CN116332698A - Sustained-release polyglutamic acid water-soluble fertilizer and preparation method thereof - Google Patents
Sustained-release polyglutamic acid water-soluble fertilizer and preparation method thereof Download PDFInfo
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- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D3/00—Calcareous fertilisers
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- C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
- C05F17/20—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation using specific microorganisms or substances, e.g. enzymes, for activating or stimulating the treatment
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- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
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- C05G5/00—Fertilisers characterised by their form
- C05G5/30—Layered or coated, e.g. dust-preventing coatings
- C05G5/35—Capsules, e.g. core-shell
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Abstract
The invention relates to the technical field of water-soluble fertilizer production, in particular to a slow-release type polyglutamic acid water-soluble fertilizer and a preparation method thereof, wherein the slow-release type polyglutamic acid water-soluble fertilizer is prepared by a complex coacervation method by taking corn porous starch as a core material carrier, taking the polyglutamic acid water-soluble fertilizer as a core material and taking a sodium alginate-chitosan-modified silicon nanowire composite material as a wall material; the polyglutamic acid water-soluble fertilizer comprises a nitrogenous fertilizer, a phosphate fertilizer, a potash fertilizer and polyglutamic acid fermentation liquor, wherein the nitrogenous fertilizer, the phosphate fertilizer, the potash fertilizer and the polyglutamic acid fermentation liquor are prepared from the following components in parts by weight (15-25): (10-20): (13-18): (60-80). According to the invention, corn porous starch is used as a core material carrier, the polyglutamic acid water-soluble fertilizer can be adsorbed and fixed, and the core material is secondarily embedded by using the wall material, so that a double-layer slow release effect is realized, the release rate of the core material is delayed, the time for completely releasing the core material is prolonged, the utilization rate of the polyglutamic acid water-soluble fertilizer is improved, and the effects of promoting plant growth and increasing yield are realized.
Description
Technical Field
The invention relates to the technical field of water-soluble fertilizer production, in particular to a slow-release polyglutamic acid water-soluble fertilizer and a preparation method thereof.
Background
The water-soluble fertilizer is a multi-element compound fertilizer which can be completely dissolved in water, can be rapidly dissolved in water and is easier to be absorbed by crops, the absorption and utilization ratio is relatively high, and more importantly, the water-soluble fertilizer can be applied to agricultural facilities such as spray drip irrigation and the like, so that the water-fertilizer integration can achieve the effects of saving water, fertilizer and labor, the water-soluble organic fertilizer has the characteristics of full water solubility, high activity, full absorption, quick response and high water-soluble potassium content, the production of the organic water-soluble fertilizer is the development requirement of modern agriculture, and the fertilization efficiency can be greatly improved.
The polyglutamic acid has the characteristics of biodegradability, no toxic or side effect, good biocompatibility and the like, can be used as a soil conditioner in the agricultural field, and has positive effects on improving soil, so that the development of the novel efficient polyglutamic acid water-soluble fertilizer has the effects of effectively reducing fertilizer application, improving fertilizer utilization rate and improving soil cultivation quality, and accords with the development formula of the fertilizer for promoting agricultural yield increase and farmer income increase and resource conservation and environmental friendliness. For example, chinese patent CN2015109397745 discloses a water-soluble fertilizer of carboenzyme particles and a manufacturing method thereof, and the water-soluble fertilizer can effectively promote root system development, enhance plant disease resistance and achieve yield increase effect; however, the water-soluble fertilizer has no slow release effect, so that when the water-soluble fertilizer is applied, in order to meet the normal demand of plants and reduce the waste of the water-soluble fertilizer, the application amount needs to be accurately controlled, and the repeated fertilization with a short period needs to be carried out, thereby wasting time and labor; and the applied water-soluble fertilizer is easy to permeate into the deep soil under the action of water flow after watering, so that the water-soluble fertilizer is lost, and the water-soluble fertilizer cannot exert the effect, so that the utilization rate of the water-soluble fertilizer is not high.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the slow-release type polyglutamic acid water-soluble fertilizer and the preparation method thereof, wherein the polyglutamic acid water-soluble fertilizer is subjected to double-layer embedding treatment to realize double-layer slow-release effect, and the long-term effective effect of one-time sprinkling is realized, so that the sprinkling period of the water-soluble fertilizer can be prolonged, time and labor are saved, and the slow-release type polyglutamic acid water-soluble fertilizer has high bonding strength with soil colloid particles, so that the loss rate of the slow-release type polyglutamic acid water-soluble fertilizer in soil can be reduced, and the improvement of the utilization efficiency of the slow-release type polyglutamic acid water-soluble fertilizer is realized.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the slow release type polyglutamic acid water-soluble fertilizer is prepared by a complex coacervation method by taking corn porous starch as a core material carrier and taking a polyglutamic acid water-soluble fertilizer as a core material and taking a sodium alginate-chitosan-modified silicon nanowire composite material as a wall material; the polyglutamic acid water-soluble fertilizer comprises a nitrogenous fertilizer, a phosphate fertilizer, a potash fertilizer and polyglutamic acid fermentation liquor, wherein the nitrogenous fertilizer, the phosphate fertilizer, the potash fertilizer and the polyglutamic acid fermentation liquor are prepared from the following components in parts by weight (15-25): (10-20): (13-18): (60-80).
As a further preferable scheme of the invention, the polyglutamic acid fermentation broth is added with a microbial agent for fermentation, wherein the microbial agent is bacillus subtilis; the concentration of the polyglutamic acid fermentation broth is 0.01-0.03wt%.
As a further preferable scheme of the invention, the slow-release polyglutamic acid water-soluble fertilizer is prepared by the following steps:
1) Uniformly mixing the nitrogen fertilizer, the phosphate fertilizer and the potash fertilizer in the proportion, adding the mixture into polyglutamic acid fermentation liquor, fully mixing the mixture to obtain a water-soluble fertilizer solution, adding corn porous starch into the water-soluble fertilizer solution, oscillating and adsorbing the corn porous starch at room temperature for 10-20min, adding sodium alginate solution, mixing the mixture, and stirring the mixture at normal temperature for 20-40min to obtain a mixed liquor for later use;
2) Mixing chitosan solution and calcium chloride solution, regulating pH value to 3-4 with sodium bicarbonate, adding modified silicon nanowire composite material, stirring, slowly dripping into the mixed solution, standing for 20-30min, filtering, separating, washing the separated capsule particles with water, and vacuum drying to obtain the slow-release polyglutamic acid water-soluble fertilizer.
As a further preferable scheme of the invention, in the mixed solution, the proportion of the corn porous starch, the water-soluble fertilizer solution and the sodium alginate solution is (1-3) g: (10-30) mL: (30-40) mL;
the concentration of the sodium alginate solution is 0.01-0.02g/mL;
the ratio of the chitosan solution, the calcium chloride solution, the modified silicon nanowire composite material and the mixed solution is (50-65) mL: (50-65) mL: (0.5-1.2) g: (40-60) mL;
the concentration of the chitosan solution is 0.01-0.02g/mL;
the concentration of the calcium chloride solution is 0.05-0.07g/mL.
As a further preferable scheme of the invention, the modified silicon nanowire composite material is prepared by the following steps:
1) Adding a silicon nanowire composite material into a container filled with dry toluene, removing air by using nitrogen, slowly dripping 3-aminopropyl triethoxysilane, reacting for 18-24 hours at 80-85 ℃, drying by using nitrogen after cleaning, then putting into a container filled with dichloromethane and triethylamine, removing air by using nitrogen, ice-bathing for 15-30min under the protection of nitrogen, slowly dripping 2-bromo-2-methylpropanoyl bromide, reacting for 1-2 hours by using ice-bath, reacting for 12-15 hours at room temperature, drying by using nitrogen after cleaning, and obtaining a pretreated silicon nanowire composite material;
2) Adding copper bromide and 2, 2-bipyridine into a container filled with methanol and dimethylaminoethyl methacrylate, fully stirring to form a mixed solution, adding the pretreated silicon nanowire composite material into the mixed solution, reacting for 24-30h at room temperature, cleaning and drying with nitrogen after the reaction is finished, and then soaking in benzyl chloride and acetone at the room temperature according to the volume ratio of 1: and (3) reacting in the mixed solution formed by (9-10) for 12-15h, cleaning, and drying with nitrogen.
As a further preferred embodiment of the present invention, the ratio of toluene, silicon nanowire composite, 3-aminopropyl triethoxysilane, dichloromethane, triethylamine, and 2-bromo-2-methylpropanoyl bromide is (10-20) mL: (1-3) g: (0.2-0.5) mL: (10-20) mL: (0.5-0.8) mL: (0.5-0.8) mL.
As a further preferred embodiment of the present invention, the ratio of copper bromide, 2-bipyridine, methanol, dimethylaminoethyl methacrylate and pretreated silicon nanowire composite is (0.1-0.2) g: (0.3-0.4) g: (20-28) mL: (0.9-1.3) mL: (1.0-1.8) g.
As a further preferable scheme of the invention, the silicon nanowire composite material is prepared by the following steps:
1) Putting the cleaned silicon wafer into a silicon wafer prepared from hydrogen peroxide and sulfuric acid according to the volume ratio of (2-3): heating the mixture in acid liquor consisting of (7-8) in an oil bath at 90-93 ℃ for 30-50min, repeatedly washing the mixture by distilled water, then placing the mixture in acetone for ultrasonic cleaning, and drying the mixture by argon for later use;
2) Adding silver nitrate into a hydrogen fluoride solution, adding deionized water, preheating in a baking oven at 47-50 ℃, slowly pouring into a reaction vessel containing a silicon wafer, reacting for 30-40min in a baking oven at 50-53 ℃, pouring the reaction solution after the reaction is finished, adding a nitric acid solution to wash off silver dendrites on the surface, washing, adding the solution into an acid solution, soaking for 2-3h at 87-90 ℃, washing with deionized water to neutrality, and drying with nitrogen to obtain the silicon nanowire;
3) Dissolving sodium tungstate, hydroxylamine hydrochloride and thiourea in deionized water at room temperature, fully stirring to be fully dissolved, adding hydrochloric acid under the stirring condition to adjust the pH value to 5.5-6.5, then adding cetyltrimethylammonium bromide and silicon nanowires, fully stirring to form mixed solution, transferring into an autoclave, sealing, reacting at 180-190 ℃ for 24-30h, cooling to room temperature after the reaction is finished, and repeatedly washing and drying after centrifugal separation.
As a further preferable embodiment of the present invention, the ratio of the silver nitrate, the hydrogen fluoride solution and the deionized water is (0.1-0.3) g: (7-10) mL: (12-15) mL;
the concentration of the nitric acid solution is 20-30wt%.
As a further preferred embodiment of the present invention, the ratio of sodium tungstate, hydroxylamine hydrochloride, thiourea, deionized water, cetyltrimethylammonium bromide and silicon nanowires is (1.6-2.0) g: (0.7-1.1) g: (1.5-1.9) g: (30-40) mL: (0.2-0.5) g: (1-3) g;
the concentration of the hydrochloric acid is 2-3mol/L.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the polyglutamic acid water-soluble fertilizer consisting of the nitrogenous fertilizer, the phosphate fertilizer, the potash fertilizer and the polyglutamic acid fermentation broth is used as a core material, then corn porous starch is used as a core material carrier, the polyglutamic acid water-soluble fertilizer can be adsorbed and fixed by utilizing a honeycomb porous structure of the carrier, and sodium alginate-chitosan-modified silicon nanowire composite material is used as a wall material, so that double-layer embedding is realized, and the corn porous starch has a larger specific surface area, a compact structure and good slow release property, is matched with the wall material, and can realize a double-layer slow release effect, so that the release rate of the core material can be further delayed, the time for completely releasing the core material is prolonged, and the improvement of the utilization rate of the core material is realized; in order to improve the interception rate of the slow-release polyglutamic acid water-soluble fertilizer in soil and reduce the loss of the slow-release polyglutamic acid water-soluble fertilizer, the invention adds a modified silicon nanowire composite material on the basis of sodium alginate and chitosan to construct a wall material, wherein the modified silicon nanowire composite material takes the silicon nanowire composite material as a matrix material, and is subjected to grafting polymerization of dimethylaminoethyl methacrylate on the surface of the matrix material under the catalysis of 2-bromomethacryloyl bromide by an atom transfer radical polymerization method, and then is subjected to benzyl chloride quaternization treatment to finish the surface modification of the silicon nanowire composite material, and quaternary ammonium salt groups with positive charges can be fixed on the silicon nanowire composite material through surface modification, so that the wall material has positive charges, meanwhile, as the main component of the soil colloidal particle is silicate, the positive charges on the outer layer of the colloidal particle are dominant, negative anions are easy to attract, so that the soil colloidal particle is negatively charged as a whole, and the microcapsule-shaped slow-release polyglutamic acid water-soluble fertilizer can be adsorbed on the soil colloidal particle through the electrostatic adsorption of positive and negative charges, so that the slow-release polyglutamic acid water-soluble fertilizer is limited and fixed, the loss of the slow-release polyglutamic acid water-soluble fertilizer is reduced, a large amount of slow-release polyglutamic acid water-soluble fertilizer can be trapped in the soil, the utilization rate of the slow-release polyglutamic acid water-soluble fertilizer can be effectively improved, the slow-release polyglutamic acid water-soluble fertilizer can fully play a role in the soil, and the effects of promoting plant growth and increasing yield are realized.
In order to improve the embedding effect of the wall material on the core material and the embedding rate of the core material, and realize the high resistance of the wall material to external force, thereby reducing the cracking of the wall material, in the invention, silicon chips are used as matrixes, the reduction reaction of silver ions and the oxidation reaction of silicon atoms are utilized to simultaneously carry out and realize the exchange between electrons on the surfaces of the silicon chips, and when the silicon part contacted with silver nano particles is oxidized into silicon dioxide, the silicon dioxide is dissolved through the corrosion action of hydrogen fluoride, thereby forming tunnels at the bottoms of the silver nano particles, silicon ash sinks and grows up along the tunnels, thereby forming silicon nano wires, and the silicon nano wires are used as a deposition matrix, sodium tungstate and thiourea are respectively used as a tungsten source and a sulfur source, the tungsten disulfide nano wires are deposited on the silicon nano wires through the hydrothermal reaction, thereby forming a silicon nano wire composite material, the deposition of the tungsten disulfide nano wires, the surfaces of the silicon nano wires form nano wire deposition layer, the mutual embedding stack between the nano wires is used, the silicon nano wires can realize the connection, thereby forming a long-chain structure, and the cross-linking structure is formed at the bottoms of the silver nano particles, thereby forming a stable cross-linking structure, the hollow-linked structure can be used for forming the embedded layer material, and the filling down-layer, thereby improving the filling rate of the core material, and the surface of the core material can be more stable, and the surface of the microcapsule-like material can be formed, and the surface of the core material is more stable, and the surface-coated with the surface of the microcapsule material, and the surface-coated with the microcapsule material, and the well-coated with the surface, and the large-shaped silicon-coated material has the large-grain-shaped and the surface-coated silicon-layer, and the high-crystalline, and the high-layer, and the high-quality, and the surface-release performance, and the surface-quality. The contact area between the slow-release type polyglutamic acid water-soluble fertilizer and soil colloid particles can be increased, and the villus covering layer can be entangled with the soil colloid particles, so that the bonding strength between the slow-release type polyglutamic acid water-soluble fertilizer and the soil colloid particles can be remarkably increased, the loss rate of the slow-release type polyglutamic acid water-soluble fertilizer in soil can be further reduced, and the utilization efficiency is improved.
According to the slow-release type polyglutamic acid water-soluble fertilizer, corn porous starch is used as a core material carrier, the polyglutamic acid water-soluble fertilizer can be adsorbed and fixed, and the core material is secondarily embedded by using the wall material, so that a double-layer slow-release effect can be realized, the release rate of the core material is delayed, the time for completely releasing the core material is prolonged, and the utilization rate of the polyglutamic acid water-soluble fertilizer is improved; meanwhile, the added modified silicon nanowire composite material in the wall material has positive charges, so that the whole slow-release type polyglutamic acid water-soluble fertilizer is positively charged and can be combined with soil colloidal particles through electrostatic adsorption, and a villus covering layer is formed on the surface of the slow-release type polyglutamic acid water-soluble fertilizer, so that the contact area between the slow-release type polyglutamic acid water-soluble fertilizer and the soil colloidal particles can be increased, the bonding strength between the slow-release type polyglutamic acid water-soluble fertilizer and the soil colloidal particles can be remarkably increased, the loss rate of the slow-release type polyglutamic acid water-soluble fertilizer in the soil can be reduced, the utilization efficiency of the slow-release type polyglutamic acid water-soluble fertilizer is improved, the slow-release type polyglutamic acid water-soluble fertilizer can fully play a role in the soil, and the effects of promoting plant growth and increasing yield are realized.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The slow release type polyglutamic acid water-soluble fertilizer is prepared by a complex coacervation method by taking corn porous starch as a core material carrier and taking a polyglutamic acid water-soluble fertilizer as a core material and taking a sodium alginate-chitosan-modified silicon nanowire composite material as a wall material; wherein, polyglutamic acid water-soluble fertilizer comprises nitrogenous fertilizer, phosphate fertilizer, potash fertilizer and polyglutamic acid fermentation liquor, and the weight portions of the nitrogenous fertilizer, the phosphate fertilizer, the potash fertilizer and the polyglutamic acid fermentation liquor are 15:10:13:60;
wherein, a microbial agent is added into the polyglutamic acid fermentation broth for fermentation, and the microbial agent is bacillus subtilis; the concentration of the polyglutamic acid fermentation broth is 0.01wt%;
the preparation method of the slow-release polyglutamic acid water-soluble fertilizer specifically comprises the following steps:
1) Uniformly mixing nitrogen fertilizer, phosphate fertilizer and potash fertilizer in the proportion, adding the mixture into polyglutamic acid fermentation liquor, fully mixing the mixture to obtain water-soluble fertilizer solution, adding 1g of corn porous starch into 10mL of water-soluble fertilizer solution, oscillating and adsorbing the mixture at room temperature for 10min, adding 30mL of sodium alginate solution with the concentration of 0.01g/mL, mixing the mixture, and stirring the mixture at the room temperature for 20min at 400r/min to obtain mixed liquor for later use;
2) Mixing 50mL of chitosan solution with the concentration of 0.01g/mL with 50mL of calcium chloride solution with the concentration of 0.05g/mL, adjusting the pH value to 3 by adopting sodium bicarbonate, adding 0.5g of modified silicon nanowire composite material, fully stirring, slowly dripping into 40mL of mixed solution, standing for 20min, filtering and separating, washing the separated capsule particles with water, and drying in vacuum to obtain the slow-release polyglutamic acid water-soluble fertilizer.
The preparation method of the modified silicon nanowire composite material comprises the following steps:
1) Adding 1g of silicon nanowire composite material into a container filled with 10mL of dry toluene, removing air by using nitrogen, slowly dripping 0.2mL of 3-aminopropyl triethoxysilane, reacting at 80 ℃ for 18 hours, repeatedly cleaning by using toluene, acetone and deionized water, drying by using nitrogen, then placing into a container filled with 10mL of dichloromethane and 0.5mL of triethylamine, removing air by using nitrogen, ice-bathing for 15 minutes under the protection of nitrogen, slowly dripping 0.5mL of 2-bromo-2-methylpropanoyl bromide, reacting for 1 hour by using ice-bathing, reacting at room temperature for 12 hours, repeatedly cleaning by using dichloromethane, acetone and deionized water, and drying by using nitrogen to obtain the pretreated silicon nanowire composite material;
2) Adding 0.1g of copper bromide and 0.3g of 2, 2-bipyridine into a container filled with 20mL of methanol and 0.9mL of dimethylaminoethyl methacrylate, fully stirring to form a mixed solution, adding 1.0g of pretreated silicon nanowire composite material into the mixed solution, reacting for 24 hours at room temperature, repeatedly cleaning with methanol and deionized water in sequence after the reaction is finished, drying with nitrogen, and soaking in benzyl chloride and acetone at room temperature according to the volume ratio of 1:9, reacting for 12 hours in the mixed solution formed by the components, repeatedly cleaning the mixed solution by acetone and deionized water, and drying the mixed solution by nitrogen.
The preparation method of the silicon nanowire composite material comprises the following steps:
1) The preparation method comprises the following steps of (1) preparing a catalyst by hydrogen peroxide and sulfuric acid according to a volume ratio of 2:8, placing the cleaned silicon wafer into the acid solution, heating the silicon wafer in an oil bath at 90 ℃ for 30min, repeatedly washing the silicon wafer by distilled water, placing the silicon wafer in acetone for ultrasonic cleaning, and drying the silicon wafer by argon for later use;
2) Putting 0.1g of silver nitrate into a container, adding 7mL of hydrogen fluoride solution, adding 12mL of deionized water, preheating in a 47 ℃ oven, slowly pouring into a reaction vessel containing a silicon wafer, putting into a 50 ℃ oven for reaction for 30min, pouring the reaction liquid after the reaction is finished, adding 20wt% of nitric acid solution to wash off silver dendrites on the surface, repeatedly cleaning with deionized water, acetone, absolute ethyl alcohol and deionized water in sequence, putting into acid liquor, soaking for 2h at 87 ℃, washing with deionized water to neutrality, and drying with nitrogen to obtain silicon nanowires;
3) 1.6g of sodium tungstate, 0.7g of hydroxylamine hydrochloride and 1.5g of thiourea are dissolved in 30mL of deionized water at room temperature, fully stirred until the sodium tungstate, the hydroxylamine hydrochloride and the thiourea are completely dissolved, 2mol/L of hydrochloric acid is added under the stirring condition of 80r/min to adjust the pH value to 5.5, then 0.2g of cetyltrimethylammonium bromide and 1g of silicon nanowire are added, the mixture is formed after the mixture is fully stirred, the mixture is transferred into an autoclave, the autoclave is reacted for 24 hours at 180 ℃ after the sealing, the mixture is cooled to the room temperature after the reaction is finished, and the mixture is repeatedly washed by deionized water and absolute ethyl alcohol after centrifugal separation and is dried for 10 hours in an oven at 60 ℃.
Example 2
The slow release type polyglutamic acid water-soluble fertilizer is prepared by a complex coacervation method by taking corn porous starch as a core material carrier and taking a polyglutamic acid water-soluble fertilizer as a core material and taking a sodium alginate-chitosan-modified silicon nanowire composite material as a wall material; wherein the polyglutamic acid water-soluble fertilizer comprises nitrogen fertilizer, phosphate fertilizer, potash fertilizer and polyglutamic acid fermentation liquor, and the weight parts of the nitrogen fertilizer, the phosphate fertilizer, the potash fertilizer and the polyglutamic acid fermentation liquor are 20:15:14:70;
wherein, a microbial agent is added into the polyglutamic acid fermentation broth for fermentation, and the microbial agent is bacillus subtilis; the concentration of the polyglutamic acid fermentation broth is 0.02wt%;
the preparation method of the slow-release polyglutamic acid water-soluble fertilizer specifically comprises the following steps:
1) Uniformly mixing nitrogen fertilizer, phosphate fertilizer and potash fertilizer in the proportion, adding the mixture into polyglutamic acid fermentation liquor, fully mixing the mixture to obtain water-soluble fertilizer solution, adding 2g of corn porous starch into 20mL of water-soluble fertilizer solution, oscillating and adsorbing the mixture at room temperature for 15min, then adding 35mL of sodium alginate solution with the concentration of 0.02g/mL, mixing the mixture, and stirring the mixture at the room temperature for 30min at 500r/min to obtain mixed liquor for later use;
2) Mixing 60mL of chitosan solution with the concentration of 0.02g/mL with 60mL of calcium chloride solution with the concentration of 0.06g/mL, adjusting the pH value to 3.5 by adopting sodium bicarbonate, adding 0.8g of modified silicon nanowire composite material, fully stirring, slowly dripping into 50mL of mixed solution, standing for 25min, filtering and separating, washing the separated capsule particles with water, and drying in vacuum to obtain the slow-release polyglutamic acid water-soluble fertilizer.
The preparation method of the modified silicon nanowire composite material comprises the following steps:
1) Adding 2g of silicon nanowire composite material into a container filled with 15mL of dry toluene, removing air by using nitrogen, slowly dripping 0.3mL of 3-aminopropyl triethoxysilane, reacting for 20 hours at 83 ℃, repeatedly cleaning by using toluene, acetone and deionized water, drying by using nitrogen, then putting into a container filled with 15mL of dichloromethane and 0.6mL of triethylamine, removing air by using nitrogen, ice-bathing for 25 minutes under the protection of nitrogen, slowly dripping 0.7mL of 2-bromo-2-methylpropanoyl bromide, reacting for 1.5 hours by using ice-bathing, reacting for 14 hours at room temperature, repeatedly cleaning by using dichloromethane, acetone and deionized water, and drying by using nitrogen to obtain the pretreated silicon nanowire composite material;
2) Adding 0.1g of copper bromide and 0.4g of 2, 2-bipyridine into a container filled with 24mL of methanol and 1.1mL of dimethylaminoethyl methacrylate, fully stirring to form a mixed solution, adding 1.5g of pretreated silicon nanowire composite material into the mixed solution, reacting at room temperature for 28h, after the reaction is finished, repeatedly cleaning with methanol and deionized water in sequence, drying with nitrogen, and soaking in benzyl chloride and acetone at room temperature according to the volume ratio of 1:9.5, reacting for 13h in the mixed solution formed by the components, repeatedly cleaning the mixed solution by acetone and deionized water, and drying the mixed solution by nitrogen.
The preparation method of the silicon nanowire composite material comprises the following steps:
1) The preparation method comprises the following steps of preparing hydrogen peroxide and sulfuric acid according to a volume ratio of 2.5:7.5, placing the cleaned silicon wafer into the acid solution, heating the silicon wafer in an oil bath at 92 ℃ for 40min, repeatedly washing the silicon wafer by distilled water, placing the silicon wafer into acetone for ultrasonic cleaning, and drying the silicon wafer by argon for later use;
2) Putting 0.2g of silver nitrate into a container, adding 8mL of hydrogen fluoride solution, adding 13mL of deionized water, preheating in a 48 ℃ oven, slowly pouring into a reaction vessel containing a silicon wafer, putting into a 52 ℃ oven for reaction for 35min, pouring the reaction solution after the reaction is finished, adding 25wt% of nitric acid solution to wash off silver dendrites on the surface, repeatedly cleaning with deionized water, acetone, absolute ethyl alcohol and deionized water in sequence, putting into acid liquor, soaking for 2.5h at 88 ℃, washing with deionized water to neutrality, and drying with nitrogen to obtain silicon nanowires;
3) 1.8g of sodium tungstate, 0.9g of hydroxylamine hydrochloride and 1.7g of thiourea are dissolved in 35mL of deionized water at room temperature, fully stirred until the sodium tungstate, the hydroxylamine hydrochloride and the thiourea are completely dissolved, 2.5mol/L of hydrochloric acid is added under the stirring condition of 129r/min to adjust the pH value to 6, then 0.3g of cetyltrimethylammonium bromide and 2g of silicon nano wires are added, the mixture is formed after the mixture is fully stirred, the mixture is transferred into an autoclave, the autoclave is reacted for 28h at 185 ℃ after the sealing, the reaction is cooled to the room temperature after the reaction is finished, the mixture is repeatedly washed by deionized water and absolute ethyl alcohol after centrifugal separation, and the mixture is dried in an oven at 65 ℃ for 13 h.
Example 3
The slow release type polyglutamic acid water-soluble fertilizer is prepared by a complex coacervation method by taking corn porous starch as a core material carrier and taking a polyglutamic acid water-soluble fertilizer as a core material and taking a sodium alginate-chitosan-modified silicon nanowire composite material as a wall material; wherein the polyglutamic acid water-soluble fertilizer comprises a nitrogenous fertilizer, a phosphate fertilizer, a potash fertilizer and polyglutamic acid fermentation liquor, and the weight parts of the nitrogenous fertilizer, the phosphate fertilizer, the potash fertilizer and the polyglutamic acid fermentation liquor are 25:20:18:80;
wherein, a microbial agent is added into the polyglutamic acid fermentation broth for fermentation, and the microbial agent is bacillus subtilis; the concentration of the polyglutamic acid fermentation broth is 0.03wt%;
the preparation method of the slow-release polyglutamic acid water-soluble fertilizer specifically comprises the following steps:
1) Uniformly mixing nitrogen fertilizer, phosphate fertilizer and potash fertilizer in the proportion, adding the mixture into polyglutamic acid fermentation liquor, fully mixing the mixture to obtain water-soluble fertilizer solution, adding 3g of corn porous starch into 30mL of water-soluble fertilizer solution, oscillating and adsorbing the mixture at room temperature for 20min, then adding 40mL of sodium alginate solution with the concentration of 0.02g/mL, mixing the mixture, and stirring the mixture at the room temperature for 40min at 600r/min to obtain mixed liquor for later use;
2) Mixing 65mL of chitosan solution with the concentration of 0.02g/mL and 65mL of calcium chloride solution with the concentration of 0.07g/mL, adjusting the pH value to 4 by adopting sodium bicarbonate, adding 1.2g of modified silicon nanowire composite material, fully stirring, slowly dripping into 60mL of mixed solution, standing for 30min, filtering and separating, washing the separated capsule particles with water, and drying in vacuum to obtain the slow-release polyglutamic acid water-soluble fertilizer.
The preparation method of the modified silicon nanowire composite material comprises the following steps:
1) Adding 3g of silicon nanowire composite material into a container filled with 20mL of dry toluene, removing air by using nitrogen, slowly dripping 0.5mL of 3-aminopropyl triethoxysilane, reacting at 85 ℃ for 24 hours, repeatedly cleaning by using toluene, acetone and deionized water, drying by using nitrogen, then placing into a container filled with 20mL of dichloromethane and 0.8mL of triethylamine, removing air by using nitrogen, ice-bathing for 30 minutes under the protection of nitrogen, slowly dripping 0.8mL of 2-bromo-2-methylpropanoyl bromide, reacting at room temperature for 2 hours by using ice-bathing, reacting at room temperature for 15 hours, repeatedly cleaning by using dichloromethane, acetone and deionized water, and drying by using nitrogen to obtain the pretreated silicon nanowire composite material;
2) Adding 0.2g of copper bromide and 0.4g of 2, 2-bipyridine into a container filled with 28mL of methanol and 1.3mL of dimethylaminoethyl methacrylate, fully stirring to form a mixed solution, adding 1.8g of pretreated silicon nanowire composite material into the mixed solution, reacting for 30h at room temperature, repeatedly cleaning with methanol and deionized water in sequence after the reaction is finished, drying with nitrogen, and soaking in benzyl chloride and acetone at room temperature according to the volume ratio of 1:10, and then the mixture is repeatedly cleaned by acetone and deionized water and dried by nitrogen.
The preparation method of the silicon nanowire composite material comprises the following steps:
1) The preparation method comprises the following steps of (1) preparing a catalyst by hydrogen peroxide and sulfuric acid according to a volume ratio of 3:7, placing the cleaned silicon wafer into the acid solution, heating the silicon wafer in an oil bath at 93 ℃ for 50min, repeatedly washing the silicon wafer by distilled water, placing the silicon wafer in acetone for ultrasonic cleaning, and drying the silicon wafer by argon for later use;
2) Putting 0.3g of silver nitrate into a container, adding 10mL of hydrogen fluoride solution, adding 15mL of deionized water, preheating in a 50 ℃ oven, slowly pouring into a reaction vessel containing a silicon wafer, putting into a 53 ℃ oven for reaction for 40min, pouring the reaction liquid after the reaction is finished, adding 30wt% of nitric acid solution to wash off silver dendrites on the surface, repeatedly cleaning with deionized water, acetone, absolute ethyl alcohol and deionized water in sequence, putting into acid liquor, soaking for 3h at 90 ℃, washing with deionized water to neutrality, and drying with nitrogen to obtain silicon nanowires;
3) At room temperature, 2.0g of sodium tungstate, 1.1g of hydroxylamine hydrochloride and 1.9g of thiourea are dissolved in 40mL of deionized water, fully stirred until the sodium tungstate, the hydroxylamine hydrochloride and the 1.9g of thiourea are completely dissolved, 3mol/L of hydrochloric acid is added under the stirring condition of 150r/min to adjust the pH value to 6.5, then 0.5g of cetyltrimethylammonium bromide and 3g of silicon nanowire are added, the mixture is formed after the full stirring, the mixture is transferred into an autoclave, the autoclave is reacted for 30 hours at 190 ℃ after the sealing, the mixture is cooled to room temperature after the reaction is finished, and the mixture is repeatedly washed by deionized water and absolute ethyl alcohol after centrifugal separation and is dried in an oven at 70 ℃ for 15 hours.
Comparative example 1: this comparative example is substantially the same as example 1 except that the modified silicon nanowire composite is not added to the wall material.
Comparative example 2: this comparative example is substantially the same as example 1 except that silicon nanowires are used in place of the modified silicon nanowire composite in the wall material.
Comparative example 3: this comparative example is substantially the same as example 1 except that a silicon nanowire composite is used in place of the modified silicon nanowire composite in the wall material.
Comparative example 4: this comparative example is substantially the same as example 1 except that the modified silicon nanowire composite is prepared without pretreatment.
Comparative example 5: this comparative example is substantially the same as example 1 except that in the preparation of the modified silicon nanowire composite, a silicon nanowire is used instead of the silicon nanowire composite.
Test experiment:
1, testing the release rate of the polyglutamic acid water-soluble fertilizer:
according to the requirements of the national standard GB/T23148-2009 of the slow-release fertilizer, the accumulated release rates of the slow-release fertilizer containing the modified diatomite in 24h, 3d, 10d and 28d in still water at 25 ℃ are detected, and specific experimental results are shown in Table 1.
24h Release Rate% 3d Release Rate% 10d Release Rate% 28d Release Rate% example 18.3+ -1.611.6 + -3.623.8 + -8.256.7 + -12.5 example 28.6+ -1.212.3 + -3.924.6 + -8.857.3 + -13.1 example 38.0+ -1.110.5 + -3.222.1 + -7.856.0 + -12.0 comparative 117.2+ -1.823.1 + -4.043.6 + -8.879.5 + -13.8 comparative 215.8+ -1.921.0 + -3.939.7 + -9.274.3 + -13.3 comparative 314.1+ -2.018.9 + -4.235.2 + -9.070.7 + -14.0 comparative 412.3 + -1.515.5 + -3.833.8 + -9.567.3 + -13.6 comparative 511.8+ -1.713.8 + -3.631.2 + -9.363.1 + -13.5
As can be seen from Table 1, the polyglutamic acid water-soluble fertilizer provided by the invention has the advantages of obviously better initial release and accumulated release effects, more meets the slow release requirement, and realizes the remarkable improvement of the utilization rate.
2, testing the retention rate of polyglutamic acid water-soluble fertilizer soil:
the slow-release type polyglutamic acid water-soluble fertilizer samples provided in examples 1 to 3 and comparative examples 1 to 5 were selected, 5 kg of water was added to 34g of the slow-release type polyglutamic acid water-soluble fertilizer sample per mu of land and sprayed, and thereafter 5 kg of water was sprayed every 5h per mu of land, and the retention rate of the slow-release type polyglutamic acid water-soluble fertilizer sample in the soil was measured at 7h, 13h, 23h and 43h, and specific results are shown in Table 2.
7h retention% 13h retention% 23h retention% 43h retention% example 197.395.192.086.7 example 298.196.592.988.0 example 397.695.492.587.3 comparative 190.178.260.840.7 comparative 291.080.565.350.2 example 394.392.188.780.6 comparative 495.793.890.685.3 comparative 595.092.789.682.5
As can be seen from Table 2, the polyglutamic acid water-soluble fertilizer provided by the invention has the advantages of better soil retention rate, low loss rate in soil after spraying, improvement of utilization efficiency, contribution to full play of the polyglutamic acid water-soluble fertilizer in the soil, and thus effects of promoting plant growth and increasing yield.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (10)
1. The slow release type polyglutamic acid water-soluble fertilizer is characterized in that corn porous starch is used as a core material carrier, the polyglutamic acid water-soluble fertilizer is used as a core material, a sodium alginate-chitosan-modified silicon nanowire composite material is used as a wall material, and a complex coacervation method is adopted; the polyglutamic acid water-soluble fertilizer comprises a nitrogenous fertilizer, a phosphate fertilizer, a potash fertilizer and polyglutamic acid fermentation liquor, wherein the nitrogenous fertilizer, the phosphate fertilizer, the potash fertilizer and the polyglutamic acid fermentation liquor are prepared from the following components in parts by weight (15-25): (10-20): (13-18): (60-80).
2. The slow release type polyglutamic acid water-soluble fertilizer according to claim 1, wherein a microbial agent is added into the polyglutamic acid fermentation broth for fermentation, and the microbial agent is bacillus subtilis; the concentration of the polyglutamic acid fermentation broth is 0.01-0.03wt%.
3. The slow release type polyglutamic acid water-soluble fertilizer according to claim 1, wherein the slow release type polyglutamic acid water-soluble fertilizer is prepared by the following steps:
1) Uniformly mixing the nitrogen fertilizer, the phosphate fertilizer and the potash fertilizer in the proportion, adding the mixture into polyglutamic acid fermentation liquor, fully mixing the mixture to obtain a water-soluble fertilizer solution, adding corn porous starch into the water-soluble fertilizer solution, oscillating and adsorbing the corn porous starch at room temperature for 10-20min, adding sodium alginate solution, mixing the mixture, and stirring the mixture at normal temperature for 20-40min to obtain a mixed liquor for later use;
2) Mixing chitosan solution and calcium chloride solution, regulating pH value to 3-4 with sodium bicarbonate, adding modified silicon nanowire composite material, stirring, slowly dripping into the mixed solution, standing for 20-30min, filtering, separating, washing the separated capsule particles with water, and vacuum drying to obtain the slow-release polyglutamic acid water-soluble fertilizer.
4. The slow release type polyglutamic acid water-soluble fertilizer according to claim 3, wherein the proportion of corn porous starch, water-soluble fertilizer solution and sodium alginate solution in the mixed solution is (1-3) g: (10-30) mL: (30-40) mL;
the concentration of the sodium alginate solution is 0.01-0.02g/mL;
the ratio of the chitosan solution, the calcium chloride solution, the modified silicon nanowire composite material and the mixed solution is (50-65) mL: (50-65) mL: (0.5-1.2) g: (40-60) mL;
the concentration of the chitosan solution is 0.01-0.02g/mL;
the concentration of the calcium chloride solution is 0.05-0.07g/mL.
5. The slow release polyglutamic acid water-soluble fertilizer according to claim 3, wherein the preparation method of the modified silicon nanowire composite material is as follows:
1) Adding a silicon nanowire composite material into a container filled with dry toluene, removing air by using nitrogen, slowly dripping 3-aminopropyl triethoxysilane, reacting for 18-24 hours at 80-85 ℃, drying by using nitrogen after cleaning, then putting into a container filled with dichloromethane and triethylamine, removing air by using nitrogen, ice-bathing for 15-30min under the protection of nitrogen, slowly dripping 2-bromo-2-methylpropanoyl bromide, reacting for 1-2 hours by using ice-bath, reacting for 12-15 hours at room temperature, drying by using nitrogen after cleaning, and obtaining a pretreated silicon nanowire composite material;
2) Adding copper bromide and 2, 2-bipyridine into a container filled with methanol and dimethylaminoethyl methacrylate, fully stirring to form a mixed solution, adding the pretreated silicon nanowire composite material into the mixed solution, reacting for 24-30h at room temperature, cleaning and drying with nitrogen after the reaction is finished, and then soaking in benzyl chloride and acetone at the room temperature according to the volume ratio of 1: and (3) reacting in the mixed solution formed by (9-10) for 12-15h, cleaning, and drying with nitrogen.
6. The slow release polyglutamic acid water-soluble fertilizer according to claim 5, wherein the ratio of toluene, silicon nanowire composite material, 3-aminopropyl triethoxysilane, dichloromethane, triethylamine and 2-bromo-2-methylpropanoyl bromide is (10-20) mL: (1-3) g: (0.2-0.5) mL: (10-20) mL: (0.5-0.8) mL: (0.5-0.8) mL.
7. The slow release polyglutamic acid water-soluble fertilizer according to claim 5, wherein the ratio of the copper bromide, the 2, 2-bipyridine, the methanol, the dimethylaminoethyl methacrylate and the pretreated silicon nanowire composite material is (0.1-0.2) g: (0.3-0.4) g: (20-28) mL: (0.9-1.3) mL: (1.0-1.8) g.
8. The slow release polyglutamic acid water-soluble fertilizer according to claim 5, wherein the silicon nanowire composite material is prepared by the following steps:
1) Putting the cleaned silicon wafer into a silicon wafer prepared from hydrogen peroxide and sulfuric acid according to the volume ratio of (2-3): heating the mixture in acid liquor consisting of (7-8) in an oil bath at 90-93 ℃ for 30-50min, repeatedly washing the mixture by distilled water, then placing the mixture in acetone for ultrasonic cleaning, and drying the mixture by argon for later use;
2) Adding silver nitrate into a hydrogen fluoride solution, adding deionized water, preheating in a baking oven at 47-50 ℃, slowly pouring into a reaction vessel containing a silicon wafer, reacting for 30-40min in a baking oven at 50-53 ℃, pouring the reaction solution after the reaction is finished, adding a nitric acid solution to wash off silver dendrites on the surface, washing, adding the solution into an acid solution, soaking for 2-3h at 87-90 ℃, washing with deionized water to neutrality, and drying with nitrogen to obtain the silicon nanowire;
3) Dissolving sodium tungstate, hydroxylamine hydrochloride and thiourea in deionized water at room temperature, fully stirring to be fully dissolved, adding hydrochloric acid under the stirring condition to adjust the pH value to 5.5-6.5, then adding cetyltrimethylammonium bromide and silicon nanowires, fully stirring to form mixed solution, transferring into an autoclave, sealing, reacting at 180-190 ℃ for 24-30h, cooling to room temperature after the reaction is finished, and repeatedly washing and drying after centrifugal separation.
9. The slow release polyglutamic acid water-soluble fertilizer according to claim 8, wherein the ratio of the silver nitrate to the hydrogen fluoride to the deionized water is (0.1-0.3) g: (7-10) mL: (12-15) mL;
the concentration of the nitric acid solution is 20-30wt%.
10. The slow release polyglutamic acid water-soluble fertilizer according to claim 8, wherein the proportion of the sodium tungstate, the hydroxylamine hydrochloride, the thiourea, the deionized water, the cetyltrimethylammonium bromide and the silicon nanowires is (1.6-2.0) g: (0.7-1.1) g: (1.5-1.9) g: (30-40) mL: (0.2-0.5) g: (1-3) g;
the concentration of the hydrochloric acid is 2-3mol/L.
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| CN117142899A (en) * | 2023-08-18 | 2023-12-01 | 安徽卓砺农业科技有限公司 | Bio-based fertilizer synergist and preparation method thereof |
| CN117338636A (en) * | 2023-12-04 | 2024-01-05 | 江西中医药大学 | Material for essential oil slow release and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117142899A (en) * | 2023-08-18 | 2023-12-01 | 安徽卓砺农业科技有限公司 | Bio-based fertilizer synergist and preparation method thereof |
| CN117142899B (en) * | 2023-08-18 | 2024-05-07 | 安徽卓砺农业科技有限公司 | Bio-based fertilizer synergist and preparation method thereof |
| CN117338636A (en) * | 2023-12-04 | 2024-01-05 | 江西中医药大学 | Material for essential oil slow release and application thereof |
| CN117338636B (en) * | 2023-12-04 | 2024-02-23 | 江西中医药大学 | Material for essential oil slow release and application thereof |
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