertilizer; combining subcritical water treatment with dipotassium hydrogen phosphate and potassium dihydrogen phosphate to remove high-valent cations in the humic acid water-soluble fertilizer, reducing the attraction of cations to negative charges on humic acid colloids, maintaining charge balance of the humic acid water-soluble fertilizer, and solving the defect of flocculation in the humic acid water-soluble fertilizer in the prior art.

[0037] The chicken manure in S1 contains rich organic matter and trace elements required for plant growth. It can serve as the main nutrient for liquid humic acid water-soluble fertilizer, providing nutrients for liquid humic acid water-soluble fertilizer. After being made into liquid humic acid water-soluble fertilizer, it can quickly penetrate nutrients into the soil.

[0038] The content of chicken manure in the raw materials in S1 is at least 50%, and the moisture content in the raw materials is 20%-40%. The fertilizer raw materials include chicken manure, rice bran, molasses, seawater, rapeseed cake, weathered lignite, potassium hydroxide, citric acid, and inorganic acid, which can provide nutrients, enhance soil structure, and adjust pH value, provide nutrients required by plants and microorganisms, ensure plant growth requirements, promote microorganisms to actively transform the soil, increase soil aeration and water retention, and place plants in a suitable acid-base environment.

[0039] When the content of chicken manure is at least 50%, it contains a higher proportion of organic matter, which can be converted into humic acid and other beneficial organic matter during subcritical water treatment, which helps to improve soil structure and increase the water and fertilizer retention capacity of the soil. Agricultural by-products such as rice bran and molasses are used as auxiliary raw materials, which can provide additional organic matter and energy. The addition of seawater can bring rich minerals, while rapeseed cake and weathered lignite provide nitrogen, phosphorus, potassium and other nutrients required by plants. Potassium hydroxide, citric acid and inorganic acids are used to adjust the pH value to ensure the suitability of the reaction environment.

[0040] When all raw materials in S1 are selected, the mass ratio of chicken manure, rice bran, molasses, seawater, rapeseed cake, weathered lignite, potassium hydroxide, citric acid, and inorganic acid is 0.5-0.7: 0.1-0.2: 0.05-0.1: 0.05-0.1: 0.05-0.1: 0.01-0.05: 0.01-0.05: 0.005-0.01: 0.005-0.01. The appropriate ratio can ensure the balance of nutrients, pH value and trace elements in the fertilizer, and can ensure the fertilization effect of the fertilizer.

[0041] The stirring method in S2 is one or more of mechanical stirring, magnetic stirring and ultrasonic stirring. Mechanical stirring generates flow in the reactor through a mechanical stirrer, such as a stirring paddle, a turbine stirrer, etc., to ensure uniform mixing of the raw materials and improve the efficiency of heat and mass transfer; a magnetic stirrer achieves stirring by acting on a magnetic stirring bar in the reactor through an external magnetic field; ultrasonic stirring achieves mixing by generating ultrasonic waves to form a cavitation effect in the liquid.

[0042] In the S2 reactor, the mass ratio of raw materials to water is 1:4.2-1:12.8. By controlling the mass ratio of water, it can be ensured that subcritical water can fully extract nutrients from the raw materials, and the soluble components in the raw materials are more fully dissolved in water, thereby improving the extraction efficiency. The appropriate water ratio helps to dilute the impurities and insoluble components in the raw materials, which helps the subsequent solid-liquid separation process, making the separated liquid purer and reducing the difficulty of subsequent processing.

[0043] The temperature of subcritical water treatment in S2 is 130℃-220℃. Extracting organic matter and nutrients from raw materials under relatively mild conditions avoids thermal decomposition or structural damage that may be caused by excessively high temperatures. In this temperature range, the solubility of water is significantly improved, which helps to extract nutrients from raw materials more effectively. Mild temperature conditions help to form a more stable humic acid structure, thereby improving the quality and effect of the final product.

[0044] The ratio of dipotassium hydrogen phosphate to potassium dihydrogen phosphate in S3 is 1:3, and the ratio of added dipotassium hydrogen phosphate and potassium dihydrogen phosphate to the raw material is 3%-5%. Phosphates can form stable insoluble phosphate solids with various metal ions, which can passivate metal ions, thereby reducing the content of these metal ions in the nutrient solution. Phosphates can also enhance the resistance of plants to adversities such as drought and salt stress, and improve the growth stability of plants. Potassium dihydrogen phosphate and dipotassium hydrogen phosphate have buffering capacity, which can help adjust the pH value of the nutrient solution to keep it within a range suitable for heavy metal passivation and plant growth.

[0045] The temperature of subcritical water treatment in S3 is 160℃-180℃. At this temperature, the solubility of dipotassium hydrogen phosphate and potassium dihydrogen phosphate increases, which helps them to capture and fix heavy metal ions in the treatment solution more effectively. And at the temperature of subcritical water treatment, the chemical properties of water change, and its ion product constant increases, resulting in an increase in the conductivity of water, which can promote the reaction of dipotassium hydrogen phosphate and potassium dihydrogen phosphate with metal ions to form insoluble compounds. At this temperature, the chemical form of heavy metal ions can be changed from a more active form to a more stable form, reducing the bioavailability and mobility of heavy metals.

[0046] S4 concentrates the separated liquid to obtain a nutrient solution, in which the organic matter content is ≥30g / L, the sum of the nitrogen content, phosphorus content and potassium content is ≥15g / L, the humic acid content is ≥8g / L, and the amino acid content is ≥5g / L. Through the concentration process, the concentration of various nutrients is increased, which improves the efficiency of fertilizer use. The high content of humic acid and amino acids also helps to improve the soil structure and promote the development of plant roots. Humic acid has good anti-flocculation properties and can effectively prevent flocculation in the nutrient solution. The concentrated nutrient solution has a reduced volume, which is convenient for storage and transportation, reduces logistics costs, and also reduces losses caused by leakage or volatilization during transportation.

[0047] The ratio of urea, potassium polyphosphate, ammonium polyphosphate, high potassium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium hydroxide, and mineral potassium humate added to S5 is 0.2-0.3: 0.1-0.15: 0.06-0.09: 0.04-0.06: 0.1-0.15: 0.08-0.12: 0.02-0.03: 0.1-0.15. By setting the ratio of various substances reasonably, crops can be provided with comprehensive nutrition, including major elements such as nitrogen, phosphorus, potassium, and other trace elements, which are conducive to crop growth and development. The appropriate ratio of additives can improve crop resistance, reduce nutrient loss from fertilizers, and balance the metal ions in liquid humic acid water-soluble fertilizers, ensuring the stability of liquid humic acid water-soluble fertilizers.

[0048] The ratio of the total mass of urea, potassium polyphosphate, ammonium polyphosphate, high potassium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium hydroxide and mineral potassium humate added to S5 to the nutrient solution is 1:40-1:70. Appropriate nutrient ratios help plants better absorb and utilize the nutrients in fertilizers. Precisely controlling the ratio of various nutrient elements can reduce fertilizer waste, improve fertilizer utilization efficiency, and reduce the impact of agriculture on the environment, such as reducing eutrophication of water bodies caused by nutrient loss.

[0049] The more cations added to the humic acid liquid, the higher the valence, the stronger the shielding effect on the negative charge on the surface of the humic acid colloid, and the stronger the force that converts the colloid from sol to gel. Different cations have different abilities to induce the coagulation of humic acid colloids. The ability of trivalent ions to cause the coagulation of humic acid colloids is higher than that of divalent ions, and divalent ions are higher than monovalent ions. Due to the different ionic radii between ions of the same valence, there will also be certain changes. The order of the magnitude of the coagulation effect of cations on colloids is Fe3+>Al3+>H+>Ca2+>Mg2+>NH4+>K+>Na+.

[0050] Embodiment 1

[0051] This embodiment prepares a humic acid water-soluble fertilizer, and the preparation method is as follows:

[0052] S1: 536 parts of chicken manure, 120 parts of rice bran, 40 parts of molasses, 40 parts of seawater, 40 parts of rapeseed cake, 8 parts of weathered lignite, 8 parts of potassium hydroxide, 4 parts of citric acid and 4 parts of inorganic acid were put into a reactor.

[0053] S2: The material in the S1 reactor was subjected to subcritical water treatment for 40 minutes under stirring, the treatment temperature was 200°C, and the mass of water in the reactor was 6400 parts.

[0054] S3: Add 4 parts of dipotassium hydrogen phosphate and 12 parts of potassium dihydrogen phosphate, and continue subcritical water treatment for 20 minutes at a treatment temperature of 160°C.

[0055] S4: The reactants in S3 are separated into solid and liquid, and the separated liquid is collected and concentrated to obtain 4200 parts of nutrient solution.

[0056] S5: Add 20 parts of urea, 10 parts of potassium polyphosphate, 6 parts of ammonium polyphosphate, 4 parts of high potassium phosphate, 10 parts of potassium dihydrogen phosphate, 8 parts of dipotassium hydrogen phosphate, 2 parts of potassium hydroxide and 10 parts of mineral potassium humate to the nutrient solution in S4 to obtain liquid humic acid water-soluble fertilizer.

[0057] Embodiment 2

[0058] This embodiment prepares a humic acid water-soluble fertilizer, and the preparation method is as follows:

[0059] S1: 536 parts of chicken manure, 120 parts of rice bran, 40 parts of molasses, 40 parts of seawater, 40 parts of rapeseed cake, 8 parts of weathered lignite, 8 parts of potassium hydroxide, 4 parts of citric acid and 4 parts of inorganic acid were put into a reactor.

[0060] S2: The material in the S1 reactor was subjected to subcritical water treatment for 40 minutes under stirring, the treatment temperature was 200°C, and the mass of water in the reactor was 6400 parts.

[0061] S3: Add 6 parts of dipotassium hydrogen phosphate and 18 parts of potassium dihydrogen phosphate, and continue subcritical water treatment for 20 minutes at a treatment temperature of 160°C.

[0062] S4: The reactants in S3 are separated into solid and liquid, and the separated liquid is collected and concentrated to obtain 4200 parts of nutrient solution.

[0063] S5: Add 20 parts of urea, 10 parts of potassium polyphosphate, 6 parts of ammonium polyphosphate, 4 parts of high potassium phosphate, 10 parts of potassium dihydrogen phosphate, 8 parts of dipotassium hydrogen phosphate, 2 parts of potassium hydroxide and 10 parts of mineral potassium humate to the nutrient solution in S4 to obtain liquid humic acid water-soluble fertilizer.

[0064] Embodiment 3

[0065] This embodiment prepares a humic acid water-soluble fertilizer, and the preparation method is as follows:

[0066] S1: 536 parts of chicken manure, 120 parts of rice bran, 40 parts of molasses, 40 parts of seawater, 40 parts of rapeseed cake, 8 parts of weathered lignite, 8 parts of potassium hydroxide, 4 parts of citric acid and 4 parts of inorganic acid were put into a reactor.

[0067] S2: The material in the S1 reactor was subjected to subcritical water treatment for 40 minutes under stirring, the treatment temperature was 200°C, and the mass of water in the reactor was 6400 parts.

[0068] S3: Add 8 parts of dipotassium hydrogen phosphate and 24 parts of potassium dihydrogen phosphate, and continue subcritical water treatment for 20 minutes at a treatment temperature of 160°C.

[0069] S4: The reactants in S3 are separated into solid and liquid, and the separated liquid is collected and concentrated to obtain 4200 parts of nutrient solution.

[0070] S5: Add 20 parts of urea, 10 parts of potassium polyphosphate, 6 parts of ammonium polyphosphate, 4 parts of high potassium phosphate, 10 parts of potassium dihydrogen phosphate, 8 parts of dipotassium hydrogen phosphate, 2 parts of potassium hydroxide and 10 parts of mineral potassium humate to the nutrient solution in S4 to obtain liquid humic acid water-soluble fertilizer.

[0071] Embodiment 4

[0072] This embodiment prepares a humic acid water-soluble fertilizer, and the preparation method is as follows:

[0073] S1: 536 parts of chicken manure, 120 parts of rice bran, 40 parts of molasses, 40 parts of seawater, 40 parts of rapeseed cake, 8 parts of weathered lignite, 8 parts of potassium hydroxide, 4 parts of citric acid and 4 parts of inorganic acid were put into a reactor.

[0074] S2: The material in the S1 reactor was subjected to subcritical water treatment for 40 minutes under stirring, the treatment temperature was 200°C, and the mass of water in the reactor was 6400 parts.

[0075] S3: Add 10 parts of dipotassium hydrogen phosphate and 30 parts of potassium dihydrogen phosphate, and continue subcritical water treatment for 20 minutes at a treatment temperature of 160°C.

[0076] S4: The reactants in S3 are separated into solid and liquid, and the separated liquid is collected and concentrated to obtain 4200 parts of nutrient solution.

[0077] S5: Add 20 parts of urea, 10 parts of potassium polyphosphate, 6 parts of ammonium polyphosphate, 4 parts of high potassium phosphate, 10 parts of potassium dihydrogen phosphate, 8 parts of dipotassium hydrogen phosphate, 2 parts of potassium hydroxide and 10 parts of mineral potassium humate to the nutrient solution in S4 to obtain liquid humic acid water-soluble fertilizer.

[0078] Embodiment 5

[0079] This embodiment prepares a humic acid water-soluble fertilizer, and the preparation method is as follows:

[0080] S1: 536 parts of chicken manure, 120 parts of rice bran, 40 parts of molasses, 40 parts of seawater, 40 parts of rapeseed cake, 8 parts of weathered lignite, 8 parts of potassium hydroxide, 4 parts of citric acid and 4 parts of inorganic acid were put into a reactor.

[0081] S2: The material in the S1 reactor was subjected to subcritical water treatment for 40 minutes under stirring, the treatment temperature was 200°C, and the mass of water in the reactor was 6400 parts.

[0082] S3: Add 12 parts of dipotassium hydrogen phosphate and 36 parts of potassium dihydrogen phosphate, and continue subcritical water treatment for 20 minutes at a treatment temperature of 160°C.

[0083] S4: The reactants in S3 are separated into solid and liquid, and the separated liquid is collected and concentrated to obtain 4200 parts of nutrient solution.

[0084] S5: Add 20 parts of urea, 10 parts of potassium polyphosphate, 6 parts of ammonium polyphosphate, 4 parts of high potassium phosphate, 10 parts of potassium dihydrogen phosphate, 8 parts of dipotassium hydrogen phosphate, 2 parts of potassium hydroxide and 10 parts of mineral potassium humate to the nutrient solution in S4 to obtain liquid humic acid water-soluble fertilizer.

[0085] Embodiment 6

[0086] This embodiment prepares a humic acid water-soluble fertilizer, and the preparation method is as follows:

[0087] S1: 536 parts of chicken manure, 120 parts of rice bran, 40 parts of molasses, 40 parts of seawater, 40 parts of rapeseed cake, 8 parts of weathered lignite, 8 parts of potassium hydroxide, 4 parts of citric acid and 4 parts of inorganic acid were put into a reactor.

[0088] S2: The material in the S1 reactor was subjected to subcritical water treatment for 40 minutes under stirring, the treatment temperature was 200°C, and the mass of water in the reactor was 6400 parts.

[0089] S3: Add 8 parts of dipotassium hydrogen phosphate and 24 parts of potassium dihydrogen phosphate, and continue subcritical water treatment for 20 minutes at a treatment temperature of 150°C.

[0090] S4: The reactants in S3 are separated into solid and liquid, and the separated liquid is collected and concentrated to obtain 4200 parts of nutrient solution.

[0091] S5: Add 20 parts of urea, 10 parts of potassium polyphosphate, 6 parts of ammonium polyphosphate, 4 parts of high potassium phosphate, 10 parts of potassium dihydrogen phosphate, 8 parts of dipotassium hydrogen phosphate, 2 parts of potassium hydroxide and 10 parts of mineral potassium humate to the nutrient solution in S4 to obtain liquid humic acid water-soluble fertilizer.

[0092] Embodiment 7

[0093] This embodiment prepares a humic acid water-soluble fertilizer, and the preparation method is as follows:

[0094] S1: 536 parts of chicken manure, 120 parts of rice bran, 40 parts of molasses, 40 parts of seawater, 40 parts of rapeseed cake, 8 parts of weathered lignite, 8 parts of potassium hydroxide, 4 parts of citric acid and 4 parts of inorganic acid were put into a reactor.

[0095] S2: The material in the S1 reactor was subjected to subcritical water treatment for 40 minutes under stirring, the treatment temperature was 200°C, and the mass of water in the reactor was 6400 parts.

[0096] S3: Add 8 parts of dipotassium hydrogen phosphate and 24 parts of potassium dihydrogen phosphate, and continue subcritical water treatment for 20 minutes at a treatment temperature of 170°C.

[0097] S4: The reactants in S3 are separated into solid and liquid, and the separated liquid is collected and concentrated to obtain 4200 parts of nutrient solution.

[0098] S5: Add 20 parts of urea, 10 parts of potassium polyphosphate, 6 parts of ammonium polyphosphate, 4 parts of high potassium phosphate, 10 parts of potassium dihydrogen phosphate, 8 parts of dipotassium hydrogen phosphate, 2 parts of potassium hydroxide and 10 parts of mineral potassium humate to the nutrient solution in S4 to obtain liquid humic acid water-soluble fertilizer.

[0099] Embodiment 8

[0100] This embodiment prepares a humic acid water-soluble fertilizer, and the preparation method is as follows:

[0101] S1: 536 parts of chicken manure, 120 parts of rice bran, 40 parts of molasses, 40 parts of seawater, 40 parts of rapeseed cake, 8 parts of weathered lignite, 8 parts of potassium hydroxide, 4 parts of citric acid and 4 parts of inorganic acid were put into a reactor.

[0102] S2: The material in the S1 reactor was subjected to subcritical water treatment for 40 minutes under stirring, the treatment temperature was 200°C, and the mass of water in the reactor was 6400 parts.

[0103] S3: Add 8 parts of dipotassium hydrogen phosphate and 24 parts of potassium dihydrogen phosphate, and continue subcritical water treatment for 20 minutes at a treatment temperature of 180°C.

[0104] S4: The reactants in S3 are separated into solid and liquid, and the separated liquid is collected and concentrated to obtain 4200 parts of nutrient solution.

[0105] S5: Add 20 parts of urea, 10 parts of potassium polyphosphate, 6 parts of ammonium polyphosphate, 4 parts of high potassium phosphate, 10 parts of potassium dihydrogen phosphate, 8 parts of dipotassium hydrogen phosphate, 2 parts of potassium hydroxide and 10 parts of mineral potassium humate to the nutrient solution in S4 to obtain liquid humic acid water-soluble fertilizer.

[0106] Embodiment 9

[0107] This embodiment prepares a humic acid water-soluble fertilizer, and the preparation method is as follows:

[0108] S1: 536 parts of chicken manure, 120 parts of rice bran, 40 parts of molasses, 40 parts of seawater, 40 parts of rapeseed cake, 8 parts of weathered lignite, 8 parts of potassium hydroxide, 4 parts of citric acid and 4 parts of inorganic acid were put into a reactor.

[0109] S2: The material in the S1 reactor was subjected to subcritical water treatment for 40 minutes under stirring, the treatment temperature was 200°C, and the mass of water in the reactor was 6400 parts.

[0110] S3: Add 8 parts of dipotassium hydrogen phosphate and 24 parts of potassium dihydrogen phosphate, and continue subcritical water treatment for 20 minutes at a treatment temperature of 190°C.

[0111] S4: The reactants in S3 are separated into solid and liquid, and the separated liquid is collected and concentrated to obtain 4200 parts of nutrient solution.

[0112] S5: Add 20 parts of urea, 10 parts of potassium polyphosphate, 6 parts of ammonium polyphosphate, 4 parts of high potassium phosphate, 10 parts of potassium dihydrogen phosphate, 8 parts of dipotassium hydrogen phosphate, 2 parts of potassium hydroxide and 10 parts of mineral potassium humate to the nutrient solution in S4 to obtain liquid humic acid water-soluble fertilizer.

[0113] Embodiment 10

[0114] This embodiment prepares a humic acid water-soluble fertilizer, and the preparation method is as follows:

[0115] S1: 536 parts of chicken manure, 120 parts of rice bran, 40 parts of molasses, 40 parts of seawater, 40 parts of rapeseed cake, 8 parts of weathered lignite, 8 parts of potassium hydroxide, 4 parts of citric acid and 4 parts of inorganic acid were put into a reactor.

[0116] S2: The material in the S1 reactor was subjected to subcritical water treatment for 40 minutes under stirring, the treatment temperature was 200°C, and the mass of water in the reactor was 6400 parts.

[0117] S3: Continue subcritical water treatment for 20 min and adjust the treatment temperature to 170°C.

[0118] S4: The reactants in S3 are separated into solid and liquid, and the separated liquid is collected and concentrated to obtain 4200 parts of nutrient solution.

[0119] S5: Add 20 parts of urea, 10 parts of potassium polyphosphate, 6 parts of ammonium polyphosphate, 4 parts of high potassium phosphate, 10 parts of potassium dihydrogen phosphate, 8 parts of dipotassium hydrogen phosphate, 2 parts of potassium hydroxide and 10 parts of mineral potassium humate to the nutrient solution in S4 to obtain liquid humic acid water-soluble fertilizer.

[0120] Comparative Example 1

[0121] 536 parts of chicken manure, 120 parts of rice bran, 40 parts of molasses, 40 parts of seawater, 40 parts of rapeseed cake, 8 parts of weathered lignite, 8 parts of potassium hydroxide, 4 parts of citric acid, 4 parts of inorganic acid and 6400 parts of water were mixed evenly and placed in a container for composting for 24 hours, and solid-liquid separation was performed, and the mass of the separated liquid was concentrated to 4200 parts to obtain humic acid water-soluble fertilizer.

[0122] Take 10 ml of each sample of the humic acid water-soluble fertilizer in Examples 1 to 9 and Comparative Example 1, dilute the sample and water at a ratio of 1:300, and let the diluted solution stand for 5 hours. Perform turbidity detection on the solution. The turbidity detection method is a turbidity detector. The detection data are shown in Table 1:

[0123] Table 1 Turbidity values ​​of samples of Examples 1 to 10 and Comparative Example 1

[0124] sample Turbidity value (NTU) Embodiment 1 4.8 Embodiment 2 3.2 Embodiment 3 2.6 Embodiment 4 2.9 Embodiment 5 5.4 Embodiment 6 4.3 Embodiment 7 1.9 Embodiment 8 2.3 Embodiment 9 5.1 Embodiment 10 13.7 Comparative Example 1 44.3

[0125] As shown in Table 1, the turbidity values ​​of the samples of Examples 1 to 9 are much smaller than the turbidity value of the sample of Comparative Example 1, indicating that the preparation method of the humic acid water-soluble fertilizer of the present application can improve the anti-flocculation property of the humic acid water-soluble fertilizer and avoid the flocculation phenomenon of the humic acid water-soluble fertilizer.

[0126] The total weight ratio of dipotassium hydrogen phosphate and potassium dihydrogen phosphate to the raw material in Examples 1 to 5 gradually increases. As the weight ratio increases, the turbidity value first decreases and then increases. The turbidity decreases because dipotassium hydrogen phosphate and potassium dihydrogen phosphate can combine with high-valent ions in the solution, passivate the high-valent ions, generate insoluble or poorly soluble substances, and reduce the concentration of high-valent ions in the solution. When the ion concentration reaches a certain level, the interaction between the colloidal particles in the solution will be enhanced, causing them to aggregate into larger agglomerates, forming flocculation, so that the turbidity values ​​of Examples 4 and 5 increase.

[0127] In Example 3 and Examples 6 to 9, the temperature after adding potassium dihydrogen phosphate and dipotassium hydrogen phosphate gradually increased. As the temperature increased, the turbidity value first decreased and then increased. The temperature can accelerate the passivation of high-valent ions by dipotassium hydrogen phosphate and potassium dihydrogen phosphate, but as the temperature further increases, the hydrogen bond network between water molecules is further destroyed, the polarity and dielectric constant of water decrease, resulting in its ability to dissolve and disperse solutes. Water in this state is not conducive to the effective passivation of heavy metal ions and the stable conversion of organic matter.

[0128] The difference between Example 7 and Example 10 is whether potassium dihydrogen phosphate and dipotassium hydrogen phosphate are added in the subcritical water treatment. The turbidity of Example 7 is less than that of Example 10, because subcritical water treatment can improve the solubility of water, and adding potassium dihydrogen phosphate and dipotassium hydrogen phosphate in the subcritical water treatment process can increase the solubility of phosphate ions in water, promote the phosphate in potassium dihydrogen phosphate and dipotassium hydrogen phosphate to combine with high-valent ions and form insoluble or insoluble precipitates, and at 170° C., the formed precipitate can be prevented from dissolving in the subcritical water treatment environment, effectively reducing the content of high-valent ions in the solution.

[0129] The above is based on the ideal embodiment of the present invention. Through the above description, relevant personnel can make various changes and modifications without departing from the technical concept of the present invention. The technical scope of the present invention is not limited to the content in the specification, and the technical scope must be determined according to the scope of the claims.

Claims

1. A method for preparing deflocculated liquid humic acid water-soluble fertilizer based on subcritical technology, characterized in that: The following steps are involved: S1: putting one or more raw materials of chicken manure, rice bran, molasses, seawater, rapeseed cake, weathered lignite, potassium hydroxide, citric acid, and inorganic acid into a reactor, wherein at least chicken manure is included; S2: subjecting the material in the S1 reactor to subcritical water treatment for 30-60 min under stirring; S3: adding dipotassium hydrogen phosphate and potassium dihydrogen phosphate, and continuing the subcritical water treatment for 10-20 minutes; S4: performing solid-liquid separation on the reactants in S3, collecting and concentrating the separated liquid to obtain a nutrient solution; S5: Adding additives to the nutrient solution in S4, wherein the additives contain urea, potassium polyphosphate, ammonium polyphosphate, high potassium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium hydroxide, and mineral potassium humate to obtain liquid humic acid water-soluble fertilizer.

2. The method for preparing a deflocculated liquid humic acid water-soluble fertilizer based on subcritical technology according to claim 1, characterized in that: The chicken manure content in the raw material in S1 is at least 50%, and the moisture content in the raw material is 20%-40%.

3. The method for preparing a deflocculated liquid humic acid water-soluble fertilizer based on subcritical technology according to claim 2, characterized in that: When all the raw materials in S1 are selected, the mass ratio of chicken manure, rice bran, molasses, seawater, rapeseed cake, weathered lignite, potassium hydroxide, citric acid, and inorganic acid is 0.5-0.7:0.1-0.2:0.05-0.1:0.05-0.1:0.05-0.1:0.01-0.05:0.01-0.05:0.005-0.01:0.005-0.

01.

4. The method for preparing a deflocculated liquid humic acid water-soluble fertilizer based on subcritical technology according to claim 1, characterized in that: In the S2 reactor, the mass ratio of raw materials to water is 1:4.2-1:12.

8.

5. The method for preparing a deflocculated liquid humic acid water-soluble fertilizer based on subcritical technology according to claim 1, characterized in that: The temperature of the subcritical water in S2 during treatment is 130°C-220°C.

6. The method for preparing a deflocculated liquid humic acid water-soluble fertilizer based on subcritical technology according to claim 1, characterized in that: The ratio of the dipotassium hydrogen phosphate to the potassium dihydrogen phosphate in S3 is 1:3, and the ratio of the total mass of the added dipotassium hydrogen phosphate and potassium dihydrogen phosphate to the raw material is 3%-5%.

7. The method for preparing a deflocculated liquid humic acid water-soluble fertilizer based on subcritical technology according to claim 1, characterized in that: The temperature of the subcritical water treatment in S3 is 160°C-180°C.

8. The method for preparing a deflocculated liquid humic acid water-soluble fertilizer based on subcritical technology according to claim 1, characterized in that: The S4 concentrates the separated liquid to obtain a nutrient solution, wherein the organic matter content of the nutrient solution is ≥30 g / L, the sum of the nitrogen content, phosphorus content and potassium content is ≥15 g / L, the humic acid content is ≥8 g / L, and the amino acid content is ≥5 g / L.

9. The method for preparing a deflocculated liquid humic acid water-soluble fertilizer based on subcritical technology according to claim 1, characterized in that: The ratio of urea, potassium polyphosphate, ammonium polyphosphate, high potassium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium hydroxide and mineral potassium humate added to S5 is 0.2-0.3:0.1-0.15:0.06-0.09:0.04-0.06:0.1-0.15:0.08-0.12:0.02-0.03:0.1-0.

15.

10. The method for preparing a deflocculated liquid humic acid water-soluble fertilizer based on subcritical technology according to claim 9, characterized in that: The ratio of the total mass of urea, potassium polyphosphate, ammonium polyphosphate, potassium perphosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium hydroxide and mineral potassium humate added to the S5 to the nutrient solution is 1:40-1:70.

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