CN109694277A - A kind of humic acid slow release selenium fertilizer and preparation method thereof - Google Patents
A kind of humic acid slow release selenium fertilizer and preparation method thereof Download PDFInfo
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- CN109694277A CN109694277A CN201811607619.3A CN201811607619A CN109694277A CN 109694277 A CN109694277 A CN 109694277A CN 201811607619 A CN201811607619 A CN 201811607619A CN 109694277 A CN109694277 A CN 109694277A
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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
- C05D9/02—Other inorganic fertilisers containing trace elements
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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
- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2397/00—Characterised by the use of lignin-containing materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/04—Alginic acid; Derivatives thereof
Abstract
The invention discloses a kind of humic acid slow release selenium fertilizer and preparation method thereof, using humate, selenium fertilizer, ascorbic acid, alginate, acrylic acid, acrylamide, initiator, crosslinking agent as raw material.Using the reproducibility of ascorbic acid, the inorganic selenium of low activity is reduced into the elemental selenium of high activity, using the complexing power chelating selenium fertilizer of a variety of functional groups of humic acid, achievees the effect that sustained release；Alginate and acrylamide, acrylic acid may make up inierpeneirating network structure, form pore canal system, the selenium successively added, humate nest into network structure as guest molecule, by pore channel slow release to achieve the effect that sustained release.Fertilizer humic acid obtained, selenium fertilizer content are high, outside the nutritive value that ensure that fertilizer, also have the effect of environmentally protective, controlled release fertilizer, water-saving fertilizer-saving, improvement soil, promote soil fertility, upgrading is increased production.
Description
Technical field
The invention belongs to agricultural fertilizer preparation process field, in particular to a kind of humic acid slow release selenium fertilizer and its preparation side
Method.
Background technique
Selenium is microelement necessary to humans and animals, and selenium deficiency can seriously affect the health of people.1972, Roetueh
It confirms that selenium is the active constituent of the sweet skin peroxidase (GPX) of paddy flesh, is acknowledged as microelement necessary to life from this selenium.
Selenium is also the required nutrient of higher plant growth, it was found that 0.1-1.0 μ g/g can promote the growth of rice, increase
Se content in yield and increase seed.
Inorganic selenium toxicity is big, activity is low, is generally not suitable for being directly appended in food.Human body selenium-supply need from rice,
It is absorbed in the foods such as wheat flour, veterinary antibiotics.Organic selenium fertilizer is the effective hand for improving the Se contents such as grain, water fruits and vegetables
Section.Current selenium-enriched fertilizer usually adds selenium mineral powder directly into fertilizer or sodium selenite powder, selenium element therein are equal
Exist in the form of inorganic selenium, and in order to blindly pursue selenium content of crops, often largely use selenium fertilizer or increases before maturation
Add selenium fertilizer amount of application, will lead to inorganic selenium in crop and have not enough time to convert completely, inorganic Se content is higher, is not suitable for human body suction
It receives.
Summary of the invention
One of the objects of the present invention is to provide a kind of humic acid slow release selenium fertilizer, will be low using the reproducibility of ascorbic acid
Active inorganic selenium is reduced into the elemental selenium of high activity, using the complexing power chelating selenium fertilizer of a variety of functional groups of humic acid, reaches
The ability of sustained release.
The second object of the present invention is to provide a kind of humic acid slow release selenium fertilizer and preparation method thereof, acrylic acid or/and third
Acrylamide is first reacted with initiator and crosslinking agent, prepares the porous type slow-release material with inierpeneirating network structure, using anti-bad
The inorganic selenium of low activity is reduced into the elemental selenium of high activity by the reproducibility of hematic acid, using elemental selenium and humate as object
Molecule nests into network structure, is discharged by the hole of network structure.This product has the work of sustained-release and controlled release, retain water and nutrients
With the utilization rate and water-saving, section fertilizer that can greatly improve fertilizer act on.
The present invention is to be achieved through the following technical solutions:
A kind of humic acid slow release selenium fertilizer, in terms of mass fraction, including following components: 50~100 parts of humate, 0.1
~50 parts of selenium fertilizer and 0.2~30 part of ascorbic acid and 0~10 part of alginate.
It further, further include following components: 15 parts of acrylic acid below or/and 15 parts of acrylamides below and 2 parts
Initiator below and 0.5 part of crosslinking agent below.
Further, the humate is humic acid potassium or/and sodium humate；The selenium fertilizer is selenite or/and selenium
Hydrochlorate；The alginate is one of calcium alginate, potassium alginate and sodium alginate or a variety of.
Further, the initiator is potassium peroxydisulfate or ammonium persulfate；The crosslinking agent is N, N'- methylene bisacrylamide acyl
One of amine, borax, boric acid and boracic organic matter.
The invention also discloses a kind of preparation methods of humic acid slow release selenium fertilizer, comprising the following steps:
1) 50~100 parts of humate, 0.1~50 part of selenium fertilizer, 0.2~30 part according to the mass fraction, are weighed respectively
Ascorbic acid and 15 parts of acrylic acid below and 2 parts of initiators below and 0.5 part of crosslinking agent below；
2) selenium fertilizer and ascorbic acid are respectively configured to solution, are then mixed, obtain the solution containing elemental selenium；
3) acrylic acid is neutralized with alkaline solution, acrylic acid aqueous solution is made；Humate is prepared into solution；
4) the same crosslinking agent of acrylic acid aqueous solution, initiator are mixed and is stirred at room temperature, react 30~60min, heating
To 40~60 DEG C, the reaction was continued after 2~4 hours solution becomes viscous, and stops stirring；
5) solution containing elemental selenium, humate solution is then added, is continuously heating to 65~75 DEG C；Reaction 3~5 is small
Shi Hou, system be in again it is thick, stop reaction, obtain release and release control fertilizer；
6) release and release control fertilizer heating, drying to water content are not more than 5.0%, crushing obtains humic acid slow release selenium fertilizer.
The invention also discloses a kind of preparation methods of humic acid slow release selenium fertilizer, comprising the following steps:
1) 50~100 parts of humate, 0.1~50 part of selenium fertilizer, 0.2~30 part according to the mass fraction, are weighed respectively
Ascorbic acid and 15 parts of acrylamides below and 2 parts of initiators below and 0.5 part of crosslinking agent below；
2) selenium fertilizer and ascorbic acid are respectively configured to solution, are then mixed, obtain the solution containing elemental selenium；It will be rotten
Phytate is prepared into solution；
3) acrylamide, the solution containing elemental selenium and humate solution are mixed at room temperature, initiator is added
And crosslinking agent, 30~60min is reacted, is warming up to 40~75 DEG C, the reaction was continued after 3~5 hours solution becomes viscous, and stops stirring；
4) release and release control fertilizer heating, drying to water content are not more than 5.0%, crushing obtains humic acid slow release selenium fertilizer.
The invention also discloses a kind of preparation methods of humic acid slow release selenium fertilizer, comprising the following steps:
1) 50~100 parts of humate, 0.1~50 part of selenium fertilizer, 0.2~30 part according to the mass fraction, are weighed respectively
Ascorbic acid, 15 parts of acrylic acid below and 15 parts of acrylamides below and 2 parts of initiators below and 0.5 part or less
Crosslinking agent；
2) selenium fertilizer and ascorbic acid are respectively configured to solution, are then mixed, obtain the solution containing elemental selenium；
3) acrylic acid is neutralized with alkaline solution, acrylic acid aqueous solution is made, humate is prepared into solution；
4) acrylic acid aqueous solution, acrylamide are mixed and is stirred, and initiator and crosslinking agent is added at room temperature, reacted
30~60min is warming up to 40~60 DEG C, and the reaction was continued after 2~4 hours solution becomes viscous, and stops stirring；
5) solution containing elemental selenium, humate solution is then added, is continuously heating to 65~75 DEG C；Reaction 3~5 is small
Shi Hou, system be in again it is thick, stop reaction, obtain release and release control fertilizer；
6) release and release control fertilizer heating, drying to water content are not more than 5.0%, crushing obtains humic acid slow release selenium fertilizer.
The invention also discloses a kind of preparation methods of humic acid slow release selenium fertilizer, comprising the following steps:
1) 50~100 parts of humate, 0.1~50 part of selenium fertilizer, 0.2~30 part according to the mass fraction, are weighed respectively
Ascorbic acid, 10 parts of alginates below and 15 parts of acrylic acid below and 2 parts of initiators below and 0.5 part or less
Crosslinking agent；
2) selenium fertilizer and ascorbic acid are respectively configured to solution, are then mixed, obtain the solution containing elemental selenium；It will be rotten
Phytate is prepared into solution；
3) acrylic acid and alkaline solution are neutralized at room temperature, acrylic acid aqueous solution is made, and alginate is added, draws
Agent and crosslinking agent are sent out, 30~60min is reacted, is warming up to 40~60 DEG C, the reaction was continued after 2~4 hours solution becomes viscous, and stops stirring
It mixes；
4) solution and humate solution containing elemental selenium is then added, is continuously heating to 65~75 DEG C；Reaction 3~5
Hour after, system be in again it is thick, stop reaction, obtain release and release control fertilizer；
5) release and release control fertilizer heating, drying to water content are not more than 5.0%, crushing obtains humic acid slow release selenium fertilizer.
The invention also discloses a kind of preparation methods of humic acid slow release selenium fertilizer, comprising the following steps:
1) 50~100 parts of humate, 0.1~50 part of selenium fertilizer, 0.2~30 part according to the mass fraction, are weighed respectively
Ascorbic acid, 10 parts of alginates below and 15 parts of acrylamides below and 2 parts of initiators below and 0.5 part with
Under crosslinking agent；
2) selenium fertilizer and ascorbic acid are respectively configured to solution, are then mixed, obtain the solution containing elemental selenium；It will be rotten
Phytate is prepared into solution；
3) acrylamide, alginate, the solution containing elemental selenium and sodium humate solution are mixed at room temperature, are added
Enter initiator and crosslinking agent, reacts 30~60min, be warming up to 40~75 DEG C, after solution becomes viscous after the reaction was continued 3~5 hours,
Stop stirring；
4) release and release control fertilizer heating, drying to water content are not more than 5.0%, crushing obtains humic acid slow release selenium fertilizer.
The invention also discloses a kind of preparation methods of humic acid slow release selenium fertilizer, comprising the following steps:
1) 50~100 parts of humate, 0.1~50 part of selenium fertilizer, 0.2~30 part according to the mass fraction, are weighed respectively
Ascorbic acid, 10 parts of alginates below and 15 parts of acrylic acid below and 2 parts of initiators below and 0.5 part or less
Crosslinking agent；
2) selenium fertilizer and ascorbic acid are respectively configured to solution, are then mixed, obtain the solution containing elemental selenium；
3) acrylic acid is neutralized with alkaline solution, acrylic acid aqueous solution is made；Humate is prepared into solution；
4) at room temperature by acrylic acid aqueous solution, acrylamide and alginate mix be stirred, and be added initiator and
Crosslinking agent reacts 30~60min, is warming up to 40~60 DEG C, and the reaction was continued after 2~4 hours solution becomes viscous, and stops stirring；
5) solution and humate solution containing elemental selenium is then added, is continuously heating to 65~75 DEG C；Reaction 3~5
Hour after, system be in again it is thick, stop reaction, obtain release and release control fertilizer；
6) release and release control fertilizer heating, drying to water content are not more than 5.0%, crushing obtains humic acid slow release selenium fertilizer.
Compared with prior art, the invention has the following beneficial technical effects:
The humic acid slow release selenium fertilizer that the present invention prepares is selected rotten using humate, selenium fertilizer and ascorbic acid as raw material
Phytate as preparing raw material, be because humate is a kind of irregular macromolecular with various active functional group, can be with
The binding site between polymer chain and active material is increased, is conducive to the integrality and stability that keep structural framing, utilizes
Various active functional group and selenium are complexed, and constitute slow-releasing system, improve the utilization efficiency and stability of selenium fertilizer；Utilize Vitamin C
The inorganic selenium of low activity, is reduced into the elemental selenium of high activity, improves the use value of selenium by the reproducibility of acid；Utilize humic acid
The complexing power chelating selenium fertilizer of a variety of functional groups, reaches the ability of sustained release, greatly reduces the toxicity of inorganic selenium, ensure that fertilizer
Nutritive value outside, also have the effect of improve soil, promoted soil fertility, upgrading volume increase.
If adding alginate, alginate has good biodegradability and biocompatibility, can be used as selenium
The stabilizer or dispersing agent of element, collaboration play the bioactivity with selenium, further improve the bioactivity of selenium, it is easier to plant
Object absorbs.
Further, using humate, selenium fertilizer and ascorbic acid as raw material on the basis of, and joined acrylic acid or/
And acrylamide, it is chemically reacted under the action of crosslinking agent, initiator, interpenetrating networks is formed by the intertexture of linear structure
Structure, selenium fertilizer and humate nest into network structure as guest molecule, constitute slow-releasing system.
Further, using humate, selenium fertilizer and ascorbic acid as raw material on the basis of, and joined alginate,
Acrylic acid or/and acrylamide chemically react under the action of crosslinking agent, initiator, pass through the intertexture shape of linear structure
At inierpeneirating network structure, during becoming sticky gel state from the liquid flowed with system, addition selenium fertilizer and humic acid
Salt nests into network structure as guest molecule, so that constitution element pore channel achievees the effect that sustained release.
Further, alginate selects one of calcium alginate, potassium alginate, sodium alginate or a variety of, alginate
It is the by-product extracted in the kelp or sargassum of brown algae after iodine and mannitol, is a kind of natural polysaccharide, it is safe to the human body,
It is nontoxic, it is cheap.
The invention discloses a kind of preparation methods of humic acid slow release selenium fertilizer, are first respectively configured to selenium fertilizer and ascorbic acid
Solution is mixed, and the solution containing elemental selenium is obtained, and using the reproducibility of ascorbic acid, the inorganic selenium of low activity is restored
At the elemental selenium of high activity；Acrylic acid aqueous solution and humate solution are prepared again, and then acrylic acid is the same as crosslinking agent and initiation
Agent hybrid reaction generates sticky system for the first time, and sticky system is the inierpeneirating network structure with hole for the first time, is then added
Solution and humate solution containing elemental selenium, elemental selenium and humate nest into interpenetrating networks knot as guest molecule
Structure is discharged by the hole of network structure.
The invention discloses a kind of preparation methods of humic acid slow release selenium fertilizer, are first respectively configured to selenium fertilizer and ascorbic acid
Solution is mixed, and the solution containing elemental selenium is obtained, and using the reproducibility of ascorbic acid, the inorganic selenium of low activity is restored
At the elemental selenium of high activity；Humate solution is prepared again, then acrylamide, the solution containing elemental selenium, humate
Solution forms the inierpeneirating network structure with hole with crosslinking agent and initiator hybrid reaction, and elemental selenium is embedding as guest molecule
Inierpeneirating network structure is packed into, is discharged by the hole of network structure.
The invention discloses a kind of preparation methods of humic acid slow release selenium fertilizer, are first respectively configured to selenium fertilizer and ascorbic acid
Solution is mixed, and the solution containing elemental selenium is obtained, and using the reproducibility of ascorbic acid, the inorganic selenium of low activity is restored
At the elemental selenium of high activity；Acrylic acid aqueous solution and humate solution are prepared again, and then acrylic acid, acrylamide are the same as crosslinking
Agent and initiator hybrid reaction generate sticky system for the first time, and sticky system is the inierpeneirating network structure with hole for the first time,
Then solution and humate solution of the addition containing elemental selenium, elemental selenium and humate nest into interpenetrating as guest molecule
Network structure is discharged by the hole of network structure.
The invention discloses a kind of preparation methods of humic acid slow release selenium fertilizer, are first respectively configured to selenium fertilizer and ascorbic acid
Solution is mixed, and the solution containing elemental selenium is obtained, and using the reproducibility of ascorbic acid, the inorganic selenium of low activity is restored
At the elemental selenium of high activity；Acrylic acid aqueous solution and humate solution are prepared again, and then acrylic acid, alginate are the same as crosslinking
Agent and initiator hybrid reaction generate sticky system for the first time, and sticky system is the inierpeneirating network structure with hole for the first time,
Then solution and humate solution of the addition containing elemental selenium, elemental selenium and humate nest into interpenetrating as guest molecule
Network structure is discharged by the hole of network structure.Alginate has good bioactivity, can guarantee the height of selenium fertilizer
Activity, while alginate is equally used as biostimulant with humate, improves " antibody " of plant, and alginate is added also
Product can be made environmentally protective, residue is more degradable.
The invention discloses a kind of preparation methods of humic acid slow release selenium fertilizer, are first respectively configured to selenium fertilizer and ascorbic acid
Solution is mixed, and the solution containing elemental selenium is obtained, and using the reproducibility of ascorbic acid, the inorganic selenium of low activity is restored
At the elemental selenium of high activity；Prepare humate solution again, then acrylamide, the solution containing elemental selenium, alginate,
Humate solution forms the inierpeneirating network structure with hole, elemental selenium is as visitor with crosslinking agent and initiator hybrid reaction
Body molecule nests into inierpeneirating network structure, is discharged by the hole of network structure.
The invention discloses a kind of preparation methods of humic acid slow release selenium fertilizer, are first respectively configured to selenium fertilizer and ascorbic acid
Solution is mixed, and the solution containing elemental selenium is obtained, and using the reproducibility of ascorbic acid, the inorganic selenium of low activity is restored
At the elemental selenium of high activity；Acrylic acid aqueous solution and humate solution are prepared again, then acrylic acid, acrylamide, seaweed
Hydrochlorate generates sticky system for the first time with crosslinking agent and initiator hybrid reaction, and sticky system is with the mutual of hole for the first time
Network structure is worn, solution and humate solution containing elemental selenium is then added, elemental selenium and humate are as guest molecule
Son nests into inierpeneirating network structure, is discharged by the hole of network structure.
Fertilizer humic acid made from above-mentioned preparation method, selenium fertilizer content are high, and foliage green content in green vegetables can be improved, and improve
The photosynthesis of crop；The content for reducing MDA in green vegetables, improves the self-insurance ability of crop；Green vegetables POD activity is improved, to increase
Pretend the ability that object resists adverse circumstance；The yield that crop also can be improved improves the utilization rate of fertilizer, in the nutrition that ensure that fertilizer
Value is outer, also has the effect of environmentally protective, controlled release fertilizer, water-saving fertilizer-saving, improvement soil, promotes soil fertility, upgrading volume increase.Former material
Expect that procurement cost is low, preparation process is simple, and residue is degradable, meets environmental requirements, convenient for widely promoting and long-term answering
With.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
Embodiment 1
The present embodiment provides a kind of preparation methods of humic acid slow release selenium fertilizer, specifically includes the following steps:
1) in terms of mass fraction, 100 parts of sodium humates, 50 parts of sodium selenites and 30 parts of ascorbic acid are taken；
2) sodium selenite is configured to the solution that mass fraction is 9%, is the progress of 8% ascorbic acid solution with mass fraction
Mixing, obtains the solution containing elemental selenium；
3) 10% sodium humate solution is added to the solution containing elemental selenium at 55 DEG C, is continuously heating to 75 DEG C, constant temperature 2
Hour；Solution heating, drying to water content are not more than 5.0%, crushing obtains humic acid slow release selenium fertilizer.
Embodiment 2
The present embodiment provides a kind of preparation methods of humic acid slow release selenium fertilizer, specifically includes the following steps:
1) in terms of mass fraction, 50 parts of sodium humates, 0.1 part of sodium selenite and 0.2 part of ascorbic acid are taken；
2) by sodium selenite be configured to mass fraction be 10% solution, with mass fraction be 10% ascorbic acid solution into
Row mixing, obtains the solution containing elemental selenium；
3) selenium fertilizer and ascorbic acid are respectively configured to solution, are then mixed, obtain the solution containing elemental selenium；
4) 5% humate solution is added to the solution containing elemental selenium at 40 DEG C, is continuously heating to 65 DEG C, constant temperature 2
Hour；Solution heating, drying to water content are not more than 5.0%, crushing obtains humic acid slow release selenium fertilizer.
Embodiment 3
The present embodiment provides a kind of preparation methods of humic acid slow release selenium fertilizer, specifically includes the following steps:
1) in terms of mass fraction, 60 parts of sodium humates, 30 parts of sodium selenites, 15 parts of ascorbic acid and 10 parts of alginic acids are taken
Sodium；
2) sodium selenite is configured to the solution that mass fraction is 8%, it is 10% that ascorbic acid, which is configured to mass fraction,
Solution, then two parts of solution are mixed, and obtain the solution containing elemental selenium；
3) 8% sodium humate solution and sodium alginate are added at 50 DEG C, is continuously heating to 55 DEG C, constant temperature 2 hours；It will be molten
Liquid heating, drying to water content are not more than 5.0%, and crushing obtains humic acid slow release selenium fertilizer.
Embodiment 4
The present embodiment provides a kind of preparation methods of humic acid slow release selenium fertilizer, specifically includes the following steps:
1) in terms of mass fraction, take 50 parts of sodium humates, 20 parts of sodium selenites, 20 parts of ascorbic acid, 5 parts of sodium alginates,
10 parts of acrylic acid, 1.5 parts of initiators and 0.3 part of crosslinking agent；
2) sodium selenite is configured to the solution that mass fraction is 6%, it is 10% that ascorbic acid, which is configured to mass fraction,
Solution, then two parts of solution are mixed, and obtain the solution containing elemental selenium；
3) acrylic acid aqueous solution that degree of neutralization is 58% is made in acrylic acid and sodium hydroxide solution at room temperature, to acrylic acid
Sodium alginate is added in aqueous solution, while crosslinking agent is added dropwise with the speed of 10s/ drop, initiator is added dropwise with the speed of 7s/ drop, instead
30min is answered, is warming up to 60 DEG C, the reaction was continued after 4 hours solution becomes viscous, and stops stirring；
4) solution containing elemental selenium and 5% sodium humate solution is then added, is continuously heating to 65 DEG C；Reaction 4 hours
Afterwards, system is in thick again, stops reaction, obtains release and release control fertilizer；
5) release and release control fertilizer heating, drying to water content are not more than 5.0%, crushing obtains humic acid slow release selenium fertilizer.
Embodiment 5
The present embodiment provides a kind of preparation methods of humic acid slow release selenium fertilizer, specifically includes the following steps:
1) in terms of mass fraction, 55 parts of sodium humates, 15 parts of sodium selenites, 20 parts of ascorbic acid, 4 parts of sodium alginates, 7 are taken
Part acrylamide, 1.8 parts of initiators and 0.5 part of crosslinking agent；
2) sodium selenite is configured to the solution that mass fraction is 1%, it is 6% that ascorbic acid, which is configured to mass fraction,
Then two kinds of solution are mixed, obtain the solution containing elemental selenium by solution；
3) acrylamide, alginate, the solution containing elemental selenium and sodium humate solution are mixed at room temperature, are pressed
Initiator is added dropwise in the speed of 12s/ drop, and initiator is added dropwise with the speed of 7s/ drop；After reacting 45min, with 35min/5 DEG C of program
Heating mode carries out heating reaction, is warming up to 65 DEG C, and the reaction was continued after 3 hours solution becomes viscous, and stops stirring；
4) release and release control fertilizer heating, drying to water content are not more than 5.0%, crushing obtains humic acid slow release selenium fertilizer.
Embodiment 6
The present embodiment provides a kind of preparation methods of humic acid slow release selenium fertilizer, specifically includes the following steps:
1) in terms of mass fraction, 60 parts of sodium humates, 30 parts of sodium selenites, 25 parts of ascorbic acid, 15 parts of acrylic acid, 2 are taken
Part initiator and 0.5 part of crosslinking agent；
2) sodium selenite is configured to the solution that mass fraction is 5%, it is 5% that ascorbic acid, which is configured to mass fraction,
Then two kinds of solution are mixed, obtain the solution containing elemental selenium by solution；
3) acrylic acid aqueous solution that degree of neutralization is 60% is made in acrylic acid and sodium hydroxide solution；
4) crosslinking agent is added dropwise with the speed of 10s/ drop into acrylic acid aqueous solution at room temperature, is drawn with the speed dropwise addition of 8s/ drop
Agent is sent out, 30min is reacted, is warming up to 60 DEG C, the reaction was continued after 4 hours solution becomes viscous, and stops stirring；
5) solution containing elemental selenium, 1% humate solution is then added, is continuously heating to 67 DEG C；Reaction 4 hours
Afterwards, system is in thick again, stops reaction, obtains release and release control fertilizer；
6) release and release control fertilizer heating, drying to water content are not more than 5.0%, crushing obtains humic acid slow release selenium fertilizer.
Embodiment 7
The present embodiment provides a kind of preparation methods of humic acid slow release selenium fertilizer, specifically includes the following steps:
1) in terms of mass fraction, take 65 parts of sodium humates, 40 parts of sodium selenites, 20 parts of ascorbic acid, 15 parts of acrylamides,
2 parts of initiators and 0.5 part of crosslinking agent；
2) sodium selenite is configured to the solution that mass fraction is 5%, it is 7% that ascorbic acid, which is configured to mass fraction,
Then two kinds of solution are mixed, obtain the solution containing elemental selenium by solution；
3) acrylamide, the solution containing elemental selenium and 2% sodium humate solution are mixed at room temperature, with 10s/ drop
Speed crosslinking agent is added dropwise, initiator is added dropwise with the speed of 10s/ drop, reaction 40min is warming up to 65 DEG C, the reaction was continued 4 hours
After solution becomes viscous, stop stirring；
4) release and release control fertilizer heating, drying to water content are not more than 5.0%, crushing obtains humic acid slow release selenium fertilizer.
Embodiment 8
The present embodiment provides a kind of preparation methods of humic acid slow release selenium fertilizer, specifically includes the following steps:
1) in terms of mass fraction, 53 parts of sodium humates, 15 parts of sodium selenites, 4 parts of ascorbic acid, 5 parts of acrylic acid, 8 parts are taken
Acrylamide, 1 part of initiator and 0.2 part of crosslinking agent；
2) sodium selenite is configured to the solution that mass fraction is 3%, it is 5% that ascorbic acid, which is configured to mass fraction,
Then two kinds of solution are mixed, obtain the solution containing elemental selenium by solution；
3) acrylic acid aqueous solution that degree of neutralization is 65% is made in acrylic acid and sodium hydroxide solution；
4) acrylic acid aqueous solution, acrylamide are mixed and is stirred at room temperature, friendship is added dropwise thereto with the speed of 6s/ drop
Join agent, initiator is added dropwise by the speed of 12s/ drop；40min is reacted, is warming up to 65 DEG C, the reaction was continued, and 3 hours solution becomes viscous
Afterwards, stop stirring；
5) solution containing elemental selenium, sodium humate solution is then added, is continuously heating to 70 DEG C；After reaction 4 hours, body
System stops reaction, obtains release and release control fertilizer again in thick；
6) release and release control fertilizer heating, drying to water content are not more than 5.0%, crushing obtains humic acid slow release selenium fertilizer.
Embodiment 9
The present embodiment provides a kind of preparation methods of humic acid slow release selenium fertilizer, specifically includes the following steps:
1) in terms of mass fraction, take 65 parts of humic acid potassiums, 30 parts of sodium selenites, 20 parts of ascorbic acid, 8 parts of sodium alginates,
15 parts of acrylic acid, 10 parts of acrylamides, 2 parts of initiators and 0.5 part of crosslinking agent.
2) sodium selenite is configured to the solution that mass fraction is 1%, it is 7% that ascorbic acid, which is configured to mass fraction,
Then two kinds of solution are mixed, obtain the solution containing elemental selenium by solution；
3) acrylic acid is neutralized with potassium hydroxide solution, the acrylic acid aqueous solution that degree of neutralization is 57% is made；
4) at room temperature by acrylic acid aqueous solution, acrylamide, sodium alginate mix be stirred, with the speed of 12s/ drop to
Crosslinking agent is added dropwise, wherein initiator is added dropwise by the speed of 12s/ drop；50min is reacted, is warming up to 65 DEG C, the reaction was continued 4 hours
After solution becomes viscous, stop stirring；
5) solution containing elemental selenium, sodium humate solution is then added, is continuously heating to 70 DEG C；After reaction 4 hours, body
System stops reaction, obtains release and release control fertilizer again in thick；
6) release and release control fertilizer heating, drying to water content are not more than 5.0%, crushing obtains humic acid slow release selenium fertilizer.
Embodiment 10
The present embodiment provides a kind of preparation methods of humic acid slow release selenium fertilizer, specifically includes the following steps:
1) in terms of mass fraction, 70 parts of humic acid potassiums, 30 parts of sodium selenates, 20 parts of ascorbic acid, 3 parts of potassium alginates, 3 parts are taken
Acrylic acid, 3 parts of acrylamides, 0.5 part of initiator and 0.2 part of crosslinking agent；
2) by sodium selenate be configured to mass fraction be 1% solution, by ascorbic acid be configured to mass fraction be 7% it is molten
Then two kinds of solution are mixed, obtain the solution containing elemental selenium by liquid；
3) acrylic acid is neutralized with sodium hydroxide, the acrylic acid aqueous solution that degree of neutralization is 60% is made；
4) at room temperature by acrylic acid aqueous solution, acrylamide, potassium alginate mix be stirred, with the speed of 10s/ drop to
Crosslinking agent is added dropwise, wherein initiator is added dropwise by the speed of 12s/ drop；60min is reacted, is warming up to 65 DEG C, the reaction was continued 4 hours
After solution becomes viscous, stop stirring；
5) solution containing elemental selenium, sodium humate solution is then added, is continuously heating to 75 DEG C；After reaction 3 hours, body
System stops reaction, obtains release and release control fertilizer again in thick；
6) release and release control fertilizer heating, drying to water content are not more than 5.0%, crushing obtains humic acid slow release selenium fertilizer.
The sustained release of Examples 1 to 10 is theoretical are as follows: using the reproducibility of ascorbic acid, the inorganic selenium of low activity is reduced into height
Active elemental selenium reaches the ability of sustained release using the complexing power chelating selenium fertilizer of a variety of functional groups of humic acid；Secondly, passing through
Water solution polymerization process forms inierpeneirating network structure by the intertexture of Natural linear structure, forms pore canal system.Next prepares more
Pass water suction slow-release material nests into network structure using selenium fertilizer, humate as guest molecule, is discharged by hole.
During becoming sticky gel state from the liquid flowed with system, addition selenium fertilizer and humate, as guest molecule
It nests into network structure, by pore channel slow release to achieve the effect that sustained release.
Humic acid slow release selenium fertilizer prepared by the present invention, in terms of mass fraction, including following components: 50~100 parts of rotten plant
Hydrochlorate, 0.1~50 part of selenium fertilizer and 0.2~30 part of ascorbic acid and 0~10 part of alginate.Further include: 15 parts are below
Acrylic acid or/and 15 parts of acrylamides below and 2 parts of initiators below and 0.5 part of crosslinking agent below.
The humate source is low-order coal, is one or more of humic acid potassium, sodium humate.The selenium
Fertilizer is selenite or/and selenate.The alginate be one of calcium alginate, potassium alginate, sodium alginate or
It is several.The initiator is potassium peroxydisulfate, ammonium persulfate or persulfate.The crosslinking agent is N, N'- di-2-ethylhexylphosphine oxide third
One of acrylamide, borax, boric acid and boracic organic matter are a variety of, and boracic organic matter is organo-borane, organic borate, hydrocarbon
Ylboronic acid etc..
Humate is a kind of irregular macromolecular with various active functional group, can increase polymer chain and work
Property substance between binding site, be conducive to selenium be complexed, constitute slow-releasing system, improve the utilization efficiency and stability of selenium fertilizer；
Using the reproducibility of ascorbic acid, the inorganic selenium of low activity is reduced into the elemental selenium of high activity, improves the use value of selenium；
It ensure that outside the nutritive value of fertilizer also have the effect of improveing soil, promote soil fertility, upgrading volume increase.Humic acid below with
The reaction formula of selenium.
Alginate is the by-product extracted after iodine and mannitol in the kelp or sargassum of brown algae, a kind of natural more
Sugar is widely applied in food industry and field of medicaments.Two kinds of monomers are mainly contained on alginate strand: ancient
Sieve uronic acid (G) and mannuronic acid (M), the carboxylic acid group in G unit are located at C-C-O former molecular triangle summit top
Portion, and the carboxylic acid group in M unit will receive the constraint of neighboring atom, therefore the activity that G unit combines metal ion is big；M
The biocompatibility of unit is preferable.Safe to the human body, nontoxic, cheap, residue is degradable, meets environmental requirements,
Convenient for widely promoting and long-term application.It is the structural formula of alginate below:
Humic acid slow release selenium fertilizer made from Examples 1 to 10 and common selenium fertilizer are subjected to the fertilising verifying of row plant, test knot
Fruit is as shown in the table:
1) influence of the humic acid slow release selenium fertilizer to green vegetables chlorophyll content
Chlorophyll is the important fastidious finger of crop life ability by influencing crop photosynthesis capacity plant physiology ability
Mark, with photosynthesis at positive linked development.
Influence of 1 different disposal of table to green vegetables chlorophyll content
As can be seen from Table 1, compared with blank sample, chlorophyll has different degrees of increase for fertilising, and common selenium fertilizer increases
0.12mg/g, and humic acid slow release selenium fertilizer averagely increases 1.08mg/g, wherein 9 chlorophyll content of example increases at most, reaches
2.30mg/g。
2) influence of the humic acid slow release selenium fertilizer to green vegetables MDA content
Malonaldehyde is to judge the index of cell membrane ability, it results from the after birth rouge after peroxidating, can be a large amount of by injury
Molecule damages various crop structure, and malonaldehyde is inversely proportional with crop self-insurance ability.Each processing pair of humic acid slow release selenium fertilizer
Green vegetables MDA influence is shown in Table 2.
Influence of 2 different disposal of table to green vegetables MDA content
As can be seen from Table 2, the green vegetables MDA of material of applying fertilizer generally is lower than blank not fertilizer treatment, and common selenium fertilizer is to green vegetables MDA
Influence lower than humic acid slow release selenium fertilizer, be sustained selenium fertilizer green vegetables MDA content reduction by 27.78%~50%.Wherein embodiment 8
MDA content reduces at most, reaches 0.09mg/g.
3) humic acid slow release selenium fertilizer is on the active influence of green vegetables POD
POD can be catalyzed the oxygenolysis to itself harmful peroxide, and POD activity is bigger, and the ability for resisting adverse circumstance is got over
By force.Each processing is shown in Table 3 to green vegetables POD influence.
3 different disposal of table is on the active influence of green vegetables POD
As shown in Table 3, after the processing of different selenium fertilizer, green vegetables blade POD activity is above blank group, humic acid slow release selenium fertilizer
It is apparently higher than common selenium fertilizer processing, wherein the POD active quantities of embodiment 4 increase at most, reach 376U/ (gmin).
Humic acid slow release selenium fertilizer made from Examples 1 to 10 and common selenium fertilizer are subjected to rice field trial, test result
It is as shown in the table:
The rice field trial of 4 different disposal of table
From test data as can be seen that the present invention significantly improves the Se content in rice with humic acid slow release selenium fertilizer, together
When with certain effect of increasing production, while there is slow release effect, improve the utilization rate of fertilizer, also improve the product of Rice enriched-Se
Matter.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of humic acid slow release selenium fertilizer, which is characterized in that in terms of mass fraction, including following components: 50~100 parts of rotten plant
Hydrochlorate, 0.1~50 part of selenium fertilizer and 0.2~30 part of ascorbic acid and 0~10 part of alginate.
2. humic acid slow release selenium fertilizer according to claim 1, which is characterized in that further include following components: 15 parts below
Acrylic acid or/and 15 parts of acrylamides below and 2 parts of initiators below and 0.5 part of crosslinking agent below.
3. humic acid slow release selenium according to claim 1 fertilizer, which is characterized in that the humate be humic acid potassium or/
And sodium humate；The selenium fertilizer is selenite or/and selenate；The alginate is calcium alginate, potassium alginate and sea
One of mosanom is a variety of.
4. humic acid slow release selenium fertilizer according to claim 2, which is characterized in that the initiator is potassium peroxydisulfate or over cure
Sour ammonium；The crosslinking agent is N, one of N'- methylene-bisacrylamide, borax, boric acid and boracic organic matter.
5. a kind of preparation method of humic acid slow release selenium fertilizer, which comprises the following steps:
1) according to the mass fraction, weigh respectively 50~100 parts humate, 0.1~50 part selenium fertilizer, 0.2~30 part it is anti-bad
Hematic acid and 15 parts of acrylic acid below and 2 parts of initiators below and 0.5 part of crosslinking agent below；
2) selenium fertilizer and ascorbic acid are respectively configured to solution, are then mixed, obtain the solution containing elemental selenium；
3) acrylic acid is neutralized with alkaline solution, acrylic acid aqueous solution is made；Humate is prepared into solution；
4) the same crosslinking agent of acrylic acid aqueous solution, initiator are mixed and is stirred at room temperature, reacted 30~60min, be warming up to 40
~60 DEG C, the reaction was continued after 2~4 hours solution becomes viscous, and stops stirring；
5) solution containing elemental selenium, humate solution is then added, is continuously heating to 65~75 DEG C；Reaction 3~5 hours
Afterwards, system is in thick again, stops reaction, obtains release and release control fertilizer；
6) release and release control fertilizer heating, drying to water content are not more than 5.0%, crushing obtains humic acid slow release selenium fertilizer.
6. a kind of preparation method of humic acid slow release selenium fertilizer, which comprises the following steps:
1) according to the mass fraction, weigh respectively 50~100 parts humate, 0.1~50 part selenium fertilizer, 0.2~30 part it is anti-bad
Hematic acid and 15 parts of acrylamides below and 2 parts of initiators below and 0.5 part of crosslinking agent below；
2) selenium fertilizer and ascorbic acid are respectively configured to solution, are then mixed, obtain the solution containing elemental selenium；By humic acid
Salt is prepared into solution；
3) acrylamide, the solution containing elemental selenium and humate solution are mixed at room temperature, initiator and friendship is added
Join agent, react 30~60min, be warming up to 40~75 DEG C, the reaction was continued after 3~5 hours solution becomes viscous, and stops stirring；
4) release and release control fertilizer heating, drying to water content are not more than 5.0%, crushing obtains humic acid slow release selenium fertilizer.
7. a kind of preparation method of humic acid slow release selenium fertilizer, which comprises the following steps:
1) according to the mass fraction, weigh respectively 50~100 parts humate, 0.1~50 part selenium fertilizer, 0.2~30 part it is anti-bad
Hematic acid, 15 parts of acrylic acid below and 15 parts of acrylamides below and 2 parts of initiators below and 0.5 part of friendship below
Join agent；
2) selenium fertilizer and ascorbic acid are respectively configured to solution, are then mixed, obtain the solution containing elemental selenium；
3) acrylic acid is neutralized with alkaline solution, acrylic acid aqueous solution is made, humate is prepared into solution；
4) acrylic acid aqueous solution, acrylamide are mixed and is stirred, and initiator and crosslinking agent is added at room temperature, reaction 30~
60min is warming up to 40~60 DEG C, and the reaction was continued after 2~4 hours solution becomes viscous, and stops stirring；
5) solution containing elemental selenium, humate solution is then added, is continuously heating to 65~75 DEG C；Reaction 3~5 hours
Afterwards, system is in thick again, stops reaction, obtains release and release control fertilizer；
6) release and release control fertilizer heating, drying to water content are not more than 5.0%, crushing obtains humic acid slow release selenium fertilizer.
8. a kind of preparation method of humic acid slow release selenium fertilizer, which comprises the following steps:
1) according to the mass fraction, weigh respectively 50~100 parts humate, 0.1~50 part selenium fertilizer, 0.2~30 part it is anti-bad
Hematic acid, 10 parts of alginates below and 15 parts of acrylic acid below and 2 parts of initiators below and 0.5 part of friendship below
Join agent；
2) selenium fertilizer and ascorbic acid are respectively configured to solution, are then mixed, obtain the solution containing elemental selenium；By humic acid
Salt is prepared into solution；
3) acrylic acid and alkaline solution are neutralized at room temperature, acrylic acid aqueous solution is made, and alginate, initiator is added
And crosslinking agent, 30~60min is reacted, is warming up to 40~60 DEG C, the reaction was continued after 2~4 hours solution becomes viscous, and stops stirring；
4) solution and humate solution containing elemental selenium is then added, is continuously heating to 65~75 DEG C；Reaction 3~5 hours
Afterwards, system is in thick again, stops reaction, obtains release and release control fertilizer；
5) release and release control fertilizer heating, drying to water content are not more than 5.0%, crushing obtains humic acid slow release selenium fertilizer.
9. a kind of preparation method of humic acid slow release selenium fertilizer, which comprises the following steps:
1) according to the mass fraction, weigh respectively 50~100 parts humate, 0.1~50 part selenium fertilizer, 0.2~30 part it is anti-bad
Hematic acid, 10 parts of alginates below and 15 parts of acrylamides below and 2 parts of initiators below and 0.5 part it is below
Crosslinking agent；
2) selenium fertilizer and ascorbic acid are respectively configured to solution, are then mixed, obtain the solution containing elemental selenium；By humic acid
Salt is prepared into solution；
3) acrylamide, alginate, the solution containing elemental selenium and sodium humate solution are mixed at room temperature, addition is drawn
Agent and crosslinking agent are sent out, 30~60min is reacted, is warming up to 40~75 DEG C, after solution becomes viscous after the reaction was continued 3~5 hours, is stopped
Stirring；
4) release and release control fertilizer heating, drying to water content are not more than 5.0%, crushing obtains humic acid slow release selenium fertilizer.
10. a kind of preparation method of humic acid slow release selenium fertilizer, which comprises the following steps:
1) according to the mass fraction, weigh respectively 50~100 parts humate, 0.1~50 part selenium fertilizer, 0.2~30 part it is anti-bad
Hematic acid, 10 parts of alginates below and 15 parts of acrylic acid below and 2 parts of initiators below and 0.5 part of friendship below
Join agent；
2) selenium fertilizer and ascorbic acid are respectively configured to solution, are then mixed, obtain the solution containing elemental selenium；
3) acrylic acid is neutralized with alkaline solution, acrylic acid aqueous solution is made；Humate is prepared into solution；
4) acrylic acid aqueous solution, acrylamide and alginate are mixed at room temperature and is stirred, and initiator and crosslinking is added
Agent reacts 30~60min, is warming up to 40~60 DEG C, and the reaction was continued after 2~4 hours solution becomes viscous, and stops stirring；
5) solution and humate solution containing elemental selenium is then added, is continuously heating to 65~75 DEG C；Reaction 3~5 hours
Afterwards, system is in thick again, stops reaction, obtains release and release control fertilizer；
6) release and release control fertilizer heating, drying to water content are not more than 5.0%, crushing obtains humic acid slow release selenium fertilizer.
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| CN110511088A (en) * | 2019-09-24 | 2019-11-29 | 广西力拓粮油加工有限公司 | A kind of nanometer selenium siliceous fertilizer and preparation method thereof |
| CN115812705A (en) * | 2022-11-29 | 2023-03-21 | 陕西科技大学 | Humic acid nutritional type plant antifreezing agent and preparation method thereof |
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