CN112250497B - Lignin-based modified coating material and preparation method and application thereof - Google Patents
Lignin-based modified coating material and preparation method and application thereof Download PDFInfo
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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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- 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
- C05G3/90—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting the nitrification of ammonium compounds or urea in the soil
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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
- C05G5/37—Layered or coated, e.g. dust-preventing coatings layered or coated with a polymer
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
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Abstract
The invention discloses a lignin-based modified coating material and a preparation method and application thereof, wherein the coating material is completely prepared from a lignin-based material, and is applied to coating of a slow release fertilizer, the coating rate of the obtained coated slow release fertilizer is 5-40%, the release period of nutrients can reach more than 45 days, and the coating material is obtained by sequentially carrying out cross-linking modification and hydrophobic esterification modification on the lignin-based material. The application method is that the coating material is evenly and smoothly coated on the surface of the fertilizer core in a rotary coating machine by utilizing the thermoplasticity of the lignin-based modified coating material, so as to obtain the coated slow-release fertilizer. The slow release time of the coated urea is adjusted by adjusting the coating rate and the mixing proportion of the coated urea and the hydrophilic lignin-based material. The lignin has wide raw material source and low price, and the degradation product of the lignin is humus, so that the physical and chemical properties of soil can be improved for a long time, the release time of urea is prolonged, the ecological environment problem caused by excessive release of fertilizer is relieved, and the agricultural production target of sustainable utilization of soil can be realized.
Description
Technical Field
The invention belongs to the field of slow release fertilizer coating preparation, and particularly relates to a lignin-based modified coating material and a preparation method and application thereof.
Background
The fertilizer consumption of China accounts for 20-30% of the total consumption of fertilizers in the world and is the first in the world, the season utilization rate of the fertilizers in developed countries is 50-60%, and the season utilization rate of the fertilizers in China is only 30-35%. A large amount of chemical fertilizers are lost and wasted, so that huge economic losses are caused, and meanwhile, the ecological environment problem caused by the chemical fertilizers is also aggravated. How to efficiently utilize fertilizer resources is the key for maintaining food production in China and the key for sustainable development of economic society and ecological environment in China. The slow release fertilizer and the controlled release fertilizer are the most feasible methods for realizing the high-efficiency utilization of the fertilizer. The slow release fertilizer developed relatively mature at present is mainly prepared from non-renewable materials such as petroleum, coal, natural gas and the like, such as sulfur-coated slow release fertilizer, polyolefin slow release fertilizer, polyester thermosetting material slow release fertilizer and urea-formaldehyde resin slow release fertilizer. However, the development of the slow release fertilizer is restricted by the problems of non-regenerability, poor biodegradability and biocompatibility of the materials, complex preparation process of the slow release fertilizer, high manufacturing cost, secondary pollution to the ecological environment in the use process of the materials and the like. Therefore, a material with renewable, degradable and good biocompatibility as a raw material is searched and developed, and the slow release fertilizer which is used as a slow release material, has a simple development and preparation process and low price becomes the key for the development of the slow release fertilizer.
The coated slow release fertilizer is the main form of a physical barrier type slow release fertilizer and is also the main form of a commercial slow release fertilizer. The coated slow-release fertilizer can be roughly divided into two parts: coating and fat core. The fertilizer core is a fertilizer nutrient element, the slow release performance is mainly realized by changing the hydrophobicity and the porosity of a coating material to adjust the dissolution speed of the fertilizer element, and the release speed of the fertilizer element is prolonged or controlled to meet the nutritional requirement of the whole growth cycle of plants. The novel biomass materials such as natural materials such as chitosan, sodium alginate, starch and derivatives thereof, cellulose and derivatives thereof, agricultural wastes, biochar, polydopamine, lignin and the like have the characteristics of good biocompatibility, degradability, renewability and the like, so that the novel biomass materials have incomparable advantages when being used as slow-release materials. The lignin is a natural high polymer, the content of the lignin is only once with cellulose in a renewable biomass material, the lignin is degraded into humic acid under the action of microorganisms or other physical and chemical actions in nature, and the humic acid has the capabilities of improving the physical and chemical properties of soil, increasing the pores of the soil, improving the permeability of the soil, improving the water retention of the soil and preventing the soil from hardening. So that the lignin-based material has excellent advantages as a slow-release coating.
The slow release coating of the organic matters is generally completed by a fluidized bed film spraying process. The preparation process has high requirement on equipment, and the use of the organic solvent in the coating process causes secondary environmental pollution and reduces the utilization rate of the coating material. Therefore, the solvent-free coating process has great significance for the development of slow release fertilizers.
Disclosure of Invention
In view of the defects of the prior art, the first object of the invention is to provide a preparation method of a lignin-based modified coating material.
The second object of the present invention is to provide the lignin-based modified coating material prepared by the above preparation method.
The third purpose of the invention is to apply the lignin-based modified coating material prepared by the preparation method, and the coating material is uniformly and smoothly coated on the surface of the fertilizer core in a coating machine by utilizing the thermoplasticity of the lignin-based modified coating material, so that the slow release performance of the fertilizer elements is improved.
In order to achieve the purpose, the invention adopts the following scheme:
the invention relates to a preparation method of a lignin-based modified coating material, which comprises the following steps: and (2) performing a crosslinking reaction on the lignin source and a crosslinking agent to obtain crosslinked lignin, and then performing an esterification reaction on the crosslinked lignin and an esterifying agent to obtain the lignin-based modified coating material.
According to the preparation method of the lignin-based modified coating material, firstly, a lignin source is subjected to a crosslinking reaction to amplify the molecular weight of the lignin source, the molecular weight is amplified to improve the glass transition temperature of a subsequent hydrophobic modified product, then, esterification reaction is carried out to carry out hydrophobic esterification modification on the crosslinked lignin, the rate of water passing through a coating layer is reduced, and the thermoplastic film forming capability of the modified material is also endowed, so that the modified coating material with excellent thermoplasticity is obtained, and the coating of a fertilizer core is realized by utilizing the thermoplasticity of the modified coating material under the condition of no solvent.
In a preferable scheme, the glass transition temperature of the lignin-based modified coating material is 50-90 DEG C
After the molecular weight is amplified through the crosslinking reaction of the lignin source and the crosslinking agent, the glass transition temperature of the finally obtained lignin-based modified coating material is 50-90 ℃. The molecular weight of the high polymer is in direct proportion to the glass transition temperature of the high polymer, and the glass transition temperature of the lignin source hydrophobic modification product without molecular weight amplification is only about 31 ℃, so that the material has high viscosity and softness at normal temperature, which is not beneficial to processing, storing and transporting the slow release fertilizer.
Preferably, the lignin source is at least one selected from lignin, alkali lignin, kaff lignin and lignosulfonate, preferably lignosulfonate, and more preferably sodium lignosulfonate.
The further preferable sodium lignosulfonate in the invention has wide raw material source and low price, and the Mw of the sodium lignosulfonate is more than that of other types of lignin; the amount of the crosslinking agent added and the reaction time can be reduced during the molecular weight amplification.
In a preferred embodiment, the crosslinking agent is at least one selected from epichlorohydrin, formaldehyde, glutaraldehyde sebacic diacid, and preferably epichlorohydrin.
Preferably, the liquid-solid volume mass ratio of the cross-linking agent to the lignin source is 100uL:10-20 g.
In a preferable scheme, the temperature of the crosslinking reaction is 80-100 ℃, and the time of the crosslinking reaction is 2-10 h.
In a preferable scheme, the cross-linked lignin and the esterifying agent are added into an organic solvent for esterification reaction, and pyridine is added as an acid-binding agent.
In a preferred embodiment, the esterifying agent is at least one selected from acetyl chloride, propionyl chloride, hexanoyl chloride, dodecanoyl chloride and hexadecanoyl chloride.
In a preferable scheme, the temperature of the esterification reaction is 20-40 ℃, and the time of the esterification reaction is 1-10 h.
Preferably, the liquid-solid volume mass ratio of the esterifying agent to the cross-linked lignin is 4ml:0.5-2 g.
In a preferred scheme, the solid-liquid mass volume ratio of the cross-linked lignin to the pyridine is 0.5-2 g:4 ml.
The invention relates to a preparation method of a lignin-based modified coating material, which comprises the following steps:
step one
Mixing a solution containing sodium lignosulfonate with epichlorohydrin, and then carrying out crosslinking reaction at 80-100 ℃ to obtain crosslinked lignin, wherein the crosslinking reaction time is 2-4h, and the liquid-solid volume mass ratio of the epichlorohydrin crosslinking agent to the sodium lignosulfonate lignin source is 100uL:10-20g, preferably 100uL:15 g;
step two
Mixing the cross-linked lignin obtained in the step one, dodecanoyl chloride, pyridine and dimethylformamide, and carrying out esterification reaction at 20-40 ℃ for 1-3h to obtain a lignin-based modified coating material; the liquid-solid volume mass ratio of the lauroyl chloride to the cross-linked lignin is 4ml:0.5-2 g; the solid-liquid mass volume ratio of the cross-linked sodium lignosulfonate to the pyridine is 0.5-2 g:4 ml.
Preferably, in the step one, the mass fraction of the sodium lignosulfonate in the solution containing the sodium lignosulfonate is 20-40%.
Preferably, in the second step, the liquid-solid volume mass ratio of the dimethylformamide to the crosslinked sodium lignin sulfonate is 30ml: 0.5-2 g.
The invention also provides the lignin-based modified coating material prepared by the preparation method.
The invention also provides application of the lignin-based modified coating material obtained by the preparation method, the lignin-based modified coating material is used as a coating material, or a mixed material obtained by mixing the lignin-based modified coating material and a lignin source is used as a coating material, the coating material is placed in a rotating drum coating machine, then a fertilizer core is preheated at 50-120 ℃, the fertilizer core is poured into the rotating drum coating machine after preheating, coating is carried out at normal temperature, preheating-coating is carried out for 2-5 times repeatedly, and finally the product obtained after coating is subjected to heat treatment to obtain the coated slow-release fertilizer, wherein the temperature of the heat treatment is 50-120 ℃.
In the application process of the invention, the lignin-based modified coating material is adopted as the coating material, the release period of nutrients can reach an effect of more than 45 days, and certainly, for some application environments, faster release is needed, the hydrophilic lignin source and the hydrophobic lignin-based modified coating material can be mixed, the release efficiency of the fertilizer can be controlled by adjusting the proportion of the hydrophilic lignin source and the hydrophobic lignin-based modified coating material, and the more hydrophilic lignin source is added, so that the more rapid release is realized.
In a preferable scheme, the coating rate of the coated slow-release fertilizer is 5-40%.
In the invention, the coating rate refers to the mass fraction of the coating in the coated slow-release fertilizer.
In a preferred scheme, the lignin-based modified coating material is ground, sieved by a 100-mesh sieve and taken out of the undersize product.
Preferably, the lignin source is at least one selected from lignin, alkali lignin, kaff lignin and lignosulfonate, preferably lignosulfonate, and more preferably sodium lignosulfonate.
Preferably, the lignin source has a particle size <200 mesh.
In a preferable scheme, the fertilizer core is urea, and the particle size of the urea is 3-4 mm.
In the preferred scheme, the lignin-based modified coating material accounts for 60-100% of the mixed coating material in mass ratio.
In a preferable scheme, the preheating time of the fertilizer core is 5min-20 min. Preferably, the rotating speed of the rotary drum coating machine is 40-100 rpm.
Preferably, the time of the heat treatment is 10min-30 min.
Principles and advantages
The lignin-based modified coating material and the preparation method and application thereof have the obvious advantages that the lignin-based modified coating material takes lignin-based materials with wide use sources, low price, good biocompatibility and degradability as modified raw materials, the lignin-based materials are subjected to cross-linking modification and hydrophobic esterification modification in sequence to obtain the coating material with excellent thermoplasticity, the coating material is applied to the coating of the slow-release fertilizer, the coating rate of the obtained coated slow-release fertilizer is 5-40%, the release period of nutrients can reach more than 45 days, and in the application process, the slow-release time of coated urea can be adjusted by adjusting the coating rate and the mixing ratio of the hydrophilic lignin material and the lignin-based modified coating material.
According to the coated slow-release fertilizer, the coating layer only contains lignin base, the fertilizer is continuously degraded into humus, the humus can continuously improve the physical and chemical environment of soil, the water and fertilizer retention capability of the soil is improved, the aim of sustainable utilization of the soil is fulfilled, and the humus is finally degraded into water and carbon dioxide after long-time degradation; in addition, the coating process is simple, uniform coating can be realized by using a rotary drum coating machine and a heating oven, the waste of slow-release materials is reduced, the secondary environmental problem caused by using an organic solvent in the coating process is avoided, the cost of the coating process is reduced, and the method has great application prospect
Drawings
FIG. 1 is a process flow diagram of the preparation method and application of the present invention.
FIG. 2 is a schematic diagram of the coated slow release fertilizer provided by the invention
FIG. 3 is a graph showing the cumulative release of nutrients of the coated slow release fertilizer obtained in example 1
FIG. 4 is a cumulative nutrient release curve of the coated slow release fertilizer obtained in example 2
FIG. 5 is a cumulative nutrient release profile of the coated slow release fertilizer obtained in example 3
Detailed Description
The present invention will be further described with reference to the following examples
Example 1: preparation of lignin modified material coated urea
(1) Crosslinking sodium lignosulfonate: reacting 30% sodium lignosulfonate solution with epoxy chloropropane for 3 hours at 90 ℃ to obtain high molecular weight crosslinked sodium lignosulfonate: the reaction ratio of the epichlorohydrin to the sodium lignosulfonate is 100ul:15g
(2) Hydrophobic esterification modification of cross-linked sodium lignosulfonate: taking cross-linked sodium lignosulfonate and dodecanoyl chloride, reacting for 2 hours at 20 ℃ by using dimethyl formamide (DMF) as a reaction solvent and pyridine as an acid-binding agent to obtain a modified coating material with a glass transition temperature of about 90 ℃: the reaction ratio of DMF, cross-linked sodium lignosulfonate, dodecanoyl chloride and pyridine is 30ml:1g:4ml
(3) Preparing coated urea: grinding the modified coating material at normal temperature, putting modified coating material powder with the particle size less than 100 meshes into a rotary drum coating machine, wherein the rotating speed of the coating machine is 50rpm, and the temperature is room temperature; heating urea granules in a drying oven at 100 ℃ for 10 minutes, and immediately pouring the hot urea granules into a drum coating machine; (II) melting the modified coating material on the surface of the urea particles heated at 100 ℃ and adhering the modified coating material to the surface of the urea particles; (III) the coated urea particles are insulated for 30 minutes in a drying oven at 100 ℃, and the modified material is evenly and smoothly coated on the surfaces of the urea particles. The processes of the steps (I) and (II) are repeated for 3 times, the coating rate is 38.1 percent, 72.9 percent of urea is released in 30 days of the obtained coated urea, 86.37 percent of urea is released in 45 days of the coated urea, and the data are shown in figure 3.
Example 2 preparation of Lignin-based Mixed Material coated Urea
(1) Crosslinking sodium lignosulfonate: reacting 30% sodium lignosulfonate solution with epichlorohydrin for 3 hours at 90 ℃ to obtain high molecular weight crosslinked sodium lignosulfonate: the reaction ratio of the epichlorohydrin to the sodium lignosulfonate is 100ul:15g
(2) Hydrophobic esterification modification of cross-linked sodium lignosulfonate: taking cross-linked sodium lignosulfonate and dodecanoyl chloride, reacting for 2 hours at 20 ℃ by using dimethyl formamide (DMF) as a reaction solvent and pyridine as an acid-binding agent to obtain a modified coating material with a glass transition temperature of about 90 ℃: the reaction ratio of DMF, cross-linked sodium lignosulfonate, dodecanoyl chloride and pyridine is 30ml:1g:4ml
(3) Preparing coated urea: grinding the modified coating material at normal temperature, mixing sodium lignosulfonate smaller than 200 meshes with the modified coating material smaller than 100 meshes, wherein the sodium lignosulfonate: the modified coating material is 1: 9, placing the mixed powder in a rotary drum coating machine, wherein the rotating speed of the coating machine is 50rpm, and the temperature is room temperature; heating urea granules in a drying oven at 100 ℃ for 10 minutes, and immediately pouring the hot urea granules into a drum coating machine; (II) melting the modified coating material on the surface of the urea particles heated at 100 ℃, and adhering the modified coating material to the surface of the urea particles; (III) keeping the temperature of the coated urea granules in a drying box at 100 ℃ for 30 minutes, and uniformly and smoothly coating the modified material on the surfaces of the granules of urea. The processes of the steps (I) and (II) are repeated for 3 times, the coating rate is 37.1 percent, and the obtained coated urea releases 89.4 percent of urea in 16 days, and the data are shown in figure 4.
Example 3 preparation of Lignin-based Mixed Material coated Urea
(1) Crosslinking sodium lignosulfonate: reacting 30% sodium lignosulfonate solution with epichlorohydrin for 3 hours at 90 ℃ to obtain high molecular weight crosslinked sodium lignosulfonate: the reaction ratio of the epichlorohydrin to the sodium lignosulfonate is 100ul:15g
(2) Hydrophobic esterification modification of cross-linked sodium lignosulfonate: taking cross-linked sodium lignosulfonate and dodecanoyl chloride, reacting for 2 hours at 20 ℃ by using dimethyl formamide (DMF) as a reaction solvent and pyridine as an acid-binding agent to obtain a modified coating material with a glass transition temperature of about 90 ℃: the reaction ratio of DMF, cross-linked sodium lignosulfonate, dodecanoyl chloride and pyridine is 30ml:1g:4ml
(3) Preparing coated urea: grinding the modified coating material at normal temperature, mixing sodium lignosulfonate smaller than 200 meshes with the modified coating material smaller than 100 meshes, wherein the sodium lignosulfonate: the modified coating material is 2: 8, placing the mixed powder in a rotary drum coating machine, wherein the rotating speed of the coating machine is 50rpm, and the temperature is room temperature; heating urea granules in a drying oven at 100 ℃ for 10 minutes, and immediately pouring the hot urea granules into a drum coating machine; (II) melting the modified coating material on the surface of the urea particles heated at 100 ℃ and adhering the modified coating material to the surface of the urea particles; (III) the coated urea particles are insulated for 30 minutes in a drying oven at 100 ℃, and the modified material is evenly and smoothly coated on the surfaces of the urea particles. The processes of the steps (I) and (II) are repeated for 3 times, the coating rate is 36.4 percent, and the obtained coated urea releases 89.82 percent of urea in 7 days, and the data are shown in figure 5.
Comparative example 1 Hydrophobically modified coated urea with sodium lignosulfonate
Compared with the example 1, the step (1) is not carried out;
(1) hydrophobic esterification modification of sodium lignosulfonate: taking cross-linked sodium lignosulfonate and dodecanoyl chloride, reacting for 2 hours at 20 ℃ by using dimethyl formamide (DMF) as a reaction solvent and pyridine as an acid-binding agent to obtain a modified coating material with a glass transition temperature of about 90 ℃: the reaction ratio of DMF, cross-linked sodium lignosulfonate, dodecanoyl chloride and pyridine is 30ml:1g:4ml
(2) Preparing coated urea: when the modified coating material is ground at normal temperature, the material has high viscosity and cannot be ground, so that coating cannot be completed, and coating fails.
Comparative example 2 aqueous modified coated urea with organic lignin
Compared with the example 1, the lignin source is changed into dioxane extracted organic lignin, the Mw is about 2000, and the step (1) is not carried out;
1) and (3) hydrophobic esterification modification of organic lignin: taking cross-linked sodium lignosulfonate and dodecanoyl chloride, reacting for 2 hours at 20 ℃ by using dimethyl formamide (DMF) as a reaction solvent and pyridine as an acid-binding agent to obtain a modified coating material with a glass transition temperature of about 90 ℃: the reaction ratio of DMF, cross-linked sodium lignosulfonate, dodecanoyl chloride and pyridine is 30ml:1g:4ml
(2) Preparing coated urea: when the modified coating material is ground at normal temperature, the material is in a sticky elastic state and cannot be ground, so that coating cannot be completed, and coating fails.
Claims (7)
1. A preparation method of a lignin-based modified coating material is characterized by comprising the following steps: the method comprises the following steps: performing a crosslinking reaction on a lignin source and a crosslinking agent to obtain crosslinked lignin, and performing an esterification reaction on the crosslinked lignin and an esterifying agent to obtain a lignin-based modified coating material;
the lignin source is selected from at least one of lignin, alkali lignin, kafu lignin and lignosulfonate, and the crosslinking agent is selected from at least one of epichlorohydrin, formaldehyde and glutaraldehyde sebacic diacid;
the liquid-solid volume mass ratio of the cross-linking agent to the lignin source is 100uL:10-20 g; the temperature of the cross-linking reaction is 80-100 ℃, and the time of the cross-linking reaction is 2-10 h;
adding cross-linked lignin and an esterifying agent into an organic solvent for esterification reaction, and simultaneously adding pyridine as an acid-binding agent; the esterifying agent is at least one of acetyl chloride, propionyl chloride, hexanoyl chloride, dodecanoyl chloride and hexadecanoyl chloride; the temperature of the esterification reaction is 20-40 ℃, and the time of the esterification reaction is 1-10 h; the liquid-solid volume mass ratio of the esterifying agent to the cross-linked lignin is 4ml:0.5-2 g; the solid-liquid mass volume ratio of the cross-linked lignin to the pyridine is 0.5-2 g:4 ml.
2. The method for preparing the lignin-based modified coating material according to claim 1, wherein the method comprises the following steps: the glass transition temperature of the lignin-based modified coating material is 50-90 ℃.
3. The method for preparing the lignin-based modified coating material according to claim 1 or 2, wherein: the method comprises the following steps:
step one
Mixing a solution containing sodium lignosulfonate with epichlorohydrin, then carrying out crosslinking reaction at 80-100 ℃ to obtain crosslinked lignin, wherein the crosslinking reaction time is 2-4h, the liquid-solid volume mass ratio of the epichlorohydrin crosslinking agent to a lignin source of sodium lignosulfonate is 100uL:10-20g,
step two
Mixing the cross-linked lignin obtained in the step one, dodecanoyl chloride, pyridine and dimethylformamide, and carrying out esterification reaction at 20-40 ℃ for 1-3h to obtain a lignin-based modified coating material; the liquid-solid volume mass ratio of the lauroyl chloride to the cross-linked lignin is 4ml:0.5-2 g; the solid-liquid mass volume ratio of the cross-linked sodium lignosulfonate to the pyridine is 0.5-2 g:4 ml.
4. A lignin-based modified coating material obtained by the production method according to any one of claims 1 to 3.
5. The use of the lignin-based modified coating material according to claim 4, wherein: taking a lignin-based modified coating material as a coating material, or taking a mixed material obtained by mixing the lignin-based modified coating material with a lignin source as a coating material, placing the coating material in a rotating drum coating machine, preheating a fertilizer core at 50-120 ℃, pouring the preheated fertilizer core into the drum coating machine, coating at normal temperature, repeatedly preheating and coating for 2-5 times, and finally carrying out heat treatment on a coated product to obtain a coated slow-release fertilizer, wherein the heat treatment temperature is 50-120 ℃; the coating rate of the coated slow-release fertilizer is 5-40%.
6. The use of the lignin-based modified coating material according to claim 5, wherein: grinding the lignin-based modified coating material, sieving with a 100-mesh sieve, and taking undersize; the particle size of the lignin source is <200 mesh;
the fertilizer core is urea, and the particle size of the urea is 3-4 mm; in the mixed coating material, the lignin-based modified coating material accounts for 60-100% of the mixed coating material in terms of mass ratio.
7. The use of the lignin-based modified coating material according to claim 5, wherein: the preheating time of the fertilizer core is 5min-20min, the rotating speed of the rotary drum coating machine is 40-100rpm, and the heat treatment time is 10min-30 min.
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| CN113582770A (en) * | 2021-08-12 | 2021-11-02 | 吉林隆源农业服务有限公司 | Slow-release long-acting compound fertilizer for corn planting and preparation method thereof |
| CN115322045A (en) * | 2022-07-21 | 2022-11-11 | 中南林业科技大学 | Modified lignin/biochar coated slow-release fertilizer and preparation method and application thereof |
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