Sustained-release small molecule peptide carbon-based fertilizer and composite carbon-based fertilizer with same
By combining cross-linked modified microporous biochar with slow-release small molecule peptide liquid, the problem of insufficient controlled-release performance of biochar-based fertilizers is solved, achieving longer-lasting nutrient release and soil improvement effects, thereby increasing crop yield and soil quality.
Patent Information
- Application Number
- CN202411106181.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-08-13
- Publication Date
- 2025-11-18
- Estimated Expiration
- 2044-08-13
AI Technical Summary
Existing biochar-based fertilizers suffer from insufficient specific surface area, inadequate cation exchange capacity, and low organic carbon content in terms of controlled release performance, resulting in poor effectiveness in improving soil structure and nutrient release. Furthermore, there is a lack of effective slow-release and controlled-release technologies on the market.
Cross-linked modified microporous biochar is combined with slow-release small molecule peptide liquid. The microporous biochar is cross-linked and modified with silicate solution to form a dense covering layer to improve the binding force. Silicate is added as a fertilizer supplement, along with penetrants and slow-release agents, to form a uniformly dispersed network structure to control nutrient release.
It improves the binding force and mechanical strength of biochar with molecular peptides and amino acids, extends its service life, enhances the slow-release effect of fertilizer, increases crop yield and quality, and improves soil structure and plant disease resistance.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to a carbon-based fertilizer and a composite carbon-based fertilizer, in particular to a slow-release small molecule peptide carbon-based fertilizer and a composite carbon-based fertilizer having the same. BACKGROUND
[0002] China's crop straw resources are large in quantity, rich in variety, widely distributed, high in carbon content, and have good resource potential. Carbon-based fertilizer prepared from straw is a soil fertility improvement and restoration material, which has developed pore structure, high specific surface area and cation exchange capacity, and can effectively improve soil fertility and crop yield. Biomass carbon-based fertilizer has many advantages, such as controlled / slow-release nutrient release, improvement of soil physical and chemical properties, enhancement of drought resistance, reduction of nutrient resource loss and improvement of fertilizer utilization rate. In addition, biochar is a stable carbon pool that can be long-term stored in soil. By pyrolyzing organic matter (such as plant residues) in an anaerobic environment at high temperature, the carbon in it can be fixed in biochar, thereby reducing the content of carbon dioxide in the atmosphere. The application of biochar can reduce the emission of methane and nitrous oxide in soil, which have stronger greenhouse effect than carbon dioxide. By improving the soil environment, biochar can inhibit the production and release of these gases. The long-term stability of biochar in soil makes it an effective carbon sink, which converts and sequesters carbon dioxide in the atmosphere in soil to achieve the purpose of carbon reduction.
[0003] Under the action of straw prohibition, straw pyrolysis biomass carbonization and carbon-based fertilizer production and application have become a new industry of agricultural waste management and ecological agriculture in China. The agricultural administrative department of China has also announced the draft of the carbon-based fertilizer industry standard, and the production and application of biomass carbon-based fertilizer has been included in the directory of China's agricultural key low-carbon technologies. However, there is too little attention to the preparation of biomass carbon-based fertilizer and the physical and chemical properties of biochar. The difference of preparation method has great influence on the yield, nutrient content and specific surface area of biochar. In order to improve the controlled release performance of biochar, it is often necessary to improve the specific surface area or key functional groups of biochar. The preparation of biochar mainly reflects that: (1) the specific surface area of biochar is insufficient, and the porosity of biochar is not enough. Biochar with high specific surface area has more pores, which can better absorb nutrients and water, and is beneficial to improve soil fertility and water retention capacity. (2) The cation exchange capacity (CEC) is not enough, and more oxygen-containing functional groups need to be introduced to improve the CEC. (3) The organic carbon content is low, and the technical scheme for improving the organic carbon content of biochar involves many factors, including raw material selection, production process optimization and post-processing. Biochar with high organic carbon content can improve soil organic matter content, promote microbial activity and improve soil structure. In terms of biochar-based fertilizer: (1) The main biochar-based fertilizers on the market are mainly mixed and coated carbon-based fertilizers. However, the current carbon-based fertilizer is mainly aimed at the controlled release of nutrients, and does not fully play the functional characteristics of biochar, such as pollutant immobilization, improvement of soil structure and adjustment of soil pH. The adsorbed and reacted carbon-based fertilizers with better controlled release effect have not been widely used due to technical problems. (2) The adsorbed biochar-based fertilizer needs to solve the binding force between biochar and impregnation liquid and the slow-release technology, and the binding force between biochar and impregnation liquid determines the nutrient release time and various physical and chemical indexes of adsorbed carbon-based fertilizer.
[0004] Therefore, how to prepare a slow-release carbon-based fertilizer which can effectively utilize straw biochar and has good slow-release and soil regulation function is a technical problem to be solved in the field. SUMMARY
[0005] The technical problem to be solved by the present application is to provide a slow-release small molecule peptide carbon-based fertilizer and a slow-release small molecule peptide carbon-based compound fertilizer.
[0006] The technical solution for solving the above technical problem is as follows: a slow-release small molecule peptide carbon-based fertilizer, comprising the following raw materials by weight: 45-50 parts of slow-release small molecule peptide liquid, 0.1-0.5 parts of penetrant, and 45-55 parts of cross-linked modified microporous biochar; the cross-linked modified microporous biochar is obtained by cross-linking modification of silicate solution microporous biochar.
[0007] The beneficial effects of the present application are: the present application adopts a crosslinking agent to modify microporous biochar, due to the addition of the crosslinking agent, firstly, a uniform and dense covering layer can be formed on the surface of the biochar, the covering layer can provide more binding sites, increase the binding area and binding opportunity between the molecular peptide, amino acid and the surface of the biochar, thereby improving the binding force between them, increasing the mechanical strength, thermal stability and durability of the biochar after adsorbing the molecular peptide, amino acid.
[0008] Secondly, the covering layer can form a crosslinked network on the surface of the biochar, this structure can stably combine the biochar and the molecular peptide, amino acid together through the chemical bond or physical crosslinking between the crosslinking agent molecules, form a stronger binding force, and enhance the combination between the biochar and the molecular peptide, amino acid.
[0009] Thirdly, the chemical properties of silicate enable it to have strong affinity, and can chemically adsorb or bond with the surface of the biochar and the molecular peptide, amino acid. This chemical affinity can strengthen the interaction between the biochar, silicate crosslinking agent and the molecular peptide, amino acid, and promote their combination.
[0010] In summary, the addition of the silicate crosslinking agent makes it not easy to adsorb the material to fall off or decompose during use, thereby prolonging its service life and sustained release function. At the same time, in addition to being used as a crosslinking agent, silicate can also be used as a fertilizer supplement, which can significantly improve the yield and quality of crops.
[0011] Based on the fact that silicate can also be used as a fertilizer supplement, firstly, it can enhance the disease resistance of crops, because silicate can enhance the cell wall structure of plants and improve the resistance of plants to pathogens, thereby reducing the occurrence of diseases and pests. Secondly, it can improve plant growth, because silicate can promote the growth of plant roots and improve the absorption efficiency of plants to water and nutrients. Thirdly, it can improve the stress resistance of crops, because silicon can help to enhance the tolerance of plants to drought, salinity and other adverse conditions. Fourthly, it can improve the soil structure: silicate can promote the aggregation of soil particles and improve the aeration and water retention capacity of soil. Fifthly, it can promote photosynthesis: silicate can enhance the photosynthetic efficiency of leaves and improve the yield of crops.
[0012] On the basis of the above technical solutions, the present application can also be improved as follows.
[0013] Further, the mass / volume concentration of the silicate solution is 0.5%-1.5%.
[0014] Further, the slow-release small molecule peptide solution is obtained by the following method: 40-50 parts of amino acids and 5-10 parts of short peptides are dissolved in 40-50 parts of deionized water, and fully stirred to completely dissolve; 0.9 parts of trace elements of minerals are added in turn, and continuously stirred to dissolve uniformly; under continuous stirring, 1-5 parts of slow-release agent is slowly added to uniformly distribute in the solution; 0.5-2 parts of PVA is added, and continuously stirred until the solution viscosity is uniform, and the mixture is continuously stirred uniformly at 50-70℃, and 1-5 parts of emulsifier is added to prepare.
[0015] The short peptide (also known as oligopeptide) of the present application is a molecule composed of a small number of amino acids, usually between 2 and 20 amino acids in length. Its main advantages include promoting plant growth, improving crop disease resistance, and improving soil quality. As a raw material for fertilizer, the short peptide has the following advantages: first, it promotes plant growth. Short peptides can stimulate the growth of plant roots and enhance the plant's ability to absorb water and nutrients. They can improve the efficiency of photosynthesis in plants, thereby increasing the biomass of plants. Second, it enhances disease resistance. Short peptides can induce plants to produce disease-resistant proteins and antioxidant enzymes, thereby enhancing the plant's disease resistance. They also improve the plant's tolerance to environmental stress, such as drought, salinity, low temperature, etc. Third, it improves soil quality. Short peptides can promote the activity of soil microorganisms and improve the structure of soil microbial communities, helping to improve soil fertility. By promoting the decomposition of organic matter, short peptides help to increase the organic carbon content in the soil. Fourth, it improves nutrient utilization efficiency. Short peptides can improve the plant's absorption and utilization efficiency of nutrients such as nitrogen, phosphorus, and potassium, reducing the amount of chemical fertilizer used, thereby reducing environmental pollution. Fifth, it has the effect of a biological stimulant. As a biological stimulant, short peptides can promote the growth and development of plants, improve crop yield and quality.
[0016] The present application adopts the synergistic effect of short peptides, amino acids and mineral elements, which has the following advantages: 1. Facilitating nutrient absorption and utilization: short peptides can effectively carry and transport amino acids and mineral elements, making it easier for plants to absorb and utilize these nutrients. 2. Improving absorption efficiency: short peptides can promote root absorption of nutrients and improve the utilization efficiency of mineral elements, reducing nutrient loss. 3. Promoting plant growth and stimulating growth factors: short peptides can activate plant growth factors, promote cell division and expansion, thereby accelerating plant growth and development. 4. Improving photosynthesis efficiency: the synergistic effect of short peptides, amino acids and mineral elements can enhance plant photosynthesis and improve energy conversion efficiency. 5. Enhancing resistance to adversity and disease: short peptides can enhance the immune system of plants and improve their resistance to disease and pests. 6. Improving soil structure and fertility: short peptides can promote the reproduction of beneficial microorganisms, improve soil microecological environment and increase soil organic matter content. 7. Improving crop quality and fruit quality: short peptides can promote the rational distribution of amino acids and mineral elements, making fruits contain more nutrients and improving fruit quality and taste. 8. Extending shelf life: by improving the antioxidant capacity of plants, short peptides can help extend the shelf life of fruits and reduce rotting and deterioration.
[0017] The permeability of short peptides refers to their ability to pass through cell membranes or other biological barriers. Short peptides are small molecules composed of amino acids connected by peptide bonds, with diverse biological activities and functions. Biochar surfaces have a large number of functional groups (such as hydroxyl, carboxyl, phenolic hydroxyl, etc.), which can interact with short peptides through electrostatic interaction, hydrogen bonding or van der Waals force, thereby promoting the attachment of short peptides. The amino acid composition and sequence of short peptides determine their charge, hydrophobicity and spatial conformation, which will affect the interaction of short peptides with biochar surfaces; positively charged amino acid residues (such as lysine, arginine) are more likely to bind to negatively charged biochar surfaces. Biochar loaded with short peptides can be used for heavy metal ion remediation, enhancing environmental remediation effects. Biochar combined with short peptides can improve soil fertility, promote plant growth and improve soil microbial community structure.
[0018] Further, the amino acids include glycine 33%, alanine 25%, glutamic acid 25%, aspartic acid 17%; the short peptides are dipeptides or tripeptides, glycyl-glutamine (Gly-Gln), asparagine-alanine (Asn-Ala), alanyl-glutamic acid (Ala-Glu), glycyl-alanine (Gly-Ala), glutamine-glycyl-alanine (Gln-Gly-Ala), glycyl-glutamine-alanine (Gly-Gln-Ala), alanyl-glycyl-glutamine (Ala-Gly-Gln) two combinations of which.
[0019] Further, the mineral trace elements include ZnSO4.7H2O 0.25 parts, FeSO4.7H2O 0.25 parts, MnSO4.H2O 0.2 parts, CuSO4.5H2O 0.1 parts, Na2MoO4.2H2O 0.05 parts, H3BO3 0.05 parts; the slow-release agent is any one or several of polyethylene glycol, polylactic acid (PLA), chitosan, ethyl cellulose (EC), carboxymethyl chitosan, sodium alginate, and methyl cellulose; the emulsifier is any one or several of Tween 20, Tween 80, OP-10, sodium dodecyl sulfate, PEG-8 stearate, oxyethylene (20) laurate, and lauryl alcohol polyoxyethylene ether.
[0020] The slow-release agent is a linear polymer containing a large number of ether bonds and hydroxyl groups in its structure, which can form hydrogen bonds with water molecules, thereby having good water solubility. After the slow-release agent dissolves in water, the formed solution has a certain viscosity, which helps to form a uniform dispersed network structure in the solution. This structure can wrap and slow-release the active ingredients (such as amino acids, short peptides, and mineral trace elements) in the solution, allowing them to be gradually released in the soil. Due to the presence of a large number of hydrophilic groups (such as hydroxyl groups) in the slow-release agent molecules, they can absorb water and swell in the environment (such as water in the soil), thereby slowing down the release rate of the active ingredients. This water absorption and swelling property allows the slow-release agent to control the release rate of the fertilizer, avoiding nutrient loss due to rapid dissolution. At the same time, the slow-release agent has good biocompatibility and biodegradability. Under the action of soil microorganisms, the slow-release agent will gradually degrade, without causing environmental pollution. Its degradation process is relatively slow, which also helps to prolong the slow-release effect of the fertilizer. In addition, the slow-release agent has good adhesion and film-forming properties, which can form a protective film on the surface of the plant roots, helping to slow down the loss of fertilizer ingredients and providing sustained nutrient supply. Through these mechanisms, the slow-release agent selected in the present application can effectively prolong the release time of the fertilizer ingredients, improve the utilization efficiency of the fertilizer, and reduce environmental pollution when used as a slow-release agent in the molecular peptide biochar-based fertilizer.
[0021] The emulsifier plays a key auxiliary role in the preparation of small molecule peptide solution adsorbed on carbon-based carriers. By improving the dispersibility and stability, promoting adsorption and loading, improving the slow-release characteristics, and enhancing the absorption and utilization of plants, the overall performance of the slow-release small molecule peptide carbon-based fertilizer is ultimately improved. Based on (1) enhancing the dispersibility and stability of small molecule peptides: emulsifiers are surface-active agents with hydrophilic and lipophilic ends. The emulsifier molecules form an interfacial film around the small molecule peptides, reducing the surface tension between them, allowing them to disperse uniformly in the liquid. Emulsifiers can increase the dispersibility and stability of small molecule peptides in liquids, preventing them from precipitating or aggregating during preparation and storage, thereby improving the stability of the preparation process and the consistency of the product. (2) Promote the adsorption and loading of small molecule peptides: emulsifier molecules bind to small molecule peptides through their hydrophilic ends and interact with the surface of carbon-based carriers through their lipophilic ends, thereby enhancing the binding force between small molecule peptides and carbon-based carriers, allowing them to be more stably adsorbed on the surface of carbon-based carriers. Emulsifiers can help small molecule peptides better adsorb to the surface of carbon-based carriers, increasing the loading of small molecule peptides and improving the effectiveness of slow-release fertilizers. (3) Improve the slow-release characteristics of small molecule peptides: emulsifiers form an interfacial film between small molecule peptides and carbon-based carriers, acting as a buffer. Small molecule peptides diffuse through the interfacial film into the soil, and this process is regulated by the properties and concentration of emulsifiers, thereby achieving the slow-release effect of small molecule peptides. Emulsifiers can regulate the release rate of small molecule peptides, allowing them to be released slowly, thereby extending their effective period in the soil and improving the long-term effect of the fertilizer. (4) Enhance the absorption of plant roots: emulsifiers improve the solubility and mobility of small molecule peptides in the soil, increasing their effective concentration in the soil, thereby increasing the chances of being absorbed by plant roots. Emulsifiers can promote the diffusion and transport of small molecule peptides in the soil, making them more easily absorbed by plant roots and improving fertilizer utilization.
[0022] Further, the microporous biochar is obtained by the following method: dividing the biomass material into two parts, adding 5-10 parts of phosphorus compounds to the first 40-50 parts of biomass material, stirring uniformly and fully absorbing and drying, then adding the second 40-50 parts of biomass material, adding 3-5 parts of potassium compounds, stirring uniformly, and putting into a pyrolysis furnace for pyrolysis treatment.
[0023] The specific surface area and pore size distribution of biochar are important factors in determining its performance as a biochar-based fertilizer. For biochar-based fertilizer carriers, the optimal pore size and specific surface area are key factors that affect its adsorption capacity, nutrient release, and microbial habitat. The optimal pore size range is 1-10 nanometers (nm), with a proper ratio of micropores (<2 nm) and mesopores (2-50 nm) to ensure good adsorption capacity and nutrient and water retention capacity. The characteristics of pore size distribution have multiple effects on the performance of biochar-based fertilizer: micropores (<2 nm) and mesopores (2-50 nm) are beneficial for adsorption and retention of smaller organic molecules and ions, improving fertilizer efficiency and nutrient absorption and slow release. Large pores (>50 nm) provide channels for larger root systems, microorganisms, and water flow, improving soil physical structure and aeration. The specific surface area and pore size distribution of biochar largely determine its performance as a biochar-based fertilizer, and reasonable regulation of these two parameters can significantly improve the application effect of biochar-based fertilizer. The optimal specific surface area range is 300-800 square meters per gram (m 2 / g). Higher specific surface area can provide more adsorption sites, which is beneficial for nutrient fixation and slow release, and also provides a better habitat for microorganisms.
[0024] The present invention changes the performance of biochar by adding phosphoric acid compounds as active agents:
[0025] Based on chemical activation: (1) Phosphoric acid compounds react with biomass. At high temperatures, phosphoric acid compounds can chemically react with organic components in biomass, such as cellulose, hemicellulose, and lignin. These reactions include dehydration and condensation of phosphoric acid compounds, leading to the decomposition and dehydration of biomass, forming a carbon-rich biochar structure. (2) Acid catalysis: Phosphoric acid compounds act as acid catalysts, accelerating the pyrolysis process of biomass, generating more small molecular volatile substances, and thus leaving more carbon skeletons. This process increases the carbon content and purity of biochar. (3) Introduction of phosphorus element: The use of phosphoric acid compounds introduces phosphorus elements, which exist in biochar and can provide specific chemical active sites for adsorption, catalysis, and other applications.
[0026] Based on modification of pore structure: (1) Formation of porous structure: The gases produced during the activation of phosphoric acid compounds, such as water vapor and carbon dioxide, form pores inside the biochar, increasing its specific surface area and porosity. These porous structures make biochar have better adsorption performance. (2) Pore size regulation: By controlling the concentration of phosphoric acid compounds, activation temperature, and time, the pore size distribution of biochar can be regulated to obtain biochar with micropores, mesopores, and macropores, thereby improving fertilizer efficiency and nutrient absorption and slow release.
[0027] Based on the modification of surface chemical properties: (1) Surface functional groups: The addition of potassium compounds can introduce or modify the surface of biochar containing oxygen-containing functional groups (such as hydroxyl, carboxyl, carbonyl, etc.) and phosphorus-containing functional groups (such as phosphoric acid ester, phosphoric acid salt, etc.), which can enhance the hydrophilicity, fertility, chemical reactivity and adsorption capacity of biochar. (2) Surface charge: The addition of potassium compounds can change the surface charge distribution of biochar, making it have better stability and adsorption properties in aqueous solution, especially for the adsorption of trace elements of minerals, which can significantly improve its CEC.
[0028] The present application changes the performance of biochar by adding potassium compounds as active agents:
[0029] Based on the chemical activation effect: (1) Potassium compounds react with carbon in biochar raw materials to generate gaseous products, which form pore structures inside the biochar, thereby increasing its specific surface area and porosity. (2) Potassium compounds react with impurities in biochar to generate soluble substances, which are removed during washing, thereby further purifying biochar, improving its purity and activity, and significantly improving its CEC.
[0030] Based on the change of physical structure: (1) High temperature treatment (usually between 400-500°C) during potassium compound activation process can significantly change the microstructure of biochar, generating a large number of micropores and mesopores, improving its adsorption capacity, and also improving its water holding capacity and air permeability as a soil conditioner. (2) After activation, the pore structure of biochar becomes more ordered and uniform, thereby improving the fertilizer efficiency and nutrient absorption and slow release.
[0031] Based on the change of surface chemical properties: (1) The addition of potassium compounds can introduce new functional groups such as hydroxyl (-OH) and carbonyl (C=O), which can significantly improve the chemical activity and surface reactivity of biochar. Enhance the hydrophilicity, fertility, chemical reactivity and adsorption capacity of biochar. (2) The increase of surface functional groups can also enhance the adsorption capacity of biochar to some ions or small peptide molecules, thereby improving the fertilizer efficiency and nutrient absorption and slow release. It can also enhance its adsorption capacity for nutrients and metal ions.
[0032] Microstructure changes: Based on the introduction of metal elements: (1) Potassium compounds contain potassium elements, and during the activation process, part of the potassium will remain in the biochar, which can significantly improve its CEC. Potassium is an essential nutrient element for plant growth, so potassium compound activated biochar can also serve as a potassium fertilizer, increasing the potassium content in the soil and promoting plant growth.
[0033] Further, the pyrolysis treatment sets the initial temperature at 350-450℃, preferably 400℃, and keeps it for 0.5-1 hour to perform preliminary pyrolysis, gradually increases the temperature to 600℃, each time by 50-100℃, and keeps each temperature segment for 0.5-2 hours, the total time being no more than 3 hours; after the pyrolysis is completed, the biochar is rapidly cooled and ground to a particle size of ≤2 mm.
[0034] The pyrolysis temperature and time have a significant influence on the performance of the biochar. In particular, the CEC, a lower pyrolysis temperature (400-600℃) can retain more surface functional groups, thereby increasing the CEC. The pyrolysis time (2-3 hours), the total pyrolysis time being no more than 3 hours, can cause excessive carbonization and loss of activity. The phosphorus-based compound as the biochar activator in the range of 400-500℃, the pore of the biochar starts to increase significantly, and a developed microporous structure is initially formed. In this temperature range, the specific surface area and pore volume of the biochar reach a high level, which is suitable for adsorbing mineral elements and amino acids and molecular peptides and other organic matters. The potassium-based compound as the biochar activator in the range of 500-600℃, the specific surface area and pore volume of the biochar reach a high level, which is suitable for adsorbing mineral elements and amino acids and molecular peptides and other organic matters.
[0035] The present application comprehensively adds two different activators to improve the specific surface area and pore volume of the biochar to reach the optimal value, which can significantly improve the CEC and greatly enhance the physicochemical properties of the biochar as a carbon-based fertilizer carrier.
[0036] The medium-temperature active agent can introduce new functional groups (such as carboxyl, hydroxyl, etc.) to the surface of the biochar, which can improve the hydrophilicity and adsorption capacity of the biochar, thereby enhancing the fertilizer efficiency of the biochar. The medium-temperature active agent may block some pores of the biochar, but at the same time, it may also increase the number of micropores and mesopores in some cases, thereby improving the specific surface area and pore volume of the biochar, and further improving its water holding capacity and nutrient release effect. The high-temperature active agent can cause the reorganization of the internal structure of the biochar, forming a more stable and durable carbon skeleton. This stable structure helps to improve the long-term stability and effectiveness of the biochar in the soil. The high-temperature active agent can further develop the pore structure of the biochar, especially increasing the number of macropores and mesopores, forming an optimal pore size distribution, thereby improving the water holding capacity and nutrient adsorption capacity of the biochar. The high-temperature active agent often contains abundant minerals (such as potassium, calcium, magnesium, etc.), which can be uniformly distributed in the biochar at high temperature, enhancing its nutrient content and improving the soil structure and plant growth environment. The use of medium-temperature and high-temperature active agents together can take advantage of the strengths of both, improving the overall performance of the biochar. For example, the medium-temperature active agent can improve the short-term fertilizer efficiency of the biochar, while the high-temperature active agent can enhance its long-term stability and nutrient supply capacity. There is a synergistic effect between the medium-temperature and high-temperature active agents. The organic functional groups introduced by the medium-temperature active agent can improve the adsorption and fixation of minerals in the high-temperature active agent, further enhancing the fertilizer efficiency of the biochar.
[0037] Further, the phosphoric acid compound is any one or several of H3PO4, H3PO3, H4P2O7, H3PO2, H5P3O 10 , H5P4O 13 , H5P5O 15 ; and the potassium compound is any one or several of K2SO4, KCl, KNO3, K2S, K2CO3, KCH3COO, K2SO3.
[0038] Further, the silicate is any one of Na2SiO3, CaSiO3, K2SiO3, MgSiO3, LI2SiO3, Na4SiO4, Na2SiO3.5H2O; and the penetrating agent is any one or several of JFC penetrating agent, modified silicone oil, fatty alcohol polyoxyethylene ether, dimethyl sulfoxide, alkyl polyglycoside, azone, and amino acid penetrating agent.
[0039] Based on a large number of experiments, it is found that the selection of suitable penetrants and their dosage is very critical for the preparation of slow-release small molecule peptide carbon-based fertilizer. Penetrants can promote adsorption and loading, improve slow-release characteristics, enhance plant absorption and utilization, and ultimately improve the overall performance of slow-release small molecule peptide carbon-based fertilizer. (1) Reduce surface tension: penetrants are usually some surfactants that can reduce the surface tension of liquids, making it easier for liquids to spread on the surface of carbon-based carriers and enter the microporous structure of the carriers. (2) Increase contact angle: by reducing surface tension, penetrants can improve the wettability of liquids on solid surfaces, increase the contact area between liquids and solid surfaces, and thus promote adsorption. Penetrants can improve the flowability of liquids, making it easier to operate during actual production and application. (3) Intermolecular forces: the molecules of penetrants have hydrophilic and lipophilic groups, which can form a uniform molecular film on the interface between liquids and solids. This film can promote the transfer and adsorption of small molecule peptides. Through more uniform and deeper adsorption, the release rate of small molecule peptides in carbon-based fertilizer can be more balanced, thereby prolonging the fertilizer effect. (4) Diffusion mechanism: penetrants can enhance the diffusion capacity of small molecule peptides by changing the viscosity and diffusion coefficient of small molecule peptide liquid, allowing them to penetrate more quickly into the pore structure of carbon-based carriers. Penetrants can help small molecule peptides distribute more uniformly in liquids, preventing uneven adsorption caused by excessive local concentration.
[0040] The present application also provides a slow-release small molecule peptide carbon-based compound fertilizer, which comprises 40-60 parts of the slow-release small molecule peptide carbon-based fertilizer, 10-20 parts of nitrogen fertilizer, 5-15 parts of phosphorus fertilizer, 5-15 parts of potassium fertilizer, 10-20 parts of organic matter and 0.5-2.0 parts of functional microbial agent.
[0041] The slow-release small molecule peptide carbon-based fertilizer of the present application can be used alone as a functional fertilizer. The slow-release small molecule peptide carbon-based fertilizer can also be mixed with N, P and K to form a compound fertilizer, mixed with organic fertilizer to form a new functional fertilizer, or mixed with microbial agents or biological bacterial fertilizer to form a new functional fertilizer. The granular product is prepared by a granulation device. The granulation process can be selected from drum granulation, disc granulation or extrusion granulation. After granulation, drying is carried out at medium temperature to ensure that the granules have sufficient mechanical strength and stability, and the slow-release small molecule peptide carbon-based functional compound fertilizer is obtained. DETAILED DESCRIPTION
[0042] The principles and characteristics of the present application are described below, and the examples are used to explain the present application and not to limit the scope of the present application.
[0043] Example 1
[0044] Slow-release small molecule peptide carbon-based fertilizer: 50 parts of slow-release small molecule peptide liquid is stirred into 0.1 parts of amino acid penetrant, 49.9 parts of cross-linked modified microporous biochar is stirred in, and it is introduced into a special device for sufficient adsorption. The slow-release small molecule peptide carbon-based fertilizer is prepared by drying the carbon-based material adsorbed with the slow-release small molecule peptide liquid.
[0045] The preparation method of the microporous biochar comprises: adding 5 parts of H5P5O 15 After stirring, adding 45 parts of treated biomass material, adding 5 parts of K2SO4, stirring uniformly, and placing in a pyrolysis furnace. The initial temperature is set to 400°C, and the temperature is kept at this temperature for 30 minutes for preliminary pyrolysis, and then the temperature is gradually increased to 600°C, with an increase of 100°C each time, and each temperature section is kept for 1 hour. The pyrolysis time is maintained at 2-3 hours, and the total pyrolysis time is not more than 3 hours. After pyrolysis is completed, the biochar is rapidly cooled to avoid oxidation. The obtained biochar is ground to a particle size of ≤2 mm to ensure uniform surface area, and microporous biochar is obtained.
[0046] The preparation method of the microporous biochar comprises: adding 5 parts of H5P5O
[0047] The preparation method of the slow-release small molecule peptide liquid comprises: dissolving 40 parts of amino acids (glycine 33%, alanine 25%, glutamic acid 25%, and aspartic acid 17%) and 2.5 parts of glycyl-glutamine (Gly-Gln), 2.5 parts of glutamine-glycine-alanine (Gln-Gly-Ala) in 44.6 parts of deionized water, and stirring until completely dissolved. 0.9 parts of trace elements (0.25 parts of zinc (ZnSO4.7H2O), 0.25 parts of iron (FeSO4.7H2O), 0.2 parts of manganese (MnSO4.H2O), 0.1 parts of copper (CuSO4.5H2O), 0.05 parts of molybdenum (Na2MoO4.2H2O), and 0.05 parts of boron (H3BO3)) are added in sequence, and stirring is continued to ensure uniform dissolution. Under continuous stirring, 4 parts of methyl cellulose is slowly added to ensure uniform distribution in the solution. 0.5 parts of PVA is added, and stirring is continued until the solution viscosity is uniform. The mixture is stirred at 60°C for 1 hour, and 5 parts of lauryl alcohol polyoxyethylene ether is added to form the slow-release small molecule peptide liquid.
[0048] Example 2
[0049] Slow-release small molecule peptide carbon-based fertilizer: 45 parts of slow-release small molecule peptide solution, stirring 0.5 parts of azone, stirring 54.5 parts of cross-linked modified microporous biochar, and introducing into a special equipment to make it fully adsorbed. The carbon-based material adsorbed with slow-release small molecule peptide solution is dried to prepare slow-release small molecule peptide carbon-based fertilizer.
[0050] The preparation method of the microporous biochar comprises: adding 10 parts of H5P4O 13 , stirring uniformly and fully absorbing and drying, then adding 47 parts of treated biomass material and 3 parts of KCl, stirring uniformly and putting into a pyrolysis furnace. The initial temperature is set to 400°C, and the temperature is kept at this temperature for 40 minutes for preliminary pyrolysis, and then the temperature is gradually increased to 600°C, with an increase of 100°C each time, and each temperature segment is kept for 1 hour. After pyrolysis is completed, the biochar is quickly cooled to avoid oxidation. The obtained biochar is ground to a particle size of ≤2 mm to ensure uniform surface area, and microporous biochar is obtained.
[0051] The preparation method of the microporous biochar comprises: adding 10 parts of H5P4O 13 , stirring uniformly and fully absorbing and drying, then adding 47 parts of treated biomass material and 3 parts of KCl, stirring uniformly and putting into a pyrolysis furnace. The initial temperature is set to 400°C, and the temperature is kept at this temperature for 40 minutes for preliminary pyrolysis, and then the temperature is gradually increased to 600°C, with an increase of 100°C each time, and each temperature segment is kept for 1 hour. After pyrolysis is completed, the biochar is quickly cooled to avoid oxidation. The obtained biochar is ground to a particle size of ≤2 mm to ensure uniform surface area, and microporous biochar is obtained.
[0052] The preparation method of the slow-release small molecule peptide solution comprises: dissolving 42.1 parts of amino acids (glycine 33%, alanine 25%, glutamic acid 25%, and aspartic acid 17%) and 3 parts of asparagine-alanine (Asn-Ala) and 5 parts of glycyl-glutamyl-alanine (Gly-Gln-Ala) in 42 parts of 40-50 parts of deionized water, and stirring thoroughly until completely dissolved. Add 0.9 parts of trace elements (zinc (ZnSO4.7H2O) 0.25 parts, iron (FeSO4.7H2O) 0.25 parts, manganese (MnSO4.H2O) 0.2 parts, copper (CuSO4.5H2O) 0.1 parts, molybdenum (Na2MoO4.2H2O) 0.05 parts, and boron (H3BO3) 0.05 parts) in sequence, and continue stirring to ensure uniform dissolution. Under continuous stirring, slowly add 2 parts of sodium alginate to uniformly distribute it in the solution. Add 2 parts of PVA, and continue stirring until the solution viscosity is uniform. The mixture is stirred uniformly at 60°C for 1 hour, and 3 parts of oxyethylene (20) laurate is added to form a slow-release small molecule peptide solution.
[0053] Example 3
[0054] Slow-release small molecule peptide carbon-based fertilizer: 47.7 parts of slow-release small molecule peptide liquid, 0.3 parts of alkyl polyglycoside (APG) are stirred and added to 52 parts of cross-linked modified microporous biochar, and introduced into a special equipment for sufficient adsorption. The carbon-based material adsorbed with the slow-release small molecule peptide liquid is dried to obtain the slow-release small molecule peptide carbon-based fertilizer.
[0055] The preparation method of the microporous biochar includes: adding 8 parts of H5P3O10 to 42 parts of treated biomass material, and stirring to obtain a mixture; and pyrolyzing the mixture in a pyrolysis furnace to obtain the microporous biochar. 10 After stirring, absorbing and drying, 46 parts of treated biomass material and 4 parts of K2SO3 are added and stirred, and then put into a pyrolysis furnace. The initial temperature is set to 400°C, and the temperature is kept at 400°C for 50 minutes for preliminary pyrolysis. Then the temperature is gradually increased to 600°C, and each temperature is kept for 1 hour. After pyrolysis, the biochar is quickly cooled to avoid oxidation. The obtained biochar is ground to a particle size of ≤2 mm to ensure uniform surface area, and the microporous biochar is obtained.
[0056] The preparation method of the LI2SiO3 cross-linked modified microporous biochar includes: the microporous biochar prepared in Example 3 is added to 10 L of 1% LI2SiO3 solution at a ratio of (1000 g). The mixture is stirred at 70°C for 120 minutes to ensure that the biochar is completely soaked in the LI2SiO3 solution. After standing for 12 hours, the LI2SiO3 is allowed to fully penetrate the structure of the biochar. The cross-linked biochar is washed and dried to remove unreacted LI2SiO3. The LI2SiO3 cross-linked modified microporous biochar is obtained.
[0057] The preparation method of the slow-release small molecule peptide solution comprises: dissolving 49.1 parts of amino acids (glycine 33%, alanine 25%, glutamic acid 25%, and aspartic acid 17%) and 1 part of alanyl-glutamic acid (Ala-Glu) and 4 parts of alanyl-glycine-glutamine (Ala-Gly-Gln) in 40 parts of deionized water, and stirring until completely dissolved. Add 0.9 parts of trace elements (zinc (ZnSO4.7H2O) 0.25 parts, iron (FeSO4.7H2O) 0.25 parts, manganese (MnSO4.H2O) 0.2 parts, copper (CuSO4.5H2O) 0.1 parts, molybdenum (Na2MoO4.2H2O) 0.05 parts, and boron (H3BO3) 0.05 parts) in sequence, and continue to stir to ensure uniform dissolution. Under continuous stirring, slowly add 1.2 parts of carboxymethyl chitosan to uniformly distribute it in the solution. Add 1.5 parts of PVA and continue to stir until the solution viscosity is uniform. Stir the mixture at 60°C for 1 hour, and then add 1.5 parts of PEG-8 stearate to form the slow-release small molecule peptide solution.
[0058] Example 4
[0059] The slow-release small molecule peptide carbon-based fertilizer is prepared by stirring 46.6 parts of the slow-release small molecule peptide solution, 0.4 parts of dimethyl sulfoxide, and 53 parts of the cross-linked modified microporous biochar, and introducing them into a special device to allow them to be fully adsorbed.
[0060] The preparation method of the microporous biochar comprises: adding 9 parts of H3PO2 to 46 parts of the treated biomass material and stirring until fully absorbed and dried, then adding 41.5 parts of the treated biomass material and 3.5 parts of KCH3COO3, and stirring to obtain a mixture. The mixture is placed in a pyrolysis furnace, and the initial temperature is set to 400°C. The temperature is maintained at 400°C for 50 minutes for preliminary pyrolysis, and then the temperature is gradually increased to 600°C at an increase of 100°C each time, and each temperature segment is maintained for 1 hour. After pyrolysis is completed, the biochar is rapidly cooled to avoid oxidation. The obtained biochar is ground to a particle size of ≤2 mm to ensure uniform surface area, and the microporous biochar is obtained.
[0061] The preparation method of the MgSiO3 cross-linked modified microporous biochar comprises: adding 1000 g of the microporous biochar prepared in Example 4 to 10 L of a 1% MgSiO3 solution. The mixture is stirred at 70°C for 120 minutes to ensure that the biochar is fully soaked in the MgSiO3 solution. After standing for 12 hours, the MgSiO3 is allowed to fully penetrate the structure of the biochar. The cross-linked biochar is washed and dried to remove unreacted MgSiO3. The MgSiO3 cross-linked modified microporous biochar is obtained.
[0062] The preparation method of the slow-release small molecule peptide solution comprises: dissolving 43 parts of amino acids (glycine 33%, alanine 25%, glutamic acid 25%, and aspartic acid 17%) and 4 glycyl-glutamine (Gly-Gln), 3 glycyl-glutamine-alanine (Gly-Gln-Ala) in 40.7 parts of 40-50 parts of deionized water, and stirring until completely dissolved. 0.9 parts of trace elements (0.25 parts of zinc (ZnSO4.7H2O), 0.25 parts of iron (FeSO4.7H2O), 0.2 parts of manganese (MnSO4.H2O), 0.1 parts of copper (CuSO4.5H2O), 0.05 parts of molybdenum (Na2MoO4.2H2O), and 0.05 parts of boron (H3BO3)) are added in sequence, and stirring is continued to ensure uniform dissolution. Under continuous stirring, 4.4 parts of ethyl cellulose (EC) is slowly added to uniformly distribute it in the solution. 1.5 parts of PVA is added and stirring is continued until the solution viscosity is uniform. The mixture is stirred at 60°C for 1 hour, and 2.5 parts of sodium dodecyl sulfate is added to form the slow-release small molecule peptide solution.
[0063] Example 5
[0064] The slow-release small molecule peptide carbon-based fertilizer is prepared by stirring 47.8 parts of the slow-release small molecule peptide solution, 0.2 parts of fatty alcohol polyoxyethylene ether (AEO), and 52 parts of the cross-linked modified microporous biochar, and introducing them into a special device for sufficient adsorption. The carbon-based material adsorbed with the slow-release small molecule peptide solution is dried to obtain the slow-release small molecule peptide carbon-based fertilizer.
[0065] The preparation method of the microporous biochar comprises: stirring and fully absorbing 44 parts of the treated biomass material with 6 parts of H4P2O7, drying, adding 45.5 parts of the treated biomass material, and stirring and uniformly adding 4.5 parts of K2CO3 into a pyrolysis furnace. The initial temperature is set to 400°C, and the temperature is kept at this temperature for 60 minutes for preliminary pyrolysis. The temperature is gradually increased to 600°C, and each temperature increase is 100°C, and each temperature segment is kept for 1 hour. After pyrolysis is completed, the biochar is quickly cooled to avoid oxidation. The obtained biochar is ground to a particle size of ≤2 mm to ensure uniform surface area, and the microporous biochar is obtained.
[0066] The preparation method of the CaSiO3 cross-linked modified microporous biochar comprises: adding 1000 g of the microporous biochar prepared in Example 5 into 10 L of a 1% CaSiO3 solution. The mixture is stirred at 70°C for 120 minutes to ensure that the biochar is fully immersed in the CaSiO3 solution. After standing for 12 hours, the CaSiO3 is allowed to fully penetrate the biochar structure. The cross-linked biochar is washed and dried to remove unreacted CaSiO3. The CaSiO3 cross-linked modified microporous biochar is obtained.
[0067] The preparation method of the slow-release small molecule peptide solution comprises the following steps: 43.7 parts of amino acids (glycine 33%, alanine 25%, glutamic acid 25%, and aspartic acid 17%) and 3 glycyl-glutamine (Gly-Gln), 3 parts of alanyl-glycyl-glutamine (Ala-Gly-Gln) are dissolved in 42 parts of deionized water, and stirring is performed until complete dissolution. 0.9 parts of trace elements (0.25 parts of zinc (ZnSO4.7H2O), 0.25 parts of iron (FeSO4.7H2O), 0.2 parts of manganese (MnSO4.H2O), 0.1 parts of copper (CuSO4.5H2O), 0.05 parts of molybdenum (Na2MoO4.2H2O), and 0.05 parts of boron (H3BO3)) are sequentially added, and stirring is continuously performed to ensure uniform dissolution. Under continuous stirring, 3.3 parts of chitosan are slowly added to uniformly distribute the chitosan in the solution. 0.6 parts of PVA are added, and stirring is continuously performed until the viscosity of the solution is uniform. The mixture is uniformly stirred at 60°C for 1 hour, and 3.4 parts of OP-10 are added to form the slow-release small molecule peptide solution.
[0068] Example 6
[0069] The slow-release small molecule peptide carbon-based fertilizer is prepared by the following steps: 45.6 parts of the slow-release small molecule peptide solution, 0.4 parts of modified silicone oil are stirred and added into 54 parts of the cross-linked modified microporous biochar, and the mixture is introduced into a special equipment to be fully adsorbed. The carbon-based material adsorbed with the slow-release small molecule peptide solution is dried to obtain the slow-release small molecule peptide carbon-based fertilizer.
[0070] The preparation method of the microporous biochar comprises the following steps: 44.5 parts of the treated biomass material are uniformly stirred and fully absorbed with 5.5 parts of H3PO3 after drying, 46.5 parts of the treated biomass material are added, and 3.5 parts of K2S is uniformly stirred and put into a pyrolysis furnace. The initial temperature is set to 400°C, and the temperature is kept at 400°C for 60 minutes to perform preliminary pyrolysis. Then, the temperature is gradually increased to 600°C, and each temperature increase is 100°C, and each temperature stage is kept for 1 hour. After the pyrolysis is completed, the biochar is rapidly cooled to avoid oxidation. The obtained biochar is ground to a particle size of ≤2 mm to ensure uniform surface area, and the microporous biochar is obtained.
[0071] The preparation method of the K2SiO3 cross-linked modified microporous biochar comprises the following steps: 1000 g of the microporous biochar prepared in Example 6 is added into 10 L of a 1% K2SiO3 solution. The mixture is stirred at 70°C for 120 minutes to ensure that the biochar is fully immersed in the solution. The mixture is left to stand for 12 hours to allow the K2SiO3 to fully penetrate the structure of the biochar. The cross-linked biochar is washed and dried to remove unreacted K2SiO3. The K2SiO3 cross-linked modified microporous biochar is obtained.
[0072] The preparation of the slow-release small molecule peptide solution is as follows: 41.1 parts of amino acids (glycine 33%, alanine 25%, glutamic acid 25%, and aspartic acid 17%) and 4.0 parts of asparagine-alanine (Asn-Ala) and 4.5 parts of glycyl-glutamyl-alanine (Gly-Gln-Ala) are dissolved in 41.4 parts of deionized water, and stirred until completely dissolved. 0.9 parts of trace elements (0.25 parts of zinc (ZnSO4.7H2O), 0.25 parts of iron (FeSO4.7H2O), 0.2 parts of manganese (MnSO4.H2O), 0.1 parts of copper (CuSO4.5H2O), 0.05 parts of molybdenum (Na2MoO4.2H2O), and 0.05 parts of boron (H3BO3)) are added in sequence, and stirring is continued to ensure uniform dissolution. While stirring continuously, 2 parts of polylactic acid (PLA) are slowly added to ensure uniform distribution in the solution. 1.8 parts of PVA are added, and stirring is continued until the solution viscosity is uniform. The mixture is stirred at 60°C for 1 hour to ensure uniformity, and 4.2 parts of Tween 80 are added to form the slow-release small molecule peptide solution.
[0073] Example 7
[0074] Slow-release small molecule peptide carbon-based fertilizer: 49.8 parts of the slow-release small molecule peptide solution is stirred with 0.2 parts of JFC penetrant and added to 50 parts of cross-linked modified microporous biochar, and introduced into a special device to ensure sufficient adsorption. The carbon-based material adsorbed with the slow-release small molecule peptide solution is dried to obtain the slow-release small molecule peptide carbon-based fertilizer.
[0075] The preparation method of the microporous biochar includes: 42.5 parts of treated biomass material, 7.5 parts of H3PO4, stirring to ensure uniform absorption and drying, then adding 45.5 parts of treated biomass material, and 4.5 parts of KNO3, stirring to ensure uniformity, and then placing in a pyrolysis furnace. The initial temperature is set to 400°C, and the temperature is kept at this temperature for 60 minutes to perform preliminary pyrolysis. The temperature is gradually increased to 600°C, and each temperature increase is 100°C. Each temperature segment is kept for 1 hour. After pyrolysis is completed, the biochar is rapidly cooled to avoid oxidation. The obtained biochar is ground to a particle size of ≤2 mm to ensure uniform surface area, and the microporous biochar is obtained.
[0076] The preparation method of the Na2SiO3 cross-linked modified microporous biochar includes: 1000 g of the microporous biochar prepared in Example 7 is added to 10 L of 1% Na2SiO3 solution. The mixture is stirred at 70°C for 120 minutes to ensure that the biochar is completely soaked in the Na2SiO3 solution. After standing for 12 hours, the Na2SiO3 is allowed to fully penetrate the structure of the biochar. The cross-linked biochar is washed and dried to remove unreacted Na2SiO3. The Na2SiO3 cross-linked modified microporous biochar is obtained.
[0077] The preparation method of the slow-release small molecule peptide solution comprises the following steps: 43.5 parts of amino acids (glycine 33%, alanine 25%, glutamic acid 25%, and aspartic acid 17%) and 3.0 parts of alanyl-glutamic acid (Ala-Glu) and 3.5 parts of alanyl-glycine-glutamine (Ala-Gly-Gln) are dissolved in 42.1 parts of deionized water, and stirring is performed until complete dissolution. 0.9 parts of trace elements (0.25 parts of zinc (ZnSO4.7H2O), 0.25 parts of iron (FeSO4.7H2O), 0.2 parts of manganese (MnSO4.H2O), 0.1 parts of copper (CuSO4.5H2O), 0.05 parts of molybdenum (Na2MoO4.2H2O), and 0.05 parts of boron (H3BO3)) are sequentially added, and stirring is continuously performed to ensure uniform dissolution. Under continuous stirring, 1.5 parts of polyethylene glycol is slowly added and uniformly distributed in the solution. 1.0 parts of PVA is added, and stirring is continuously performed until the solution viscosity is uniform. The mixture is uniformly stirred at 60°C for 1 hour, and 4.5 parts of Tween 20 is added to form the slow-release small molecule peptide solution.
[0078] Example 8
[0079] The preparation of the slow-release small molecule peptide carbon-based compound fertilizer: 60 parts of the slow-release small molecule peptide carbon-based fertilizer of Example 1 is mixed with 10 parts of urea, 5 parts of diammonium phosphate, 8 parts of potassium sulfate, 15 parts of decomposed organic fertilizer, and 2.0 parts of nitrogen-fixing bacteria, and uniformly stirred and granulated by a granulation device to obtain a granular product. The granulation process can be selected from drum granulation, disc granulation, or extrusion granulation. After granulation, drying is performed at medium temperature to ensure that the granules have sufficient mechanical strength and stability, and the slow-release small molecule peptide carbon-based compound fertilizer is obtained.
[0080] Example 9
[0081] The preparation of the slow-release small molecule peptide carbon-based compound fertilizer: 40 parts of the slow-release small molecule peptide carbon-based fertilizer of Example 2 is mixed with 20 parts of ammonium nitrate, 15 parts of monoammonium phosphate, 14.5 parts of potassium nitrate, 10 parts of organic matter of humic acid, and 0.5 parts of Bacillus functional microbial agent, and uniformly stirred and granulated by a granulation device to obtain a granular product. The granulation process can be selected from drum granulation, disc granulation, or extrusion granulation. After granulation, drying is performed at medium temperature to ensure that the granules have sufficient mechanical strength and stability, and the slow-release small molecule peptide carbon-based compound fertilizer is obtained.
[0082] Example 10
[0083] Preparation of slow-release small-molecule peptide carbon-based compound fertilizer: 50 parts of slow-release small-molecule peptide carbon-based fertilizer of Example 3, 15 parts of ammonium sulfate, 8.5 parts of calcium superphosphate, 10 parts of potassium sulfate, 15 parts of organic matter of humic acid, and 1.5 parts of silicate bacteria are mixed in proportion, stirred uniformly, and granulated by a granulation device to obtain a granular product. The granulation process can be selected from drum granulation, disc granulation, or extrusion granulation. After granulation, drying is performed at medium temperature to ensure that the granules have sufficient mechanical strength and stability, thereby obtaining slow-release small-molecule peptide carbon-based compound fertilizer.
[0084] Example 11
[0085] Preparation of slow-release small-molecule peptide carbon-based compound fertilizer: 55 parts of slow-release small-molecule peptide carbon-based fertilizer of Example 4, 5 parts of urea, 5 parts of ammonium nitrate, 5 parts of monoammonium phosphate, 5 parts of diammonium phosphate, 8.5 parts of potassium chloride, 15 parts of humic acid, and 1.5 parts of phosphorus-potassium dissolving bacteria are mixed in proportion, stirred uniformly, and granulated by a granulation device to obtain a granular product. The granulation process can be selected from drum granulation, disc granulation, or extrusion granulation. After granulation, drying is performed at medium temperature to ensure that the granules have sufficient mechanical strength and stability, thereby obtaining slow-release small-molecule peptide carbon-based compound fertilizer.
[0086] Example 12
[0087] Preparation of slow-release small-molecule peptide carbon-based compound fertilizer: 48 parts of slow-release small-molecule peptide carbon-based fertilizer of Example 5, 10 parts of urea, 7 parts of ammonium sulfate, 13 parts of calcium superphosphate, 5 parts of potassium nitrate, 5 parts of potassium sulfate, 10 parts of compost, and 2 parts of cellulolytic bacteria are mixed in proportion, stirred uniformly, and granulated by a granulation device to obtain a granular product. The granulation process can be selected from drum granulation, disc granulation, or extrusion granulation. After granulation, drying is performed at medium temperature to ensure that the granules have sufficient mechanical strength and stability, thereby obtaining slow-release small-molecule peptide carbon-based compound fertilizer.
[0088] Example 13
[0089] Preparation of slow-release small-molecule peptide carbon-based compound fertilizer: 56 parts of slow-release small-molecule peptide carbon-based fertilizer of Example 6, 10 parts of urea, 2 parts of ammonium nitrate, 12 parts of calcium superphosphate, 5 parts of potassium chloride, 13.5 parts of compost, and 1.5 parts of growth-promoting bacteria are mixed in proportion, stirred uniformly, and granulated by a granulation device to obtain a granular product. The granulation process can be selected from drum granulation, disc granulation, or extrusion granulation. After granulation, drying is performed at medium temperature to ensure that the granules have sufficient mechanical strength and stability, thereby obtaining slow-release small-molecule peptide carbon-based compound fertilizer.
[0090] Example 14
[0091] Preparation of slow-release small-molecule peptide carbon-based compound fertilizer: 50 parts of slow-release small-molecule peptide carbon-based fertilizer of Example 7, 9 parts of urea, 3 parts of ammonium nitrate, 3 parts of ammonium sulfate, 3 parts of diammonium phosphate, 3 parts of monoammonium phosphate, 4 parts of superphosphate, 4 parts of potassium sulfate, 4 parts of potassium nitrate, 2 parts of potassium chlorate, 13 parts of humic acid, and 1.0 part of disease antagonistic bacteria and 1.0 part of bacillus were mixed and stirred uniformly according to the proportion, and granulated by a granulation device to obtain a granular product; the granulation process can be selected from drum granulation, disc granulation, or extrusion granulation, etc. After granulation, drying is performed at medium temperature to ensure that the granules have sufficient mechanical strength and stability, and a slow-release small-molecule peptide carbon-based compound fertilizer is obtained.
[0092] Table 1 is the performance parameters of the influence of phosphorus compounds on the microporous structure of charcoal in the preparation experiment of the microporous biochar of the present application. CK1 is not added any additive. Experimental examples 1-1 to 1-7 are only added with the corresponding mass of phosphorus compounds of Examples 1 to 7. The influence of phosphorus compounds on the microporous structure of charcoal is compared in Table 1.
[0093] Table 1. Influence of phosphorus compounds on the microporous structure of charcoal
[0094]
[0095]
[0096] From the data performance parameters in Table 1, it can be seen that: the BET specific surface area, total pore volume, micropore ratio, small-molecule peptide adsorption capacity, potential (zeta potential), compressive strength, tensile strength, bonding strength, elastic modulus, catalytic activity, effective carbon, organic matter, N, P, K content, glass transition temperature, strength retention rate after thermal aging, average number of binding sites are obviously improved, especially the cation exchange capacity is significantly improved. The relative average pore size, surface energy, adsorption equilibrium time, mass loss in acidic environment, mass loss in alkaline environment, thermal expansion coefficient are significantly reduced.
[0097] Table 1 is the performance parameters of the influence of potassium compounds on the microporous structure of charcoal in the preparation experiment of the microporous biochar of the present application. CK2 is CK1 in Table 1 added with potassium compounds. Experimental examples 2-1 to 2-7 are the results of adding the corresponding type and mass of potassium compounds in Example 1-7 to the basis of experimental examples 1-1 to 1-7. The influence of potassium compounds on the microporous structure of charcoal is compared in Table 2.
[0098] Table 2. Influence of potassium compounds on the microporous structure of charcoal
[0099]
[0100]
[0101] From Table 1 and Table 2 CK1 and CK2, it can be seen that potassium compounds alone have little effect on overall performance, but adding potassium compounds on the basis of phosphorus compounds has a significant effect on various performance indicators of charcoal microporous structure, indicating that the two have a synergistic effect on charcoal microporous structure.
[0102] Table 1 Effect of pyrolysis temperature and time on CEC of biochar, CK1 is the CEC data and surface functional group content of biochar without adding any additives at 300℃, 400℃, 500℃, 600℃ respectively corresponding to 1 hour, 2 hours, 3 hours of biochar; Set Example 1 to add phosphorus compounds and potassium compounds at the same time at 400℃, 500℃, 600℃ respectively corresponding to 1 hour, 2 hours, 3 hours of biochar CEC data and surface functional group content.
[0103] Table 3 Effect of pyrolysis temperature and time on CEC of biochar
[0104]
[0105]
[0106] From the experimental data in Table 3, it can be seen that CK1 has significantly lower CEC data than Example 1 at 300℃, 400℃, 500℃, 600℃ respectively corresponding to 1 hour, 2 hours, 3 hours of biochar; At the same time, comparing 1 hour, 2 hours, 3 hours, at 300℃, 400℃, it increases with time, at 500℃, it first increases and then decreases, at 600℃, it decreases with time, the overall trend is increasing. Example 1 shows that the CEC of 500℃ biochar increases with time, the increasing trend is not obvious, and 600℃ shows an increasing trend after decreasing; Therefore, according to the above experimental data and the required void size and quantity, the initial temperature is determined to be 350℃-450℃, preferably 400℃, and the temperature is maintained at 0.5-1 hour for preliminary pyrolysis, and the temperature is gradually increased to 600℃, with an increase of 50-100℃ each time, and the temperature is maintained for 0.5-2 hours at each temperature segment, and the total time is not more than 3 hours.
[0107] The performance indicators of the cross-linked modified microporous biochar in Examples 1 to 7 are shown in Table 4.
[0108] Table 4. Performance indicators of silicate cross-linked modified microporous biochar in Examples 1 to 7
[0109]
[0110]
[0111]
[0112] From Table 4, it can be seen that after cross-linking modification, the micro-porous biochar has a significant effect on various performance indicators of the charcoal micro-porous structure. Compared with Table 2, the cross-linked modified micro-porous biochar has a significant increase in BET specific surface area, total pore volume, micro-pore ratio, small molecule peptide adsorption capacity, potential (Zeta potential), compressive strength, tensile strength, bonding strength, elastic modulus, catalytic activity, effective carbon, organic matter, N, P, K content, glass transition temperature, strength retention rate after thermal aging, and average number of binding sites. The relative average pore size, surface energy, adsorption equilibrium time, acid environment quality loss, alkaline environment quality loss, and thermal expansion coefficient are significantly reduced.
[0113] Table 5 shows the effect of emulsifiers on biochar-based absorption and slow-release peptide solution.
[0114] Table 5. Effect of emulsifiers on biochar-based absorption and slow-release peptide solution
[0115]
[0116] Table 5 shows that after adding emulsifiers, the surface properties of biochar-based materials change significantly, including specific surface area, pore size distribution, surface chemical properties, potential, surface energy, adsorption capacity, and stability. These changes reflect the effective adsorption of nutrients and the modification effect.
[0117] Table 6. Effect of penetrants on biochar-based absorption and slow-release peptide solution
[0118]
[0119] Table 6 shows that after adding penetrants, the surface properties of carbon-based materials will change significantly. Penetrants may fill part of the pores, resulting in a decrease in micro-pores and an increase in mesopores and macropores. The adsorption capacity of small molecule peptide nutrients is further enhanced, but the adsorption amount of water and gas may decrease; after adding penetrants, the adsorption capacity of carbon-based materials for small molecule peptides is significantly enhanced, as shown in the improvement of adsorption capacity and adsorption efficiency; although the specific surface area and porosity decrease slightly, the overall adsorption effect is significantly improved.
[0120] Table 7 。 Physicochemical indicators of slow-release small molecule peptide fertilizer
[0121]
[0122]
[0123] As shown in Table 7, the physicochemical indicators of slow-release small molecule peptide fertilizer are superior, and the performance is stable.
[0124] Table 8. Comparison data of slow-release small molecule peptide carbon-based fertilizer release performance
[0125]
[0126]
[0127] CK8-1 is a common quick-acting fertilizer, CK8-2 is a commercially available slow-release carbon-based fertilizer
[0128] Release rate and performance comparison
[0129] 1. Release rate experiment:
[0130] Take an equal amount of prepared fertilizer particles and place them in a simulated soil environment.
[0131] Sample every 24 hours to determine the concentration of amino acids, short peptides, and minerals in the solution.
[0132] 2. Data comparison:
[0133] The comparative experiment uses commercially available common quick-acting fertilizer and slow-release fertilizer as reference groups.
[0134] Determine and record the release rate of each group of fertilizers at different time points.
[0135] 3. Performance indicators:
[0136] Initial release rate: assess the release rate of fertilizer nutrients within the first 72 hours, and the control effect of slow-release agents on the initial rate.
[0137] Sustained release performance: assess the sustained release of fertilizer nutrients over the next 7 days.
[0138] Total release amount: calculate the total nutrient amount released by each group of fertilizers during the entire experimental period.
[0139] Table 9. Release rate of each nutrient component of slow-release small molecule peptide carbon-based fertilizer (Example 1)
[0140]
[0141]
[0142] Release rate test:
[0143] Take a certain amount of synthetic fertilizer and place it in a certain volume of water, take samples at regular intervals and measure the concentration of amino acids and mineral elements.
[0144] Test time intervals: 1 hour, 6 hours, 12 hours, 24 hours, 48 hours, 72 hours.
[0145] The concentration changes of amino acids and short peptides were analyzed using high-performance liquid chromatography (HPLC), and the concentration changes of mineral elements were analyzed using atomic absorption spectroscopy (AAS).
[0146] The above data show that the slow-release small molecule peptide carbon-based fertilizer has good slow-release properties and can gradually release amino acids, short peptides, and trace elements within 72 hours, providing continuous nutrition supply for plants.
[0147] Table 10. Planting effect of slow-release small molecule peptide carbon-based fertilizer
[0148]
[0149]
[0150] 1. The activity of microorganisms in the soil was determined using microbial biomass carbon (MBC) and respiration rate (CO2 release) as indicators.
[0151] The slow-release small molecule peptide carbon-based fertilizer had little effect on the activity of soil microorganisms under experimental conditions, and the microbial activity remained above 90%, meeting the requirements of environmental friendliness.
[0152] 2. Heavy metal content test: Atomic absorption spectroscopy (AAS) or inductively coupled plasma mass spectrometry (ICP-MS) was used to determine the heavy metal content in the soil.
[0153] The heavy metal content of the soil after applying the slow-release small molecule peptide carbon-based fertilizer was far below the environmental standard limit value, with no obvious pollution, meeting the environmental friendliness standard.
[0154] 3. Tomato
[0155] Experimental group: Apply newly synthesized small molecule fertilizer. CK group: Apply traditional macromolecular fertilizer.
[0156] Experimental period: 3 months. Measurement indicators: plant growth rate (cm / week), leaf color (chlorophyll content, SPAD value), yield (kg / plant), and soil nutrient content changes (N, P, K content)
[0157] The newly synthesized slow-release small molecule peptide carbon-based fertilizer is superior to traditional fertilizers in promoting plant growth, increasing yield, and improving soil nutrient utilization efficiency. Specifically, the slow-release small molecule peptide carbon-based fertilizer can significantly improve the growth rate, leaf color, and yield of plants due to its easy-to-absorb nutrients, and more effectively maintain and utilize soil nutrients.
[0158] Plant selection: Selecting short growth cycle and fertilizer sensitive plant Brassica chinensis. Experimental design: Traditional carbon-based slow-release fertilizer group CK and slow-release small molecule peptide carbon-based fertilizer group. Each group has 3 replicates. Fertilizer application: Apply fertilizer according to recommended dosage. Experimental conditions: Keep the same light, moisture and temperature conditions, and observe for 30 days.
[0159] The plant growth indicators of the slow-release small molecule peptide carbon-based fertilizer group are significantly better than those of the control group and the traditional fertilizer group. The plant height, leaf number, fresh weight and root length are significantly increased.
[0160] Based on the above experimental results, the slow-release small molecule peptide carbon-based fertilizer has obvious promoting effect on plant growth, and the effect is better than that of traditional fertilizer.
[0161] Table 12. Performance of slow-release small molecule peptide carbon-based compound fertilizer
[0162]
[0163]
[0164] Maturity is commonly used to evaluate the maturity and stability of organic fertilizers (such as compost), and the germination index (GI) is a commonly used measurement method. The germination index combines seed germination rate and radicle growth rate, which can reflect the toxicity and inhibition effect of compost on plant seeds, thereby indirectly representing maturity. GI value varies between 0-100%. The higher the GI value, the lower the toxicity of the compost to the seeds, and the higher the maturity; the lower the GI value, the less mature the compost, which may be toxic to plants. It is generally believed that when the GI value is greater than 80%, the compost has been fully matured and can be safely used for agricultural production.
[0165] Table 13. Effect of slow-release small molecule peptide carbon-based compound fertilizer on plants
[0166]
[0167]
[0168] The effect of small molecule fertilizer on soil microorganisms is small, and the microbial activity remains above 90%.
[0169] The growth rate of crops using small molecule fertilizer is faster, and the yield and quality are better than those of crops using ordinary fertilizer.
[0170] The above only describes the preferred embodiments of the present application, and does not limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.
Claims
1. A slow-release small molecule peptide-based carbon fertilizer, characterized in that, The raw materials include the following parts by weight: 45-50 parts of slow-release small molecule peptide solution, 0.1-0.5 parts of penetrant, and 45-55 parts of cross-linked modified microporous biochar; wherein the cross-linked modified microporous biochar is obtained by cross-linking modified microporous biochar with silicate solution; The sustained-release small molecule peptide solution is obtained by the following method: 40-50 parts of amino acids and 5-10 parts of short peptides are dissolved in 40-50 parts of deionized water and stirred thoroughly until completely dissolved; 0.9 parts of trace mineral elements are added sequentially and stirred continuously until dissolved evenly; while stirring continuously, 1-5 parts of a sustained-release agent are slowly added to distribute it evenly in the solution; 0.5-2 parts of PVA are added and stirring is continued until the solution viscosity is uniform; the mixture is stirred continuously at 50-70℃ until homogeneous, and 1-5 parts of emulsifier are added to prepare the solution. The short peptide is a combination of two of the following: glycyl-glutamine (Gly-Gln), asparagine-alanine (Asn-Ala), alanyl-glutamic acid (Ala-Glu), glycyl-alanine (Gly-Ala), glutamine-glycine-alanine (Gln-Gly-Ala), glycyl-glutamine-alanine (Gly-Gln-Ala), and alanyl-glycine-glutamine (Ala-Gly-Gln). The microporous biochar is obtained by the following method: Biomass material is divided into two parts. 40-50 parts of the first part of biomass material are mixed with 5-10 parts of a phosphate compound, stirred until fully absorbed and dried, and then 40-50 parts of the second part of biomass material are added with 3-5 parts of a potassium compound. The mixture is stirred until homogeneous and then placed in a pyrolysis furnace for pyrolysis. The phosphate compound is H3PO4, H3PO3, H4P2O7, H3PO2, or H5P3O. 10 H5P4O 13 H5P5O 15 The potassium compound is any one or more of the following: K2SO4, KCl, KNO3, K2S, K2CO3, KCH3COO, and K2SO3.
2. The slow-release small molecule peptide-based fertilizer according to claim 1, characterized in that, The silicate solution has a mass-volume concentration of 0.5%-1.5%.
3. The slow-release small molecule peptide-based fertilizer according to claim 1, characterized in that, The amino acids include 33% glycine, 25% alanine, 25% glutamic acid, and 17% aspartic acid.
4. The slow-release small molecule peptide-based fertilizer according to claim 3, characterized in that, The mineral trace elements include 0.25 parts ZnSO4·7H2O, 0.25 parts FeSO4·7H2O, 0.2 parts MnSO4·H2O, 0.1 parts CuSO4·5H2O, 0.05 parts Na2MoO4·2H2O, and 0.05 parts H3BO3; the slow-release agent is any one or more of polyethylene glycol, polylactic acid (PLA), chitosan, ethyl cellulose (EC), carboxymethyl chitosan, sodium alginate, and methyl cellulose; the emulsifier is any one or more of Tween 20, Tween 80, OP-10, sodium dodecyl sulfate, PEG-8 stearate, ethylene oxide (20) laurate, and lauryl alcohol polyoxyethylene ether.
5. The slow-release small molecule peptide-based fertilizer according to claim 1, characterized in that, The pyrolysis process is set with an initial temperature of 350℃-450℃, which is maintained at this temperature for 0.5-1 hour for preliminary pyrolysis. The temperature is then gradually increased to 600℃, with each increase being 50-100℃. Each temperature range is maintained for 0.5-2 hours, with a total duration not exceeding 3 hours. After pyrolysis, the biochar is rapidly cooled and ground to a particle size ≤2 mm.
6. A slow-release small molecule peptide-based fertilizer according to any one of claims 1 to 5, characterized in that, The silicate is any one of Na2SiO3, CaSiO3, K2SiO3, MgSiO3, L12SiO3, Na4SiO4, and Na2SiO3·5H2O; the penetrant is any one or more of JFC penetrant, modified silicone oil, fatty alcohol polyoxyethylene ether, dimethyl sulfoxide, alkyl polysaccharide glycoside, azone, and amino acid penetrant.
7. A slow-release small molecule peptide-based carbon compound fertilizer, characterized in that, It includes 40-60 parts of the slow-release small molecule peptide-carbon-based fertilizer as described in any one of claims 1 to 6, 10-20 parts of nitrogen fertilizer, 5-15 parts of phosphate fertilizer, 5-15 parts of potassium fertilizer, 10-20 parts of organic matter, and 0.5-2.0 parts of functional microbial inoculant.
Citation Information
Patent Citations
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