Micromolecular carbon total-nutrient composite bio-organic fertilizer for conditioning soil and preparation method of micromolecular carbon total-nutrient composite bio-organic fertilizer

Abstract

The invention belongs to the technical field of water-soluble composite bio-organic fertilizers, and discloses a micromolecular carbon total-nutrient composite bio-organic fertilizer for conditioning soil and a preparation method of the micromolecular carbon total-nutrient composite bio-organic fertilizer. The organic fertilizer is prepared from the following raw materials in parts by mass: 40 to 48 parts of coal, 4.3 to 7 parts of nitric acid, 8.5 to 13 parts of potassium hydroxide, 20 to 35 parts of nitrogen fertilizer, 6.5 to 10 parts of phosphate fertilizer, 0.3 to 0.6 part of dispersing agent, 1.2 to 2.0 parts of amino acid, 0.04 to 0.08 part of trace element and 0.25 to 0.55 part of fungus bag. The prepared organic water-soluble fertilizer is high in humic acid content which is more than 4 times of the existing industrial standard NY1106-2010, good in water solubility, convenient to use, capable of being applied in a flushing mode, a drip irrigation mode, a spray irrigation mode, a flying prevention mode and the like, simple in technological process, free of dust, waste water, waste gas and waste residues in the production process, environmentally friendly, efficient, easy to operate and suitable for large-scale industrial production.

Description

Technical Field

[0001] This invention belongs to the field of water-soluble compound bio-organic fertilizer preparation technology, and in particular, a small-molecule carbon-rich compound bio-organic fertilizer for soil conditioning and its preparation method. Background Technology

[0002] Humic acid is a complex mixture of high-molecular-weight aromatic carboxylic acids, formed from the decomposition and synthesis of dead plant and animal remains (mainly plants) through microbial processes and complex geochemical processes. It is dark brown, weakly acidic, and widely distributed in low-grade coal, soil and its sediments, animal manure, organic fertilizers, and plant and animal remains. The black color of soil is often due to its humic acid content (soil containing little or no humic acid is yellow). Because it contains a large number of active groups (mainly carboxyl and phenolic hydroxyl groups), it has high chemical and biological activity. It can be used as a plant and animal growth conditioner, fertilizer synergist, pesticide slow-release synergist, soil conditioner, surfactant, binder, solubilizer, and anti-inflammatory and antibacterial agent, etc. Humic acid fertilizers have the effects of improving soil, increasing fertilizer utilization, stimulating crop growth, enhancing crop resistance, and increasing yield and quality.

[0003] In recent years, research and development of humic acid fertilizers has received increasing attention. Numerous studies and inventions based on humic acid have emerged in the market. However, most of these studies and inventions suffer from problems such as complex processes, huge equipment investment costs, high energy consumption, and potential environmental pollution, making it difficult to translate inventions into practical applications.

[0004] For example, the published patent CN107312183.A discloses an environmentally friendly production process for potassium nitrohumate. This patent discloses a process flow for producing nitrogen-containing potassium humate through a combination of mixed acid, alkalization, primary and secondary centrifugation, purification, spray granulation, and the generation of yellow smoke exhaust gas. The product obtained by this method is particulate potassium humate containing nitrogen. The process flow disclosed in this patent is complex, requires high equipment investment, has a long production cycle, high energy consumption, and poses a risk of air pollution.

[0005] Patent CN107011047B, published on September 11, 2018, discloses an organic water-soluble carbon fertilizer and its preparation method. This carbon fertilizer is made from humic acid, sodium oxide, nitric acid, phosphorus pentoxide, urea, boric acid, zinc sulfate, potassium oxide, a filtration loss reducer, and a suspending agent as raw materials. In the preparation process, humic acid reacts with sodium oxide, and then undergoes a nitration reaction with nitric acid to obtain a sodium nitrohumate slurry. A filtration loss reducer is then added, allowing phosphorus pentoxide to be added in a slurry environment for subsequent chelation reactions of multiple nutrients. This overcomes the drawback of traditional solid-state kneading reactions and phosphorus pentoxide grafting reactions, which require drying intermediate materials. The entire reaction process is a full slurry reaction, enabling continuous feeding and fully automated production. The process is simple and highly efficient. Furthermore, the nitration and chelation reactions are carried out in two separate reaction vessels, allowing for continuous cyclic production and reducing production costs. However, while the aforementioned comparative documents improved the humic acid content and water solubility of the product to some extent, they also had the following drawbacks: 1. Long reaction time: 15–24 hours from raw material input to pre-packaged product production. 2. High energy consumption: the method requires maintaining a temperature of 75–85°C for more than 11 hours. 3. Due to the use of sodium oxide in production, the generated sodium humate is not only detrimental but also harmful to crop growth. Related studies have shown that sodium humate is unsuitable for agriculture, mainly due to the high sodium content. + Sodium is not an element needed by plants. It will destroy chlorophyll, affecting plant photosynthesis and growth. In addition, too much sodium can lead to plant death. Furthermore, sodium ions have a strong dispersing effect and will damage soil structure.

[0006] Other commercially available fertilizers containing humic acid, as well as water-soluble fertilizers containing humic acid, are generally directly blended with lignite, weathered coal powder, or a small amount of potassium humate. The problems are: 1. Low humic acid content. Humic acid content should be ≥3% (solid type) or ≥30g / L (liquid type); 2. Low utilization rate. The humic acid in lignite and weathered coal powder is mainly water-insoluble brown humic acid and black humic acid; 3. Environmental pollution factors such as dust, wastewater, waste gas, and waste residue exist during the production process; 4. The process is cumbersome, complex, and has many uncontrollable factors, making continuous mass production impossible.

[0007] To address the problems raised in the background art, this invention proposes a small-molecule carbon-based complete nutrient compound bio-organic water-soluble fertilizer for soil conditioning and its preparation method. Summary of the Invention

[0008] The purpose of this invention is to overcome the shortcomings of the prior art and provide a small-molecule carbon-based complete nutrient compound bio-organic fertilizer for soil conditioning and its preparation method.

[0009] The technical solution adopted by this invention to solve its technical problem is:

[0010] A small-molecule carbon-rich, complete-nutrient compound bio-organic fertilizer for soil conditioning, wherein the organic fertilizer is prepared from the following raw materials in parts by weight:

[0011] Coal 40-48 parts, nitric acid 4.3-7 parts, potassium hydroxide 8.5-13 parts, nitrogen fertilizer 20-35 parts, phosphate fertilizer 6.5-10 parts, dispersant 0.3-0.6 parts, amino acids 1.2-2.0 parts, trace elements 0.04-0.08 parts, mushroom bags 0.25-0.55 parts.

[0012] Furthermore, it is prepared from the following raw materials in parts by weight: 44 parts coal, 11 parts potassium hydroxide, 6 parts nitric acid, 28.75 parts nitrogen fertilizer, 8 parts phosphate fertilizer, 0.43 parts dispersant, 1.42 parts amino acids, 0.05 parts trace elements, and 0.35 parts mushroom bags.

[0013] Furthermore, the coal is weathered lignite, lignite, or weathered coal; the nitrogen fertilizer is urea; the phosphate fertilizer is ammonium dihydrogen phosphate or diammonium hydrogen phosphate; and the dispersant is calcium lignosulfonate or sodium dodecylbenzenesulfonate.

[0014] Alternatively, the trace elements include amino acid chelated iron, 20% by mass of chelated iron (DTPA-Fe), 15% by mass of chelated zinc (EDTA-Zn), 10% by mass of humic acid chelated manganese, manganese sulfate, and 5% by mass of boric acid. The total mass fraction of all added substances is 100%. The above trace elements account for 1-3% of the mass of the final product of this invention. The pH is adjusted to 6.5-7.0 with humic acid to obtain the trace elements. The chelating ability of humic acid enhances the stability of the trace elements.

[0015] Furthermore, the inoculum package is a complex microbial agent containing a reasonable combination of various bacteria, including Bacillus, Pseudomonas, Trichoderma, nitrogen-fixing bacteria, and actinomycetes, possessing functional properties such as nitrogen fixation, phosphorus solubilization, potassium solubilization, secretion of plant growth hormones, and inhibition of pathogen growth. All the inoculum packages contain publicly available functional microbial strains. A single strain can be propagated in three stages: slant culture → seed culture → fermentation culture. Optimized nutrients and culture conditions are used for liquid fermentation to obtain a high-concentration, high-activity inoculum solution (viable cell count must reach 10^6). 8 -10 9 (CFU / mL or higher). After single-strain culture, the cultures must be mixed in proportion to ensure that each strain has a reasonable proportion in the composite system (to avoid dominant strains inhibiting other strains).

[0016] The inoculum package is a compound microbial inoculum, specifically composed of the following by volume ratio: 52% Bacillus subtilis inoculum, 23% Bacillus licheniformis inoculum, 6% Bacillus megaterium inoculum, 5% Bacillus mucilaginosus inoculum, 5% Azotobacter chrysophagus inoculum, 3% Pseudomonas fluorescens inoculum, 3% Trichoderma viride inoculum, and 3% Frankincense inoculum. The viable count of each inoculum reaches 10. 8 -10 9 CFU / mL or higher.

[0017] The application of small-molecule carbon complete nutrient compound bio-organic fertilizer in crop cultivation, as described above.

[0018] The preparation method of the small-molecule carbon-complete nutrient compound bio-organic fertilizer as described above includes the following steps:

[0019] S1. Take the crushed and sieved coal and put it into a container with a pre-added amount of water using a vacuum feeder according to the mass fraction. Stir the coal and water evenly to obtain material A.

[0020] S2. Pump material A into the second container, add a measured amount of nitric acid with adjusted pH and carry out nitration reaction for 3 hours. Maintain the reaction temperature between 1.0 and 3.0 to ensure oxidation efficiency, and obtain material B.

[0021] S3. Pump material B into the third container, add a certain amount of water and stir evenly, then add dispersant, potassium hydroxide, phosphate fertilizer, nitrogen fertilizer, amino acids and trace elements, stir at 50-180 r / min, and carry out neutralization, chelation and complexation reaction for 55 min to obtain material C.

[0022] S4. After material C is screened to remove impurities, it is pumped into the fourth container, and the inoculum bag is added. The mixture is stirred evenly, and the pH value is controlled between 5.5 and 7.5. The medium temperature is 30-40℃. After semi-anaerobic fermentation for 3-5 hours, it is ready for pre-packaging to obtain small molecule carbon full nutrient compound biological organic water-soluble fertilizer.

[0023] Furthermore, in step S1, the mass ratio of water to coal in the container is 0.6-0.9:1.

[0024] Furthermore, in step S2, the pH is adjusted to 1.0-3.0 with nitric acid. During the preparation of humic acid fertilizer via oxidation reaction using nitric acid, the pH of the reaction system needs to be precisely controlled in stages (maintaining 1.0-3.0 during the reaction stage to ensure oxidation efficiency, and adjusting the final product to 5.5-7.5 to suit fertilizer application). Weathered lignite, lignite, and weathered coal (organic matter ≥80%) are suitable for use with 50% nitric acid, and the initial pH can be stabilized at 1.5-2.0.

[0025] Furthermore, in step S3, the mass ratio of water to coal added is 1.08-1.25:1.

[0026] Furthermore, in step S3, the total time for the neutralization, chelation, and complexation reactions is 55 minutes. Reasonable control of the time can reduce energy consumption (such as shortening the ineffective reaction time) and improve production economy while ensuring product quality.

[0027] The advantages and positive effects of this invention are as follows:

[0028] 1. The compound bio-organic water-soluble fertilizer prepared by this invention has a humic acid content (on a dry basis) of over 35%, exceeding the requirement of a total humic acid mass fraction of ≥25% for superior grade humic acid bio-organic fertilizers, as specified in the chemical industry standard HG / T 5332-2018. It also reaches more than four times the humic acid content requirement of ≥30g / L in the existing agricultural industry standard (NY 1106-2010 "Water-soluble Fertilizers Containing Humic Acid"). It exhibits good water solubility (based on the relevant requirements of the "Water-soluble Fertilizers Containing Humic Acid" standard (NY 1106-2010), the measured water-insoluble matter (indirectly reflecting water solubility) content is <10g / L, lower than the explicit standard requirement of <50g / L). It is convenient to use, suitable for fertigation, drip irrigation, sprinkler irrigation, and aerial spraying. Furthermore, the process is simple, with no dust, wastewater, waste gas, or waste residue generated during production, making it environmentally friendly, efficient, easy to operate, and suitable for large-scale industrial production.

[0029] 2. This invention's compound bio-organic fertilizer is rich in humic acid and biological agents, possessing functions such as fertilizer enhancement, soil improvement, crop growth stimulation, and improved agricultural product quality (humic acid content ≥130g / L; biological agents conform to NY / T 798-2015 standard, with an effective viable count ≥0.2 billion / mL, a miscellaneous bacteria rate ≤3.0%, and no detectable pathogens). Combined with the trial results analysis from the Shandong Shouguang Vegetable Research and Development Center of the Chinese Academy of Agricultural Sciences, applying 100mg / plant of bio-humic acid to tomato roots increases soluble solids content by 12%-15%, vitamin C content by 8%-10%, lycopene content by increasing, and total sugar content reaches its peak, while titratable acid content is at its lowest. In greenhouses with continuous tomato cropping, the application of humic acid bio-fertilizer reduces blossom-end rot incidence by 80%, increases the sugar-acid ratio of fruit by 2.1 times, and achieves a marketable fruit rate of 95%. It is suitable for various crops and soil conditions, especially for facility agriculture, horticultural crops, and cash crops where high fertilizer quality and utilization rates are required. When using fertilizer, the amount and method of application should be determined rationally based on factors such as crop type, growth stage, and soil fertility (select application according to crop growth stage; focus on the root-promoting effects of humic acid and amino acids during the seedling stage, and increase the amount of nitrogen, phosphorus, and potassium during the fruit-expanding stage. At the same time, soil testing should be carried out. If the soil is deficient in elements (such as calcium), a formula product with targeted chelated trace elements can be selected to improve the corrective effect).

[0030] 3. The method of this invention combines mineral physicochemical reactions with biological fermentation. The process chelates metal ions, macro-, meso-, and micro-elements, resulting in a product rich in nitrogen, phosphorus, potassium, macro-, meso-, and micro-elements, humic acid, small-molecule carbon, polypeptides, amino acids, and beneficial soil bacteria. It is nutritionally comprehensive and possesses excellent water solubility (after nitric acid oxidation-ammoniation treatment, the water-soluble humic acid content of lignite can be increased from 5%-10% in the raw ore to over 95%, and the proportion of small-molecule components (molecular weight < 5000 Da) reaches over 80%, making it easier for crop roots to directly absorb. The product's water solubility index shows a water-insoluble content ≤ 10 g / L (NY 1106-2010 standard ≤ 50 g / L) (the actual measured value of water-insoluble content, as determined by third-party testing, is 3 g / L), and it can completely pass through an 80-mesh sieve, making it suitable for drip irrigation and sprinkler irrigation systems, preventing clogging.

[0031] In greenhouse vegetables, water-soluble humic acid fertilizer, when applied via drip irrigation, increases fertilizer utilization by 40%-60% compared to traditional organic fertilizer, and reduces irrigation water consumption by more than 30% (compared to furrow application of organic fertilizer). This fertilizer can improve soil, reduce the use of traditional chemical fertilizers, increase fertilizer utilization, increase yield, and improve crop quality, especially in alleviating and improving soil degradation problems such as acidification, salinization, and compaction. When the microorganisms in the aforementioned inoculum are introduced for fermentation, the microorganisms can not only decompose organic matter to produce polypeptides and amino acids (free amino acid content can reach 5%-10%), but also secrete plant hormones such as auxin and cytokinin through metabolic activities, enhancing the function of "stimulating crop growth". During fermentation, microorganisms can convert some inorganic nitrogen into organic nitrogen (such as amino acid nitrogen), reducing nitrogen loss; at the same time, the polysaccharide components of the microbial cell wall can react with metal ions (such as Fe). 3+ Zn 2+ It forms stable chelates, improving the availability of trace elements (chelation rate can reach 30%-50%).

[0032] The compound bio-organic fertilizer prepared by this invention has a high humic acid content, is nutritionally complete, has good water solubility, and is easy to use. It can be applied through fertigation, drip irrigation, sprinkler irrigation, and aerial spraying. After two years of continuous application of this product to the soil, the organic matter content increases by 0.3-0.5 percentage points, and the bulk density decreases by 0.1-0.2 g / cm³. 3 (Clay soil) shows an increase in porosity of 5%-8%, effectively improving it. Moreover, the process is simple, with no dust, wastewater, waste gas, or waste residue generated during production. It is highly efficient, clean, environmentally friendly, easy to operate, and suitable for large-scale industrial production.

[0033] The main raw material, lignite, is produced through a process of soaking, wet ball milling, and high-pressure homogenization (solid-liquid ratio 1:3). The particle size can reach over 200 mesh, and the dust emission concentration during the grinding process is ≤10mg / m³. 3 (far below the national standard of 30mg / m³) 3Furthermore, the grinding liquid can directly enter the next process, generating no solid waste. The bio-fermentation stage uses a closed fermenter with a waste gas recovery device. Through the metabolism of compound microorganisms, the organic matrix is ​​converted into active substances. The small amount of carbon dioxide produced during fermentation can be used to adjust the pH value after washing with water, with no toxic waste gas emissions. The fermentation residue, with an organic matter content of ≥60%, can be completely recycled for fertilizer granulation, achieving "zero waste residue". Chelation and blending stage: The entire process is completed in a semi-solid system, with the temperature controlled at 40-50℃ and the mixture stirred evenly. The chelation reaction conversion rate of metal ions with humic acid and amino acids reaches over 90%, with no wastewater discharge (the mother liquor can be recycled, and the water replenishment is only used to balance the evaporation rate).

[0034] This invention, a compound bio-organic fertilizer, retains the activity of humic acid and biological agents (the effective live bacteria count remains ≥150 million / mL after 6 months of storage) while achieving the characteristics of "low emissions, high efficiency, and easy operation" for large-scale production. Its products not only meet the requirements of standards such as NY 1106-2010 (water-soluble fertilizer containing humic acid) and HG / T 5332-2018 (humic acid bio-organic fertilizer), but also pass "clean production certification." In the current context of reducing fertilizer use and increasing efficiency, and increasingly stringent environmental policies, it possesses significant technological and market competitiveness.

[0035] 4. The production process (combination of mineral physicochemical reaction and biological fermentation) and product characteristics of this invention embody the invention concept of "synergistic effect" of modern fertilizers by using the synergistic effect of physicochemical reaction and biological fermentation. Attached Figure Description

[0036] Figure 1 This is a flowchart illustrating the preparation process of the small-molecule carbon-based complete nutrient compound bio-organic water-soluble fertilizer of this invention.

[0037] Figure 2 These are comparison images of greenhouse tomatoes after being irrigated with the product of this invention;

[0038] Figure 3 These are comparison images of greenhouse peppers irrigated with the product of this invention.

[0039] Figure 4 These are comparison images of watermelons irrigated with the product of this invention.

[0040] Figure 5 This is a comparison image of field grapes after being irrigated with the product of this invention. Detailed Implementation

[0041] The present invention will be further described below with reference to the embodiments. The following embodiments are descriptive and not limiting, and should not be used to limit the scope of protection of the present invention.

[0042] The various experimental operations involved in the specific embodiments are all conventional techniques in the field. For parts not specifically annotated in this document, those skilled in the art can refer to various commonly used reference books, scientific and technological documents or related instructions and manuals prior to the filing date of this invention to carry out the operations.

[0043] A small-molecule carbon-rich, complete-nutrient compound bio-organic fertilizer for soil conditioning, wherein the organic fertilizer is prepared from the following raw materials in parts by weight:

[0044] Coal 40-48 parts, nitric acid 4.3-7 parts, potassium hydroxide 8.5-13 parts, nitrogen fertilizer 20-35 parts, phosphate fertilizer 6.5-10 parts, dispersant 0.3-0.6 parts, amino acids 1.2-2.0 parts, trace elements 0.04-0.08 parts, mushroom bags 0.25-0.55 parts.

[0045] Preferably, it is prepared from the following raw materials in parts by weight: 44 parts coal, 11 parts potassium hydroxide, 6 parts nitric acid, 28.75 parts nitrogen fertilizer, 8 parts phosphate fertilizer, 0.43 parts dispersant, 1.42 parts amino acids, 0.05 parts trace elements, and 0.35 parts mushroom bags.

[0046] Preferably, the coal is weathered lignite, lignite or weathered coal, the nitrogen fertilizer is urea, the phosphate fertilizer is ammonium dihydrogen phosphate or diammonium hydrogen phosphate, and the dispersant is calcium lignosulfonate or sodium dodecylbenzenesulfonate.

[0047] Alternatively, the trace elements include amino acid chelated iron, 20% by mass of chelated iron (DTPA-Fe), 15% by mass of chelated zinc (EDTA-Zn), 10% by mass of humic acid chelated manganese, manganese sulfate, and 5% by mass of boric acid. The total mass fraction of all added substances is 100%. The above trace elements account for 1-3% of the mass of the final product of this invention. The pH is adjusted to 6.5-7.0 with humic acid to obtain the trace elements. The chelating ability of humic acid enhances the stability of the trace elements.

[0048] Preferably, the inoculum package is a compound microbial agent containing a reasonable combination of various bacteria, including Bacillus, Pseudomonas, Trichoderma, nitrogen-fixing bacteria, and actinomycetes, possessing functional properties such as nitrogen fixation, phosphorus solubilization, potassium solubilization, secretion of plant growth hormones, and inhibition of pathogen growth. All the inoculum packages contain publicly available functional microbial strains. A single strain can be propagated in three stages: slant culture → seed culture → fermentation culture. Optimized nutrients and culture conditions are used for liquid fermentation to obtain a high-concentration, high-activity inoculum solution (viable cell count must reach 10^6). 8 -10 9 (CFU / mL or higher). After single-strain culture, the cultures must be mixed in proportion to ensure that each strain has a reasonable proportion in the composite system (to avoid dominant strains inhibiting other strains).

[0049] The inoculum package is a compound microbial inoculum, specifically composed of the following by volume ratio: 52% Bacillus subtilis inoculum, 23% Bacillus licheniformis inoculum, 6% Bacillus megaterium inoculum, 5% Bacillus mucilaginosus inoculum, 5% Azotobacter chrysophagus inoculum, 3% Pseudomonas fluorescens inoculum, 3% Trichoderma viride inoculum, and 3% Frankincense inoculum. The viable count of each inoculum reaches 10. 8 -10 9 CFU / mL or higher.

[0050] The application of small-molecule carbon complete nutrient compound bio-organic fertilizer in crop cultivation, as described above.

[0051] The preparation method of the small-molecule carbon-complete nutrient compound bio-organic fertilizer as described above includes the following steps:

[0052] S1. Take the crushed and sieved coal and put it into a container with a pre-added amount of water using a vacuum feeder according to the mass fraction. Stir the coal and water evenly to obtain material A.

[0053] S2. Pump material A into the second container, add a measured amount of nitric acid with adjusted pH and carry out nitration reaction for 3 hours. Maintain the reaction temperature between 1.0 and 3.0 to ensure oxidation efficiency, and obtain material B.

[0054] S3. Pump material B into the third container, add a certain amount of water and stir evenly, then add dispersant, potassium hydroxide, phosphate fertilizer, nitrogen fertilizer, amino acids and trace elements, stir at 50-180 r / min, and carry out neutralization, chelation and complexation reaction for 55 min to obtain material C.

[0055] S4. After material C is screened to remove impurities, it is pumped into the fourth container, and the inoculum bag is added. The mixture is stirred evenly, and the pH value is controlled between 5.5 and 7.5. The medium temperature is 30-40℃. After semi-anaerobic fermentation for 3-5 hours, it is ready for pre-packaging to obtain small molecule carbon full nutrient compound biological organic water-soluble fertilizer.

[0056] Preferably, in step S1, the mass ratio of water to coal in the container is 0.6-0.9:1.

[0057] Preferably, in step S2, the pH adjusted by nitric acid is 1.0-3.0. During the preparation of humic acid fertilizer via oxidation reaction using nitric acid, the pH of the reaction system needs to be precisely controlled in stages (maintaining 1.0-3.0 during the reaction stage to ensure oxidation efficiency, and adjusting the final product to 5.5-7.5 to suit fertilizer application). Weathered lignite, lignite, and weathered coal (organic matter ≥80%) are suitable for use with 50% nitric acid, and the initial pH can be stabilized at 1.5-2.0.

[0058] Preferably, in step S3, the mass ratio of water to coal is 1.08-1.25:1.

[0059] Preferably, in step S3, the total time for neutralization, chelation, and complexation reactions is 55 minutes. Reasonable control of the time can reduce energy consumption (such as shortening the ineffective reaction time) and improve production economy while ensuring product quality.

[0060] Specifically, the relevant preparation and testing methods are as follows:

[0061] Example 1

[0062] A small-molecule carbon-based complete nutrient compound bio-organic water-soluble fertilizer for soil conditioning is prepared from the following raw materials in parts by weight: 40 parts coal, 10.3 parts potassium hydroxide, 6.5 parts nitric acid, 31 parts nitrogen fertilizer, 8.5 parts phosphate fertilizer, 0.35 parts dispersant, 1.77 parts amino acids, 0.05 parts trace elements, and 0.43 parts microbial bags.

[0063] The coal is lignite, the nitrogen fertilizer is urea, the dispersant is calcium lignosulfonate, the phosphate fertilizer is diammonium hydrogen phosphate, and the inoculum package is a compound microbial agent containing multiple excellent characteristics such as Bacillus subtilis, Bacillus licheniformis, phosphate-solubilizing bacteria, and potassium-solubilizing bacteria, with reasonable compatibility and strong functionality.

[0064] The bacterial culture bags contain known functional microbial strains. A single strain can be propagated in three stages: slant culture → seed culture → fermentation culture. Optimized nutrients and culture conditions are used for liquid fermentation to obtain a high-concentration, high-activity bacterial solution (viable cell count must reach 10^6). 8 -10 9 (CFU / mL or higher). After single-strain culture, the cultures must be mixed in proportion to ensure a reasonable ratio of each strain in the composite system (to avoid dominant strains inhibiting other strains). The inoculum package is a composite microbial agent, specifically composed of Bacillus subtilis 52% culture, Bacillus licheniformis 23% culture, Bacillus megaterium 6% culture, Bacillus mucilaginosus 5% culture, Azotobacter chrysophagus 5% culture, Pseudomonas fluorescens 3% culture, Trichoderma viride 3% culture, and Frankelbrium 3% culture, with each culture containing at least 10 live bacteria. 8 -10 9 CFU / mL or higher.

[0065] The trace elements include amino acid chelated iron, 20% chelated iron (DTPA-Fe), 15% chelated zinc (EDTA-Zn), 10% humic acid chelated manganese, manganese sulfate, and 5% boric acid. The total mass fraction of all added substances is 100%. The above trace elements account for 1-3% of the mass of the final product of this invention. The pH is adjusted to 6.5-7.0 with humic acid. The chelating ability of humic acid is used to enhance the stability of the trace elements, thus obtaining the trace elements.

[0066] A method for preparing a small-molecule carbon-based, fully nutrient-rich, compound bio-organic water-soluble fertilizer for soil conditioning, such as... Figure 1 As shown, it includes the following steps:

[0067] S1. Take the crushed and screened lignite and put it into a container with a pre-added amount of water using a vacuum feeder. After mixing the coal and water evenly, material A is obtained.

[0068] S2. Pump material A into the second container, add a measured amount of pH-adjusted nitric acid, and carry out a nitration reaction for 3 hours to obtain material B. Maintain the reaction temperature between 1.0 and 3.0 during the reaction stage to ensure oxidation efficiency.

[0069] S3. Pump material B into the third container, add a certain amount of water and dispersant, stir evenly, then add potassium hydroxide, phosphate fertilizer, nitrogen fertilizer, amino acids and trace elements, stir at 50-180 r / min, and carry out neutralization, chelation and complexation reaction for 55 min to obtain material C.

[0070] S4. After material C is screened to remove impurities, it is pumped into the fourth container, and a quantitative inoculum packet is added and stirred evenly. The pH value is controlled between 5.5 and 7.5, and the temperature is 30-40℃. Semi-anaerobic fermentation is carried out for 4 hours before use. This yields the small-molecule carbon-based complete nutrient compound bio-organic water-soluble fertilizer.

[0071] In step S1, the mass ratio of water to coal in the container is 0.7:1.

[0072] In step S3, the mass ratio of water to coal added to the liquid humic acid bio-organic fertilizer is 1.14:1.

[0073] Example 2

[0074] This embodiment is basically the same as Embodiment 1, except that a small molecule carbon complete nutrient compound bio-organic water-soluble fertilizer for soil conditioning is prepared from the following raw materials in parts by weight: 47 parts coal, 11 parts potassium hydroxide, 6.9 parts nitric acid, 28 parts nitrogen fertilizer, 6.8 parts phosphate fertilizer, 0.54 parts dispersant, 0.06 parts trace elements, and 0.25 parts microbial bags.

[0075] The coal is weathered coal, the nitrogen fertilizer is urea, the phosphate fertilizer is ammonium dihydrogen phosphate, the dispersant is sodium lignosulfonate, and the inoculum package is a compound microbial agent containing multiple excellent characteristics such as Bacillus subtilis, Bacillus licheniformis, phosphate-solubilizing bacteria, and potassium-solubilizing bacteria, with reasonable compatibility and strong functionality.

[0076] The bacterial culture bags contain known functional microbial strains. A single strain can be propagated in three stages: slant culture → seed culture → fermentation culture. Optimized nutrients and culture conditions are used for liquid fermentation to obtain a high-concentration, high-activity bacterial solution (viable cell count must reach 10^6). 8 -10 9 (CFU / mL or higher). After single-strain culture, the cultures must be mixed in proportion to ensure a reasonable ratio of each strain in the composite system (to avoid dominant strains inhibiting other strains). The inoculum package is a composite microbial agent, specifically composed of Bacillus subtilis 52% culture, Bacillus licheniformis 23% culture, Bacillus megaterium 6% culture, Bacillus mucilaginosus 5% culture, Azotobacter chrysophagus 5% culture, Pseudomonas fluorescens 3% culture, Trichoderma viride 3% culture, and Frankelbrium 3% culture, with each culture containing at least 10 live bacteria. 8 -10 9 CFU / mL or higher.

[0077] The trace elements include amino acid chelated iron, 20% chelated iron (DTPA-Fe), 15% chelated zinc (EDTA-Zn), 10% humic acid chelated manganese, manganese sulfate, and 5% boric acid. The total mass fraction of all added substances is 100%. The above trace elements account for 1-3% of the mass of the final product of this invention. The pH is adjusted to 6.5-7.0 with humic acid. The chelating ability of humic acid is used to enhance the stability of the trace elements, thus obtaining the trace elements.

[0078] 47 parts coal, 11 parts potassium hydroxide, 6.9 parts nitric acid, 28 parts nitrogen fertilizer, 6.8 parts phosphate fertilizer, 0.54 parts dispersant, 0.06 parts trace elements, and 0.25 parts mushroom bags.

[0079] A method for preparing a small-molecule carbon-based, fully nutrient-rich, compound bio-organic water-soluble fertilizer for soil conditioning includes the following steps:

[0080] S1. Take the crushed and screened weathered coal and put it into a container with a pre-added amount of water using a vacuum feeder. After mixing the coal and water evenly, material A is obtained.

[0081] S2. Pump material A into the second container, add a certain amount of nitric acid and carry out a nitration reaction for 3 hours to obtain material B. Maintain the reaction phase at 1.0-3.0 to ensure oxidation efficiency.

[0082] S3. Pump material B into the third container, add a certain amount of water and dispersant, stir evenly, then add potassium hydroxide, phosphate fertilizer, nitrogen fertilizer, amino acids and trace elements, stir at 50-180 r / min, and carry out chelation and complexation reaction for 50 min to obtain material C.

[0083] S4. After material C is screened to remove impurities, it is pumped into the fourth container, a quantitative inoculum packet is added and stirred evenly, the pH value is controlled between 5.5 and 7.5, the medium temperature is 30-40℃, and it is semi-anaerobic fermented for 5 hours for later use. The small molecule carbon complete nutrient compound biological organic water-soluble fertilizer is then obtained.

[0084] In step S1, the mass ratio of water to coal in the container is 0.9:1.

[0085] In step S3, the mass ratio of water to coal added to the small molecule carbon total nutrient compound bio-organic water-soluble fertilizer is 1.25:1.

[0086] The core component functions and detection criteria of the small molecule carbon composite bio-organic fertilizer produced by the method of this invention in the two embodiments are shown in the table below.

[0087]

[0088] Comparative Example

[0089] The preparation method is largely the same as in the examples, except that:

[0090] In Comparative Example 1, coal was replaced with other humic acid / organic matter sources. Coal (such as lignite and weathered coal) mainly provides humic acid and mineral-derived organic matter, and the replacement material needs to have similar organic matter content and soil-improving function. In comparison, coal was replaced with an equal amount of "peat (30% humic acid content)" or "straw biochar (60% carbon content, 80% organic matter)," while the remaining raw materials (calcium lignosulfonate, phosphate-solubilizing bacteria, potassium-solubilizing bacteria, etc.) and process parameters remained unchanged, identical to Example 1. Peat tends to have higher humic acid activity, but its rapid mineralization may lead to a decrease in the long-term effectiveness of humic acid in the product; biochar organic matter is mainly composed of a carbon skeleton, with a low humic acid content (usually <10%), which may reduce the water-soluble humic acid content of the product by 10%-20%, weakening its immediate nutrient supply capacity to crops.

[0091] In Comparative Example 2, calcium lignosulfonate was replaced with other chelating / dispersing agents with similar functions. Calcium lignosulfonate mainly functions to chelate metal ions and improve fertilizer dispersibility and water solubility; the replacement material needs to have similar surface activity and chelating ability. In comparison, calcium lignosulfonate was replaced by sodium carboxymethyl cellulose (CMC, viscosity 500 mPa·s) or sodium alginate (low molecular weight, 200-300 Da), with other raw materials and processes remaining unchanged, identical to Example 1. This can easily result in weaker chelating ability of CMC (for Fe). 3+ Zn 2+The chelation rate is 20%-30% lower than that of calcium lignosulfonate, which may lead to a decrease in the availability of trace elements and an increase in the water-insoluble content of the product by 5%-8%. Sodium alginate has good water solubility, but its cost is higher (about 3 times that of calcium lignosulfonate), and it is easily decomposed by microorganisms during high-temperature fermentation, which may reduce the stability of the product.

[0092] In Comparative Example 3, phosphate-solubilizing bacteria were replaced with other phosphorus-activating microorganisms. Phosphate-solubilizing bacteria (such as Bacillus) decompose insoluble phosphorus in the soil by secreting organic acids. The replacements needed to have equivalent phosphorus-solubilizing efficiency and environmental adaptability. In comparison, "Bacillus megaterium (effective viable count 2 billion / g)" or "Aspergillus niger (spore powder, viable count 1 billion / g)" were used to replace the original phosphate-solubilizing bacteria. The addition amount was adjusted to ensure the total viable count was consistent with Example 1 (e.g., 1% of the original phosphate-solubilizing bacteria was added, while 2% was added when replaced with Aspergillus niger to ensure equivalent activity). All other raw materials and processes remained unchanged, the same as in Example 1. The results showed that the phosphorus-solubilizing ability of Bacillus megaterium was close to that of the original bacteria, but its activity decreased by 30% in acidic soil (pH < 5.5), which may lead to a decrease in the effective phosphorus enhancement effect when applied to acidic plots. Aspergillus niger is a fungus with high phosphorus-solubilizing efficiency (especially for calcium phosphate), but its compatibility with potassium-solubilizing bacteria (bacteria) is poor, which may lead to a 15%-20% decrease in the total viable count of the product.

[0093] In Comparative Example 4, potassium-solubilizing bacteria were replaced with other potassium-activating microorganisms. Potassium-solubilizing bacteria (such as silicate bacteria) release potassium by decomposing feldspar and mica, and the replacements need to have similar silicate degradation capabilities. In comparison, "Bacillus mucilaginosus (2 billion viable cells / g)" or "Bacillus circulans (1.5 billion viable cells / g)" were used to replace the original potassium-solubilizing bacteria. The addition amount was adjusted according to the principle of equivalent viable cell count (e.g., 1.5% for the original potassium-solubilizing bacteria, 2% for Bacillus circulans), with all other raw materials and processes remaining unchanged, as in Example 1. The results showed that Bacillus mucilaginosus has a strong potassium-solubilizing ability but a high carbon source requirement. If the product lacks organic matter, the viable cell count may decrease by up to 40% during storage (>6 months) compared to <20% for the original potassium-solubilizing bacteria. Bacillus circulans has strong environmental adaptability, but its potassium-solubilizing efficiency is only 70%-80% of that of the original potassium-solubilizing bacteria, which may lead to a 5%-10% reduction in crop potassium absorption (taking corn seedlings as an example).

[0094] By comparing Example 1, Comparative Example 1, and Comparative Example 2, it can be seen that coal and calcium lignosulfonate have a synergistic effect in this invention, which can synergistically improve the relevant performance of the prepared small molecule carbon complete nutrient compound bio-organic fertilizer. In particular, when the mass ratio of coal to dispersant is 40:0.35, coal and calcium lignosulfonate have a significant synergistic effect, which can significantly improve the relevant performance of the prepared small molecule carbon complete nutrient compound bio-organic fertilizer.

[0095] By comparing Example 1, Comparative Example 1 and Comparative Example 3, it can be seen that coal and potassium-solubilizing bacteria have a synergistic effect in this invention, which can synergistically improve the relevant performance of the prepared small molecule carbon complete nutrient compound bio-organic fertilizer, especially when coal.

[0096] By comparing Example 1, Comparative Example 2 and Comparative Example 3, it can be seen that calcium lignosulfonate and potassium-solubilizing bacteria in this invention have a synergistic effect, which can synergistically improve the relevant performance of the prepared small molecule carbon complete nutrient compound bio-organic fertilizer, especially when coal.

[0097] Experimental Example 1

[0098] In 2022, an experimental planting of Chinese yam was conducted in Xiangyun Town, Wen County, Henan Province. The experimental field was divided into two plots, each 0.2 mu (approximately 0.03 hectares). Plot 1: 16 kg of compound fertilizer (nitrogen:phosphorus:potassium = 15:15:15) was applied as base fertilizer, and 2 kg of commercially available compound fertilizer was applied as top dressing during the seedling stage and the elongation stage, for a total fertilizer application of 20 kg.

[0099] Block 2: Apply 16 kg of ternary compound fertilizer (nitrogen: phosphorus: potassium = 15:15:15) as base fertilizer, and apply 2 kg of small molecule biological organic carbon fertilizer produced by this technology at the seedling stage and the elongation stage, for a total fertilizer application of 20 kg.

[0100] There were no significant differences in plant height, stem, and leaf color between the two blocks during the seedling stage (from sowing to mid-May) and the vigorous growth period of stems and vines (late May to late June). During the underground tuber elongation and swelling period (early July to early October), the leaves in Block 2 were significantly larger and thicker than those in Block 1, and the leaves were dark green and glossy.

[0101] During the senescence period (mid-October to early November), 70% of the leaves above ground in Block 1 turned yellow, and 60% of the leaves above ground in Block 2 turned yellow, indicating that Block 2 has a longer photosynthetic cycle and can produce more nutrients to supply the growth of underground rhizomes.

[0102] During the harvest season, the average length of Block 1 was 55.62cm, the average diameter was 2.25cm, the color was light yellow with black spots, the appearance was good, and the grade was qualified.

[0103] Block 2 has an average length of 65.86cm, an average diameter of 2.66cm, a light yellow color, no black spots, good condition, and is graded as excellent.

[0104] Yield: Block 1 yielded 1332.81 kg / mu, and Block 2 yielded 1599.17 kg / mu. Block 2 yielded 226.36 kg / mu more than Block 1, representing an increase of 19.98%.

[0105] Experiment Example 2

[0106] From 2022 to 2024, this fertilizer was continuously used for three consecutive years in a 20-mu (approximately 3.3 hectares) strawberry field at the You's Strawberry Garden of Henan Runtu Biotechnology Co., Ltd. in Zhengyang County, Zhumadian City. The resulting strawberries were naturally plump, brightly colored, and significantly sweeter than those grown with other fertilizers. Regular-sized berries (weighing approximately 20-30g) were 2-3g heavier than those grown with other fertilizers. They had a shelf life of 5-7 days at room temperature. The taste was sweet but not cloying, making them a delightful treat. The strawberry plants were healthy, with well-developed root systems and thick leaves. No diseases occurred during the three consecutive years of cultivation.

[0107] Experimental Example 3

[0108] From 2022 to 2025, a three-year wheat planting experiment was conducted on a 1.2-mu plot of land in Yangqiao Village, Xulou Administrative Village, Zhidian Town, Shenqiu County, Henan Province. The wheat seeds used were selected by the farmers themselves. Before sowing, 20 kg of small-molecule carbon complete nutrient bio-organic fertilizer and 20 kg of balanced NPK compound fertilizer per mu were applied as base fertilizer. Small-molecule carbon complete nutrient bio-organic fertilizer was sprayed foliarly once each at three stages: jointing, heading, and flowering, at a rate of 50 g / mu diluted with 15 kg of water. Significant results were achieved for three consecutive years in 2023, 2024, and 2025. The wheat seedlings were strong, the ears were plump, and the grains were full. The yield per mu exceeded that of surrounding plots by 8-10%. The flour milled from the harvested wheat had a high gluten content and a rich wheat aroma. Compared with conventional fertilization, the small-molecule carbon complete nutrient compound bio-organic fertilizer prepared by this invention can effectively improve soil chemical properties, increasing the content of soil organic matter, available nitrogen, phosphorus, and available potassium by 4.8%–8.0%, 10%–12.8%, 18.6%–33.2%, and 32.2%–40.7%, respectively.

[0109] Using this invented product can increase crop yield and improve product quality. Experiments with other field crops such as corn and wheat, and greenhouse vegetables and fruits such as tomatoes, green beans, peppers, strawberries, and melons, have yielded increases ranging from 10% to 40%, with significant improvements in fruit quality. In pepper cultivation, applying this fertilizer as both basal and top dressing significantly develops the plant's root system, enhancing its ability to acquire nutrients, resulting in a 15%-25% increase in yield and a 20% increase in the percentage of first-grade fruit (with a better fruit shape index). After application to grapes, the soluble solids content increased by 1.5-2.0°Brix, anthocyanin content increased by 10%-15%, and taste and color were significantly improved. Furthermore, after application in greenhouses, common soil nematode diseases in greenhouse cultivation were significantly reduced and eliminated, demonstrating a significant soil improvement effect. Figures 2 to 5 As shown.

[0110] Although embodiments of the invention have been disclosed for illustrative purposes, those skilled in the art will understand that various substitutions, variations, and modifications are possible without departing from the spirit and scope of the invention and the appended claims. Therefore, the scope of the invention is not limited to the contents disclosed in the embodiments.

Claims

1. A small-molecule carbon-based, fully nutrient-rich, compound bio-organic fertilizer for soil conditioning, characterized in that: The organic fertilizer is prepared from the following raw materials in parts by weight: Coal 40-48 parts, nitric acid 4.3-7 parts, potassium hydroxide 8.5-13 parts, nitrogen fertilizer 20-35 parts, phosphate fertilizer 6.5-10 parts, dispersant 0.3-0.6 parts, amino acids 1.2-2.0 parts, trace elements 0.04-0.08 parts, mushroom bags 0.25-0.55 parts.

2. The small-molecule carbon-rich, fully nutritious, compound bio-organic fertilizer according to claim 1, characterized in that: It is prepared from the following raw materials in parts by weight: 44 parts coal, 11 parts potassium hydroxide, 6 parts nitric acid, 28.75 parts nitrogen fertilizer, 8 parts phosphate fertilizer, 0.43 parts dispersant, 1.42 parts amino acids, 0.05 parts trace elements, and 0.35 parts mushroom bags.

3. The small-molecule carbon-rich, fully nutritious, compound bio-organic fertilizer according to claim 1 or 2, characterized in that: The coal is weathered lignite, lignite or weathered coal, the nitrogen fertilizer is urea, the phosphate fertilizer is ammonium dihydrogen phosphate or diammonium hydrogen phosphate, and the dispersant is calcium lignosulfonate or sodium dodecylbenzene sulfonate. Alternatively, the trace elements include amino acid chelated iron, 20% by mass of chelated iron (DTPA-Fe), 15% by mass of chelated zinc (EDTA-Zn), 10% by mass of humic acid chelated manganese, manganese sulfate, and 5% by mass of boric acid. The total mass fraction of all added substances is 100%, and the pH is adjusted to 6.5-7.0 with humic acid to obtain the trace elements.

4. The small-molecule carbon-rich, fully nutritious, compound bio-organic fertilizer according to claim 3, characterized in that: The inoculum package is a compound microbial inoculum, specifically composed of the following by volume ratio: 52% Bacillus subtilis inoculum, 23% Bacillus licheniformis inoculum, 6% Bacillus megaterium inoculum, 5% Bacillus mucilaginosus inoculum, 5% Azotobacter chrysophagus inoculum, 3% Pseudomonas fluorescens inoculum, 3% Trichoderma viride inoculum, and 3% Frankincense inoculum. The viable count of each inoculum reaches 10. 8 -10 9 CFU / mL or higher.

5. The application of the small molecule carbon complete nutrient compound bio-organic fertilizer as described in any one of claims 1 to 4 in crop cultivation.

6. The method for preparing the small-molecule carbon-complete nutrient compound bio-organic fertilizer according to any one of claims 1 to 4, characterized in that: Includes the following steps: S1. Take the crushed and sieved coal and put it into a container with a pre-added amount of water using a vacuum feeder according to the mass fraction. Stir the coal and water evenly to obtain material A. S2. Pump material A into the second container, add a measured amount of nitric acid with adjusted pH and carry out nitration reaction for 3 hours. Maintain the reaction temperature between 1.0 and 3.0 to ensure oxidation efficiency, and obtain material B. S3. Pump material B into the third container, add a certain amount of water and stir evenly, then add dispersant, potassium hydroxide, phosphate fertilizer, nitrogen fertilizer, amino acids and trace elements, stir at 50-180 r / min, and carry out neutralization, chelation and complexation reaction for 55 min to obtain material C. S4. After material C is screened to remove impurities, it is pumped into the fourth container, and the inoculum bag is added. The mixture is stirred evenly, and the pH value is controlled between 5.5 and 7.

5. The medium temperature is 30-40℃. After semi-anaerobic fermentation for 3-5 hours, it is ready for pre-packaging to obtain small molecule carbon full nutrient compound biological organic water-soluble fertilizer.

7. The preparation method according to claim 6, characterized in that: In step S1, the mass ratio of water to coal in the container is 0.6-0.9:

1.

8. The preparation method according to claim 6, characterized in that: In step S2, the pH is adjusted by nitric acid to be 1.0-3.

0.

9. The preparation method according to claim 6, characterized in that: In step S3, the mass ratio of water to coal added is 1.08-1.25:

1.

10. The preparation method according to any one of claims 6 to 9, characterized in that: In step S3, the total time for the neutralization, chelation, and complexation reactions is 55 minutes.

Images