CN118561641B - Fertilizer synergist, preparation method and application thereof - Google Patents
Fertilizer synergist, preparation method and application thereof Download PDFInfo
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- CN118561641B CN118561641B CN202411034688.5A CN202411034688A CN118561641B CN 118561641 B CN118561641 B CN 118561641B CN 202411034688 A CN202411034688 A CN 202411034688A CN 118561641 B CN118561641 B CN 118561641B
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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
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C11/00—Other nitrogenous fertilisers
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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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- 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
- C05G3/80—Soil conditioners
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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
- C05G5/00—Fertilisers characterised by their form
- C05G5/30—Layered or coated, e.g. dust-preventing coatings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/22—Improving land use; Improving water use or availability; Controlling erosion
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
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Abstract
The invention provides a fertilizer synergist, a preparation method and application thereof, belonging to the technical field of fertilizer synergists; the preparation method comprises the steps of preparing functional biochar, preparing gamma-polyglutamic acid/functional biochar compound, preparing stabilizer and mixing materials; the preparation method comprises the steps of preparing a gamma-polyglutamic acid/functional biochar compound, placing the functional biochar in dimethyl sulfoxide, adding gamma-polyglutamic acid, uniformly mixing, controlling the stirring rotation speed to 165-174rpm, adding N, N' -diisopropylcarbodiimide in a stirring state, stirring for reacting for 18-22h, adding absolute ethyl alcohol after the reaction is finished, continuously stirring, filtering, pre-cooling and freeze-drying, and naturally recovering to room temperature to obtain the gamma-polyglutamic acid/functional biochar compound; the fertilizer synergist solves the problems of quick release of early-stage nutrients and slow release of middle-stage and later-stage nutrients, and has stable slow release effect at different temperatures.
Description
Technical Field
The invention belongs to the technical field of fertilizer synergists, and particularly relates to a fertilizer synergist, a preparation method and application thereof.
Background
The fertilizer can provide necessary nutrient elements for plants, improve soil properties and soil fertility, is one of the material foundations of agricultural production, but the utilization rate of the fertilizer in China is low, the loss of the nitrogen fertilizer through volatilization, leaching, runoff and other ways is more, farmland can be damaged, and the problems of surface water eutrophication, exceeding of nitrate in vegetables, serious lake pollution and the like can be caused.
The fertilizer synergist is an active substance for improving nutrient availability, increases nutrient supply of crops by holding nitrogen and activating phosphorus and potassium elements which are difficult to utilize in soil, plays a certain role in regulating physiological functions of plants, and can properly reduce the fertilizer dosage and improve the utilization rate of the fertilizer by adding the fertilizer synergist into conventional fertilizers;
therefore, in order to improve the utilization rate of the fertilizer and alleviate the environmental problems caused by the fertilizer, a fertilizer synergist can be added into the fertilizer.
At present, a plurality of fertilizer synergists are adopted in the market, and some fertilizer can achieve a slow-release and controlled-release effect by adding a nitrification inhibitor and a urease inhibitor or adopting a coating principle;
however, urease preparations and nitrifying preparations are not suitable for paddy fields or areas with much precipitation, because water can reduce the concentration of the nitrifying inhibitor and the urease inhibitor, and the effectiveness is reduced;
In the coating technology, the slow release effect of zeolite powder and starch coating is poor, and the resin coating can effectively improve the slow release effect, but residues are easily left in soil to damage the structure of the soil and affect the growth and development of crops;
Therefore, the fertilizer synergist is wide in application area, obvious in fertilizer increasing effect and capable of promoting crop growth, and is a technical problem to be solved in the prior art.
CN117142899a discloses a bio-based fertilizer synergist and a preparation method thereof, and specifically discloses the fertilizer synergist which comprises the following raw materials: modified polyglutamic acid, tobacco stalk biochar, polyphosphate, bentonite, zeolite powder, gamma-aminobutyric acid, sodium humate, organic acid and trace element composition; the modified polyglutamic acid is prepared by dissolving polyglutamic acid in dimethyl sulfoxide, adding allyl thiourea and thifluzamide, adding a cross-linking agent and a catalyst, and stirring and mixing for reaction;
The fertilizer synergist not only has excellent fertilizer retention capacity, can enhance the slow release property of the fertilizer and remarkably improve the utilization rate of the fertilizer, but also has a certain bactericidal property, can reduce soil-borne bacterial diseases, and is beneficial to improving the yield and quality of crops.
However, the fertilizer synergist prepared by the method has the advantages of faster release of early-stage nutrients, slower release of middle-stage and later-stage nutrients, and slow release performance greatly influenced by temperature, and has the advantages of faster slow release rate when the temperature is higher and slower slow release rate when the temperature is lower.
Disclosure of Invention
In order to solve the technical problems, the invention provides a fertilizer synergist, a preparation method and application thereof, which can solve the problems of faster nutrient release in the early stage and slower nutrient release in the middle and later stages, and has stable slow release effect at different temperatures.
Aiming at the technical problems, the invention adopts the following technical scheme:
the preparation method of the fertilizer synergist comprises the steps of preparing functional biochar, preparing gamma-polyglutamic acid/functional biochar compound, preparing stabilizer and mixing, and specifically comprises the following steps:
1. preparation of functional biochar
(1) Preparation of biochar
Cleaning and airing peanut shells, crushing for 8-12min at 638-660rpm, placing the crushed peanut shells in a pyrolysis furnace, heating to 375-384 ℃ at the speed of 2.8-3.2 ℃/min, pyrolyzing for 18-22min at 375-384 ℃, heating to 634-645 ℃ at the speed of 0.8-1.2 ℃/min, pyrolyzing for 3.0-3.5h at 634-645 ℃, controlling the pyrolysis atmosphere to be nitrogen, controlling the flow rate of the nitrogen to be 95-104mL/min, and naturally cooling to room temperature to obtain biochar;
(2) Acid leaching
Placing the biochar in a closed container, then adding 4.5-5.5 times of nitric acid solution for soaking for 4.4-4.6 hours at the soaking temperature of 96-98 ℃, filtering after soaking, washing with deionized water, and then drying at 104-106 ℃ to obtain the biochar subjected to acid leaching;
The mass concentration of the nitric acid solution is 56-58%;
(3) Functionalization
Placing the acid leached biochar in a plasma device for plasma treatment, wherein the treatment atmosphere is ammonia gas, the treatment power is 424-436W, the treatment time is 4-6min, the treatment temperature is 10-14 ℃, the ammonia gas flow is 47-53mL/min, the plasma treated biochar is prepared after the plasma treatment is finished, the plasma treated biochar is put into ethylenediamine solution, then cetyl trimethyl ammonium bromide is added for ball milling treatment, the ball milling time is 28-32min, the ball milling rotating speed is 250-260rpm, the ball material ratio is 3-5:1, after the ball milling is finished, the temperature is raised to 68-72 ℃ at the speed of 2.4-2.6 ℃/min, the standing is carried out for 2.4-2.7h at the temperature of 68-72 ℃, the standing is naturally restored to room temperature, and the functional biochar is prepared after the standing is finished, and the filtering and drying are carried out;
The mass concentration of the ethylenediamine solution is 12-14%;
The mass ratio of the biochar, ethylenediamine solution and cetyltrimethylammonium bromide treated by the plasma is 97-102:446-453:2.4-2.6.
2. Preparation of gamma-polyglutamic acid/functional biochar complex
Placing functional biochar in dimethyl sulfoxide, adding gamma-polyglutamic acid, uniformly mixing, controlling the stirring rotation speed to be 165-174rpm, controlling the stirring temperature to be 23-27 ℃, adding N, N' -diisopropylcarbodiimide in a stirring state, stirring for reacting for 18-22h, adding absolute ethyl alcohol after the reaction is finished, stirring for 27-33min at 214-223rpm, filtering after the stirring is finished, pre-cooling and freeze-drying, wherein the pre-cooling temperature is-39 to-35 ℃, the pre-cooling time is 5.8-6.2h, the freezing temperature is-48 to-45 ℃, the freezing time is 19-22h, the vacuum degree is 40-44Pa, and naturally recovering to room temperature after the drying is finished to obtain the gamma-polyglutamic acid/functional biochar compound;
the mass ratio of the functional biochar to the dimethyl sulfoxide to the gamma-polyglutamic acid to the N, N' -diisopropylcarbodiimide to the absolute ethyl alcohol is 8-12:116-124:3.3-3.7:1.1-1.3:490-510.
3. Preparation of the stabilizer
(1) Preparation of composite diatomite
Placing diatomite into the composite liquid for ultrasonic treatment, wherein the ultrasonic time is 18-23min, the ultrasonic power is 235-245W, the ultrasonic frequency is 25-29kHz, and filtering and drying are carried out after the ultrasonic treatment is finished to obtain the composite diatomite;
The particle size of the diatomite is 230-250nm, the mass content of silicon dioxide in the diatomite is 92.5-93.0%, and the mass content of aluminum oxide is 3.4-3.6%;
the compound liquid consists of deionized water, pentaerythritol tetrastearate and sucrose fatty acid ester, wherein the mass ratio of the deionized water to the pentaerythritol tetrastearate to the sucrose fatty acid ester is 105-114:2.3-2.7:2.8-3.2;
The mass ratio of the diatomite to the composite liquid is 18-22:126-135;
(2) Preparation of the Mixed solution
Adding tris (hydroxymethyl) aminomethane hydrochloride and dopamine hydrochloride into deionized water, stirring at 24-26 ℃ and 163-176rpm, and regulating pH to 8.3-8.5 to obtain a mixed solution;
The mass ratio of the deionized water to the tris (hydroxymethyl) aminomethane hydrochloride to the dopamine hydrochloride is 990-1010:1.20-1.22:1.9-2.1;
(3) Coating
Homogenizing the composite diatomite in a mixed solution for 4-6min under the condition that the homogenizing pressure is 5.0-5.4MPa, stirring and reacting for 8.7-9.3h at the reaction temperature of 34-36 ℃, washing and drying after the homogenizing treatment is finished, then placing the composite diatomite in a muffle furnace for high-temperature treatment, heating the composite diatomite to 205-215 ℃ at the speed of 5.0-5.5 ℃/min, preserving the temperature for 27-33min at the speed of 205-215 ℃, heating the composite diatomite to 364-373 ℃ at the speed of 2.2-2.7 ℃/min, preserving the temperature for 1.9-2.2h at the temperature of 364-373 ℃ and naturally cooling the composite diatomite to room temperature after the homogenizing treatment is finished to obtain the stabilizer;
the mass ratio of the composite diatomite to the mixed solution is 8-12:320-340;
4. Mixing material
Mixing the gamma-polyglutamic acid/functional biochar compound, the stabilizer and the trace elements, uniformly stirring, adding sodium humate, organic acid and diethyl aminoethyl hexanoate, controlling the temperature to be 43-47 ℃, and stirring at 116-125rpm for 33-38min to obtain a fertilizer synergist;
The trace elements are a mixture of magnesium sulfate and borax, and the mass ratio of the magnesium sulfate to the borax is 1:0.8-1.1;
The organic acid is a mixture of oxalic acid and citric acid, and the mass ratio of the oxalic acid to the citric acid is 1.1:1.2-1.5;
the gamma-polyglutamic acid/functional biochar compound, the stabilizer and the trace elements are mixed, and the mass ratio of the sodium humate to the organic acid to the diethyl aminoethyl hexanoate is 45-48:33-36:5.2-5.4:10-12:6.6-7.0:5.5-5.8.
A fertilizer synergist is prepared by the preparation method.
The mass ratio of the fertilizer to the fertilizer synergist is 6.3:1.
Compared with the prior art, the invention has the following beneficial effects:
1. According to the invention, peanut shells are adopted to prepare the biochar, the biochar is subjected to functionalization treatment, impurities on the surface of the biochar can be removed by acid leaching treatment, then plasma treatment is carried out under an ammonia gas atmosphere, and the biochar is placed in an ethylenediamine solution for ball milling treatment, so that the activity performance of the biochar is improved, agglomeration among particles is avoided, amino groups are uniformly distributed on the surface of the biochar, functionalization of the biochar is realized, gamma-polyglutamic acid is adopted to be compounded with the functional biochar, carboxyl groups of the gamma-polyglutamic acid react with amino groups of the functional biochar in the presence of a condensing agent, strong crosslinking is formed between the gamma-polyglutamic acid and the functional biochar, the binding force is strong and stable, and a three-dimensional network structure is formed, and the slow release performance of the structure is stable;
In the preparation of the stabilizer, diatomite is subjected to surface activation, polydopamine is adopted for coating, amine, imine and other groups in polydopamine are introduced to the surface of the diatomite, so that the diatomite and gamma-polyglutamic acid/functional biochar compound have good compatibility and good dispersibility, and the specific surface area of the diatomite is improved and the adsorption performance is enhanced through high-temperature calcination treatment;
The organic acid, the diethyl aminoethyl hexanoate and other components can promote the absorption of plants to nitrogen, phosphorus, potassium and other nutrients, strengthen the absorption of plants to magnesium and other mineral metals, better promote the development of plants, and combine the gamma-polyglutamic acid/functional biochar compound, the stabilizer and other components to prepare the fertilizer synergist, so that the fertilizer synergist has good dispersibility, excellent adsorption performance, good fertilizer retaining capacity and slow release performance, avoids the rapid loss of nutrient components in the fertilizer, enhances the fertilizer retaining performance, has stable slow release performance at different temperatures and improves the utilization rate of the fertilizer;
2. The fertilizer synergist prepared by the invention has nutrient release performance measured according to the method in GB/T23348-2009 slow release fertilizer, the test temperature is 32 ℃, the release rate of 1d is measured to be 2.3-2.7%, the release rate of 10d is measured to be 8.6-9.0%, the release rate of 20d is measured to be 18.2-18.7%, the release rate of 30d is measured to be 30.7-31.2%, and the release rate of 60d is measured to be 75.3-76.0%;
3. The fertilizer synergist prepared by the invention has nutrient release performance measured according to the method in GB/T23148-2009 slow release fertilizer, the test temperature is 10 ℃, the release rate of 1d is measured to be 2.1-2.6%, the release rate of 10d is measured to be 8.3-8.7%, the release rate of 20d is measured to be 16.9-17.5%, the release rate of 30d is measured to be 28.2-28.9%, and the release rate of 60d is measured to be 73.0-74.1%.
Detailed Description
For a clearer understanding of the technical features, objects and effects of the present invention, specific embodiments of the present invention will be described.
Example 1
1. Preparation of functional biochar
(1) Preparation of biochar
Cleaning and airing peanut shells, crushing for 10min at 650rpm, placing the crushed peanut shells in a pyrolysis furnace, heating to 380 ℃ at the speed of 3.0 ℃/min, pyrolyzing at 380 ℃ for 20min, heating to 640 ℃ at the speed of 1.0 ℃/min, pyrolyzing at 640 ℃ for 3.2h, controlling the pyrolysis atmosphere to be nitrogen, controlling the nitrogen flow rate to be 100mL/min, and naturally cooling to room temperature to obtain biochar;
(2) Acid leaching
Placing the biochar in a closed container, then adding nitric acid solution with the volume of 5 times for soaking for 4.5 hours, wherein the soaking temperature is 97 ℃, filtering after the soaking is finished, washing with deionized water, and then drying at 105 ℃ to obtain the biochar after acid leaching;
The mass concentration of the nitric acid solution is 57%;
(3) Functionalization
Placing the acid leached biochar in a plasma device for plasma treatment, wherein the treatment atmosphere is ammonia gas, the treatment power is 430W, the treatment time is 5min, the treatment temperature is 12 ℃, the ammonia gas flow is 50mL/min, the plasma treated biochar is prepared after the plasma treatment is finished, 100g of the plasma treated biochar is put into 450g of ethylenediamine solution, then 2.5g of cetyltrimethylammonium bromide is added for ball milling treatment, the ball milling time is 30min, the ball milling rotation speed is 255rpm, the ball material ratio is 4:1, after the ball milling is finished, the temperature is raised to 70 ℃ at the speed of 2.5 ℃/min, the mixture is kept stand for 2.5h at 70 ℃, after the standing is finished, the mixture is naturally restored to room temperature, and the mixture is filtered and dried to prepare the functional biochar;
the mass concentration of the ethylenediamine solution is 13%.
2. Preparation of gamma-polyglutamic acid/functional biochar complex
Placing 10g of functional biochar in 120g of dimethyl sulfoxide, adding 3.5g of gamma-polyglutamic acid, uniformly mixing, controlling the stirring rotation speed to 170rpm, controlling the stirring temperature to 25 ℃, adding 1.2g of N, N' -diisopropylcarbodiimide under the stirring state, stirring for reacting for 20h, adding 500g of absolute ethyl alcohol after the reaction is finished, stirring for 30min at 220rpm, filtering after the stirring is finished, pre-cooling and freeze-drying, wherein the pre-cooling temperature is-37 ℃, the pre-cooling time is 6h, the freezing temperature is-46 ℃, the freezing time is 20h, the vacuum degree is 42Pa, and naturally recovering to room temperature after the drying is finished to obtain the gamma-polyglutamic acid/functional biochar compound.
3. Preparation of the stabilizer
(1) Preparation of composite diatomite
Placing 20g of diatomite into 130g of composite liquid for ultrasonic treatment, wherein the ultrasonic time is 20min, the ultrasonic power is 240W, the ultrasonic frequency is 27kHz, and filtering and drying are carried out after the ultrasonic treatment is finished to obtain the composite diatomite;
The particle size of the diatomite is 240nm, the mass content of silicon dioxide in the diatomite is 92.7%, and the mass content of aluminum oxide is 3.5%;
The compound liquid consists of deionized water, pentaerythritol tetrastearate and sucrose fatty acid ester, wherein the mass ratio of the deionized water to the pentaerythritol tetrastearate to the sucrose fatty acid ester is 110:2.5:3.0;
(2) Preparation of the Mixed solution
1.21G of tris (hydroxymethyl) aminomethane hydrochloride and 2.0g of dopamine hydrochloride are added into 1000g of deionized water, and then the mixture is stirred at 25 ℃ and at 170rpm, and the pH is adjusted to 8.4 to prepare a mixed solution;
(3) Coating
And (3) placing 10g of composite diatomite into 330g of mixed solution for homogenizing treatment, wherein the homogenizing time is 5min, the homogenizing pressure is 5.2MPa, stirring and reacting for 9h, the reacting temperature is 35 ℃, washing and drying after the reacting is finished, then placing the mixture into a muffle furnace for high-temperature treatment, wherein the treatment atmosphere is argon, firstly heating to 210 ℃ at a speed of 5.2 ℃/min, preserving heat for 30min at 210 ℃, then heating to 370 ℃ at a speed of 2.5 ℃/min, preserving heat for 2.0h at 370 ℃, and naturally reducing to room temperature after the preserving heat is finished, thus obtaining the stabilizer.
4. Mixing material
Mixing 46g of gamma-polyglutamic acid/functional biochar compound, 35g of stabilizer and 5.3g of trace elements, uniformly stirring, adding 11g of sodium humate, 6.8g of organic acid and 5.7g of diethyl aminoethyl hexanoate, controlling the temperature to 45 ℃, the stirring rotation speed to 120rpm and the stirring time to 35min, and preparing the fertilizer synergist;
The trace elements are a mixture of magnesium sulfate and borax, and the mass ratio of the magnesium sulfate to the borax is 1:1;
the organic acid is a mixture of oxalic acid and citric acid, and the mass ratio of the oxalic acid to the citric acid is 1.1:1.3.
Example 2
1. Preparation of functional biochar
(1) Preparation of biochar
Cleaning and airing peanut shells, crushing for 8min at 638rpm, placing the crushed peanut shells in a pyrolysis furnace, heating to 375 ℃ at a speed of 2.8 ℃/min, pyrolyzing at 375 ℃ for 18min, heating to 634 ℃ at a speed of 0.8 ℃/min, pyrolyzing at 634 ℃ for 3.0h, controlling the pyrolysis atmosphere to be nitrogen, controlling the nitrogen flow rate to be 95mL/min, and naturally cooling to room temperature to obtain biochar;
(2) Acid leaching
Placing the biochar in a closed container, then adding 4.5 times of nitric acid solution for soaking for 4.4 hours at the soaking temperature of 96 ℃, filtering after the soaking is finished, washing with deionized water, and then drying at 104 ℃ to obtain the biochar after acid leaching;
The mass concentration of the nitric acid solution is 56%;
(3) Functionalization
Placing the acid leached biochar in a plasma device for plasma treatment, wherein the treatment atmosphere is ammonia gas, the treatment power is 424W, the treatment time is 4min, the treatment temperature is 10 ℃, the ammonia gas flow is 47mL/min, the plasma treated biochar is prepared after the plasma treatment is finished, 97g of the plasma treated biochar is put into 446g of ethylenediamine solution, then 2.4g of cetyltrimethylammonium bromide is added for ball milling treatment, the ball milling time is 28min, the ball milling rotation speed is 250rpm, the ball material ratio is 3:1, after the ball milling is finished, the temperature is raised to 68 ℃ at the speed of 2.4 ℃/min, the mixture is kept stand for 2.4h at 68 ℃, after the standing is finished, the mixture is naturally restored to room temperature, and the mixture is filtered and dried to prepare the functional biochar;
The mass concentration of the ethylenediamine solution is 12%.
2. Preparation of gamma-polyglutamic acid/functional biochar complex
Placing 8g of functional biochar in 116g of dimethyl sulfoxide, adding 3.3g of gamma-polyglutamic acid, uniformly mixing, controlling the stirring rotation speed to 165rpm, controlling the stirring temperature to 23 ℃, adding 1.1g of N, N' -diisopropylcarbodiimide under the stirring state, stirring for 18h, adding 490g of absolute ethyl alcohol after the reaction is finished, stirring for 27min under 214rpm, filtering after the stirring is finished, pre-cooling and freeze-drying, wherein the pre-cooling temperature is-39 ℃, the pre-cooling time is 5.8h, the freezing temperature is-48 ℃, the freezing time is 19h, the vacuum degree is 40Pa, and naturally recovering to room temperature after the drying is finished, thereby preparing the gamma-polyglutamic acid/functional biochar compound.
3. Preparation of the stabilizer
(1) Preparation of composite diatomite
Putting 18g of diatomite into 126g of composite liquid for ultrasonic treatment, wherein the ultrasonic time is 18min, the ultrasonic power is 235W, the ultrasonic frequency is 25kHz, and filtering and drying are carried out after the ultrasonic treatment is finished to obtain composite diatomite;
The particle size of the diatomite is 230nm, the mass content of silicon dioxide in the diatomite is 92.5%, and the mass content of aluminum oxide is 3.4%;
The compound liquid consists of deionized water, pentaerythritol tetrastearate and sucrose fatty acid ester, wherein the mass ratio of the deionized water to the pentaerythritol tetrastearate to the sucrose fatty acid ester is 105:2.3:2.8;
(2) Preparation of the Mixed solution
Adding 1.20g of tris (hydroxymethyl) aminomethane hydrochloride and 1.9g of dopamine hydrochloride to 990g of deionized water, stirring at 24 ℃ and 163rpm, and regulating the pH to 8.3 to obtain a mixed solution;
(3) Coating
And (3) placing 8g of composite diatomite into 320g of mixed solution for homogenizing treatment, wherein the homogenizing time is 4min, the homogenizing pressure is 5.0MPa, stirring and reacting for 8.7h, the reaction temperature is 34 ℃, washing and drying after the reaction is finished, placing the mixture into a muffle furnace for high-temperature treatment, heating the mixture to 205 ℃ at a speed of 5.0 ℃/min, preserving heat for 27min at 205 ℃, heating to 364 ℃ at a speed of 2.2 ℃/min, preserving heat for 1.9 h at 364 ℃ after the heat preservation is finished, and naturally reducing to room temperature to obtain the stabilizer.
4. Mixing material
Mixing 45g of gamma-polyglutamic acid/functional biochar compound, 33g of stabilizer and 5.2g of trace elements, uniformly stirring, adding 10g of sodium humate, 6.6g of organic acid and 5.5g of diethyl aminoethyl hexanoate, controlling the temperature to be 43 ℃, controlling the stirring rotation speed to be 116rpm, and stirring for 33min to obtain a fertilizer synergist;
the trace elements are a mixture of magnesium sulfate and borax, and the mass ratio of the magnesium sulfate to the borax is 1:0.8;
The organic acid is a mixture of oxalic acid and citric acid, and the mass ratio of the oxalic acid to the citric acid is 1.1:1.2.
Example 3
1. Preparation of functional biochar
(1) Preparation of biochar
Cleaning and airing peanut shells, crushing for 12min at 660rpm, placing the crushed peanut shells in a pyrolysis furnace, heating to 384 ℃ at a speed of 3.2 ℃/min, pyrolyzing at 384 ℃ for 22min, heating to 645 ℃ at a speed of 1.2 ℃/min, pyrolyzing at 645 ℃ for 3.5h, controlling the pyrolysis atmosphere to be nitrogen, controlling the nitrogen flow rate to be 104mL/min, and naturally cooling to room temperature to obtain biochar;
(2) Acid leaching
Placing the biochar in a closed container, then adding 5.5 times of nitric acid solution for soaking for 4.6 hours at the soaking temperature of 98 ℃, filtering after the soaking is finished, washing with deionized water, and then drying at the temperature of 106 ℃ to obtain the biochar subjected to acid leaching;
the mass concentration of the nitric acid solution is 58%;
(3) Functionalization
Placing the acid leached biochar in a plasma device for plasma treatment, wherein the treatment atmosphere is ammonia gas, the treatment power is 436W, the treatment time is 6min, the treatment temperature is 14 ℃, the ammonia gas flow is 53mL/min, the plasma treated biochar is prepared after the plasma treatment is finished, 102g of the plasma treated biochar is put into 453g of ethylenediamine solution, then 2.6g of cetyltrimethylammonium bromide is added for ball milling treatment, the ball milling time is 32min, the ball milling rotation speed is 260rpm, the ball material ratio is 5:1, after the ball milling is finished, the temperature is raised to 72 ℃ at the speed of 2.6 ℃/min, the mixture is kept stand for 2.7h at the temperature of 72 ℃, after the standing is finished, the mixture is naturally restored to room temperature, and the mixture is filtered and dried to prepare the functional biochar;
The mass concentration of the ethylenediamine solution is 14%.
2. Preparation of gamma-polyglutamic acid/functional biochar complex
Placing 12g of functional biochar in 124g of dimethyl sulfoxide, adding 3.7g of gamma-polyglutamic acid, uniformly mixing, controlling the stirring rotation speed to 174rpm, controlling the stirring temperature to 27 ℃, adding 1.3g of N, N' -diisopropylcarbodiimide under the stirring state, stirring for reacting for 22h, adding 510g of absolute ethyl alcohol after the reaction is finished, stirring for 33min at 223rpm, filtering after the stirring is finished, pre-cooling and freeze-drying, wherein the pre-cooling temperature is-35 ℃, the pre-cooling time is 6.2h, the freezing temperature is-45 ℃, the freezing time is 22h, the vacuum degree is 44Pa, and naturally recovering to room temperature after the drying is finished to obtain the gamma-polyglutamic acid/functional biochar compound.
3. Preparation of the stabilizer
(1) Preparation of composite diatomite
Putting 22g of diatomite into 135g of composite liquid for ultrasonic treatment, wherein the ultrasonic time is 23min, the ultrasonic power is 245W, the ultrasonic frequency is 29kHz, and filtering and drying are carried out after the ultrasonic treatment is finished to obtain the composite diatomite;
the particle size of the diatomite is 250nm, the mass content of silicon dioxide in the diatomite is 93.0%, and the mass content of aluminum oxide is 3.6%;
The compound liquid consists of deionized water, pentaerythritol tetrastearate and sucrose fatty acid ester, wherein the mass ratio of the deionized water to the pentaerythritol tetrastearate to the sucrose fatty acid ester is 114:2.7:3.2;
(2) Preparation of the Mixed solution
1.22G of tris (hydroxymethyl) aminomethane hydrochloride and 2.1g of dopamine hydrochloride are added into 1010g of deionized water, and then the mixture is stirred at 26 ℃ and 176rpm, and the pH is adjusted to 8.5, so as to prepare a mixed solution;
(3) Coating
And (3) placing 12g of composite diatomite into 340g of mixed solution for homogenizing treatment, wherein the homogenizing time is 6min, the homogenizing pressure is 5.4MPa, stirring and reacting for 9.3h, the reacting temperature is 36 ℃, washing and drying after the reacting is finished, placing the mixture into a muffle furnace for high-temperature treatment, wherein the treatment atmosphere is argon, firstly heating to 215 ℃ at the speed of 5.5 ℃/min, preserving heat for 33min at 215 ℃, then heating to 373 ℃ at the speed of 2.7 ℃/min, preserving heat for 2.2h at 373 ℃, and naturally reducing to room temperature after the preserving heat is finished, thus obtaining the stabilizer.
4. Mixing material
Mixing 48g of gamma-polyglutamic acid/functional biochar compound, 36g of stabilizer and 5.4g of trace elements, uniformly stirring, adding 12g of sodium humate, 7.0g of organic acid and 5.8g of diethyl aminoethyl hexanoate, controlling the temperature to 47 ℃, the stirring rotation speed to 125rpm and the stirring time to 38min, and preparing the fertilizer synergist;
the trace elements are a mixture of magnesium sulfate and borax, and the mass ratio of the magnesium sulfate to the borax is 1:1.1;
the organic acid is a mixture of oxalic acid and citric acid, and the mass ratio of the oxalic acid to the citric acid is 1.1:1.5.
Comparative example 1
On the basis of example 1, the modification was that, in the preparation of functional biochar,
(1) Omitting the step of functionalization, and directly adopting the acid leached biochar in the step of preparing the gamma-polyglutamic acid/functional biochar compound;
(2) The preparation method of the gamma-polyglutamic acid/functional biochar compound comprises the steps of mixing the acid leached biochar with gamma-polyglutamic acid, stirring, stirring at 25 ℃ at 170rpm for 20 hours to obtain the gamma-polyglutamic acid/functional biochar compound;
the mass ratio of the biochar after acid leaching to the gamma-polyglutamic acid is 10:3.5;
the rest of the operations are the same.
Comparative example 2
On the basis of example 1, the process of preparing the stabilizer was omitted, and in the process of mixing, the stabilizer was replaced with diatomaceous earth which was not subjected to any treatment in equal amounts;
The particle size of the diatomite is 240nm, the mass content of silicon dioxide in the diatomite is 92.7%, and the mass content of aluminum oxide is 3.5%;
the rest of the operations are the same.
Test examples
Mixing the fertilizer synergists prepared in the examples 1-3 and the comparative examples 1-2 with a compound fertilizer to prepare a compound synergism fertilizer, and controlling the particle size of the compound synergism fertilizer to be 1.0mm; wherein the mass ratio of the compound fertilizer to the synergist is 6.3:1, and the specific content of the compound fertilizer is as follows: n20%, P 2O512%,K2 O17%;
(1) Sustained release performance at 35 DEG C
The nutrient release performance of the compound synergistic fertilizer at different time is measured according to the method in GB/T23148-2009 slow release fertilizer, the test temperature is 32 ℃, and the test result is as follows:
(2) Sustained release performance at 10 DEG C
The nutrient release performance of the compound synergistic fertilizer at different time is measured according to the method in GB/T23148-2009 slow release fertilizer, the test temperature is 10 ℃, and the test result is as follows:
From the above results, in comparative example 1, in the step of preparing the γ -polyglutamic acid/functional biochar composite, the acid-leached biochar and γ -polyglutamic acid are directly mixed to prepare the composite, and the acid-leached biochar and γ -polyglutamic acid are only physically mixed, and chemical crosslinking cannot be achieved, so that the binding force inside the composite is poor, the adsorption performance is poor, the release rate of the prepared fertilizer synergist is faster in the early stage, the release performance is greatly affected by temperature, the retention rate of the release rate is lower when the temperature is lower, and the release stability is poor;
The preparation of the stabilizing agent is omitted in the comparative example 2, diatomite which is not subjected to any treatment is directly adopted as the stabilizing agent, the dispersing performance in the mixing process is poor, the compatibility with the gamma-polyglutamic acid/functional biochar compound and other components is poor, so that the homogeneity of the fertilizer synergist is poor, the adsorption performance is poor, the nutrient release rate of the fertilizer synergist is greatly influenced by temperature, the stabilizing performance is poor, the early release rate is high, and the later growth and development of plants are influenced.
According to the invention, peanut shells are adopted to prepare the biochar, the biochar is subjected to functionalization treatment, impurities on the surface of the biochar can be removed by acid leaching treatment, then plasma treatment is carried out under an ammonia gas atmosphere, and the biochar is placed in an ethylenediamine solution for ball milling treatment, so that the activity performance of the biochar is improved, agglomeration among particles is avoided, amino groups are uniformly distributed on the surface of the biochar, functionalization of the biochar is realized, gamma-polyglutamic acid is adopted to be compounded with the functional biochar, carboxyl groups of the gamma-polyglutamic acid react with amino groups of the functional biochar in the presence of a condensing agent, strong crosslinking is formed between the gamma-polyglutamic acid and the functional biochar, the binding force is strong and stable, and a three-dimensional network structure is formed, and the slow release performance of the structure is stable;
In the preparation of the stabilizer, diatomite is subjected to surface activation, polydopamine is adopted for coating, amine, imine and other groups in polydopamine are introduced to the surface of the diatomite, so that the diatomite and gamma-polyglutamic acid/functional biochar compound have good compatibility and good dispersibility, and the specific surface area of the diatomite is improved and the adsorption performance is enhanced through high-temperature calcination treatment;
The organic acid, diethyl aminoethyl hexanoate and other components can promote the absorption of plants to nitrogen, phosphorus, potassium and other nutrients, strengthen the absorption of plants to magnesium and other mineral metals, better promote the development of plants, and the fertilizer synergist prepared by combining the gamma-polyglutamic acid/functional biochar compound, the stabilizer and other components has good dispersibility, excellent adsorption performance, good fertilizer retaining capacity and slow release performance, avoids the rapid loss of nutrient components in the fertilizer, enhances the fertilizer retaining performance, has stable slow release performance at different temperatures and improves the utilization rate of the fertilizer.
The proportions described in the invention are mass proportions, and the percentages are mass percentages unless otherwise specified.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some of the technical features thereof. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A preparation method of a fertilizer synergist is characterized in that,
The preparation method comprises the steps of preparing functional biochar, preparing gamma-polyglutamic acid/functional biochar compound, preparing stabilizer and mixing;
the preparation of the functional biochar comprises the steps of biochar preparation, acid leaching and functionalization;
The method comprises the steps of placing the acid leached biochar in a plasma device for plasma treatment, wherein the treatment atmosphere is ammonia, the treatment power is 424-436W, the treatment time is 4-6min, the treatment temperature is 10-14 ℃, the ammonia flow is 47-53mL/min, the plasma treated biochar is prepared after the plasma treatment is finished, the plasma treated biochar is put into ethylenediamine solution, cetyl trimethyl ammonium bromide is added for ball milling treatment, the ball milling time is 28-32min, the ball milling rotating speed is 250-260rpm, the ball material ratio is 3-5:1, after the ball milling is finished, the temperature is raised to 68-72 ℃ at the speed of 2.4-2.6 ℃/min, the standing is carried out for 2.4-2.7h at the temperature of 68-72 ℃, the standing is naturally restored to room temperature, and the functional biochar is prepared after the standing is finished, and the functional biochar is filtered and dried;
The mass concentration of the ethylenediamine solution is 12-14%;
the mass ratio of the biochar, ethylenediamine solution and cetyltrimethylammonium bromide treated by the plasma is 97-102:446-453:2.4-2.6;
The preparation method comprises the steps of placing functional biochar in dimethyl sulfoxide, adding gamma-polyglutamic acid, uniformly mixing, controlling the stirring rotation speed to be 165-174rpm, the stirring temperature to be 23-27 ℃, adding N, N' -diisopropylcarbodiimide in a stirring state, stirring for reacting for 18-22h, adding absolute ethyl alcohol after the reaction is finished, stirring for 27-33min at 214-223rpm, filtering after the stirring is finished, and then pre-cooling and freeze-drying, wherein the pre-cooling temperature is-39 to-35 ℃, the pre-cooling time is 5.8-6.2h, the freezing temperature is-48 to-45 ℃, the freezing time is 19-22h, the vacuum degree is 40-44Pa, and naturally recovering to room temperature after the drying is finished to obtain the gamma-polyglutamic acid/functional biochar compound;
the mass ratio of the functional biochar to the dimethyl sulfoxide to the gamma-polyglutamic acid to the N, N' -diisopropylcarbodiimide to the absolute ethyl alcohol is 8-12:116-124:3.3-3.7:1.1-1.3;
The step of preparing the stabilizer comprises the steps of preparing composite diatomite, preparing a mixed solution and coating;
The preparation method comprises the steps of placing diatomite in a composite liquid for ultrasonic treatment, wherein the ultrasonic time is 18-23min, the ultrasonic power is 235-245W, the ultrasonic frequency is 25-29kHz, and filtering and drying are carried out after the ultrasonic treatment is finished to obtain the composite diatomite;
The particle size of the diatomite is 230-250nm, the mass content of silicon dioxide in the diatomite is 92.5-93.0%, and the mass content of aluminum oxide is 3.4-3.6%;
The mass ratio of the diatomite to the composite liquid is 18-22:126-135;
the compound liquid consists of deionized water, pentaerythritol tetrastearate and sucrose fatty acid ester, wherein the mass ratio of the deionized water to the pentaerythritol tetrastearate to the sucrose fatty acid ester is 105-114:2.3-2.7:2.8-3.2;
the coating step comprises the steps of placing the composite diatomite into a mixed solution for homogenizing treatment, wherein the homogenizing time is 4-6min, the homogenizing pressure is 5.0-5.4MPa, stirring and reacting for 8.7-9.3h after the homogenizing treatment is finished, the reaction temperature is 34-36 ℃, washing and drying after the reaction is finished, placing the mixture into a muffle furnace for high-temperature treatment, wherein the treatment atmosphere is argon, firstly heating to 205-215 ℃ at the speed of 5.0-5.5 ℃/min, preserving heat for 27-33min at the temperature of 205-215 ℃, then heating to 364-373 ℃ at the speed of 2.2-2.7 ℃/min, preserving heat for 1.9-2.2h at the temperature of 364-373 ℃, and naturally reducing to room temperature after the heat preservation is finished to obtain the stabilizer;
the mass ratio of the composite diatomite to the mixed solution is 8-12:320-340.
2. The method for preparing the fertilizer synergist according to claim 1, wherein,
The preparation method of the biochar comprises the steps of cleaning and airing peanut shells, crushing for 8-12min at 638-660rpm, placing the crushed peanut shells in a pyrolysis furnace, heating to 375-384 ℃ at the speed of 2.8-3.2 ℃/min, pyrolyzing at 375-384 ℃ for 18-22min, heating to 634-645 ℃ at the speed of 0.8-1.2 ℃/min, pyrolyzing at 634-645 ℃ for 3.0-3.5h, controlling the pyrolysis atmosphere to be nitrogen, controlling the flow rate of nitrogen to be 95-104mL/min, and naturally cooling to room temperature to obtain the biochar.
3. The method for preparing the fertilizer synergist according to claim 1, wherein,
Placing the biochar in a closed container, then adding 4.5-5.5 times of nitric acid solution for soaking for 4.4-4.6 hours at the soaking temperature of 96-98 ℃, filtering after soaking, washing with deionized water, and then drying at 104-106 ℃ to obtain the biochar after acid leaching;
The mass concentration of the nitric acid solution is 56-58%.
4. The method for preparing the fertilizer synergist according to claim 1, wherein,
Adding tris (hydroxymethyl) aminomethane hydrochloride and dopamine hydrochloride into deionized water, stirring at 24-26 ℃ and 163-176rpm, and regulating the pH to 8.3-8.5 to obtain a mixed solution;
The mass ratio of the deionized water to the tris (hydroxymethyl) aminomethane hydrochloride to the dopamine hydrochloride is 990-1010:1.20-1.22:1.9-2.1.
5. The method for preparing the fertilizer synergist according to claim 1, wherein,
Mixing the gamma-polyglutamic acid/functional biochar compound, the stabilizer and the trace elements, uniformly stirring, adding sodium humate, organic acid and diethyl aminoethyl hexanoate, controlling the temperature to be 43-47 ℃, and stirring at 116-125rpm for 33-38min to obtain the fertilizer synergist;
The trace elements are a mixture of magnesium sulfate and borax, and the mass ratio of the magnesium sulfate to the borax is 1:0.8-1.1;
The organic acid is a mixture of oxalic acid and citric acid, and the mass ratio of the oxalic acid to the citric acid is 1.1:1.2-1.5;
the gamma-polyglutamic acid/functional biochar compound, the stabilizer and the trace elements are mixed, and the mass ratio of the sodium humate to the organic acid to the diethyl aminoethyl hexanoate is 45-48:33-36:5.2-5.4:10-12:6.6-7.0:5.5-5.8.
6. A fertilizer synergist made by the method of any one of claims 1-5.
7. The use of a fertilizer synergist as defined in any one of claims 1-5, wherein the mass ratio of fertilizer to fertilizer synergist is 6.3:1.
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