CN113636890A - Selenium-rich slow-release cadmium inhibitor and preparation method thereof - Google Patents
Selenium-rich slow-release cadmium inhibitor and preparation method thereof Download PDFInfo
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- CN113636890A CN113636890A CN202111110564.7A CN202111110564A CN113636890A CN 113636890 A CN113636890 A CN 113636890A CN 202111110564 A CN202111110564 A CN 202111110564A CN 113636890 A CN113636890 A CN 113636890A
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
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- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- 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
- 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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- 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
- C05G5/35—Capsules, e.g. core-shell
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Abstract
The invention provides a preparation method of a selenium-rich slow-release cadmium inhibitor, which comprises the following steps: s1, preparing the silica microspheres with porous capillary structures; s2, soaking the silicon dioxide microspheres obtained in the step S1 in a saturated solution of inorganic selenium salt, filtering and drying to obtain selenium-containing silicon dioxide microspheres; s3, preparing wax wall water-absorbing resin microcapsules; s4, fully dry-mixing the selenium-containing silicon dioxide microspheres obtained in the step S2, the wax wall water-absorbing resin microcapsules obtained in the step S3, starch, water glass and inorganic selenium salt, adding water glass for granulation, and drying by hot air at the temperature of 30-35 ℃ to obtain an inner core; s5, spraying a coating agent on the surface of the inner core obtained in the step S4 for coating treatment, wherein the coating agent comprises modified sodium carboxymethyl cellulose and inorganic selenium salt; the selenium-rich slow-release cadmium inhibitor prepared by the preparation method of the invention provides proper concentration of selenium for plants, has good cadmium inhibition effect and does not influence the growth of the plants.
Description
Technical Field
The invention relates to the technical field of soil conditioners, in particular to a selenium-rich slow-release cadmium inhibitor and a preparation method thereof.
Background
Plants need to draw various nutrients for their growth, and the carrier for the nutrients is usually soil. In the soil, not only are various nutrients required for plant growth contained, but also components harmful to plants, such as various heavy metals, most commonly cadmium pollution, exist. Cadmium is a metal element with strong toxicity, has strong mobility and concealment of plant absorption, and can cause great influence on human health after entering human bodies through food chains.
Aiming at the cadmium pollution condition in soil, the currently adopted means is to utilize selenium to detoxify cadmium. On one hand, selenium can form a metal-selenium-protein compound with cadmium and then is discharged by a plant body, so that the effects of detoxifying and expelling toxins are achieved, on the other hand, selenium is an important component of antioxidant enzymes (glutathione peroxidase) and selenium-P protein in animals and human bodies, and plays a role in balancing redox atmosphere in the bodies, and researches prove that the selenium has the effect of improving the immunity of animals.
However, selenium has a problem that it has a significant low growth rate and high growth inhibition effect on plants, and if the content of selenium in soil is too high in the seedling stage of plants, the growth of plants is inhibited, and the yield is affected, and if the content of selenium in soil is too low, the cadmium-inhibiting and cadmium-reducing effects are not achieved in the growth stage of plants.
Therefore, how to make the selenium content in the soil lower in the seedling stage of the plant and higher in the growth stage of the plant is a technical problem to be solved urgently in the field.
Disclosure of Invention
The invention provides a selenium-rich slow-release cadmium inhibitor and a preparation method thereof, which can effectively solve the problems.
The invention provides a preparation method of a selenium-rich slow-release cadmium inhibitor, which comprises the following steps:
s1, preparing the silica microspheres with porous capillary structures;
s2, soaking the silicon dioxide microspheres obtained in the step S1 in a saturated solution of inorganic selenium salt, filtering and drying to obtain selenium-containing silicon dioxide microspheres;
s3, preparing wax wall water-absorbing resin microcapsules;
s4, fully dry-mixing the selenium-containing silicon dioxide microspheres obtained in the step S2, the wax wall water-absorbing resin microcapsules obtained in the step S3, starch and inorganic selenium salt, adding water glass for granulation, and drying by hot air at the temperature of 30-35 ℃ to obtain an inner core;
s5, spraying a coating agent on the surface of the inner core obtained in the step S4 for coating treatment, wherein the coating agent comprises modified sodium carboxymethyl cellulose and inorganic selenium salt.
The technical scheme of the embodiment of the invention at least has the following advantages and beneficial effects:
the selenium-rich slow-release cadmium inhibitor prepared by the preparation method provided by the invention comprises an inner core and an envelope, wherein the envelope is in a fully-closed structure and can effectively coat the inner core, the fertilizer efficiency of the inner core is preserved in the seedling stage of plants, and the envelope material contains a small amount of inorganic selenium salt, so that the inorganic selenium salt is dissipated into soil to provide low-concentration selenium for the plants in the seedling stage on one hand, and the concentration difference between the inner film and the outer film is reduced on the other hand, so that the dissipation of the inorganic selenium salt in the inner core is inhibited; in the rapid growth period of plants, after the envelope is hydrolyzed, the inner core is exposed, on one hand, a large amount of selenium salt exists in the inner core and can release a large amount of selenium, and on the other hand, the wax wall water-absorbing resin microcapsule in the inner core absorbs water and expands, so that the inner core is disintegrated, and the release of a large amount of selenium is facilitated; in the plant maturation period, the selenium in the silicon dioxide microspheres is slowly released, so that the selenium with lower concentration exists in the soil for a long time; thus, the effect of slow release and long acting is achieved, namely, the plants have good growth vigor while the cadmium content is low.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
A preparation method of a selenium-rich slow-release cadmium inhibitor comprises the following steps:
s1, preparing the silica microspheres with porous capillary structures;
s11, pouring 45-55 parts by weight of dimethyldichlorosilane into a beaker, adding 15-20 parts by weight of 45 wt% concentrated hydrochloric acid into the beaker, and stirring for 30-40min at 40-50 ℃ to obtain oily octamethylcyclotetrasiloxane;
s12, mixing 20-30 parts by weight of the octamethylcyclotetrasiloxane prepared in the step S11 with 8-10 parts by weight of 30 wt% ammonia water, heating and stirring for 20-25min, performing suction filtration, and washing with absolute ethyl alcohol to obtain octamethylcyclotetrasiloxane polymerized microspheres;
s13, calcining the octamethylcyclotetrasiloxane polymerized microsphere obtained in the step S12 at the calcining temperature of 500-700 ℃ for 60-70min, and taking out and naturally cooling to obtain the silicon dioxide microsphere.
Wherein, the particle size of the prepared silicon dioxide microsphere is 100-120 microns.
S2, soaking the silicon dioxide microspheres obtained in the step S1 in a saturated solution of inorganic selenium salt, filtering and drying to obtain the selenium-containing silicon dioxide microspheres.
Wherein, the mass of the selenium-containing silicon dioxide microspheres is 1.5 to 1.8 times of that of the silicon dioxide microspheres, and preferably 1.5 times.
S3, preparing the wax wall water-absorbing resin microcapsule.
S31, adding 300ml of diphenyl ether into a three-neck flask, and heating to 70-80 ℃ in a water bath;
s32, respectively putting paraffin powder and water-absorbent resin powder into the three-neck flask, and stirring for 30-40 min;
and S33, removing the three-neck flask from the water bath, cooling to room temperature, performing suction filtration, washing with acetone, and drying with hot air at 30-35 ℃ to obtain the wax wall water-absorbent resin microcapsule.
Wherein, in step S32, the paraffin powder: water-absorbent resin powder 1: (8-10).
Wherein the water-absorbing resin powder is processed by selenium enrichment, and the processing method comprises the following steps:
dissolving inorganic selenium salt in deionized water to prepare saturated inorganic selenium salt solution, heating and stirring uniformly, adding water-absorbent resin, continuously stirring until the water-absorbent resin swells to the highest multiplying power, standing, drying, and grinding into powder to obtain the water-absorbent resin powder after selenium-rich treatment.
S4, fully dry-mixing the selenium-containing silicon dioxide microspheres obtained in the step S2, the wax wall water-absorbing resin microcapsules obtained in the step S3, starch and inorganic selenium salt, adding water glass for granulation, and drying by hot air at the temperature of 30-35 ℃ to obtain the inner core.
Wherein, in step S4, the selenium-containing silica microspheres are 100 parts by weight, the wax wall water-absorbent resin microcapsules are 20-30 parts by weight, the starch is 30-36 parts by weight, the water glass is 30-36 parts by weight, the inorganic selenium salt is 180-200 parts by weight, and the water is 15-17 parts by weight.
Wherein the diameter of the inner core is 2-4 cm.
S5, spraying a coating agent on the surface of the inner core obtained in the step S4 for coating treatment, wherein the coating agent comprises modified sodium carboxymethyl cellulose and inorganic selenium salt.
In step S5, the following are calculated by mass ratio:
coating agent: the kernel is 1: 8-10;
in the coating agent, modified sodium carboxymethylcellulose: inorganic selenium salt 1: 0.12-0.14.
The modified sodium carboxymethylcellulose is modified by epoxy resin to enhance the wear resistance and impact resistance of the coating, and the specific modification method comprises the following steps:
preparing 100ml of sodium carboxymethylcellulose solution with the mass fraction of 6%, adding 12 g of epoxy resin, stirring uniformly, adding 5 g of dibutyl phthalate, and continuously stirring for 1 hour to obtain the modified sodium carboxymethylcellulose.
In this embodiment, the inorganic selenium salt is sodium selenate.
The selenium-rich slow-release cadmium inhibitor prepared by the preparation method comprises an inner core and an envelope, wherein the envelope is made of easily-hydrolyzed sodium carboxymethyl cellulose, wherein a small amount of selenium is contained, the inner core is composed of sodium selenate powder, silicon dioxide microspheres and wax wall water-absorbent resin microcapsules, and starch and water glass are jointly used as an adhesive.
In the seedling stage of the plant, the coating (sodium carboxymethylcellulose) tightly wraps the inner core, the inner core cannot be exposed, namely a large amount of selenium cannot be released, at this stage, a small amount of selenium in the coating is continuously released to provide low-concentration selenium for the plant in the seedling stage, and the low-concentration selenium cannot inhibit the growth of the plant.
In the rapid growth period of plants, the coating material is hydrolyzed and broken, the core is exposed and dispersed when meeting water, the sodium selenate powder releases a large amount of selenium to promote the growth of the plants, in addition, after long-time sunshine, the outer wall of the paraffin of the wax wall water-absorbent resin microcapsule is gradually softened and deformed, the water-absorbent resin in the wax wall water-absorbent resin microcapsule is exposed, and the volume is expanded after water absorption, so that the core is disintegrated, the release rate of the selenium is increased, the water-absorbent resin also contains a large amount of selenium, the release amount of the selenium is increased, and the large amount of release of the selenium effectively ensures the cadmium blocking effect of the plants in the growth period; in addition, at this stage, a part of starch and water-absorbent resin are sticky after meeting water, and the silicon dioxide microspheres are coated, so that the release of selenium in the silicon dioxide microspheres is temporarily inhibited.
In the mature period of the plant, the sodium selenate powder in the core material is gradually consumed, at the moment, the selenium concentration in the soil is reduced, but due to the long-term soaking of water in the soil, the starch paste and the water-absorbent resin which coat the silicon dioxide microspheres are continuously diluted, the silicon dioxide microspheres are exposed, the selenium in the pores can be continuously released, and the diffusion rate of the selenium in the pores is extremely slow because the pores are not in a straight-through pore structure, so that the selenium in the soil can be always kept at a certain concentration content, and the cadmium-resisting effect of the plant in the mature period is effectively ensured by the continuous low-concentration selenium.
In addition, the silica microspheres also play a role in loosening the soil.
Example 1
A preparation method of a selenium-rich slow-release cadmium inhibitor comprises the following steps:
s1, preparing a silica microsphere with a porous capillary structure, wherein the particle size of the silica microsphere is 110 microns;
s11, pouring 50 parts by weight of dimethyldichlorosilane into a beaker, adding 18 parts by weight of 45 wt% concentrated hydrochloric acid into the beaker, and stirring at 45 ℃ for 35min to obtain oily octamethylcyclotetrasiloxane;
s12, mixing 25 parts by weight of the octamethylcyclotetrasiloxane prepared in the step S11 with 9 parts by weight of ammonia water with the concentration of 30 wt%, heating and stirring for 22min, performing suction filtration, and washing with absolute ethyl alcohol to obtain octamethylcyclotetrasiloxane polymerized microspheres;
and S13, calcining the octamethylcyclotetrasiloxane polymerized microspheres obtained in the step S12 at the temperature of 600 ℃ for 65min, and taking out and naturally cooling to obtain the silicon dioxide microspheres.
S2, soaking the silica microspheres obtained in the step S1 in a saturated solution of inorganic selenium salt for 2 hours, filtering and drying after soaking is finished, and obtaining selenium-containing silica microspheres, wherein the mass of the selenium-containing silica microspheres is 1.5 times that of the silica microspheres.
S3, preparing wax wall water-absorbing resin microcapsules;
s31, adding 300ml of diphenyl ether into a three-neck flask, and heating to 75 ℃ in a water bath;
s32, respectively putting paraffin powder and water-absorbent resin powder into a three-neck flask, wherein the mass ratio of the paraffin powder to the water-absorbent resin powder is 1:9, and stirring for 35 min;
the water-absorbing resin powder is subjected to selenium enrichment treatment, and specifically comprises the following steps: dissolving sodium selenate in deionized water to prepare a saturated sodium selenate solution, heating and stirring uniformly, adding water-absorbent resin, continuously stirring until the water-absorbent resin is completely dissolved, standing, drying, and grinding into powder to obtain selenium-enriched water-absorbent resin powder, wherein the mass of the selenium-enriched water-absorbent resin powder is 2 times that of the water-absorbent resin powder before treatment.
And S33, removing the three-neck flask from the water bath, cooling to room temperature, performing suction filtration, washing with acetone, and drying with hot air at 32 ℃ to obtain the wax wall water-absorbent resin microcapsule.
S4, fully dry-mixing the selenium-containing silicon dioxide microspheres obtained in the step S2, the wax wall water-absorbing resin microcapsules obtained in the step S3, starch and inorganic selenium salt, adding water glass for granulation, drying by hot air at 32 ℃ and screening to obtain an inner core with the diameter of 2-4 cm.
In step S4, the selenium-containing silica microspheres, the wax-wall water-absorbent resin microcapsules, the starch, the water glass, the inorganic selenium salt and the water are respectively 100 parts by weight, 25 parts by weight, 33 parts by weight, 190 parts by weight and 16 parts by weight, respectively.
S5, spraying a coating agent on the surface of the inner core obtained in the step S4 for coating treatment, wherein the coating agent comprises modified sodium carboxymethylcellulose and inorganic selenium salt, and the coating agent comprises the following components in percentage by mass: the kernel is 1:9, and in the coating agent, the ratio of modified sodium carboxymethyl cellulose: inorganic selenium salt 1: 0.13.
finally, the selenium-rich slow-release cadmium inhibitor A1 is prepared.
Example 2
A preparation method of a selenium-rich slow-release cadmium inhibitor comprises the following steps:
s1, preparing a silica microsphere with a porous capillary structure, wherein the particle size of the silica microsphere is 110 microns;
s11, pouring 50 parts by weight of dimethyldichlorosilane into a beaker, adding 18 parts by weight of 45 wt% concentrated hydrochloric acid into the beaker, and stirring at 45 ℃ for 35min to obtain oily octamethylcyclotetrasiloxane;
s12, mixing 25 parts by weight of the octamethylcyclotetrasiloxane prepared in the step S11 with 9 parts by weight of ammonia water with the concentration of 30 wt%, heating and stirring for 22min, performing suction filtration, and washing with absolute ethyl alcohol to obtain octamethylcyclotetrasiloxane polymerized microspheres;
and S13, calcining the octamethylcyclotetrasiloxane polymerized microspheres obtained in the step S12 at the temperature of 600 ℃ for 65min, and taking out and naturally cooling to obtain the silicon dioxide microspheres.
S2, soaking the silica microspheres obtained in the step S1 in a saturated solution of inorganic selenium salt for 2 hours, filtering and drying after soaking is finished, and obtaining selenium-containing silica microspheres, wherein the mass of the selenium-containing silica microspheres is 1.5 times that of the silica microspheres.
S3, preparing wax wall water-absorbing resin microcapsules;
s31, adding 300ml of diphenyl ether into a three-neck flask, and heating to 70 ℃ in a water bath;
s32, respectively putting paraffin powder and water-absorbent resin powder into a three-neck flask, wherein the mass ratio of the paraffin powder to the water-absorbent resin powder is 1:8, and stirring for 30 min;
the water-absorbing resin powder is subjected to selenium enrichment treatment, and specifically comprises the following steps: dissolving sodium selenate in deionized water to prepare a saturated sodium sulfate solution, heating and stirring uniformly, adding water-absorbent resin, continuously stirring until the water-absorbent resin is completely dissolved, standing, drying, and grinding into powder to obtain selenium-enriched water-absorbent resin powder, wherein the mass of the selenium-enriched water-absorbent resin powder is 2 times that of the water-absorbent resin powder before treatment.
And S33, removing the three-neck flask from the water bath kettle, cooling to room temperature, performing suction filtration, washing with acetone, and drying with hot air at 30 ℃ to obtain the wax wall water-absorbent resin microcapsule.
S4, fully dry-mixing the selenium-containing silicon dioxide microspheres obtained in the step S2, the wax wall water-absorbing resin microcapsules obtained in the step S3, starch and inorganic selenium salt, adding water glass for granulation, drying by hot air at 30 ℃ and screening to obtain an inner core with the diameter of 2-4 cm.
In step S4, the selenium-containing silica microspheres, the wax-wall water-absorbent resin microcapsules, the starch, the water glass, the inorganic selenium salt and the water are respectively 100 parts by weight, 20 parts by weight, 30 parts by weight, 180 parts by weight and 15 parts by weight, respectively.
S5, coating the surface of the inner core obtained in the step S4 with a coating agent, wherein the coating agent comprises modified sodium carboxymethyl cellulose and inorganic selenium salt, and the coating agent comprises the following components in percentage by mass: and (3) kernel 1:8, wherein in the coating agent, the ratio of modified sodium carboxymethylcellulose: inorganic selenium salt 1: 0.12.
finally, the selenium-rich slow-release cadmium inhibitor A2 is prepared.
Example 3
A preparation method of a selenium-rich slow-release cadmium inhibitor comprises the following steps:
s1, preparing a silica microsphere with a porous capillary structure, wherein the particle size of the silica microsphere is 110 microns;
s11, pouring 50 parts by weight of dimethyldichlorosilane into a beaker, adding 18 parts by weight of 45 wt% concentrated hydrochloric acid into the beaker, and stirring at 45 ℃ for 35min to obtain oily octamethylcyclotetrasiloxane;
s12, mixing 25 parts by weight of the octamethylcyclotetrasiloxane prepared in the step S11 with 9 parts by weight of ammonia water with the concentration of 30 wt%, heating and stirring for 22min, performing suction filtration, and washing with absolute ethyl alcohol to obtain octamethylcyclotetrasiloxane polymerized microspheres;
and S13, calcining the octamethylcyclotetrasiloxane polymerized microspheres obtained in the step S12 at the temperature of 600 ℃ for 65min, and taking out and naturally cooling to obtain the silicon dioxide microspheres.
S2, soaking the silica microspheres obtained in the step S1 in a saturated solution of inorganic selenium salt for 2 hours, filtering and drying after soaking is finished, and obtaining selenium-containing silica microspheres, wherein the mass of the selenium-containing silica microspheres is 1.5 times that of the silica microspheres.
S3, preparing wax wall water-absorbing resin microcapsules;
s31, adding 300ml of diphenyl ether into a three-neck flask, and heating to 80 ℃ in a water bath;
s32, respectively putting paraffin powder and water-absorbent resin powder into a three-neck flask, wherein the mass ratio of the paraffin powder to the water-absorbent resin powder is 1:10, and stirring for 40 min;
the water-absorbing resin powder is subjected to selenium enrichment treatment, and specifically comprises the following steps: dissolving sodium selenate in deionized water to prepare a saturated sodium selenate solution, heating and stirring uniformly, adding water-absorbent resin, continuously stirring until the water-absorbent resin is completely dissolved, standing, drying, and grinding into powder to obtain selenium-enriched water-absorbent resin powder, wherein the mass of the selenium-enriched water-absorbent resin powder is 2 times that of the water-absorbent resin powder before treatment.
And S33, removing the three-neck flask from the water bath kettle, cooling to room temperature, performing suction filtration, washing with acetone, and drying with hot air at 35 ℃ to obtain the wax wall water-absorbent resin microcapsule.
S4, fully dry-mixing the selenium-containing silicon dioxide microspheres obtained in the step S2, the wax wall water-absorbing resin microcapsules obtained in the step S3, starch and inorganic selenium salt, adding water glass for granulation, drying by hot air at 35 ℃ and screening to obtain an inner core with the diameter of 2-4 cm.
In step S4, the selenium-containing silica microspheres, the wax-wall water-absorbent resin microcapsules, the starch, the water glass, the inorganic selenium salt and the water are respectively 100 parts by weight, 30 parts by weight, 36 parts by weight, 200 parts by weight and 17 parts by weight, respectively.
S5, coating the surface of the inner core obtained in the step S4 with a coating agent, wherein the coating agent comprises modified sodium carboxymethyl cellulose and inorganic selenium salt, and the coating agent comprises the following components in percentage by mass: the core is 1:10, and in the coating agent, the ratio of modified sodium carboxymethyl cellulose: inorganic selenium salt 1: 0.14.
finally, the selenium-rich slow-release cadmium inhibitor A3 is prepared.
Comparative example 1
The remaining characteristics are the same as those of example 1, except that, in the step S4, when preparing the core, the selenium-containing silica microspheres are not added, and in addition, 33.3 parts by weight of inorganic selenium salt is added to the core, so as to ensure that the total selenium content is unchanged after removing the selenium-containing silica microspheres from the core, and finally, the cadmium inhibitor D1 is obtained.
Comparative example 2
The remaining characteristics were the same as in example 1, except that, in the preparation of the core in step S4, the wax wall water-absorbent resin microcapsules were not added, and 12.5 parts by weight of an inorganic selenium salt was additionally added to the core to ensure that the total amount of selenium remained unchanged after the removal of the wax wall water-absorbent resin microcapsules from the core, and finally, the cadmium blocking agent D2 was obtained.
Comparative example 3
The remaining characteristics were the same as in example 1, except that, in the preparation of the inner core in step S4, the wax wall water-absorbent resin microcapsules were replaced with the water-absorbent resin microcapsules, that is, the wax wall coating treatment was not performed, and finally the cadmium inhibitor D3 was obtained.
Comparative example 4
The remaining characteristics are the same as those of example 1, except that in step S4, the amount of the wax wall water-absorbent resin microcapsule added is 15 parts by weight, and 5 parts by weight of inorganic selenium salt is additionally added to ensure that the total selenium content is unchanged, and finally the cadmium inhibitor D4 is obtained.
Comparative example 5
The remaining characteristics are the same as those of example 1, except that in step S4, the amount of the wax wall water absorbent resin microcapsule added is 45 parts by weight, and 10 parts by weight of inorganic selenium salt is reduced, that is, 180 parts by weight of inorganic selenium salt in step S4 is used to ensure that the total selenium content is unchanged, and finally the cadmium inhibitor D5 is obtained.
Comparative example 6
The rest characteristics are the same as those of the example 1, except that in the step S5, the sodium carboxymethyl cellulose is not doped with the inorganic selenium salt, and 5.6 parts by weight of the inorganic selenium salt is additionally added, that is, 195.6 parts by weight of the inorganic selenium salt in the step S4 is added, so as to ensure that the total selenium content is unchanged, and finally, the cadmium inhibitor D6 is obtained.
Comparative example 7
The rest characteristics are the same as those of the example 1, except that in the step S5, the mass ratio of the sodium carboxymethylcellulose to the inorganic selenium salt is 1:0.2, 3 parts by weight of the inorganic selenium salt is reduced, namely 187 parts by weight of the inorganic selenium salt in the step S4 is reduced, the total selenium content is ensured to be unchanged, and finally the cadmium inhibitor D7 is obtained.
Experimental example 1
The cadmium inhibitors A1-A3 and D1-D7 produced in examples 1-3 and comparative examples 1-7 of the invention are used for carrying out fertilizer effect tests on late rice.
Subject: late rice (you Xiang I)
The cultivation method comprises the following steps: test field seeding culture
Test time: 120 days
Area of the test field: total 300m3Is divided into 30 test cells, and each test cell has an area of 10m3。
The cadmium content of the soil: 2.0mg/Kg
Preparing a compound fertilizer as a base fertilizer: uniformly mixing the waste mushroom dregs, 100 parts of green manure, 20 parts of coal slime and 5 parts of fermentation strain in parts by weight, then fermenting, wherein the temperature of a compost is not more than 70 ℃, the germination index is more than 80%, obtaining a fermented organic material for later use, then respectively adding 5 parts of zinc sulfate, 3 parts of magnesium sulfate, 3 parts of calcium ammonium nitrate, 2 parts of manganese sulfate, 1 part of copper sulfate, 1 part of borax and 0.5 part of ammonium molybdate into the organic material, and uniformly mixing and stirring to obtain the compound fertilizer (base fertilizer).
The compound fertilizer is used as a base fertilizer to be applied to each experimental plot, and the fertilizing amount of the compound fertilizer in each experimental plot is 60 kg/mu.
The cadmium inhibitors A1-A3 and D1-D7 obtained in the above examples and comparative examples were treated in total for 10 treatments, each treatment was set to 3 times, and the treated cadmium inhibitors were applied to test cells together with the compound fertilizer in a random block test, wherein the amount of applied fertilizer was 40 kg/mu.
After the test is finished, the cadmium content, the selenium content and the yield of the late rice in each test cell are detected and recorded, and the data are shown in table 1.
TABLE 1 late rice Condition
The data analysis in table 1 shows that the selenium-rich slow-release cadmium inhibitor A1-A3 prepared by the preparation method provided by the invention has low selenium content in the soil in the seedling stage of late rice, high selenium content in the growth stage and stable selenium content in the mature stage after the selenium content in the late rice is reduced after the compound fertilizer is compounded into the cadmium-containing soil, the change situation of the selenium content enables the late rice to grow well, the cadmium content in the rice is lower than 0.06mg/Kg, and the selenium content is close to 0.3mg/Kg, which indicates that the selenium-rich slow-release cadmium inhibitor A1-A3 achieves good cadmium-inhibiting effect, and the yield can reach more than 600 Kg/mu.
Experimental example 2
The cadmium inhibitors A1-A3 and D1-D7 provided by the examples and the comparative examples are used as test materials, the initial dissolution rate, 28-day release rate, 60-day release rate, 90-day release rate and 120-day release rate of the coated fertilizer are determined by referring to the rapid detection method of the release period and release rate of the nutrients of the slow release/controlled release fertilizer and the method recommended by the chemical industry standard (HG/T4216-2011), and the cumulative release rate is determined by taking selenium element as a detection index. The measurement results are shown in Table 2.
TABLE 2 Release Rate of selenium
From the selenium release rates in table 2, it can be seen that a1-A3 has a low selenium release rate in the seedling stage of late rice, can have a cadmium blocking effect without inhibiting the growth of late rice plants, has a steep selenium release rate in the growth stage, can meet the growth requirements of late rice plants with high selenium content, has a steady selenium release rate reduction in the maturation stage, and can provide selenium with a certain concentration for late rice plants for a long time.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a selenium-rich slow-release cadmium inhibitor is characterized by comprising the following steps:
s1, preparing the silica microspheres with porous capillary structures;
s2, soaking the silicon dioxide microspheres obtained in the step S1 in a saturated inorganic selenium salt solution, filtering and drying to obtain selenium-containing silicon dioxide microspheres;
s3, preparing wax wall water-absorbing resin microcapsules;
s4, fully dry-mixing the selenium-containing silicon dioxide microspheres obtained in the step S2, the wax wall water-absorbing resin microcapsules obtained in the step S3, starch and inorganic selenium salt, adding water glass for granulation, and drying by hot air at the temperature of 30-35 ℃ to obtain an inner core;
s5, spraying a coating agent on the surface of the inner core obtained in the step S4 for coating treatment, wherein the coating agent comprises modified sodium carboxymethyl cellulose and inorganic selenium salt.
2. The preparation method of the selenium-rich slow-release cadmium inhibitor according to claim 1, wherein the step S1 specifically comprises:
s11, pouring 45-55 parts by weight of dimethyldichlorosilane into a beaker, adding 15-20 parts by weight of 45 wt% concentrated hydrochloric acid into the beaker, and stirring for 30-40min at 40-50 ℃ to obtain oily octamethylcyclotetrasiloxane;
s12, mixing 20-30 parts by weight of the octamethylcyclotetrasiloxane prepared in the step S11 with 8-10 parts by weight of 30 wt% ammonia water, heating and stirring for 20-25min, performing suction filtration, and washing with absolute ethyl alcohol to obtain octamethylcyclotetrasiloxane polymerized microspheres;
s13, calcining the octamethylcyclotetrasiloxane polymerized microsphere obtained in the step S12 at the calcining temperature of 500-700 ℃ for 60-70min, and taking out and naturally cooling to obtain the silicon dioxide microsphere.
3. The method for preparing the selenium-rich slow-release cadmium inhibitor as claimed in claim 1, wherein in step S1, the particle size of the silica microspheres is 100-120 μm.
4. The method for preparing the selenium-rich slow-release cadmium inhibitor as claimed in claim 1, wherein in step S2, the mass of the selenium-containing silica microspheres is 1.5-1.8 times of the mass of the silica microspheres.
5. The preparation method of the selenium-rich slow-release cadmium inhibitor according to claim 1, wherein the step S3 specifically comprises:
s31, adding 300ml of diphenyl ether into a three-neck flask, and heating to 70-80 ℃ in a water bath;
s32, respectively putting paraffin powder and water-absorbent resin powder into the three-neck flask, and stirring for 30-40 min;
and S33, removing the three-neck flask from the water bath, cooling to room temperature, performing suction filtration, washing with acetone, and drying with hot air at 30-35 ℃ to obtain the wax wall water-absorbent resin microcapsule.
6. The method for preparing the selenium-rich slow-release cadmium inhibitor according to claim 5, wherein in step S32, the ratio by mass of the paraffin powder: water-absorbent resin powder 1: (8-10).
7. The preparation method of the selenium-rich slow-release cadmium inhibitor according to claim 5 or 6, wherein the water-absorbing resin powder is processed by selenium-rich treatment, and the processing method comprises the following steps:
dissolving inorganic selenium salt in deionized water to prepare saturated inorganic selenium salt solution, heating and stirring uniformly, adding water-absorbent resin, continuously stirring until the water-absorbent resin swells to the highest multiplying power, standing, drying, and grinding into powder to obtain the water-absorbent resin powder after selenium-rich treatment.
8. The method for preparing the selenium-rich slow-release cadmium inhibitor as claimed in claim 1, wherein in step S4, the selenium-containing silica microspheres are 100 parts by weight, the wax wall water-absorbent resin microcapsules are 20-30 parts by weight, the starch is 30-36 parts by weight, the water glass is 30-36 parts by weight, the inorganic selenium salt is 180-200 parts by weight, and the water is 15-17 parts by weight.
9. The preparation method of the selenium-rich slow-release cadmium inhibitor according to claim 1, wherein in step S5, the coating agent comprises, by mass: the kernel is 1: 8-10;
wherein, in the coating agent, the ratio of modified sodium carboxymethylcellulose: inorganic selenium salt 1: 0.12-0.14.
10. A selenium-rich slow-release cadmium inhibitor, which is characterized by being prepared by the preparation method of the selenium-rich slow-release cadmium inhibitor in any one of claims 1 to 9.
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