CN111995456B - Agricultural chitosan oligosaccharide, fertilizer and preparation method thereof - Google Patents

Agricultural chitosan oligosaccharide, fertilizer and preparation method thereof Download PDF

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CN111995456B
CN111995456B CN202010936643.2A CN202010936643A CN111995456B CN 111995456 B CN111995456 B CN 111995456B CN 202010936643 A CN202010936643 A CN 202010936643A CN 111995456 B CN111995456 B CN 111995456B
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chitosan oligosaccharide
agricultural
chitosan
enzymolysis
fertilizer
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CN111995456A (en
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韩国涛
于景晴
班宜民
张兴华
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Shandong Aiguozhi Biotechnology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05CNITROGENOUS FERTILISERS
    • C05C3/00Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05DINORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D1/00Fertilisers containing potassium
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05FORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F17/00Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
    • C05F17/20Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation using specific microorganisms or substances, e.g. enzymes, for activating or stimulating the treatment
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES 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
    • C05G5/00Fertilisers characterised by their form
    • C05G5/10Solid or semi-solid fertilisers, e.g. powders
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES 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
    • C05G5/00Fertilisers characterised by their form
    • C05G5/20Liquid fertilisers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/40Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Tropical Medicine & Parasitology (AREA)
  • Engineering & Computer Science (AREA)
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  • Biotechnology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Molecular Biology (AREA)
  • Inorganic Chemistry (AREA)
  • Fertilizers (AREA)

Abstract

The invention relates to a preparation method of chitosan oligosaccharide and fertilizer for agriculture, which is characterized in that chitosan oligosaccharide is obtained by enzymolysis of chitosan in an acid environment by lysozyme, and the chitosan oligosaccharide is added into the fertilizer to obtain the chitosan oligosaccharide fertilizer.

Description

Agricultural chitosan oligosaccharide, fertilizer and preparation method thereof
Technical Field
The invention relates to agricultural chitosan oligosaccharide, a fertilizer and a preparation method thereof.
Background
At present, enzymatic extraction of chitosan oligosaccharide mostly adopts cellulase, however, cellulase is a general name of a group of enzymes for degrading cellulose to produce glucose, is not a monomer enzyme, is a synergistic multi-component enzyme system, is a complex enzyme, mainly comprises exo-beta-glucanase, endo-beta-glucanase, beta-glucosidase and the like, and has the action principle that the endo-glucanase randomly cuts amorphous regions in cellulose polysaccharide chains to generate oligosaccharides with different lengths and ends of new chains, the exo-glucanase acts on the ends of the reductive and non-reductive cellulose polysaccharide chains to release glucose or cellobiose, and the beta-glucosidase hydrolyzes cellobiose to generate two molecules of glucose.
The cellulase generally used for production is from fungi, and typically, Trichoderma (Trichoderma), Aspergillus (Aspergillus) and Penicillium (Penicillium), the crude enzyme solution of paecilomyces lilacinus originally used by the company and papain carry out combined enzymolysis on chitosan in an acid environment, the crude enzyme solution of paecilomyces lilacinus is actually cellulase, the enzymolysis of the cellulase is combined enzymolysis of several enzymes because the cellulase is complex enzyme, and the cooperation of several enzymes is needed, however, the crude enzyme solution of paecilomyces lilacinus is influenced by a culture environment, the mass ratio among exo beta-glucanase, endo beta-glucanase and beta-glucosidase in the crude enzyme prepared each time is not stable, and therefore, the quality of chitosan oligosaccharide finally prepared by enzymolysis is also not stable, and the patent number of the company is CN 106755208. The hydrogen peroxide is adopted to oxidize the chitosan, two groups which are easy to oxidize exist in the chitosan and are respectively a hydroxyl group and a beta-1, 4 glycosidic bond, the hydroxyl group is oxidized into an aldehyde group by oxidizing the hydroxyl group, the carboxylic group is further oxidized by the aldehyde group, and the oligosaccharide is decomposed by acting on the beta-1, 4 glycosidic bond, so that unstable factors exist in the product, even the chitosan oxidized by the hydrogen peroxide is insoluble in water and needs to be filtered, the waste is caused, and the production cost is increased.
Since the organic acid is prepared in an acidic environment, the organic acid is a risk in a solution, in the case of succinic acid, a small amount of succinic acid promotes the growth of crops, but the application amount of succinic acid is large, so that the growth of crops is inhibited, the product is required to be diluted and used, the product popularization of a company is troublesome, the organic acid and chitosan oligosaccharide are mutually dissolved, the organic acid is difficult to separate from the chitosan oligosaccharide, and the problem of enzymolysis in the acidic environment and final organic acid residue is not solved at present.
The ortho positions of free amino groups of chitosan and chitosan oligosaccharide are hydroxyl groups, so that the chitosan and chitosan oligosaccharide chelating divalent metal ions are high-performance metal ion trapping agents, the chitosan and chitosan oligosaccharide chelating agents react with divalent metal ions to generate water-insoluble macromolecular chelating salt, flocculent precipitates are formed, and plant absorption is not facilitated, so that the problem of poor compatibility with medium trace elements exists, in order to improve the compatibility with the divalent metal ions, the pH value is usually adjusted to be below 5, the chitosan oligosaccharide and the divalent metal ions coexist in an acidic environment, however, the acidic environment is not conducive to plant growth, and the problem that the chitosan oligosaccharide and the divalent metal ions precipitate in a neutral environment and are not conducive to plant absorption is not solved.
Disclosure of Invention
The invention provides agricultural chitosan oligosaccharide, a fertilizer and a preparation method thereof, and solves the technical problems that 1) the quality of a product is unstable by using cellulase enzymolysis; 2) hydrogen peroxide is used for hydrolysis, and hydrolysis products are uncontrollable, so that waste is caused to chitosan; 3) organic acid residues after enzymolysis affect the using effect of the product; 4) has poor compatibility with medium and trace elements, and is not beneficial to the absorption of the medium and trace elements by plants.
In order to solve the technical problems, the invention adopts the following technical scheme:
the chitosan is subjected to enzymolysis by lysozyme in an acidic environment to obtain chitosan oligosaccharide enzymatic hydrolysate for agriculture; or
And drying the agricultural chitosan oligosaccharide enzymolysis liquid to obtain the agricultural chitosan oligosaccharide for enzymolysis.
The acid environment comprises water, water-soluble unsaturated dibasic organic acid or water-soluble unsaturated dibasic organic acid anhydride and ammonium ions; the pH value of the acidic environment is 4.0-5.5;
the enzymolysis lasts for 6-48 h, and the enzymolysis temperature is 30-60 ℃;
the mass ratio of the chitosan to the acid environment to the lysozyme is 1-10: 89.9-98.9: 0.1-1.
The mass ratio of water, water-soluble unsaturated dibasic organic acid or water-soluble unsaturated dibasic organic acid anhydride and ammonium ions in the acidic environment is 60-92: 6.5-39: 1-8.
The enzymolysis time is 10-72 h; the water is distilled water or deionized water;
further reaction is also included, the further reaction is carried out according to the following steps:
heating the chitosan oligosaccharide enzymolysis liquid under certain conditions;
adding alkali for hydrolysis to obtain chitosan oligosaccharide hydrolysate for agriculture; or
Drying the agricultural chitosan oligosaccharide hydrolysate to obtain hydrolyzed agricultural chitosan oligosaccharide;
the alkali is one or more of sodium hydroxide, potassium hydroxide and their water solution.
The certain conditions are that the pressure is 3 atm-45 atm, the heating temperature is 130-280 ℃, and the heating time is 20-60 min.
The mass ratio of the alkali to the chitosan oligosaccharide enzymolysis liquid is 2-40: 60-98; the hydrolysis time is 2-30 min.
The preparation method of the fertilizer comprises the steps of adding fertilizer raw materials into the chitosan oligosaccharide enzymolysis liquid for agriculture to obtain a liquid fertilizer containing chitosan oligosaccharide; or
Uniformly mixing a fertilizer raw material and chitosan oligosaccharide for enzymolysis agriculture to obtain a fertilizer containing the chitosan oligosaccharide; or
Adding fertilizer raw materials into the chitosan oligosaccharide hydrolysate for agriculture to obtain a liquid fertilizer containing chitosan oligosaccharide; or
And (3) uniformly mixing the fertilizer raw material and the chitosan oligosaccharide for hydrolysis agriculture to obtain the fertilizer containing the chitosan oligosaccharide.
Also comprises adding one or more of water, biostimulant and microorganism.
Also comprises the steps of mixing uniformly and granulating.
The invention has the following beneficial technical effects:
1. the chitosan oligosaccharide quality of this application preparation is stable, and this application utilizes lysozyme to destroy beta-1, 4 glycosidic bond between the chitosan, makes the chitosan enzymolysis, and lysozyme in this application is a single enzyme, and the stable quality does not need the cooperation between the various enzymes, consequently, can make the chitosan oligosaccharide quality of this application more stable.
2. The enzymolysis product is controllable, lysozyme only destroys beta-1, 4 glycosidic bonds between chitosan, and the lysozyme can not oxidize beta-1, 4 glycosidic bonds and hydroxyl groups like hydrogen peroxide, so that the quality of the final product is unstable, and even water-insoluble substances are generated, and the chitosan is required to be filtered, thereby causing waste.
3. The application does not need to separate out residual organic acid, and when the application is carried out by a user, the application has no side effect even if the application is not diluted according to requirements.
4. The water-soluble unsaturated dibasic organic acid or the water-soluble unsaturated dibasic organic acid anhydride reacts with ammonium ions to generate, unsaturated amic acid, under certain pressure and temperature, the unsaturated amic acid is thermally polymerized to generate polyimide, the polyimide is hydrolyzed to obtain polyamino acid salt, the polyamino acid salt has better chelation property, and is chelated with metal cations, so that no precipitate can be generated, meanwhile, the metal cations and the chitosan oligosaccharide can be prevented from reacting to generate precipitate, and the compatibility of the chitosan oligosaccharide and the fertilizer is improved.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
The agricultural chitosan oligosaccharide enzymolysis liquid is prepared by carrying out enzymolysis on chitosan for 12 hours by lysozyme at the temperature of 45 ℃ in an acidic environment; or
And drying the agricultural chitosan oligosaccharide enzymolysis liquid to obtain the agricultural chitosan oligosaccharide for enzymolysis.
The acid environment is obtained by mixing deionized water, maleic acid and ammonium bicarbonate according to the mass ratio of 62:20:18, adding 5% of sodium hydroxide after mixing, and adjusting the pH value to 4.5;
the mass ratio of the chitosan, the acidic environment and the lysozyme is 6:93.7: 0.3.
Example 2
The agricultural chitosan oligosaccharide enzymolysis liquid is prepared by carrying out enzymolysis on chitosan for 12 hours by lysozyme at the temperature of 45 ℃ in an acidic environment; or
And drying the agricultural chitosan oligosaccharide enzymolysis liquid to obtain the agricultural chitosan oligosaccharide for enzymolysis.
The acid environment is obtained by mixing deionized water, maleic acid and ammonium bicarbonate according to the mass ratio of 62:20:18, adding 5% of sodium hydroxide after mixing, and adjusting the pH value to 4.5;
the mass ratio of the chitosan, the acidic environment and the lysozyme is 6:93.7: 0.3.
Example 3
The agricultural chitosan oligosaccharide enzymolysis liquid is prepared by carrying out enzymolysis on chitosan for 12 hours by lysozyme at the temperature of 45 ℃ in an acidic environment; or
And drying the agricultural chitosan oligosaccharide enzymolysis liquid to obtain the agricultural chitosan oligosaccharide for enzymolysis.
The acid environment is obtained by mixing deionized water, maleic acid and ammonium bicarbonate according to the mass ratio of 62:20:18, adding 5% of sodium hydroxide after mixing, and adjusting the pH value to 4.5;
the mass ratio of the chitosan, the acidic environment and the lysozyme is 6:93.7: 0.3.
Further reaction is also included, the further reaction is carried out according to the following steps:
reacting for 30min under the conditions that the pressure is 11atm and the temperature is 180 ℃;
adding potassium hydroxide, and hydrolyzing to obtain agricultural chitosan oligosaccharide hydrolysate; or
And drying the agricultural chitosan oligosaccharide hydrolysate to obtain the hydrolyzed agricultural chitosan oligosaccharide.
The mass ratio of the potassium hydroxide to the chitosan oligosaccharide enzymolysis liquid is 2: 98; the hydrolysis time was 10 min.
Example 4
Agricultural chitosan oligosaccharide is prepared by performing enzymolysis on chitosan in acid environment at 30 deg.C for 26 hr with lysozyme to obtain agricultural chitosan oligosaccharide enzymolysis solution
And drying the agricultural chitosan oligosaccharide enzymolysis liquid to obtain the agricultural chitosan oligosaccharide for enzymolysis.
The acid environment is obtained by mixing deionized water, pentenoic acid anhydride and ammonium sulfate according to the mass ratio of 86:8:6, adding 5% of sodium hydroxide after mixing, and adjusting the pH value to 4.2;
the mass ratio of the chitosan, the acidic environment and the lysozyme is 8:91.6: 0.4.
Further reaction is also included, the further reaction is carried out according to the following steps:
reacting for 20min under the conditions that the pressure is 28atm and the temperature is 230 ℃;
adding 8% potassium hydroxide water solution, and hydrolyzing to obtain chitosan oligosaccharide hydrolysate for agriculture; or
And drying the agricultural chitosan oligosaccharide hydrolysate to obtain the hydrolyzed agricultural chitosan oligosaccharide.
The mass ratio of the 8 percent potassium hydroxide aqueous solution to the chitosan oligosaccharide enzymolysis liquid is 25: 75; the hydrolysis time was 3 min.
Adding urea into the chitosan oligosaccharide enzymatic hydrolysate for agriculture to obtain a liquid fertilizer containing chitosan oligosaccharide; or
Uniformly mixing urea and chitosan oligosaccharide for enzymolysis agriculture to obtain a fertilizer containing chitosan oligosaccharide; or
Adding urea into the agricultural chitosan oligosaccharide hydrolysate to obtain a liquid fertilizer containing chitosan oligosaccharide; or
And (3) uniformly mixing urea and the chitosan oligosaccharide for hydrolysis agriculture to obtain the fertilizer containing the chitosan oligosaccharide.
Example 5
Agricultural chitosan oligosaccharide is prepared by performing enzymolysis on chitosan in acid environment at 50 deg.C for 24 hr with lysozyme to obtain agricultural chitosan oligosaccharide enzymolysis solution
And drying the agricultural chitosan oligosaccharide enzymolysis liquid to obtain the agricultural chitosan oligosaccharide for enzymolysis.
The acid environment is obtained by mixing distilled water, maleic anhydride and ammonium sulfate according to the mass ratio of 73:15:12, adding 5% of sodium hydroxide after mixing, and adjusting the pH value to 4.2;
the mass ratio of the chitosan, the acidic environment and the lysozyme is 3:96.9: 0.1.
Further reaction is also included, the further reaction is carried out according to the following steps:
reacting for 40min under the conditions that the pressure is 10atm and the temperature is 160 ℃;
adding 10% sodium hydroxide aqueous solution, and hydrolyzing to obtain agricultural chitosan oligosaccharide hydrolysate; or
And drying the agricultural chitosan oligosaccharide hydrolysate to obtain the hydrolyzed agricultural chitosan oligosaccharide.
The mass ratio of the 10 percent sodium hydroxide aqueous solution to the chitosan oligosaccharide enzymolysis solution is 21: 79; the hydrolysis time was 3 min.
Adding the agricultural chitosan oligosaccharide enzymolysis liquid into urine, spraying slurry, granulating and drying to obtain urea containing chitosan oligosaccharide; or
Adding chitosan oligosaccharide for enzymolysis agriculture into a water-soluble fertilizer raw material, and uniformly mixing to obtain a water-soluble fertilizer containing chitosan oligosaccharide; or
Adding the agricultural chitosan oligosaccharide hydrolysate into urine, spraying, granulating and drying to obtain urea containing chitosan oligosaccharide; or
Adding the chitosan oligosaccharide for hydrolysis agriculture into urine, mixing uniformly, spraying slurry, granulating, and drying to obtain the fertilizer containing chitosan oligosaccharide.
Example 6
Agricultural chitosan oligosaccharide is prepared by performing enzymolysis on chitosan in acid environment at 35 deg.C for 36 hr with lysozyme to obtain agricultural chitosan oligosaccharide enzymolysis solution
And drying the agricultural chitosan oligosaccharide enzymolysis liquid to obtain the agricultural chitosan oligosaccharide for enzymolysis.
The acid environment is obtained by mixing deionized water, maleic anhydride, glutaconic acid, monoammonium phosphate and ammonium sulfate according to the mass ratio of 74:5:8:3:10, adding 5% of sodium hydroxide after mixing, and adjusting the pH value to 5.0;
the mass ratio of the chitosan, the acidic environment and the lysozyme is 7:92.8: 0.2.
Further reaction is also included, the further reaction is carried out according to the following steps:
reacting for 40min under the conditions that the pressure is 40atm and the temperature is 260 ℃;
adding 12% potassium hydroxide water solution, and hydrolyzing to obtain chitosan oligosaccharide hydrolysate for agriculture; or
And drying the agricultural chitosan oligosaccharide hydrolysate to obtain the hydrolyzed agricultural chitosan oligosaccharide.
The mass ratio of the 12 percent sodium hydroxide aqueous solution to the chitosan oligosaccharide enzymolysis solution is 20: 80; the hydrolysis time was 3 min.
Adding the agricultural chitosan oligosaccharide enzymolysis liquid into slurry of monoammonium phosphate and potassium hydrogen sulfate, and carrying out guniting granulation and drying to obtain a guniting compound fertilizer containing chitosan oligosaccharide; or
Uniformly mixing chitosan oligosaccharide for enzymolysis agriculture, potassium sulfate, monoammonium phosphate, ammonium sulfate and urea, and granulating by using a roller to obtain a compound fertilizer containing chitosan oligosaccharide; or
Adding the agricultural chitosan oligosaccharide hydrolysate into an organic inorganic fertilizer to obtain the organic inorganic fertilizer containing chitosan oligosaccharide; or
Adding chitosan oligosaccharide for hydrolysis agriculture into a biological organic fertilizer raw material, uniformly mixing, granulating, and drying to obtain the biological organic fertilizer containing chitosan oligosaccharide.
Example 7
Agricultural chitosan oligosaccharide is prepared by performing enzymolysis on chitosan in acid environment at 50 deg.C for 24 hr with lysozyme to obtain agricultural chitosan oligosaccharide enzymolysis solution
And drying the agricultural chitosan oligosaccharide enzymolysis liquid to obtain the agricultural chitosan oligosaccharide for enzymolysis.
The acid environment is obtained by mixing distilled water, maleic anhydride and ammonium sulfate according to the mass ratio of 73:15:12, adding 5% of sodium hydroxide after mixing, and adjusting the pH value to 5.0;
the mass ratio of the chitosan, the acidic environment and the lysozyme is 3:96.9: 0.1.
Further reaction is also included, the further reaction is carried out according to the following steps:
reacting for 40min under the conditions that the pressure is 10atm and the temperature is 160 ℃;
adding 10% sodium hydroxide aqueous solution, and hydrolyzing to obtain agricultural chitosan oligosaccharide hydrolysate; or
And drying the agricultural chitosan oligosaccharide hydrolysate to obtain the hydrolyzed agricultural chitosan oligosaccharide.
The mass ratio of the 10 percent sodium hydroxide aqueous solution to the chitosan oligosaccharide enzymolysis solution is 21: 79; the hydrolysis time was 3 min.
Adding ammonium nitrate calcium into the agricultural chitosan oligosaccharide hydrolysate to obtain agricultural chitosan oligosaccharide calcium; or
And (3) uniformly mixing the hydrolyzed agricultural chitosan oligosaccharide and ammonium nitrate calcium to obtain the agricultural chitosan oligosaccharide calcium.
The beneficial effects of the present invention are further illustrated below in conjunction with experimental data:
experiment one
Test material
1, materials and methods:
1.1 test site: hipport fruit Biotech Co., Ltd.
1.2 test detection: content of chitosan oligosaccharide.
1.3 test materials: comparative example 1 (except that lysozyme was replaced by cellulase, the preparation method was the same as that of example 1), comparative example 2 (except that the preparation process of chitosan oligosaccharide produced originally by this company was the same as that of example 3 in CN 106755208, the other experimental treatments were the same as that of example 1), and agricultural chitooligosaccharide enzymatic hydrolysates obtained in examples 1 and 2 were obtained.
1.4 Experimental implementation: the method comprises the steps of performing parallel experiments for three times respectively aiming at different batches of crude enzyme liquid and lysozyme of paecilomyces lilacinus provided by the same manufacturer, wherein the activities of the crude enzyme liquid and the lysozyme of the paecilomyces lilacinus are both 1000 wu/g, and detecting the content of chitosan oligosaccharide in each experiment.
The method is consistent with other management methods except different processing.
2 results and analysis
The content (%) of chitosan oligosaccharide is shown in Table 1.
TABLE 1
Chitosan oligosaccharide content (%)
Comparative example 1 Sample 1 5.1
Sample 2 4.6
Sample 3 4.3
Comparative example 2 Sample 1 4.7
Sample 2 4.2
Sample 3 3.8
Example 1 Sample 1 5.3
Sample 2 5.4
Sample 3 5.2
Example 2 Sample 1 5.7
Sample 2 5.8
Sample 3 5.9
As can be seen from the comparison of the data of comparative examples 1 and 2 and example 1, the quality of comparative examples 1 and 2 is not stable, but the quality of example 1 of the present application is stable.
As can be seen from the data of example 1 and example 2, the content of chitosan oligosaccharide in example 2 using deionized water was high.
Experiment two
Test material
1, materials and methods:
1.1 test site: hipport fruit Biotech Co., Ltd.
1.2 test detection: the experimental phenomenon was observed.
1.3 test materials: example 2 and example 3, and the pH of example 2 and example 3 were adjusted to 6.5.
1.4 Experimental implementation: 2 parts of 5% calcium nitrate solution were prepared, each 100ml, 100ml of each of the samples prepared in examples 2 and 3 were taken, 1 part of the calcium nitrate solution was mixed with example 2, and one part of the calcium nitrate solution was mixed with example 3, and the mixture was allowed to stand for 1 hour.
The method is consistent with other management methods except different processing.
2 results and analysis
The experimental phenomena are shown in Table 2
TABLE 2
Experimental phenomena
Example 2 Bottom with flocculation
Example 3 No flocculation generation
As can be seen from Table 2, example 3 can increase the compatibility of chitosan oligosaccharide for agriculture by further reaction, thus being beneficial to the absorption of trace elements in plants and reducing phytoalexin deficiency.
Experiment three
Test material
1, materials and methods:
1.1 test site: hipport fruit Biotech Co., Ltd.
1.2 test detection: average height (cm) of corn before treatment, average height (cm) of corn 10 days after treatment and experimental phenomenon.
1.3 test materials: blank (water), comparative 2 (chitosan oligosaccharide originally produced by this company, except for the preparation process according to the preparation method of example 3 in CN 106755208, other experimental treatments are consistent with example 1 of this application), example 2 and example 3.
1.4 Experimental implementation: the corn seedlings were divided into 4 experimental cells and 20 cells in each cell, and the corn seedlings were sprayed with 200ml of the treatment solution in each treatment, respectively, in comparative example 2, example 3 and blank after dilution, respectively, in example 2 (chitosan oligosaccharide originally produced by this enterprise, except for the preparation process according to the preparation method of example 3 in CN 106755208, other experimental treatments were identical to those in example 1 of this application), example 2 and example 3 were diluted by 100 times, respectively.
The method is consistent with other management methods except different processing.
2 results and analysis
The heights of the corn before and after the experimental treatment and the experimental phenomena are shown in Table 3
TABLE 3
Average height (cm) of corn before treatment Average height (cm) of corn after treatment Experimental phenomena
Blank space 12.3 17.6 The plant grows normally, and the leaves are light green
Comparative example 2 12.4 12.6 The leaves of the plants become yellow and dwarf
Example 2 12.5 12.7 The leaves of the plants become yellow and dwarf
Example 3 12.2 18.3 The plant grows normally and the leaves are dark green
As can be seen from Table 3, comparative example 2 and example 2 did not treat the organic acid in the chitosan oligosaccharide enzymatic hydrolysate for agricultural use, and therefore, when the chitosan oligosaccharide enzymatic hydrolysate for agricultural use was used, phytotoxicity may occur if the chitosan oligosaccharide enzymatic hydrolysate for agricultural use was diluted improperly, whereas example 3 treated the chitosan oligosaccharide enzymatic hydrolysate for agricultural use, so that the water-soluble unsaturated dibasic organic acid or the water-soluble unsaturated dibasic organic acid anhydride finally forms the polymeric amino acid, which not only increases the compatibility of the chitosan oligosaccharide for agricultural use, but also does not cause phytotoxicity due to improper dilution.

Claims (4)

1. A preparation method of chitosan oligosaccharide for agriculture is characterized in that chitosan is subjected to enzymolysis through lysozyme in an acid environment to obtain chitosan oligosaccharide enzymolysis liquid for agriculture, the chitosan oligosaccharide enzymolysis liquid for agriculture is heated under a certain condition, and alkali is added for hydrolysis to obtain chitosan oligosaccharide hydrolysis liquid for agriculture;
drying the agricultural chitosan oligosaccharide hydrolysate to obtain hydrolyzed agricultural chitosan oligosaccharide;
the acid environment is obtained by mixing deionized water, maleic acid and ammonium bicarbonate according to the mass ratio of 62:20:18, adding 5% of sodium hydroxide after mixing, and adjusting the pH value to 4.5;
the enzymolysis is carried out for 6-48 h at the temperature of 30-60 ℃;
the mass ratio of the chitosan to the acid environment to the lysozyme is 6:93.7: 0.3;
the water is distilled water or deionized water;
the alkali is one or more of sodium hydroxide, potassium hydroxide and their water solution;
the certain condition is that the pressure is 11atm, the heating temperature is 180 ℃, and the heating time is 30 min;
the mass ratio of the alkali to the chitosan oligosaccharide enzymolysis liquid is 2-40: 60-98; the hydrolysis time is 2-30 min.
2. A method for preparing chitosan oligosaccharide fertilizer for agriculture is characterized in that,
adding fertilizer raw materials into the agricultural chitosan oligosaccharide hydrolysate as claimed in claim 1 to obtain a liquid fertilizer containing chitosan oligosaccharide; or
Uniformly mixing a fertilizer raw material and the hydrolyzed agricultural chitosan oligosaccharide as claimed in claim 1 to obtain the fertilizer containing chitosan oligosaccharide.
3. The method of preparing a fertilizer comprising chitosan oligosaccharide for agricultural use according to claim 2, further comprising adding one or more of water, biostimulant and microorganism.
4. The method for producing a fertilizer containing chitosan oligosaccharide for agricultural use according to claim 2 or 3, further comprising granulating after the mixing.
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