CN111875442A - Long-acting slow-release fertilizer containing trace elements and preparation method thereof - Google Patents
Long-acting slow-release fertilizer containing trace elements and preparation method thereof Download PDFInfo
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- CN111875442A CN111875442A CN202010698721.XA CN202010698721A CN111875442A CN 111875442 A CN111875442 A CN 111875442A CN 202010698721 A CN202010698721 A CN 202010698721A CN 111875442 A CN111875442 A CN 111875442A
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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
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
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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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- 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
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- C05G5/40—Fertilisers incorporated into a matrix
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The invention relates to the field of fertilizers, in particular to a long-acting slow-release fertilizer containing trace elements, which comprises a porous microsphere, wherein an expanded soil layer is coated outside the porous microsphere, and a degradable plastic layer is coated outside the expanded soil layer; the surface of the porous microsphere is loaded with a compound containing iron, manganese and molybdenum elements; the inside of the expansion soil layer contains compounds of iron, copper, zinc and manganese elements; the degradable plastic layer contains compounds of zinc and boron elements. The invention overcomes the defect that the trace element fertilizer in the prior art can not release corresponding trace elements according to the actual growth conditions of plants, has the advantages of releasing different trace elements according to different requirements of plants in different growth periods of the plants on the basis of supplementing the trace elements required by the growth of the plants in time in the growth process of the plants, can effectively meet the requirements of crops on different trace elements by only fertilizing once in the whole growth period of the crops, and is more convenient and labor-saving to use.
Description
Technical Field
The invention relates to the field of fertilizers, in particular to a long-acting slow-release fertilizer containing trace elements and a preparation method thereof.
Background
Chemical fertilizers are generally divided into two classes, macroelement fertilizers and micronutrient fertilizers. Wherein the macroelement fertilizer is a fertilizer with large absorption and consumption amount of crops, such as nitrogenous fertilizer, phosphate fertilizer, potash fertilizer, calcium fertilizer, magnesium fertilizer and sulfur fertilizer.
Micronutrient fertilizers, often referred to simply as trace elements. It refers to a fertilizer containing micronutrients and having low crop absorption consumption (relative to a macroelement fertilizer). Although trace elements are required in crops in small quantities, they are equally important to crops as macroelements and cannot be replaced by each other. The application of the micro-fertilizer can play the fertilizer effect on the basis of nitrogen, phosphorus and potassium fertilizers. Meanwhile, the crop reaction to the trace element rope is different under different nitrogen, phosphorus and potassium levels. In general, low-yield soil is easy to lack trace elements; the requirement of crops on trace elements is increased along with the continuous increase of the yield level of the high-yield soil. Therefore, micro-fertilizer must be applied in the plant planting process.
The existing trace element fertilizer needs to be matched and adjusted according to different growth stages of plants in the using process, so that the trace element fertilizer needs to be applied repeatedly, and wastes time and labor. Meanwhile, the applied fertilizer may be continuously lost under the washing of rainwater, so that the fertilizer effect cannot be maintained for a long time.
For example, the compound microorganism granular fertilizer containing the medium trace elements with the application number of CN201410330509.2 comprises the following components in parts by weight: 50-90% of medium trace elements, 0.2-5% of compound microbial agent and 8-12% of binder; the medium trace element is monohydrate or anhydrous compound. The invention provides rich soil scarce nutrients by using medium trace elements, provides excellent root microecological environment by using compound microorganisms, secretes growth hormone-related substances, further promotes the absorption of the crops to the large, medium and trace elements, has reasonable nutrient proportion and high fertilizer efficiency, can greatly improve the fertilizer absorption level of the crops, reduces the production cost, overcomes the problems of various nutrient deficiency symptoms, weak root system disease resistance and stress resistance and the like, enhances the resistance of the crops, and improves the yield and the quality. The granulating process fully utilizes the characteristic of stable water absorption of all materials, reduces energy consumption and does not discharge greenhouse gas three wastes; can meet different requirements of various soil types and crop varieties on medium trace elements and compound microorganisms in China. However, the method also has the disadvantages that various trace elements are released simultaneously, but are not released in time division according to different growth cycles of plants, so that the trace elements are easy to lose, and the fertilizer efficiency of the fertilizer is low.
Disclosure of Invention
The long-acting slow-release fertilizer containing the trace elements is used for overcoming the defect that the trace element fertilizer in the prior art cannot release corresponding trace elements according to the actual growth conditions of plants, and the long-acting slow-release fertilizer containing the trace elements can release different trace element fertilizers according to different growth cycles of the plants, so that the use efficiency of the plants on the trace elements is effectively improved.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a long-acting slow-release fertilizer containing trace elements comprises a porous microsphere, wherein an expanded soil layer is coated outside the porous microsphere, and a degradable plastic layer is coated outside the expanded soil layer;
wherein: the surface of the porous microsphere is loaded with a compound containing iron, manganese and molybdenum elements;
the inside of the expansion soil layer contains compounds of iron, copper, zinc and manganese elements;
the degradable plastic layer contains compounds of zinc and boron elements;
the mass ratio of the porous microspheres to the expanded soil layer to the degradable plastic layer is 100: (40-60): (30-50).
The long-acting slow-release fertilizer containing the trace elements is of a three-layer structure, each layer of the structure is loaded with the fertilizer containing different trace elements, the outermost layer is a degradable plastic layer and can be gradually decomposed when being applied to soil, so that the trace elements in the fertilizer are decomposed, after the degradable plastic layer is decomposed, the volume of an expansion soil layer can be greatly expanded due to the fact that the expansion soil layer can be in contact with moisture, the damage of the decomposed degradable plastic layer is further accelerated, the release of the trace elements in the degradable plastic layer is improved, meanwhile, the expansion soil layer also contains iron, copper, zinc and manganese elements, and the fertilizer can provide nutrients required by growth of plants in the middle section of plant growth. When the plants grow in the later stage, nutrients in the porous microspheres can be leached out from the porous microspheres along with water, so that the nutrients are absorbed by the plants.
Therefore, the long-acting slow-release fertilizer provided by the invention can provide different trace element fertilizers for plants along with different growth stages of the plants, so that the growth, the driving and the navigation of the plants are effectively protected. Meanwhile, unnecessary trace element loss is saved, and the absorption utilization rate is improved. In addition, only need spill once in using this fertilizer process, just can guarantee a whole growth cycle of crops, consequently, use labour saving and time saving more.
In the invention, zinc and boron are supplemented in the early stage of plant growth, and the two can effectively prevent the problems that the plant growth is inhibited, and the plant is short and even withered and dead. Meanwhile, the boron is supplemented in the early stage, so that the problem that pollen, buds, ovaries and the like are easy to fall off in the flowering process in the middle growth stage of the plant can be solved. And in the middle period of plant growth, a large amount of chlorophyll is needed by the plants in the process of flowering and fruiting so as to provide nutrients for the plants, so that iron and copper are supplemented in time, and the chlorophyll can be effectively formed by the plants. Meanwhile, the iron element can effectively improve the activity of peroxidase in the plant root system, and is beneficial to the generation and lignification of plant cell walls. And the copper element can be beneficial to flowering and scion in the middle period of plant growth, thereby improving the yield of crops. The manganese element is added in the middle stage of plant growth and can be matched with the iron element, so that the generation of the indole acetic acid oxidase prosthetic group is improved, and the activation effect on various enzymes in the plant is achieved. At the terminal stage of plant growth, the invention compounds molybdenum element on the basis of iron and manganese, can synthesize azotase and nitrate reductase in the plant body, and can convert nitrate nitrogen into ammonia nitrogen, thereby effectively improving the utilization rate of nitrogen and playing a good role in promoting the growth of fruits. Therefore, the long-acting slow-release fertilizer containing the trace elements can adjust the release of the trace elements according to different stages of plant growth, thereby helping plants to grow healthier.
Preferably, each 100 parts of the porous microspheres are loaded with 0.5-2 parts of ferrous sulfate, 0.1-0.3 part of ammonium ferrous sulfate, 0.2-0.6 part of manganese sulfate, 0.0015-0.005 part of ammonium molybdate and 0.001-0.003 part of sodium molybdate in parts by weight.
Preferably, the porous microspheres are spherical activated carbon or porous calcium carbonate with the diameter of 1-10 mm.
The surface of the porous microsphere is loaded with a compound containing iron, manganese and molybdenum elements, wherein
Preferably, the expansive soil layer comprises 100 parts of montmorillonite powder, 5-10 parts of urea, 0.5-2 parts of ammonium ferrous sulfate, 0.01-0.15 part of copper sulfate, 0.01-0.05 part of zinc sulfate, 0.1-0.3 part of calcium hydroxide and 0.05-0.2 part of manganese sulfate in parts by weight.
Preferably, the degradable plastic layer comprises 100 parts of borosilicate modified starch-based degradable plastic and 0.01-0.05 part of zinc sulfate.
Preferably, the preparation method of the borosilicate modified starch-based degradable plastic comprises the following steps:
(1) hydrophobic starch synthesis: dispersing 30-50 parts by weight of starch in 100 parts by weight of water, heating to 50-60 ℃ for gelatinization, dropwise adding a mixed solution consisting of 1-5 parts by weight of acetic acid, 10-30 parts by weight of methacryloxypropyltrimethoxysilane and 20-30 parts by weight of ethanol, reacting for 0.5-3 h, stopping heating, adding 100-200 parts by weight of water, stirring uniformly, standing, filtering to obtain a white precipitate, and drying to obtain the hydrophobic modified starch;
(2) and (3) cross-linking agent synthesis: dissolving 5 parts by weight of boric acid in a solution composed of 50 parts by weight of tetrahydrofuran and 25 parts by weight of triethylamine, then dropwise adding 110-120 parts by weight of gamma- (methacryloyloxy) propyl dimethylchlorosilane in a mixed solution composed of 50 parts by weight of tetrahydrofuran at-20 ℃, naturally heating to room temperature after dropwise adding, continuously reacting for 2-3 hours, filtering to remove triethylamine hydrochloride, washing the filtrate with water and carrying out rotary evaporation to obtain tris [ gamma- (methacryloyloxy) propyl dimethylchlorosilane ] borate;
(3) and (3) crosslinking polymerization: uniformly dispersing 100 parts of the hydrophobic modified starch in 100 parts of toluene solution, adding 10-30 parts of tris [ gamma- (methacryloyloxy) propyldimethylchlorosilane ] borate, dissolving in an organic solvent, adding 0.5-1 part of initiator benzoyl peroxide, reacting at 80-90 ℃ for 3-5 h, and then
Obtaining the borosilicate modified starch-based degradable plastic slurry.
Boric acid in the borosilicate modified starch-based degradable plastic is added into the starch-based plastic in the form of a cross-linking agent, and due to the characteristic that boron-oxygen-silicon bonds are easy to hydrolyze, after the fertilizer is spread in the land, the boron-oxygen-silicon bonds can be broken due to the erosion of water, so that free boric acid is formed, and boron is provided for plant growth. The borosiloxane in the prior art is usually used as a high-temperature resistant material, so that the molecular modification is required to strictly prevent the hydrolysis tendency of the borosiloxane, and the borosiloxane is a slow release method of boron element by utilizing the characteristic that a boron-oxygen-silicon bond is easy to hydrolyze, so that the original side reaction is transferred to agricultural production.
A preparation method of a long-acting slow-release fertilizer containing trace elements comprises the following steps:
(S.1) loading trace elements on the porous microspheres: dissolving ferrous sulfate, ammonium ferrous sulfate, manganese sulfate, ammonium molybdate and sodium molybdate in water according to a ratio to obtain a mixed solution, then soaking the porous microspheres in the mixed solution, and evaporating to remove water under a stirring condition to obtain porous microspheres loaded with iron, manganese and molybdenum elements;
(S.2) loading expansive soil on the surface of the porous microsphere: uniformly mixing montmorillonite powder, urea, ammonium ferrous sulfate, copper sulfate, zinc sulfate, calcium hydroxide and manganese sulfate according to a ratio, adding water, stirring into paste to obtain expansive soil paste, placing the porous microspheres in the expansive soil paste, taking out and drying to obtain the porous microspheres coated with expansive soil;
(S.3) coating a degradable plastic layer: and (3) placing the porous microspheres coated with the expansive soil obtained in the step (S.2) into a mixture of the borosilicate modified starch-based degradable plastic slurry and zinc sulfate, uniformly coating a layer of the borosilicate modified starch-based degradable plastic slurry on the surface, taking out and drying to obtain the long-acting slow-release fertilizer containing the trace elements and coated with the expansive soil.
Preferably, the ratio of the montmorillonite powder to water in the step (S.2) is 1 (0.5-1.5), the drying temperature is 60-80 ℃, and the drying time is 3-8 h.
Preferably, in the step (S.3), the drying temperature is 30-50 ℃, the drying time is 1-3 h, and after drying is finished, the temperature is raised to 100-120 ℃ for plasticizing for 15-30 min.
Therefore, the invention has the following beneficial effects:
(1) trace elements required by plant growth can be supplemented in time in the plant growth process;
(2) different trace elements can be released according to different growth cycles of plants and different requirements of the plants;
(3) only need fertilize once, just can effectively satisfy crops to the demand of different microelement, it is more convenient laborsaving to use.
Drawings
Fig. 1 is a schematic cross-sectional view of the present invention.
Wherein: porous microballon 1, inflation soil layer 2 and degradable plastic layer 3.
Detailed Description
The invention is further described with reference to the drawings and the specific embodiments. Those skilled in the art will be able to implement the invention based on these teachings. Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
Example 1
The utility model provides a contain long-term slow-release fertilizer of microelement, its includes a porous microballon 1, the 1 outside cladding of porous microballon has one deck inflation soil layer 2, the 2 outside cladding of inflation soil layer has one deck degradable plastic layer 3, and wherein porous microballon 1, inflation soil layer 2 and 3 three's of degradable plastic layer mass ratio is 100: 40: 30.
wherein: the porous microspheres are spherical activated carbon or porous calcium carbonate with the diameter of 1mm, and each 100 parts of the porous microspheres are respectively loaded with 0.5 part of ferrous sulfate, 0.1 part of ammonium ferrous sulfate, 0.2 part of manganese sulfate, 0.0015 part of ammonium molybdate and 0.001 part of sodium molybdate.
The expanded soil layer comprises 100 parts of montmorillonite powder, 5 parts of urea, 0.5 part of ammonium ferrous sulfate, 0.01 part of copper sulfate, 0.01 part of zinc sulfate, 0.1 part of calcium hydroxide and 0.05 part of manganese sulfate in parts by weight.
The degradable plastic layer comprises 100 parts of borosilicate modified starch-based degradable plastic and 0.01 part of zinc sulfate.
The preparation method of the borosilicate modified starch-based degradable plastic comprises the following steps:
(1) hydrophobic starch synthesis: dispersing 30 parts of starch in 100 parts of water according to parts by weight, heating to 50 ℃ for gelatinization, dropwise adding a mixed solution consisting of 1 part of acetic acid, 1 part of methacryloxypropyltrimethoxysilane and 20 parts of ethanol, reacting for 0.5h, stopping heating, adding 100 parts of water, uniformly stirring, standing, filtering to generate white precipitate, and drying to obtain the hydrophobic modified starch;
(2) and (3) cross-linking agent synthesis: dissolving 5 parts by weight of boric acid in a solution composed of 50 parts of tetrahydrofuran and 25 parts of triethylamine, then dropwise adding a mixed solution composed of 110 parts of gamma- (methacryloyloxy) propyl dimethylchlorosilane and 50 parts of tetrahydrofuran at-20 ℃, naturally heating to room temperature after dropwise adding, continuously reacting for 2 hours, filtering to remove triethylamine hydrochloride, washing the filtrate with water and carrying out rotary evaporation to obtain tris [ gamma- (methacryloyloxy) propyl dimethylchlorosilane ] borate;
(3) and (3) crosslinking polymerization: uniformly dispersing 100 parts of the hydrophobically modified starch in 100 parts of toluene solution, adding 10 parts of tris [ gamma- (methacryloyloxy) propyldimethylchlorosilane ] borate, dissolving in and dispersing in an organic solvent, adding 0.5 part of benzoyl peroxide as an initiator, reacting at 80 ℃ for 3 hours, and then
Obtaining the borosilicate modified starch-based degradable plastic slurry.
A preparation method of a long-acting slow-release fertilizer containing trace elements comprises the following steps:
(S.1) loading trace elements on the porous microspheres: dissolving ferrous sulfate, ammonium ferrous sulfate, manganese sulfate, ammonium molybdate and sodium molybdate in water according to a ratio to obtain a mixed solution, then soaking the porous microspheres in the mixed solution, and evaporating to remove water under a stirring condition to obtain porous microspheres loaded with iron, manganese and molybdenum elements;
(S.2) loading expansive soil on the surface of the porous microsphere: uniformly mixing montmorillonite powder, urea, ammonium ferrous sulfate, copper sulfate, zinc sulfate, calcium hydroxide and manganese sulfate according to a ratio, adding water, stirring into paste, wherein the ratio of montmorillonite powder to water is 1:0.5 to obtain expansive soil paste, placing porous microspheres into the expansive soil paste, fishing out, and drying for 3 hours at 60 ℃ to obtain the porous microspheres coated with expansive soil;
(S.3) coating a degradable plastic layer: and (3) placing the porous microspheres coated with the expansive soil obtained in the step (S.2) into a mixture of the borosilicate modified starch-based degradable plastic slurry and zinc sulfate, uniformly coating a layer of the borosilicate modified starch-based degradable plastic slurry on the surface, fishing out, drying at 30 ℃ for 1h, raising the temperature to 100 ℃ after drying, and plasticizing for 15min to obtain the long-acting slow-release fertilizer coated with the expansive soil and containing the trace elements.
Example 2
The utility model provides a long-term slow-release fertilizer who contains microelement, its includes a porous microballon, the cladding of the porous microballon outside has one deck inflation soil layer, the cladding of inflation soil layer outside has one deck degradable plastic layer, and wherein porous microballon, inflation soil layer and degradable plastic layer three's mass ratio is 100: 60: 50.
wherein: the porous microspheres are spherical active carbon or porous calcium carbonate with the diameter of 10mm, and each 100 parts of the porous microspheres are respectively loaded with 2 parts of ferrous sulfate, 0.3 part of ammonium ferrous sulfate, 0.6 part of manganese sulfate, 0.005 part of ammonium molybdate and 0.003 part of sodium molybdate.
The expanded soil layer comprises, by weight, 100 parts of montmorillonite powder, 10 parts of urea, 2 parts of ammonium ferrous sulfate, 0.15 part of copper sulfate, 0.05 part of zinc sulfate, 0.3 part of calcium hydroxide and 0.2 part of manganese sulfate.
The degradable plastic layer comprises 100 parts of borosilicate modified starch-based degradable plastic and 0.05 part of zinc sulfate.
The preparation method of the borosilicate modified starch-based degradable plastic comprises the following steps:
(1) hydrophobic starch synthesis: dispersing 50 parts of starch in 100 parts of water according to parts by weight, heating to 60 ℃ for gelatinization, dropwise adding a mixed solution consisting of 5 parts of acetic acid, 30 parts of methacryloxypropyltrimethoxysilane and 30 parts of ethanol, reacting for 3 hours, stopping heating, adding 200 parts of water, uniformly stirring, standing, filtering to generate white precipitate, and drying to obtain the hydrophobic modified starch;
(2) and (3) cross-linking agent synthesis: dissolving 5 parts by weight of boric acid in a solution composed of 50 parts of tetrahydrofuran and 25 parts of triethylamine, then dropwise adding a mixed solution composed of 120 parts of gamma- (methacryloyloxy) propyl dimethylchlorosilane and 50 parts of tetrahydrofuran at-20 ℃, naturally heating to room temperature after dropwise adding, continuously reacting for 3 hours, filtering to remove triethylamine hydrochloride, washing the filtrate with water and performing rotary evaporation to obtain tris [ gamma- (methacryloyloxy) propyl dimethylchlorosilane ] borate;
(3) and (3) crosslinking polymerization: uniformly dispersing 100 parts of the hydrophobically modified starch in 100 parts of toluene solution, adding 30 parts of tris [ gamma- (methacryloyloxy) propyldimethylchlorosilane ] borate and the solution of the tris [ gamma- (methacryloyloxy) propyldimethylchlorosilane ] borate into the organic solvent, adding 1 part of benzoyl peroxide serving as an initiator, reacting at 90 ℃ for 5 hours, and then obtaining the product
Obtaining the borosilicate modified starch-based degradable plastic slurry.
A preparation method of a long-acting slow-release fertilizer containing trace elements comprises the following steps:
(S.1) loading trace elements on the porous microspheres: dissolving ferrous sulfate, ammonium ferrous sulfate, manganese sulfate, ammonium molybdate and sodium molybdate in water according to a ratio to obtain a mixed solution, then soaking the porous microspheres in the mixed solution, and evaporating to remove water under a stirring condition to obtain porous microspheres loaded with iron, manganese and molybdenum elements;
(S.2) loading expansive soil on the surface of the porous microsphere: uniformly mixing montmorillonite powder, urea, ammonium ferrous sulfate, copper sulfate, zinc sulfate, calcium hydroxide and manganese sulfate according to a ratio, adding water, stirring into paste, wherein the ratio of montmorillonite powder to water is 1:1.5 to obtain expansive soil paste, placing porous microspheres into the expansive soil paste, fishing out the expanded soil paste at the temperature of 80 ℃, and drying for 8 hours to obtain the porous microspheres coated with expansive soil;
(S.3) coating a degradable plastic layer: and (3) placing the porous microspheres coated with the expansive soil obtained in the step (S.2) into a mixture of the borosilicate modified starch-based degradable plastic slurry and zinc sulfate, uniformly coating a layer of the borosilicate modified starch-based degradable plastic slurry on the surface, fishing out the slurry, drying the slurry at 50 ℃ for 3 hours, raising the temperature to 120 ℃ after drying, and plasticizing the slurry for 30 minutes to obtain the long-acting slow-release fertilizer coated with the expansive soil and containing the trace elements.
Example 3
The utility model provides a long-term slow-release fertilizer who contains microelement, its includes a porous microballon, the cladding of the porous microballon outside has one deck inflation soil layer, the cladding of inflation soil layer outside has one deck degradable plastic layer, and wherein porous microballon, inflation soil layer and degradable plastic layer three's mass ratio is 100: 50: 40.
wherein: the porous microspheres are spherical activated carbon or porous calcium carbonate with the diameter of 5mm, and each 100 parts of the porous microspheres are respectively loaded with 1 part of ferrous sulfate, 0.2 part of ammonium ferrous sulfate, 0.4 part of manganese sulfate, 0.0025 part of ammonium molybdate and 0.002 part of sodium molybdate.
The expanded soil layer comprises 100 parts of montmorillonite powder, 8 parts of urea, 1 part of ammonium ferrous sulfate, 0.1 part of copper sulfate, 0.03 part of zinc sulfate, 0.2 part of calcium hydroxide and 0.1 part of manganese sulfate in parts by weight.
The degradable plastic layer comprises 100 parts of borosilicate modified starch-based degradable plastic and 0.03 part of zinc sulfate.
The preparation method of the borosilicate modified starch-based degradable plastic comprises the following steps:
(1) hydrophobic starch synthesis: dispersing 40 parts of starch in 100 parts of water according to parts by weight, heating to 55 ℃ for gelatinization, dropwise adding a mixed solution consisting of 3 parts of acetic acid, 20 parts of methacryloxypropyltrimethoxysilane and 25 parts of ethanol, reacting for 2 hours, stopping heating, adding 150 parts of water, uniformly stirring, standing, filtering to generate white precipitate, and drying to obtain the hydrophobic modified starch;
(2) and (3) cross-linking agent synthesis: dissolving 5 parts by weight of boric acid in a solution composed of 50 parts of tetrahydrofuran and 25 parts of triethylamine, then dropwise adding a mixed solution composed of 115 parts of gamma- (methacryloyloxy) propyldimethylchlorosilane and 50 parts of tetrahydrofuran at-20 ℃, naturally heating to room temperature after dropwise adding, continuously reacting for 2.5 hours, filtering to remove triethylamine hydrochloride, washing the filtrate with water and performing rotary evaporation to obtain tris [ gamma- (methacryloyloxy) propyldimethylchlorosilane ] borate;
(3) and (3) crosslinking polymerization: uniformly dispersing 100 parts of the hydrophobically modified starch in 100 parts of toluene solution, adding 20 parts of tris [ gamma- (methacryloyloxy) propyldimethylchlorosilane ] borate, dissolving in and dispersing in an organic solvent, adding 0.8 part of benzoyl peroxide as an initiator, reacting at 85 ℃ for 4 hours, and then
Obtaining the borosilicate modified starch-based degradable plastic slurry.
A preparation method of a long-acting slow-release fertilizer containing trace elements comprises the following steps:
(S.1) loading trace elements on the porous microspheres: dissolving ferrous sulfate, ammonium ferrous sulfate, manganese sulfate, ammonium molybdate and sodium molybdate in water according to a ratio to obtain a mixed solution, then soaking the porous microspheres in the mixed solution, and evaporating to remove water under a stirring condition to obtain porous microspheres loaded with iron, manganese and molybdenum elements;
(S.2) loading expansive soil on the surface of the porous microsphere: uniformly mixing montmorillonite powder, urea, ammonium ferrous sulfate, copper sulfate, zinc sulfate, calcium hydroxide and manganese sulfate according to a ratio, adding water, stirring into paste, wherein the ratio of montmorillonite powder to water is 1:1 to obtain expansive soil paste, placing porous microspheres in the expansive soil paste, taking out the porous microspheres at 70 ℃, and drying for 5 hours to obtain the porous microspheres coated with expansive soil;
(S.3) coating a degradable plastic layer: and (3) placing the porous microspheres coated with the expansive soil obtained in the step (S.2) into a mixture of the borosilicate modified starch-based degradable plastic slurry and zinc sulfate, uniformly coating a layer of the borosilicate modified starch-based degradable plastic slurry on the surface, fishing out the slurry, drying the slurry at 40 ℃ for 2 hours, raising the temperature to 110 ℃ after drying, and plasticizing the slurry for 20 minutes to obtain the long-acting slow-release fertilizer coated with the expansive soil and containing the trace elements.
Example 4
The utility model provides a long-term slow-release fertilizer who contains microelement, its includes a porous microballon, the cladding of the porous microballon outside has one deck inflation soil layer, the cladding of inflation soil layer outside has one deck degradable plastic layer, and wherein porous microballon, inflation soil layer and degradable plastic layer three's mass ratio is 100: 45: 35.
wherein: the porous microspheres are spherical activated carbon or porous calcium carbonate with the diameter of 3mm, and each 100 parts of the porous microspheres are respectively loaded with 0.8 part of ferrous sulfate, 0.15 part of ammonium ferrous sulfate, 0.3 part of manganese sulfate, 0.002 part of ammonium molybdate and 0.001 part of sodium molybdate.
The expanded soil layer comprises 100 parts of montmorillonite powder, 6 parts of urea, 1 part of ammonium ferrous sulfate, 0.05 part of copper sulfate, 0.02 part of zinc sulfate, 0.2 part of calcium hydroxide and 0.1 part of manganese sulfate in parts by weight.
The degradable plastic layer comprises 100 parts of borosilicate modified starch-based degradable plastic and 0.02 part of zinc sulfate.
The preparation method of the borosilicate modified starch-based degradable plastic comprises the following steps:
(1) hydrophobic starch synthesis: dispersing 35 parts of starch in 100 parts of water according to parts by weight, heating to 53 ℃ for gelatinization, dropwise adding a mixed solution consisting of 2 parts of acetic acid, 16 parts of methacryloxypropyltrimethoxysilane and 22 parts of ethanol, reacting for 1 hour, stopping heating, adding 120 parts of water, stirring uniformly, standing, filtering to generate white precipitate, and drying to obtain the hydrophobic modified starch;
(2) and (3) cross-linking agent synthesis: dissolving 5 parts by weight of boric acid in a solution composed of 50 parts of tetrahydrofuran and 25 parts of triethylamine, then dropwise adding a mixed solution composed of 115 parts of gamma- (methacryloyloxy) propyldimethylchlorosilane and 50 parts of tetrahydrofuran at-20 ℃, naturally heating to room temperature after dropwise adding, continuously reacting for 2 hours, filtering to remove triethylamine hydrochloride, washing the filtrate with water and performing rotary evaporation to obtain tris [ gamma- (methacryloyloxy) propyldimethylchlorosilane ] borate;
(3) and (3) crosslinking polymerization: uniformly dispersing 100 parts of the hydrophobically modified starch in 100 parts of toluene solution, adding 15 parts of tris [ gamma- (methacryloyloxy) propyldimethylchlorosilane ] borate, dissolving in and dispersing in an organic solvent, adding 0.6 part of benzoyl peroxide as an initiator, reacting at 85 ℃ for 3.5 hours, and then
Obtaining the borosilicate modified starch-based degradable plastic slurry.
A preparation method of a long-acting slow-release fertilizer containing trace elements comprises the following steps:
(S.1) loading trace elements on the porous microspheres: dissolving ferrous sulfate, ammonium ferrous sulfate, manganese sulfate, ammonium molybdate and sodium molybdate in water according to a ratio to obtain a mixed solution, then soaking the porous microspheres in the mixed solution, and evaporating to remove water under a stirring condition to obtain porous microspheres loaded with iron, manganese and molybdenum elements;
(S.2) loading expansive soil on the surface of the porous microsphere: uniformly mixing montmorillonite powder, urea, ammonium ferrous sulfate, copper sulfate, zinc sulfate, calcium hydroxide and manganese sulfate according to a ratio, adding water, stirring into paste, wherein the ratio of montmorillonite powder to water is 1:1 to obtain expansive soil paste, placing porous microspheres in the expansive soil paste, taking out the porous microspheres at 65 ℃, and drying for 4 hours to obtain the porous microspheres coated with expansive soil;
(S.3) coating a degradable plastic layer: and (3) placing the porous microspheres coated with the expansive soil obtained in the step (S.2) into a mixture of the borosilicate modified starch-based degradable plastic slurry and zinc sulfate, uniformly coating a layer of the borosilicate modified starch-based degradable plastic slurry on the surface, fishing out the slurry, drying the slurry at 35 ℃ for 2 hours, raising the temperature to 105 ℃ after drying, and plasticizing the dried slurry for 20 minutes to obtain the long-acting slow-release fertilizer coated with the expansive soil and containing the trace elements.
Example 5
The utility model provides a long-term slow-release fertilizer who contains microelement, its includes a porous microballon, the cladding of the porous microballon outside has one deck inflation soil layer, the cladding of inflation soil layer outside has one deck degradable plastic layer, and wherein porous microballon, inflation soil layer and degradable plastic layer three's mass ratio is 100: 55: 45.
wherein: the porous microspheres are spherical activated carbon or porous calcium carbonate with the diameter of 8mm, and each 100 parts of the porous microspheres are respectively loaded with 1.5 parts of ferrous sulfate, 0.25 part of ammonium ferrous sulfate, 0.5 part of manganese sulfate, 0.0045 part of ammonium molybdate and 0.002 part of sodium molybdate.
The expanded soil layer comprises 100 parts of montmorillonite powder, 8 parts of urea, 1.5 parts of ammonium ferrous sulfate, 0.12 part of copper sulfate, 0.04 part of zinc sulfate, 0.25 part of calcium hydroxide and 0.18 part of manganese sulfate in parts by weight.
The degradable plastic layer comprises 100 parts of borosilicate modified starch-based degradable plastic and 0.04 part of zinc sulfate.
The preparation method of the borosilicate modified starch-based degradable plastic comprises the following steps:
(1) hydrophobic starch synthesis: dispersing 48 parts of starch in 100 parts of water according to parts by weight, heating to 58 ℃ for gelatinization, dropwise adding a mixed solution consisting of 4.5 parts of acetic acid, 28 parts of methacryloxypropyltrimethoxysilane and 28 parts of ethanol, reacting for 2.5 hours, stopping heating, adding 180 parts of water, uniformly stirring, standing, filtering to generate white precipitate, and drying to obtain the hydrophobic modified starch;
(2) and (3) cross-linking agent synthesis: dissolving 5 parts by weight of boric acid in a solution composed of 50 parts of tetrahydrofuran and 25 parts of triethylamine, then dropwise adding 118 parts of gamma- (methacryloyloxy) propyldimethylchlorosilane in a mixed solution composed of 50 parts of tetrahydrofuran at-20 ℃, naturally heating to room temperature after dropwise adding, continuously reacting for 2.5 hours, filtering to remove triethylamine hydrochloride, washing the filtrate with water and performing rotary evaporation to obtain tris [ gamma- (methacryloyloxy) propyldimethylchlorosilane ] borate;
(3) and (3) crosslinking polymerization: uniformly dispersing 100 parts of the hydrophobically modified starch in 100 parts of toluene solution, adding 28 parts of tris [ gamma- (methacryloyloxy) propyldimethylchlorosilane ] borate, dissolving in the organic solvent, adding 0.8 part of benzoyl peroxide as an initiator, reacting at 88 ℃ for 4.5 hours, and then
Obtaining the borosilicate modified starch-based degradable plastic slurry.
A preparation method of a long-acting slow-release fertilizer containing trace elements comprises the following steps:
(S.1) loading trace elements on the porous microspheres: dissolving ferrous sulfate, ammonium ferrous sulfate, manganese sulfate, ammonium molybdate and sodium molybdate in water according to a ratio to obtain a mixed solution, then soaking the porous microspheres in the mixed solution, and evaporating to remove water under a stirring condition to obtain porous microspheres loaded with iron, manganese and molybdenum elements;
(S.2) loading expansive soil on the surface of the porous microsphere: uniformly mixing montmorillonite powder, urea, ammonium ferrous sulfate, copper sulfate, zinc sulfate, calcium hydroxide and manganese sulfate according to a ratio, adding water, stirring into paste, wherein the ratio of montmorillonite powder to water is 1:1.2 to obtain expansive soil paste, placing porous microspheres into the expansive soil paste, fishing out, and drying for 7 hours at 75 ℃ to obtain the porous microspheres coated with expansive soil;
(S.3) coating a degradable plastic layer: and (4) placing the porous microspheres coated with the expansive soil obtained in the step (S.2) into a mixture of the borosilicate modified starch-based degradable plastic slurry and zinc sulfate, uniformly coating a layer of the borosilicate modified starch-based degradable plastic slurry on the surface, fishing out, drying at 45 ℃ for 2.5 hours, raising the temperature to 115 ℃ after drying, and plasticizing for 25min to obtain the long-acting slow-release fertilizer coated with the expansive soil and containing the trace elements.
The slow release fertilizer prepared in the examples 1 to 5 is applied to a corn field, the slow release fertilizer prepared in the invention is not additionally added to another corn field as a comparative example, the addition amounts of the other nitrogen, phosphorus and potassium fertilizers are consistent, and the growth results are shown in the following table:
| item | Plant height (m) | Plant morphology | Corn yield per mu |
| Comparative example | 1.82 | Yellowing of leaves, short internodes, incomplete fruits and low seed setting rate | 750 |
| Example 1 | 2.26 | Emerald green leaves, long internodes, full fruits and high seed setting rate | 1090 |
| Example 2 | 2.30 | Emerald green leaves, long internodes, full fruits and high seed setting rate | 1220 |
| Example 3 | 2.25 | Emerald green leaves, long internodes, full fruits and high seed setting rate | 1180 |
| Example 4 | 2.28 | Emerald green leaves, long internodes, full fruits and high seed setting rate | 1095 |
| Example 5 | 2.26 | Emerald green leaves, long internodes, full fruits and high seed setting rate | 1140 |
From the above table, it can be known that the plant height of corn can be greatly increased by using the trace element slow release fertilizer, and the problem of growth and development of plants caused by the lack of trace elements can be solved. In addition, from the yield aspect, the yield per mu of the trace element slow-release fertilizer is greatly improved, and the economic benefit is effectively improved.
Claims (9)
1. The long-acting slow-release fertilizer containing the trace elements is characterized by comprising porous microspheres, wherein an expanded soil layer is coated outside the porous microspheres, and a degradable plastic layer is coated outside the expanded soil layer;
wherein: the surface of the porous microsphere is loaded with a compound containing iron, manganese and molybdenum elements;
the inside of the expansion soil layer contains compounds of iron, copper, zinc and manganese elements;
the degradable plastic layer contains compounds of zinc and boron elements;
the mass ratio of the porous microspheres to the expanded soil layer to the degradable plastic layer is 100: (40-60): (30-50).
2. The long-acting slow-release fertilizer containing trace elements as claimed in claim 1, wherein each 100 parts by weight of porous microspheres are loaded with 0.5-2 parts by weight of ferrous sulfate, 0.1-0.3 part by weight of ammonium ferrous sulfate, 0.2-0.6 part by weight of manganese sulfate, 0.0015-0.005 part by weight of ammonium molybdate and 0.001-0.003 part by weight of sodium molybdate.
3. The long-acting slow-release fertilizer containing trace elements as claimed in claim 1 or 2, wherein the porous microspheres are spherical activated carbon or porous calcium carbonate with the diameter of 1-10 mm.
4. The long-acting slow-release fertilizer containing trace elements as claimed in claim 1, wherein the expansive soil layer comprises 100 parts by weight of montmorillonite powder, 5-10 parts by weight of urea, 0.5-2 parts by weight of ammonium ferrous sulfate, 0.01-0.15 part by weight of copper sulfate, 0.01-0.05 part by weight of zinc sulfate, 0.1-0.3 part by weight of calcium hydroxide and 0.05-0.2 part by weight of manganese sulfate.
5. The long-acting slow-release fertilizer containing trace elements as claimed in claim 1, wherein the degradable plastic layer comprises 100 parts of borosilicate modified starch-based degradable plastic and 0.01-0.05 part of zinc sulfate.
6. The long-acting slow-release fertilizer containing trace elements according to claim 5, wherein the borosilicate-modified starch-based degradable plastic is prepared by the following method:
(1) hydrophobic starch synthesis: dispersing 30-50 parts by weight of starch in 100 parts by weight of water, heating to 50-60 ℃ for gelatinization, dropwise adding a mixed solution consisting of 1-5 parts by weight of acetic acid, 10-30 parts by weight of methacryloxypropyltrimethoxysilane and 20-30 parts by weight of ethanol, reacting for 0.5-3 h, stopping heating, adding 100-200 parts by weight of water, stirring uniformly, standing, filtering to obtain a white precipitate, and drying to obtain the hydrophobic modified starch;
(2) and (3) cross-linking agent synthesis: dissolving 5 parts by weight of boric acid in a solution composed of 50 parts by weight of tetrahydrofuran and 25 parts by weight of triethylamine, then dropwise adding 110-120 parts by weight of gamma- (methacryloyloxy) propyl dimethylchlorosilane in a mixed solution composed of 50 parts by weight of tetrahydrofuran at-20 ℃, naturally heating to room temperature after dropwise adding, continuously reacting for 2-3 hours, filtering to remove triethylamine hydrochloride, washing the filtrate with water and carrying out rotary evaporation to obtain tris [ gamma- (methacryloyloxy) propyl dimethylchlorosilane ] borate;
(3) and (3) crosslinking polymerization: uniformly dispersing 100 parts of the hydrophobic modified starch in 100 parts of toluene solution, adding 10-30 parts of tris [ gamma- (methacryloyloxy) propyldimethylchlorosilane ] borate, dissolving in an organic solvent, adding 0.5-1 part of initiator benzoyl peroxide, reacting at 80-90 ℃ for 3-5 h, and then
Obtaining the borosilicate modified starch-based degradable plastic slurry.
7. A method for preparing a long-acting slow-release fertilizer containing trace elements as claimed in any one of claims 1 to 6, wherein the method comprises the following steps:
(S.1) loading trace elements on the porous microspheres: dissolving ferrous sulfate, ammonium ferrous sulfate, manganese sulfate, ammonium molybdate and sodium molybdate in water according to a ratio to obtain a mixed solution, then soaking the porous microspheres in the mixed solution, and evaporating to remove water under a stirring condition to obtain porous microspheres loaded with iron, manganese and molybdenum elements;
(S.2) loading expansive soil on the surface of the porous microsphere: uniformly mixing montmorillonite powder, urea, ammonium ferrous sulfate, copper sulfate, zinc sulfate, calcium hydroxide and manganese sulfate according to a ratio, adding water, stirring into paste to obtain expansive soil paste, placing the porous microspheres in the expansive soil paste, taking out and drying to obtain the porous microspheres coated with expansive soil;
(S.3) coating a degradable plastic layer: and (3) placing the porous microspheres coated with the expansive soil obtained in the step (S.2) into a mixture of the borosilicate modified starch-based degradable plastic slurry and zinc sulfate, uniformly coating a layer of the borosilicate modified starch-based degradable plastic slurry on the surface, taking out and drying to obtain the long-acting slow-release fertilizer containing the trace elements and coated with the expansive soil.
8. The preparation method of the trace element-containing long-acting slow-release fertilizer as claimed in claim 7, wherein the ratio of the montmorillonite powder to water in the step (S.2) is 1 (0.5-1.5), the drying temperature is 60-80 ℃, and the drying time is 3-8 h.
9. The preparation method of the trace element-containing long-acting slow-release fertilizer as claimed in claim 7, wherein in the step (S.3), the drying temperature is 30-50 ℃, the drying time is 1-3 h, and after drying, the temperature is raised to 100-120 ℃ for plasticizing for 15-30 min.
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