CN113816810B - Polyaspartic acid liquid water-soluble fertilizer for preventing and treating physiological diseases of northern deciduous fruit trees and preparation method thereof - Google Patents

Polyaspartic acid liquid water-soluble fertilizer for preventing and treating physiological diseases of northern deciduous fruit trees and preparation method thereof Download PDF

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CN113816810B
CN113816810B CN202111196386.4A CN202111196386A CN113816810B CN 113816810 B CN113816810 B CN 113816810B CN 202111196386 A CN202111196386 A CN 202111196386A CN 113816810 B CN113816810 B CN 113816810B
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polyaspartic acid
soluble fertilizer
water
liquid water
fruit trees
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CN113816810A (en
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焦永康
于雪松
吴学强
赵龙梅
李文曦
范占权
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Hebei Xieli Chemical Co ltd
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    • 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
    • C05G5/23Solutions
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05BPHOSPHATIC FERTILISERS
    • C05B7/00Fertilisers based essentially on alkali or ammonium orthophosphates
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05CNITROGENOUS FERTILISERS
    • C05C5/00Fertilisers containing other nitrates
    • C05C5/02Fertilisers containing other nitrates containing sodium or potassium nitrate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1092Polysuccinimides

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Abstract

The invention discloses a polyaspartic acid liquid water-soluble fertilizer for preventing and treating physiological diseases of northern deciduous fruit trees, which comprises polyaspartic acid with weight average molecular weight of 1000-2000D and interval distribution rate of not less than 90% obtained by hydrolyzing polysuccinimide under the catalysis of endopeptidase at 45-75 ℃. The polyaspartic acid liquid water-soluble fertilizer with obvious prevention and treatment effects on physiological diseases of deciduous fruit trees is obtained by reasonably controlling hydrolysis conditions to obtain polyaspartic acid which can stably and effectively promote nutrient elements to be absorbed in the growth process of deciduous fruit trees and is used as a main agent or a synergistic auxiliary agent of the water-soluble fertilizer.

Description

Polyaspartic acid liquid water-soluble fertilizer for preventing and treating physiological diseases of northern deciduous fruit trees and preparation method thereof
Technical Field
The invention relates to the technical field of water-soluble fertilizers, in particular to a polyaspartic acid liquid water-soluble fertilizer for preventing and treating physiological diseases of northern deciduous fruit trees and a preparation method of the water-soluble fertilizer.
Background
The water-soluble fertilizer refers to a compound fertilizer containing nutrients such as nitrogen, phosphorus, potassium, calcium, magnesium, trace elements, amino acids, humic acid, alginic acid and the like which can be completely dissolved in water, and the nutrient content is divided into a macroelement water-soluble fertilizer, a medium element water-soluble fertilizer, a trace element water-soluble fertilizer, an amino acid-containing water-soluble fertilizer, a humic acid-containing water-soluble fertilizer, an organic water-soluble fertilizer and the like. The water-soluble fertilizer is used as an important component of agricultural fertilizer, is mainly used for foliage spraying, spray (drip) irrigation, flushing and the like, and can supplement nutrient elements needed urgently in the key period of crop growth. With the development of the national water-saving engineering and the development of the water-fertilizer integrated technology, the production scale of the domestic water-soluble fertilizer is changed every year, and the production scale of the domestic water-soluble fertilizer is only 30 ten thousand tons in 2009, and is close to 370 ten thousand tons in 2015, so that the water-soluble fertilizer is popularized and applied on a large scale. Besides scale expansion, the water-soluble fertilizer in China is gradually developed from single mineral nutrition water-soluble fertilizer to diversification, specialization and synergism.
Polyaspartic acid, which is a world-accepted green chemical, has been widely used in the field of agricultural fertilizer synergism, but has not been reported in detail in the field of direct application to physiological diseases of fruit trees. The existing polyaspartic acid in the market has scattered molecular weight distribution, uneven absorption rate and uneven effect, which is contrary to the characteristic of rapid absorption and high utilization rate of water-soluble fertilizers, so that the polyaspartic acid with obvious synergism in conventional fertilizers (urea, compound fertilizers and the like) is limited in application in the water-soluble fertilizers.
Disclosure of Invention
The polyaspartic acid liquid water-soluble fertilizer is prepared by hydrolyzing specific raw materials under specific conditions, and the polyaspartic acid with specific molecular weight range is used as a main agent or a synergistic auxiliary agent of the water-soluble fertilizer, so that the water-soluble fertilizer can play a role in preventing and treating physiological diseases of northern deciduous fruit trees stably and efficiently.
In order to achieve the aim, the polyaspartic acid liquid water-soluble fertilizer for preventing and controlling physiological diseases of northern deciduous fruit trees provided by the invention comprises the following components:
polyaspartic acid with weight average molecular weight of 1000-2000D and interval distribution rate not lower than 90% is obtained by hydrolyzing polysuccinimide under the catalysis of endopeptidase at 45-75 ℃.
As a limitation to the above technical scheme, the polyaspartic acid is prepared by the following method:
taking polysuccinimide as a main raw material, adding water, fully stirring uniformly to form paste, adding pre-activated catalyst endopeptidase, carrying out hydrolysis reaction at 45-75 ℃, and adding alkaline substances to quickly terminate the reaction when the weight average molecular weight of the hydrolysis product reaches the required range to obtain the polyaspartic acid.
The polyaspartic acid liquid water-soluble fertilizer provided by the invention utilizes the polyaspartic acid with the weight average molecular weight of 1000-2000D, which is prepared by polysuccinimide under the specific enzymatic hydrolysis condition, has the characteristics of small weight average molecular weight, concentrated molecular weight, easy dissolution in water and fast absorption rate, so that the polyaspartic acid liquid water-soluble fertilizer can play the advantages of activating soil nutrition, improving fertilizer utilization rate, increasing yield and improving quality, and the like, stably and effectively promotes the absorption of nutrient elements in the growth process of deciduous fruit trees, effectively improves the stress resistance of crops, and further obviously improves the stress resistance of crops, and comprehensively improves the application effect of the water-soluble fertilizer in the aspect of physiological disease control of deciduous fruit trees. The polyaspartic acid obtained by the scheme of the invention can be used as a main agent of the water-soluble fertilizer, can be used as a synergistic agent to be added into the existing water-soluble fertilizer, and can obviously improve the physiological disease control effect of the water-soluble fertilizer on deciduous fruit trees, thereby forming a green and efficient water-soluble fertilizer.
As the limitation of the technical scheme, the polysuccinimide is prepared from a product prepared by a thermal polymerization method.
As a limitation to the above technical scheme, serine protease and/or aspartic protease is/are selected as the endopeptidase.
As the limitation of the technical scheme, the alkaline substance is selected from one or more of oxides, hydroxides and carbonates containing potassium, ammonium, calcium, zinc, manganese, magnesium and iron.
Further limiting the hydrolysis condition of the polyaspartic acid so as to ensure the stability and high efficiency of the polyaspartic acid as a raw material of the water-soluble fertilizer, thereby ensuring the control effect of the water-soluble fertilizer.
As the limitation to the technical scheme, the polyaspartic acid liquid water-soluble fertilizer comprises the following components in parts by mass: 1-50 parts of polyaspartic acid, 0-50 parts of nutrient substances and 100 parts of water;
the nutrient substances comprise 0-30 parts of nitrogen-containing nutrient substances, 0-30 parts of phosphorus-containing nutrient substances, 0-30 parts of potassium-containing nutrient substances and 0-30 parts of beneficial medium trace element substances, and the total sum of the nutrient substances is not more than 50 parts.
Wherein the nitrogen-containing nutrient substances comprise one or more of urea, urea phosphate, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium chloride and ammonia water; the phosphorus-containing nutrient substances comprise one or more of urea phosphate, ammonium phosphate, potassium phosphate and phosphoric acid; the potassium-containing nutrient substance comprises one or more of potassium phosphate, potassium nitrate, potassium chloride, potassium sulfate, potassium carbonate and potassium hydroxide; the beneficial trace element substances comprise one or more of water-soluble inorganic salts containing zinc, boron, iron, manganese, calcium, magnesium and the like which can be applied to agriculture.
As the limitation of the technical scheme, the polyaspartic acid is added into the existing water-soluble fertilizer to obtain the polyaspartic acid liquid water-soluble fertilizer, and the adding amount of the polyaspartic acid in 100 parts by mass of the polyaspartic acid liquid water-soluble fertilizer is 1-50 parts.
As the limitation of the technical scheme, the physiological diseases of the northern deciduous fruit trees comprise apple water-borne heart disease and yellow-crown pear chicken feet disease.
The formula of the polyaspartic acid liquid water-soluble fertilizer or the addition amount of the polyaspartic acid to the water-soluble fertilizer and the specific physiological diseases of deciduous fruit trees are further limited, and comprehensive, stable and effective technical guidance is provided for disease control application of the polyaspartic acid liquid water-soluble fertilizer.
The invention also provides a preparation method of the polyaspartic acid liquid water-soluble fertilizer for preventing and treating physiological diseases of northern deciduous fruit trees, which comprises the following preparation steps:
a. obtaining polysuccinimide: selecting polysuccinimide prepared by thermal polymerization, wherein the content of free aspartic acid is less than or equal to 2.0%;
b. preparing polyaspartic acid: taking polysuccinimide as a main raw material, adding water, fully stirring uniformly to form a paste, adding catalyst endopeptidase which is activated in a water bath at 30 ℃ for 3-4 hours in advance, uniformly adding and fully mixing the catalyst, heating to 45-75 ℃ after the catalyst is completely added for hydrolysis reaction, adding alkaline substances to quickly terminate the reaction after 12-48 hours, and simultaneously adjusting the pH of the material to obtain polyaspartic acid with the weight average molecular weight of 1000-2000D and the interval distribution rate of not less than 90%; wherein the content of polyaspartic acid is more than or equal to 25% (w/w), the content of nutrient elements in the polyaspartic acid is 2.4-6.4% (w/w), and the solid content is 30-50% (w/w);
c. preparing a water-soluble fertilizer: and d, uniformly mixing the polyaspartic acid prepared in the step b with other components of the water-soluble fertilizer, or adding the polyaspartic acid prepared in the step b into the existing liquid water-soluble fertilizer, and uniformly stirring to obtain the polyaspartic acid liquid water-soluble fertilizer.
As the limitation to the technical scheme, the water addition amount in the step b accounts for 40-60% of the total mass of the reaction system, the catalyst addition amount accounts for 0.5-1.5% of the total mass of the reaction system, and the alkaline substance addition amount accounts for 10-20% of the total mass of the reaction system.
The polyaspartic acid liquid water-soluble fertilizer is prepared by hydrolyzing polyaspartic acid. Defining the source of raw material polysuccinimide, and ensuring the dominant performance of the hydrolyzed product; endopeptidase is used as a hydrolysis catalyst, hydrolysis is carried out under medium and low temperature conditions, and the reaction is stopped by adding alkaline substances, so that the control of the molecular weight range and concentration of the hydrolysis product is realized, the physiological disease control effect of the water-soluble fertilizer on deciduous fruit trees is ensured, the safety and efficiency of a production process can be improved by the hydrolysis process, and the safety of crop growth is further facilitated.
In conclusion, the polyaspartic acid liquid water-soluble fertilizer disclosed by the invention has the advantages that the specific polyaspartic acid is used as a water-soluble fertilizer main agent or used as a synergistic agent to be added into the existing water-soluble fertilizer, so that the absorption of nutrient elements in the growth process of deciduous fruit trees can be stably and effectively promoted, and the application effect of preventing and treating physiological diseases of deciduous fruit trees is improved. The preparation of the polyaspartic acid liquid water-soluble fertilizer takes the hydrolysis of polyaspartic acid as a technical key, and the green and efficient water-soluble fertilizer is obtained by effectively controlling the hydrolysis conditions.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Examples
The embodiment relates to a polyaspartic acid liquid water-soluble fertilizer for preventing and treating physiological diseases of northern deciduous fruit trees and a preparation method thereof.
Selecting raw materials, wherein polysuccinimide is an industrial grade product produced by a thermal polymerization method, and the content of free aspartic acid is not more than 0.2%; the aspartic proteinase is industrial grade product with enzyme activity of 5W; the other raw materials are industrial grade products.
Example 1
A water-soluble fertilizer for preventing and treating apple water-borne heart disease comprises 20kg of calcium-containing polyaspartic acid, 30kg of potassium-containing polyaspartic acid, 5kg of potassium sulfate, 10kg of monopotassium phosphate, 3kg of phosphoric acid and 32kg of water, and the total weight is 100kg.
Wherein the calcium-containing polyaspartic acid and the potassium-containing polyaspartic acid are prepared by the following steps:
5.5kg of water was added to the reactor, 3.0kg of polysuccinimide was added at one time, and stirring was started. Adding aspartic proteinase which is activated in a water bath at 30 ℃ for 4 hours in advance after the aspartic proteinase is uniformly added, wherein the adding time is controlled to be 30+/-5 minutes in the enzyme adding process, the adding amount is 50g, the temperature of the reactor is controlled to be 45+/-5 ℃ after the catalyst is completely added, and the time counting and the heat preservation are started for 36 hours after the reaction temperature reaches the set temperature. When the temperature is close to the end of the heat preservation period, the molecular weight is monitored at any time through Gel Permeation Chromatography (GPC), and when the required molecular weight range is reached, 1.1kg of calcium hydroxide (or 0.9kg of potassium hydroxide) is rapidly and uniformly added to terminate the reaction, generally, the control of the alkali adding time is determined according to the temperature of a material system, the temperature of the material system is required to be controlled to be less than or equal to 100 ℃, and the temperature is as close to the critical temperature of 100 ℃ as possible, and meanwhile, the problem that the hydrolysis molecular weight is low due to slow alkali adding caused by the control of the temperature is avoided, so that the effect of polyaspartic acid is influenced. And adding alkaline substances and simultaneously adjusting the pH of the material to prepare calcium-containing polyaspartic acid (or potassium-containing polyaspartic acid), and detecting when the temperature of the material is reduced to be lower than 40 ℃, wherein the detection result shows that the polyaspartic acid content is more than or equal to 25%, the aspartic acid content is less than or equal to 4.0%, the weight average molecular weight is 1500D, the interval distribution rate is not lower than 90%, the pH is 6.2, and the calcium content is more than or equal to 5.0% or the potassium content is more than or equal to 6.0%.
The prepared calcium-containing polyaspartic acid, potassium-containing polyaspartic acid and other components are uniformly mixed according to the following operation: adding 32kg of water into a container at one time, adding 30kg of potassium-containing polyaspartic acid, uniformly stirring, continuously adding 5kg of potassium sulfate, 10kg of monopotassium phosphate and 3kg of phosphoric acid until the potassium sulfate, the potassium-containing polyaspartic acid and the phosphoric acid are dissolved, slowly adding 20kg of calcium-containing polyaspartic acid, and fully stirring for 2 hours to obtain the calcium-potassium-containing polyaspartic acid liquid water-soluble fertilizer. The content of polyaspartic acid in the obtained water-soluble fertilizer is more than or equal to 12%, the content of calcium is more than or equal to 1.0%, and K 2 The O content is more than or equal to 7.0 percent, P 2 O 5 The content is more than or equal to 6.0 percent. The contents are mass fractions.
The application test was carried out on the calcium-potassium-containing polyaspartic acid liquid water-soluble fertilizer obtained in this example, and compared with the comparative example, the use amount of each water-soluble fertilizer was 5kg/667m 2 Specific data are shown in the following table:
the normal apples are 7 yuan/kg according to wholesale price, the water-bearing fruits are 3 yuan/kg according to wholesale price, and compared with comparative examples 1-1 to 1-4 and 1-6, example 1 increases the income of farmers by 70 to 810 yuan/667 m in a single year 2 The method comprises the steps of carrying out a first treatment on the surface of the Example 1 increased the farmer's income by 1520 yuan/667 m for a single year as compared with comparative examples 1-5 2
Example 2
The water-soluble fertilizer for preventing and treating apple water-borne heart disease is prepared by adding zinc-containing polyaspartic acid with the addition amount of 8.5% based on the existing water-soluble fertilizer which accords with the elements in NY2266-2012 or water-soluble fertilizer which accords with the trace elements in NY1428-2010 or water-soluble fertilizer which accords with the major elements in NY1107-2010, and uniformly mixing and stirring the materials, wherein the specific proportion of the water-soluble fertilizer is 8.5kg of zinc-containing polyaspartic acid liquid, 40kg of potassium nitrate, 30kg of monopotassium phosphate and 100kg of water, and accords with the relevant regulations of relevant product standards and product types.
The zinc-containing polyaspartic acid is prepared by the following steps:
4.5kg of water was added to the reactor, 3.0kg of polysuccinimide was added at one time, and stirring was started. Adding aspartic protease activated in water bath at 30deg.C for 4 hr, controlling the adding time to 30+ -5 min and adding amount to 50g, controlling the reaction temperature to 50+ -5deg.C, timing after the temperature reaches the set temperature, and maintaining for 24 hr. When the temperature is close to the end of the heat preservation period, the molecular weight is monitored at any time through Gel Permeation Chromatography (GPC), and when the required molecular weight range is reached, 1.1kg of zinc hydroxide is rapidly and uniformly added to stop the reaction, generally, the control of the alkali adding time is determined according to the temperature of a material system, the temperature of the material system is required to be controlled to be less than or equal to 100 ℃, and the temperature is as close to the critical temperature of 100 ℃ as possible, and meanwhile, the influence on the efficacy of polyaspartic acid due to low hydrolysis molecular weight caused by slow alkali adding caused by the control temperature is avoided. And adding alkaline substances, adjusting the pH of the material, and obtaining the zinc-containing polyaspartic acid, and carrying out sample feeding detection when the temperature of the material is reduced to be lower than 40 ℃. The detection result shows that the polyaspartic acid content is more than or equal to 32%, the aspartic acid content is less than or equal to 4.0%, the weight average molecular weight is 2000D, the interval distribution rate is not less than 90%, the pH value is 6.5, and the zinc content is more than or equal to 8.0%. The contents are mass fractions.
The zinc-containing polyaspartic acid liquid water-soluble fertilizer obtained in the example is subjected to application test, and compared with the comparative example, the application amount of each water-soluble fertilizer is 5kg/667m 2 3 times per season, the specific data are shown in the following table:
normal apples are calculated according to wholesale price of 7 yuan/kg and the water chestnut is calculated according to wholesale price of 3 yuan/kg. Example 2 increased the income of farmers by 70 to 450 yuan/667 m for a single year compared with comparative examples 2-1 to 2-4 and comparative examples 2-6 2 The method comprises the steps of carrying out a first treatment on the surface of the Compared with comparative examples 2 to 5Example 2 increase the income of farmers by 750 yuan/667 m in a single year 2
Example 3
A water-soluble fertilizer for preventing and treating chicken feet disease of Huangguan pears comprises 50kg of ammonia nitrogen-containing polyaspartic acid, 15.3kg of calcium nitrate tetrahydrate, 10.2kg of potassium nitrate, 4kg of urea and 20.5kg of water, and the total weight is 100kg.
Wherein the polyaspartic acid containing ammonia nitrogen is prepared by the following steps:
4.0kg of water was added to the reactor, and 4.0kg of polysuccinimide was added at one time, and stirring was started. Adding aspartic protease activated in water bath at 30deg.C for 4 hr, controlling the adding time to 50+ -5 min, adding 100g, controlling the reaction temperature to 50+ -5deg.C, timing after the temperature reaches the set temperature, and maintaining for 48 hr. When the molecular weight is monitored at any time by Gel Permeation Chromatography (GPC) and reaches the required molecular weight range, 1.2kg of ammonia water (25-28% of industrial product mass concentration) is rapidly and uniformly added to terminate the reaction, the control of the alkali adding time is generally determined according to the temperature of a material system, the temperature of the material system is required to be controlled to be less than or equal to 100 ℃, and the temperature is as close to the critical temperature of 100 ℃ as possible, and meanwhile, the problem that the hydrolysis molecular weight is low due to slow alkali adding caused by the control of the temperature is avoided, so that the effect of polyaspartic acid is influenced. And adding alkaline substances and simultaneously adjusting the pH of the material to obtain ammonia nitrogen-containing polyaspartic acid, and carrying out sample feeding detection when the temperature of the material is reduced to be lower than 40 ℃, wherein the polyaspartic acid content is more than or equal to 40%, the aspartic acid content is less than or equal to 3.0%, the weight average molecular weight is 1000D, the interval distribution rate is not lower than 90%, the pH is 5.8, and the total nitrogen content is more than or equal to 6.0%.
The prepared polyaspartic acid containing ammonia nitrogen is uniformly mixed with other components according to the following scheme: adding 20.5kg of water, 50kg of polyaspartic acid containing ammonia nitrogen into a container at one time, starting heating to set the temperature to 45+/-5 ℃, sequentially adding 15.3kg of calcium nitrate tetrahydrate, 10.2kg of potassium nitrate and 4kg of urea, and obtaining the liquid water-soluble fertilizer containing ammonia nitrogen polyaspartic acid after all materials are completely dissolved after the materials are dissolved and the temperature is stabilized for 5 min. The polyaspartic acid content in the obtained water-soluble fertilizer is more than or equal to 20%, the total nitrogen content is more than or equal to 6.0%, and K is higher than or equal to 6.0% 2 The O content is more than or equal to 2.5 percent,The content of calcium is more than or equal to 4.0 percent, and the calcium is the mass content.
The application test of the liquid water-soluble fertilizer containing ammonia nitrogen type polyaspartic acid obtained in the example is carried out, and compared with the comparative example, the application amount of the liquid water-soluble fertilizer is 5kg/667m 2 Specific data are shown in the following table:
the normal pear is calculated according to 5 yuan/kg of wholesale price and the chicken feet are calculated according to 2 yuan/kg of wholesale price. Example 3 increased the farmer income by 170 to 520 yuan/667 m for a single year as compared with comparative examples 3-1 to 3-4 and 3-6 2 The method comprises the steps of carrying out a first treatment on the surface of the Example 3 increased the farmer by 1360 yuan/667 m for a single year as compared with comparative examples 3-5 2
Example 4
A water-soluble fertilizer for preventing and treating chicken foot disease of Huangguan pears is prepared by adding calcium-containing polyaspartic acid based on the existing water-soluble fertilizer conforming to NY2266-2012 medium element or trace element or water-soluble fertilizer conforming to NY1428-2010 major element or the original formula of the water-soluble fertilizer, and uniformly mixing and stirring the mixture to obtain the calcium-containing polyaspartic acid liquid water-soluble fertilizer, wherein the specific mass ratio of the water-soluble fertilizer is 15kg of calcium-containing polyaspartic acid liquid, 35kg of potassium nitrate, 35kg of monopotassium phosphate and 100kg of water, and the water is in accordance with the relevant specifications of relevant product standards and product types.
The calcium-containing polyaspartic acid is prepared by the following steps:
4.5kg of water was added to the reactor, 3.0kg of polysuccinimide was added at one time, and stirring was started. Adding aspartic protease activated in water bath at 30deg.C for 4 hr, controlling the adding time to 30+ -5 min, adding 50g, controlling the reaction temperature to 55+ -5deg.C, timing after the temperature reaches the set temperature, and maintaining for 36 hr. When the molecular weight is monitored at any time by Gel Permeation Chromatography (GPC) and reaches the required molecular weight range, 1.1kg of calcium hydroxide is rapidly and uniformly added to terminate the reaction, the control of the alkali adding time is generally determined according to the temperature of a material system, the temperature of the material system is required to be controlled to be less than or equal to 100 ℃, and the temperature is as close to the critical temperature of 100 ℃ as possible, so that the problem that the effect of polyaspartic acid is influenced due to low hydrolysis molecular weight caused by slow alkali adding caused by the control of the temperature is avoided. And adding alkaline substances and simultaneously adjusting the pH of the material to obtain calcium-containing polyaspartic acid, and carrying out sample feeding detection when the temperature of the material is reduced to be lower than 40 ℃, wherein the polyaspartic acid content is more than or equal to 25%, the aspartic acid content is less than or equal to 4.0% and the weight average molecular weight is 1500D, the interval distribution rate is not lower than 90%, the pH is 6.0, and the calcium content is more than or equal to 6.0%.
The calcium-containing polyaspartic acid liquid water-soluble fertilizer obtained in this example was subjected to application test, and compared with the comparative example, the calcium-containing polyaspartic acid liquid water-soluble fertilizer was used in an amount of 5kg/667m 2 3 times per season, the specific data are shown in the following table:
the normal pear is calculated according to 5 yuan/kg of wholesale price and the chicken feet are calculated according to 2 yuan/kg of wholesale price. Compared with comparative examples 4-1 to 4-4 and comparative examples 4-6, example 4 increased the income of farmers by 120 to 640 yuan/667 m for a single year 2 The method comprises the steps of carrying out a first treatment on the surface of the In example 4, 970 yuan/667 m was increased for farmers a single year as compared with comparative examples 4-5 2
Comparative example
The formulation and preparation method of each comparative example are shown in the following table
The main reasons for the formation and occurrence of physiological diseases of northern deciduous fruit trees are imbalance of the C/N ratio in crop nutrition and imbalance of macroelement/medium microelement absorption; wherein the imbalance of the C/N ratio comprises the mass application of chemical fertilizers and the reduction of organic fertilizers, the mass application of the chemical fertilizers leads to the weakening of the activity of soil flora on organic matters, the mass application of the chemical fertilizers leads to the destruction of soil structure and the like; imbalances in macroelement/mesomicroelement absorption include over-application of macroelement chemical fertilizers and fixation of microelements in the soil, over-application of macroelement chemical fertilizers and attenuation of soil porosity, over-application of macroelement chemical fertilizers and attenuation of seed microelement absorption by crops, and the like. The invention researches find that polyaspartic acid prepared by an enzymolysis method has various functions of regulating the reasons: firstly, the polyaspartic acid has concentrated molecular weight, has the characteristic of enzyme, can excite the absorption and utilization of trace elements in crops, activate the trace elements in soil and reduce the fixation of the trace elements; secondly, the polyaspartic acid in the molecular weight section has the lasting effect of common polyaspartic acid and the quick-acting effect of common organic fertilizer due to the synergistic and chelating functions, and is more superior in improving the yield and quality of crops, so that the use proportion of chemical fertilizer can be reduced; finally, the polyaspartic acid is a polymer of amino acid, can be taken as a nutrient component and decomposed by microorganisms, and can be also utilized and decomposed by crops, so that C sources can be better supplied for crops and soil microorganisms, and the soil structure can be improved.
As can be seen from comparison results, the polyaspartic acid liquid water-soluble fertilizer which can stably and effectively promote nutrient elements to be absorbed in the growth process of deciduous fruit trees is obtained by reasonably controlling enzymolysis conditions and is used as a main agent or a synergistic auxiliary agent of the water-soluble fertilizer, so that the polyaspartic acid liquid water-soluble fertilizer with obvious prevention and treatment effects on physiological diseases of deciduous fruit trees is obtained.

Claims (8)

1. The polyaspartic acid liquid water-soluble fertilizer for preventing and treating physiological diseases of northern deciduous fruit trees is characterized by comprising the following components:
polyaspartic acid with weight average molecular weight of 1000-2000D and interval distribution rate of not less than 90% is obtained by hydrolyzing polysuccinimide at 45-75 ℃ under the catalysis of endopeptidase;
the polyaspartic acid is prepared by the following method:
taking polysuccinimide as a main raw material, adding water, fully stirring uniformly to form paste, adding pre-activated catalyst endopeptidase, carrying out hydrolysis reaction at the temperature of 45-75 ℃, and adding alkaline substances to quickly terminate the reaction when the weight average molecular weight of the hydrolysis product reaches the required range to obtain polyaspartic acid; the polysuccinimide is prepared by a thermal polymerization method.
2. The polyaspartic acid liquid water-soluble fertilizer for preventing and treating physiological diseases of northern deciduous fruit trees according to claim 1, which is characterized in that: the endopeptidase is serine protease or/and aspartic protease.
3. The polyaspartic acid liquid water-soluble fertilizer for preventing and treating physiological diseases of northern deciduous fruit trees according to claim 1, which is characterized in that: the alkaline substance is one or more of oxides, hydroxides and carbonates containing potassium, ammonium, calcium, zinc, manganese, magnesium and iron.
4. The polyaspartic acid liquid water-soluble fertilizer for preventing and controlling physiological diseases of northern deciduous fruit trees according to any one of claims 1-3, wherein the polyaspartic acid liquid water-soluble fertilizer comprises the following components in parts by mass: 1-50 parts of polyaspartic acid, 0-50 parts of nutrient substances and 100 parts of water;
the nutrient substances comprise 0-30 parts of nitrogen-containing nutrient substances, 0-30 parts of phosphorus-containing nutrient substances, 0-30 parts of potassium-containing nutrient substances and 0-30 parts of beneficial medium trace element substances, and the total sum of the nutrient substances is not more than 50 parts.
5. The polyaspartic acid liquid water-soluble fertilizer for preventing and controlling physiological diseases of northern deciduous fruit trees according to any one of claims 1-3, wherein polyaspartic acid is added into the water-soluble fertilizer to obtain the polyaspartic acid liquid water-soluble fertilizer, and the addition amount of polyaspartic acid in 100 parts by mass of the polyaspartic acid liquid water-soluble fertilizer is 1-50 parts.
6. The polyaspartic acid liquid water-soluble fertilizer for preventing and treating physiological diseases of northern deciduous fruit trees according to claim 1, which is characterized in that: the physiological diseases of northern deciduous fruit trees comprise apple water-borne heart disease and yellow crown pear chicken feet disease.
7. A method for preparing the polyaspartic acid liquid water-soluble fertilizer for preventing and treating physiological diseases of northern deciduous fruit trees according to any one of claims 1-6, which is characterized by comprising the following preparation steps:
a. obtaining polysuccinimide: selecting polysuccinimide prepared by thermal polymerization, wherein the content of free aspartic acid in the polysuccinimide is required to be less than or equal to 2.0%;
b. preparing polyaspartic acid: taking polysuccinimide as a main raw material, adding water, fully stirring uniformly to form a paste, adding catalyst endopeptidase activated in a water bath at 30 ℃ for 3-4 hours in advance, uniformly adding and fully mixing the catalyst, heating to 45-75 ℃ after the catalyst is completely added for hydrolysis reaction, adding alkaline substances to quickly stop the reaction after 12-48 hours, and simultaneously adjusting the pH of the material to obtain polyaspartic acid with the weight average molecular weight of 1000-2000D and the interval distribution rate of not less than 90%;
c. preparing a water-soluble fertilizer: and d, uniformly mixing the polyaspartic acid prepared in the step b with other components of the water-soluble fertilizer, or adding the polyaspartic acid prepared in the step b into the liquid water-soluble fertilizer, and uniformly stirring to obtain the polyaspartic acid liquid water-soluble fertilizer.
8. The method for preparing polyaspartic acid liquid water-soluble fertilizer for preventing and treating physiological diseases of northern deciduous fruit trees according to claim 7, which is characterized in that: in the step b, the water addition amount accounts for 40-60% of the total mass of the reaction system, the catalyst addition amount accounts for 0.5-1.5% of the total mass of the reaction system, and the alkaline matter addition amount accounts for 10-20% of the total mass of the reaction system.
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Citations (4)

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Publication number Priority date Publication date Assignee Title
CN103059299A (en) * 2013-01-22 2013-04-24 石家庄开发区德赛化工有限公司 Compound type MSOD (Models of Superoxide Dismutase) and production process thereof
CN103351218A (en) * 2013-06-19 2013-10-16 余丽 Synergist for polyaspartic acid fertilizer and preparation method thereof
CN104150971A (en) * 2014-08-27 2014-11-19 石家庄开发区德赛化工有限公司 Calcium-reinforced SOD urea fertilizer, preparation method and application thereof
CN110862540A (en) * 2019-12-13 2020-03-06 山东泰和水处理科技股份有限公司 Synthesis method of polyaspartic acid zinc salt

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103059299A (en) * 2013-01-22 2013-04-24 石家庄开发区德赛化工有限公司 Compound type MSOD (Models of Superoxide Dismutase) and production process thereof
CN103351218A (en) * 2013-06-19 2013-10-16 余丽 Synergist for polyaspartic acid fertilizer and preparation method thereof
CN104150971A (en) * 2014-08-27 2014-11-19 石家庄开发区德赛化工有限公司 Calcium-reinforced SOD urea fertilizer, preparation method and application thereof
CN110862540A (en) * 2019-12-13 2020-03-06 山东泰和水处理科技股份有限公司 Synthesis method of polyaspartic acid zinc salt

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