AU2020102034A4 - Chelating carrier for secondary and micronutrients and use thereof - Google Patents

Chelating carrier for secondary and micronutrients and use thereof Download PDF

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AU2020102034A4
AU2020102034A4 AU2020102034A AU2020102034A AU2020102034A4 AU 2020102034 A4 AU2020102034 A4 AU 2020102034A4 AU 2020102034 A AU2020102034 A AU 2020102034A AU 2020102034 A AU2020102034 A AU 2020102034A AU 2020102034 A4 AU2020102034 A4 AU 2020102034A4
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weight
parts
water
micronutrients
chelating carrier
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AU2020102034A
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Yanting LI
Zhi'an Lin
Wei Wang
Liang YUAN
Shuiqin ZHANG
Bingqiang Zhao
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Institute of Agricultural Resources and Regional Planning of CAAS
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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
    • C05DINORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D3/00Calcareous fertilisers
    • 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
    • C05G3/00Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/40Mixtures 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Fertilizers (AREA)

Abstract

The present invention relates to a chelating carrier for secondary and micronutrients and use thereof. The chelating carrier for secondary and micronutrients includes alcohol amine, choline, polyamine, amino acid and solvent. Compared with a control, the chelating carrier prepared in present invention increases the fresh weight and activity of the wheat root by an average of 58.2% and 43.5%, respectively. The alkaline liquid fertilizers of the microelement zinc prepared in the present invention can significantly increase the aboveground biomass, utilization rate of microelement of Brassica chinensis L. and improve crop quality.

Description

CHELATING CARRIER FOR SECONDARY AND MICRONUTRIENTS AND USE THEREOF TECHNICAL FIELD The present invention belongs to the technical field of fertilizer production. In particular, the present invention relates to a chelating carrier for secondary and micronutrients, and use thereof.
BACKGROUND In the past 30 years, nitrogen, phosphorus and potassium fertilizers were applied in large quantities to increase crop yields. Economic crops such as fruit trees and vegetables have been quickly developed due to structural adjustment of planting industry. The above brings about an increasing number of crops suffering from malnutrition of microelement, which limits further improvement of crop yield and quality. There is 64% of existing cultivated soil in area with a calcium content below the deficiency threshold, and 53% for magnesium, 40% for sulfur, and for micronutrients, 84% for boron, 31% for iron, 42% for zinc, 48% for manganese, 25% for copper and 59% for molybdenum, respectively. Compared with the results from the second national soil survey, the element-deficiency area almost doubles. Irrational fertilization results in a lowered pH of cultivated soil by 0.85 units, the area of acidified soil accounting for 21.6% of the total cultivated area. There is an intensive need of alkaline fertilizers, especially alkaline liquid fertilizers of secondary and micronutrients with desired water solubility, to ensure national food safety and agricultural product quality in a new ear. Conventional secondary and micronutrients such as calcium, magnesium, copper, zinc, iron and manganese show desired water solubility only under acidic conditions. However, they have poor performance when applied under alkaline conditions due to precipitation and thus are not convenient in use. Therefore, a series of chelating materials are used to improve the water solubility of secondary and micronutrients such as ethylenediaminetetraacetic acid (EDTA), organic acids, sugar alcohols and amino acids. But such methods can further acidify an acidic soil and reduce availability in the presence of alkaline hard water due to precipitation which blocks drip irrigation tubes, thereby affects normal agricultural production. CN106748096A discloses an alkaline fertilizer prepared by raw materials of secondary nutrients, pine pollen, polyglutamic acid solution, sulfuric acid, ammonium chloride, red potassium chloride, Si-Ca-K fertilizer and monoammonium phosphate and the like. CN104876769B discloses a silicon alkaline fertilizer for improving soil acidification and a preparation method thereof. The fertilizer is prepared by raw materials of potassium silicate, potassium humate, urea, ammonium molybdate, EDTA, diethylaminoethanol caproate, compound sodium nitrophenolate, ground phosphate rock, calcium chloride, natural potassium magnesium sulfate fertilizer and mature compost. The fertilizer can improve acidic soils. CN1279002C discloses a production process of organic matter chelated microelement fertilizer. The process is carried out with extracting humus from lignite, precipitating to obtain a required liquid, adding the organic chelating agent (citric acid or its salts) and microelements, adjusting pH to neutral with acid or base, and drying to obtain the product. CN106146163A discloses a method for producing sugar alcohol chelated secondary elements. The method is carried out by adding secondary elements, sugar alcohol and solvent to a reactor, and the chelation reaction will happen at a certain temperature to obtain the sugar alcohol chelated secondary elements. CN105948955A discloses a method for producing a fertilizer containing sugar alcohol chelated microelements. The method is carried out by preparing sugar alcohol chelated microelements, and then adding sugar alcohol chelated microelements to a fertilizer to obtain the fertilizer containing sugar alcohol chelated microelements. However, there are no patent applications or literatures about chelating carrier for secondary or microelement fertilizer in the prior art. In view of the above, the present invention carries out a large amount of experimental research and analysis, so as to solve the technical problems existing in the prior art.
SUMMARY
[Technical Problem to Be Solved] An objective of the present invention is to provide a chelating carrier for secondary and micronutrients. Another objective of the present invention is to provide use of the chelating carrier for a secondary and micronutrients.
[Technical Solution] The present invention is achieved by the following technical solutions. The present invention relates to a chelating carrier for secondary and micronutrients. The chelating carrier includes 100 parts by weight of alcohol amine, 2-10 parts by weight of choline, 1-5 parts by weight of polyamine, 20-60 parts by weight of amino acid and 1,000 parts by weight of solvent, where the solvent includes 10-100 parts by weight of ethylene glycol or glycerin, 2-10 parts by weight of phenol and 1,000 parts by weight of water. According to a preferred implementation of the present invention, the alcohol amine is one or more selected from monoethanolamine, diethanolamine, triethanolamine and N methyldiethanolamine. According to another preferred implementation of the present invention, the choline is one or more selected from choline, acetylcholine or choline chloride. According to another preferred implementation of the present invention, the polyamine is one or more selected from putrescine, spermidine or spermine. According to another preferred implementation of the present invention, the amino acid is one or more selected from lysine, arginine, methionine or omithine. According to another preferred implementation of the present invention, a weight ratio of the ethylene glycol or the glycerin to the phenol to the water is (10-75):(2-8):1,000, and/or a weight ratio of the alcohol amine to the choline to the polyamine to the amino acid is 100:(2-8):(1 4):(20-50). According to another preferred implementation of the present invention, a weight ratio of the ethylene glycol or the glycerin to the phenol to the water is (20-75):(3-8):1,000, and/or a weight ratio of the alcohol amine to the choline to the polyamine to the amino acid is 100:(3-8):(2 4):(30-50). The present invention also relates to use of the chelating carrier in preparation of an alkaline liquid fertilizer of secondary and micronutrients. According to a preferred implementation of the present invention, preparation of an alkaline liquid fertilizer of secondary and micronutrients includes steps as follows: A. Solvent preparation dissolving 10-100 parts by weight of ethylene glycol or glycerin and 2-10 parts by weight of phenol in 1,000 parts by weight of water, stirring and mixing well to obtain the solvent; B. Preparation of an alkaline chelating carrier dissolving 100 parts by weight of alcohol amine, 2-10 parts by weight of choline and 1-5 parts by weight of polyamine in 1,000 parts by weight of the solvent obtained in step A, mixing evenly, heating to a temperature of 60-80°C, then adding 20-60 parts by weight of amino acid, stirring to dissolve, cooling, and adjusting pH above 8.0 by using an aqueous potassium pyrophosphate solution to obtain an alkaline chelating carrier; C. Preparation of an alkaline liquid fertilizer of secondary and micronutrients mixing a water-soluble salt of a secondary and micronutrients of calcium, magnesium, zinc, manganese, copper or iron with the chelating carrier obtained in step B in a weight ratio of 1:(1 100) and dissolving to obtain the alkaline liquid fertilizer of secondary and micronutrients. According to another preferred implementation of the present invention, the concentration of the aqueous potassium pyrophosphate solution is 1-5 mol/L. According to another preferred implementation of the present invention, the water-soluble calcium salt is calcium nitrate or calcium chloride; the water-soluble magnesium salt is magnesium nitrate or magnesium chloride; the water-soluble zinc salt is zinc sulfate or zinc chloride; the water-soluble manganese salt is manganese sulfate or manganese chloride; the water-soluble copper salt is copper sulfate or copper chloride; the water-soluble iron salt is ferrous sulfate or ammonium ferrous sulfate. The present invention is described in further detail below. The present invention relates to a chelating carrier for secondary and micronutrients. In this specification, it should be particularly pointed out that a chelating carrier for secondary and micronutrients can be abbreviated as chelating carrier, and both of them have the same meaning. The chelating carrier includes 100 parts by weight of alcohol amine, 2-10 parts by weight of choline, 1-5 parts by weight of polyamine, 20-60 parts by weight of amino acid and 1,000 parts by weight of solvent, where the solvent includes 10-100 parts by weight of ethylene glycol or glycerin, 2-10 parts by weight of phenol and 1,000 parts by weight of water. In the present invention, the alcohol amine in the chelating carrier is mainly used for chelating secondary and micronutrients to form a chelate which is soluble under alkaline conditions. The alcohol amine used in the present invention is one or more selected from monoethanolamine, diethanolamine, triethanolamine or N-methyldiethanolamine. The alcohol amine is a commercially available product, for example, a product sold by Shanghai Minchen Chemical Co., Ltd. under the trade name "monoethanolamine (MEA)", or a product sold by Zouping County Guoan Chemical Co., Ltd. under the trade name "N-methyldiethanolamine (MDEA)". In the present invention, the choline in the chelating carrier is mainly used to increase alkalinity of an alkaline liquid fertilizer of secondary and micronutrients and to enhance the stability of the secondary and micronutrients in the alkaline liquid fertilizer. Moreover, the choline has a biological activity in promoting synthesis and transportation of photosynthates in crops. The choline used in the present invention is one or more selected from choline, acetylcholine or choline chloride. The choline is a commercially available product, for example, a product sold by Xi'an Laweiya Biotechnology Co., Ltd. under the trade name "choline", or a product sold by He'nan Xingyuan Chemical Products Co., Ltd. under the trade name "acetylcholine", or a product sold by Wuxi Shengshihongcheng Biotechnology Co., Ltd. under the trade name "choline chloride". In the chelating carrier of the present invention, when the amount of other components is within the above range, if the amount of choline is less than 2 parts by weight, there will be no obvious increase in stability of secondary and micronutrients in this alkaline liquid fertilizer; if the amount of choline exceeds 10 parts by weight, the production cost of the chelating carrier will be increased. Therefore, the amount of the choline is reasonably 2-10 parts by weight, and preferably 3-8 parts by weight. In the present invention, the polyamine in the chelating carrier is mainly used to promote crop growth, improve seed activity and germination; stimulate generation of adventitious root to promote absorption of inorganic ions by root system; inhibit the increase of protease and RNase activities and delay chlorophyll decomposition to delay leaf senescence; regulate the phytochrome-related growth and morphologic formation, and regulate the flowering process; and improve stress resistance and osmotic stress resistance. The polyamine used in the present invention is one or more selected from putrescine, spermidine or spermine. The polyamine is a commercially available product, for example, a product sold by Shanghai Yihe Biotechnology Co., Ltd. under the trade name "putrescine", a product sold by Hubei Wande Chemical Co., Ltd. under the trade name "spermidine", or a product sold by Qingdao Jieshikang Biotechnology Co., Ltd. under the trade name "spermine". In the chelating carrier of the present invention, when the amount of other components is within the above range, if the amount of polyamine is less than 1 part by weight, there will be no obvious effect on promoting crop growth, improving seed activity and germination and the like; if the amount of polyamine exceeds 5 parts by weight, the production cost of the chelating carrier will be increased. Therefore, the amount of the polyamine is suitably 1-5 parts by weight, and preferably 2-4 parts by weight. In the present invention, the amino acid in the chelating carrier is mainly used to react with an organic base to form an organic chelate for dissolution of secondary and micronutrients. The amino acid also participates in synthesis of polyamine in a plant, and improves the stability of the secondary and micronutrients in the alkaline liquid fertilizer of secondary and micronutrients. The amino acid used in the present invention is one or more selected from lysine, arginine, methionine or ornithine. The amino acid is a commercially available product, for example, a product sold by Xijie (Shenyang) Biotechnology Co., Ltd. under the trade name "lysine", a product sold by Shandong Dongrun Biotechnology Co., Ltd. under the trade name "L-arginine", a product sold by Jiangsu Xinheyuan Biotechnology Co., Ltd. under the trade name "L methionine" or a product sold by Jiangsu Caiwei Biotechnology Co., Ltd. under the trade name "ornithine". In the chelating carrier of the present invention, when the amount of other components is within the above range, if the amount of amino acid is less than 20 parts by weight, there will be a limited chelating effect due to the low content of amino acid-organic base chelate formed; if the amount of amino acid exceeds 60 parts by weight, amino acid may precipitate out due to storage temperature or other factors. Therefore, the amount of the amino acid is suitably 20-60 parts by weight, preferably 30-50 parts by weight and more preferably 36-42 parts by weight.
Preferably, a weight ratio of the alcohol amine to the choline to the polyamine to the amino acid is 100:(2-8):(1-4):(20-50) or 100:(3-8):(2-4):(30-50). In the chelating carrier, the solvent includes 10-100 parts by weight of ethylene glycol or glycerin, 2-10 parts by weight of phenol and 1,000 parts by weight of water. Ethylene glycol or glycerin is a polyol which can promote dissolution of an organic base, and increase the stability and fluidity of the alkaline liquid fertilizer of secondary and micronutrients. If the amount of the ethylene glycol or glycerin is less than 10 parts by weight, the prepared alkaline liquid fertilizer of secondary and micronutrients will show poor stability. If the amount of the ethylene glycol or glycerin exceeds 100 parts by weight, the prepared alkaline liquid fertilizer of secondary and micronutrients will show a high viscosity, which affects dissolution of organic base and secondary and micronutrients. Phenol can promote dissolution of an organic base, and further enhance the stability of the secondary and micronutrients in the alkaline liquid fertilizer of secondary and micronutrients. If the amount of phenol is less than 2 parts by weight, there will be no obvious increase in stability of the alkaline liquid fertilizer of secondary and micronutrients. If the amount of phenol exceeds parts by weight, the production cost will be increased. Preferably, a weight ratio of the ethylene glycol or the glycerin to the phenol to the water is (10-75):(2-8):1,000 or (20-75):(3-8):1,000. The present invention also relates to the use of the chelating carrier in preparation of an alkaline liquid fertilizer of secondary and micronutrients. The preparation of an alkaline liquid fertilizer of secondary and micronutrients includes steps as follows: A. Solvent preparation dissolving 10-100 parts by weight of ethylene glycol or glycerin and 2-10 parts by weight of phenol in 1,000 parts by weight of water, stirring and mixing evenly to obtain the solvent. B. Preparation of an alkaline chelating carrier dissolving 100 parts by weight of alcohol amine, 2-10 parts by weight of choline and 1-5 parts by weight of polyamine in 1,000 parts by weight of the solvent obtained in step A, mixing evenly, heating to 60-80°C, then adding 20-60 parts by weight of amino acid, stirring to dissolve, cooling, and adjusting pH above 8.0 by using an aqueous potassium pyrophosphate solution to obtain a chelating carrier. According to the present invention, the concentration of the aqueous potassium pyrophosphate solution is 1-5 mol/L. The information about ethylene glycol or glycerin, phenol, alcohol amine, choline, polyamine or amino acid has been described above and will be not repeated here.
C. Preparation of an alkaline liquid fertilizer of secondary and micronutrients mixing a water-soluble salt of calcium, magnesium, zinc, manganese, copper and/or iron with the chelating carrier obtained in step B in a weight ratio of 1:(1-100) and dissolving to obtain the alkaline liquid fertilizer of secondary and micronutrients. According to the present invention, the water-soluble calcium salt is calcium nitrate or calcium chloride; the water-soluble magnesium salt is magnesium nitrate or magnesium chloride; the water-soluble zinc salt is zinc sulfate or zinc chloride; the water-soluble manganese salt is manganese sulfate or manganese chloride; the water-soluble copper salt is copper sulfate or copper chloride; the water-soluble iron salt is ferrous sulfate or ammonium ferrous sulfate. The chelating carrier for secondary and micronutrients in the present invention has the following features: A. The chelating carrier of the present invention can be used in preparation of an alkaline liquid fertilizer of secondary and micronutrients. B. The chelating carrier of the present invention is alkaline which can be used to adjust pH of acidic soils. C. The alkaline liquid fertilizer, produced by using the chelating carrier of the present invention to chelate calcium or magnesium, will not precipitate when dissolved in water with high hardness for irrigation or foliar spray. D. The alkaline liquid fertilizer of secondary and micronutrients of the present invention, when used for foliar spray, can promote absorption of secondary and microelement, increase the accumulation of carbon dioxide on foliage of crops, and enhance photosynthesis. When the fertilizer is applied to soils, secondary and microelement can also be absorbed by crops. In addition, this fertilizer can stimulate root growth of crop, improve root activity and promote absorption of nutrients.
[Beneficial Effects] The present invention has the following beneficial effects: A. The chelating carrier for secondary and micronutrients of the present invention can be used in preparation of an alkaline liquid fertilizer of secondary and micronutrients, and makes the secondary and micronutrients soluble under alkaline conditions to achieve a higher use efficiency. B. The chelating carrier for secondary and micronutrients of the present invention is alkaline which can be used to adjust pH of acidic soils. C. The alkaline liquid fertilizer of secondary and micronutrients of the present invention will not precipitate when used for irrigation or foliar spray with high-hardness water. D. The alkaline liquid fertilizer of secondary and micronutrients of the present invention, when used for foliar spray, can promote absorption of secondary and microelement, increase the accumulation of carbon dioxide on foliage of crops, and enhance photosynthesis. Compared with CK, foliar spray with the alkaline liquid fertilizer of secondary and micronutrients of the present invention increases the fresh weight, vitamin C (Vc) content, soluble sugar content and zinc utilization rate of Brassica chinensis L. by 38.6%, 85.7%, 196% and 64.6% on average respectively. E. When the alkaline liquid fertilizer of secondary and micronutrients of the present invention is applied to soils, secondary and microelement is absorbed by crops. In addition, this fertilizer can stimulate growth of root system, improve root activity and promote absorption of nutrients. Compared with CK, the irrigation with the alkaline liquid fertilizer of secondary and micronutrients of the present invention increases the fresh weight, Vc content, soluble sugar content and zinc utilization rate of Brassica chinensis L. by 43.0%, 12.4%, 40.8% and 45.8% on average respectively. Compared with CK, the irrigation with the alkaline liquid fertilizer of secondary and micronutrients of the present invention increases the root fresh weight and activity of wheat by 58.2% and 43.5% on average respectively.
DETAILED DESCRIPTION The present invention will be better understood with reference to the examples below. I. Preparation Examples Example 1: Preparation of a chelating carrier of the present invention The example included steps as follows: A. Solvent preparation 40 parts by weight of ethylene glycol and 5 parts by weight of phenol were dissolved in 1,000 parts by weight of water, stirred and mixed evenly to obtain the solvent. B. Preparation of an alkaline chelating carrier 100 parts by weight of monoethanolamine, 5 parts by weight of choline and 3 parts by weight of putrescine were dissolved in 1,000 parts by weight of the solvent obtained in step A, mixed evenly and heated to 60°C. Then 50 parts by weight of lysine was added, stirred for dissolution and cooled. A 4 mol/L aqueous potassium pyrophosphate solution was used to adjust pH to 9 to obtain the chelating carrier. Example 2: Preparation of a chelating carrier of the present invention The example included steps as follows: A. Solvent preparation 10 parts by weight of glycerin and 2 parts by weight of phenol were dissolved in 1,000 parts by weight of water, stirred and mixed evenly to obtain the solvent.
B. Preparation of an alkaline chelating carrier 100 parts by weight of diethanolamine, 3 parts by weight of acetylcholine and 1 part by weight of spermidine were dissolved in 1,000 parts by weight of the solvent obtained in step A, mixed evenly and heated to 60°C. Then 20 parts by weight of arginine was added, stirred for dissolution and cooled. 1 mol/L aqueous potassium pyrophosphate solution was used to adjust pH to 9 to obtain the chelating carrier. Example 3: Preparation of a chelating carrier of the present invention The example included steps as follows: A. Solvent preparation 100 parts by weight of ethylene glycol and 10 parts by weight of phenol were dissolved in 1,000 parts by weight of water, stirred and mixed evenly to obtain the solvent; B. Preparation of an alkaline chelating carrier 100 parts by weight of triethanolamine, 8 parts by weight of choline chloride and 3 parts by weight of spermine were dissolved in 1,000 parts by weight of the solvent obtained in step A, mixed evenly and heated to 60°C. Then 60 parts by weight of methionine was added, stirred for dissolution and cooled. A 5 mol/L aqueous potassium pyrophosphate solution was used to adjust pH to 9 to obtain the chelating carrier. Example 4: Preparation of a chelating carrier of the present invention The example included steps as follows: A. Solvent preparation 20 parts by weight of glycerin and 3 parts by weight of phenol were dissolved in 1,000 parts by weight of water, stirred and mixed evenly to obtain the solvent; B. Preparation of an alkaline chelating carrier 100 parts by weight of N-methyldiethanolamine, 2 parts by weight of a mixture of choline and acetylcholine (with a weight ratio of 1:1) and 2 parts by weight of a mixture of putrescine and spermine (with a weight ratio of 2:1) were dissolved in 1,000 parts by weight of the solvent obtained in step A, mixed evenly and heated to 60°C. Then 30 parts by weight of omithine was added, stirred for dissolution and cooled. A 2 mol/L aqueous potassium pyrophosphate solution was used to adjust pH to 9 to obtain the chelating carrier. Example 5: Preparation of a chelating carrier of the present invention The example included steps as follows: A. Solvent preparation 75 parts by weight of ethylene glycol and 8 parts by weight of phenol were dissolved in 1,000 parts by weight of water, stirred and mixed evenly to obtain the solvent. B. Preparation of an alkaline chelating carrier
100 parts by weight of a mixture of diethanolamine and N-methyldiethanolamine (with a weight ratio of 2:1), 9 parts by weight of a mixture of acetylcholine and choline chloride (with a weight ratio of 1:3) and 4 parts by weight of a mixture of spermidine and spermine (with a weight ratio of 1:4) were dissolved in 1,000 parts by weight of the solvent obtained in step A, mixed evenly and heated to 60°C. Then 40 parts by weight of a mixture of lysine and arginine (with a weight ratio of 1:1) was added, stirred for dissolution and cooled. A 3 mol/L aqueous potassium pyrophosphate solution was used to adjust pH to 9 to obtain the chelating carrier. Example 6: Preparation of a chelating carrier of the present invention The example included steps as follows: A. Solvent preparation 90 parts by weight of ethylene glycol and 7 parts by weight of phenol were dissolved in 1,000 parts by weight of water, stirred and mixed evenly to obtain the solvent. B. Preparation of an alkaline chelating carrier 100 parts by weight of a mixture of monoethanolamine and diethanolamine (with a weight ratio of 1:2), 10 parts by weight of a mixture of choline and acetylcholine (with a weight ratio of 1:1) and 5 parts by weight of a mixture of putrescine, spermidine and spermine (with a weight ratio of 1:1:1) were dissolved in 1,000 parts by weight of the solvent obtained in step A, mixed evenly and heated to 60°C. Then 45 parts by weight of a mixture of lysine, arginine and methionine (with a weight ratio of 1:2:1) was added, stirred for dissolution and cooled. A 3 mol/L aqueous potassium pyrophosphate solution was used to adjust pH to 9 to obtain the chelating carrier. Example 7: Preparation of an alkaline liquid fertilizer of secondary nutrients with the chelating carrier The example included steps as follows: The chelating carrier prepared in Example 1 was used in this example. A water-soluble calcium nitrate and a water-soluble magnesium nitrate were mixed evenly in a weight ratio of 1:1. The mixture was then mixed with the chelating carrier prepared in Example 1 in a weight ratio of 1:40 and dissolved with water to obtain the alkaline liquid fertilizer of secondary nutrients. Example 8: Preparation of an alkaline liquid fertilizer of secondary and micronutrients with the chelating carrier The example included steps as follows: The chelating carrier prepared in Example 2 was used in this example. A water-soluble calcium chloride, a water-soluble magnesium chloride, a water-soluble zinc sulfate, and a water-soluble manganese sulfate were mixed evenly in a weight ratio of
1:0.5:0.1:0.1. The mixture was then mixed with the chelating carrier prepared in Example 2 in a weight ratio of 1:60 and dissolved with water to obtain the alkaline liquid fertilizer of secondary ) and micronutrients. Example 9: Preparation of an alkaline liquid fertilizer of secondary and micronutrients with the chelating carrier The example included steps as follows: The chelating carrier prepared in Example 3 was used in this example. A water-soluble calcium nitrate, a water-soluble magnesium chloride, a water-soluble zinc chloride, a water-soluble manganese sulfate, and a water-soluble copper sulfate were mixed evenly in a weight ratio of 1:1:0.2:0.1:0.05. The mixture was then mixed with the chelating carrier prepared in Example 3 in a weight ratio of 1:1 and dissolved with water to obtain the alkaline liquid fertilizer of secondary and micronutrients. Example 10: Preparation of an alkaline liquid fertilizer of secondary and micronutrients with the chelating carrier The example included steps as follows: The chelating carrier prepared in Example 4 was used in this example. A water-soluble calcium chloride, a water-soluble magnesium nitrate, a water-soluble zinc sulfate, a water-soluble manganese chloride, and a water-soluble copper sulfate were mixed evenly in a weight ratio of 1:0.5:0.2:0.1:0.1. The mixture was then mixed with the chelating carrier for secondary and micronutrients prepared in Example 4 in a weight ratio of 1:20 and dissolved with water to obtain the alkaline liquid fertilizer of secondary and micronutrients. Example 11: Preparation of an alkaline liquid fertilizer of secondary and micronutrients with the chelating carrier The example included steps as follows: The chelating carrier prepared in Example 5 was used in this example. A water-soluble calcium nitrate, a water-soluble magnesium chloride, a water-soluble zinc chloride, a water-soluble manganese chloride, a water-soluble copper chloride, and a water soluble ferrous sulfate were mixed evenly in a weight ratio of 1:1:0.5:0.2:0.1:0.2. The mixture was then mixed with the chelating carrier prepared in Example 5 in a weight ratio of 1:80 and dissolved with water to obtain the alkaline liquid fertilizer of secondary and micronutrients. Example 12: Preparation of an alkaline liquid fertilizer of micronutrients with the chelating carrier The example included steps as follows: The chelating carrier prepared in Example 6 was used in this example. A water-soluble zinc sulfate, a water-soluble manganese chloride, a water-soluble copper sulfate, and a water-soluble ammonium ferrous sulfate were mixed evenly in a weight ratio of 1:0.4:0.2:0.2. The mixture was then mixed with the chelating carrier prepared in Example 6 in a weight ratio of 1:100 and dissolved with water to obtain the alkaline liquid fertilizer of micronutrients. In the above Examples 7-12, the alkaline liquid fertilizer of secondary and micronutrients was successfully prepared, where secondary and micronutrients were soluble, and there was no precipitation. II. Test Examples Test Example 1: Effect of the chelating carrier for secondary and micronutrients of the present invention on growth and activity of crop roots A sand culture experiment was conducted to study the effect of the chelating carriers prepared in Examples 1, 2 and 4 on growth and activity of wheat roots. Test samples: The chelating carriers prepared in Examples 1, 2 and 4 were added to Hoagland nutrient solutions in an amount of 0.2 g/L, and marked as A, B, or C, respectively. The Hoagland nutrient solution with no chelating carrier was also prepared as control, labeled with CK. Test method: A 500 mL culture bowl (which had a drainage hole at the bottom) was filled with the conventionally treated quartz sand, and the surface of the quartz sand was kept 2-3 cm away from an edge of the bowl. The test crop was planted in the culture bowl, and each treatment was repeated 6 times. 100 mL nutrient solution was used for irrigation every 4 d to maintain a certain humidity and nutrient concentration. Measurement method: On the 21st day after the crop emerges, the plant was harvested to weigh the fresh root, and determine the root activity with 2,3,5-triphenyltetrazolium chloride (TTC) by using a routine colorimetric method as described in Experimental Guide for Plant Physiology (South China University of Technology Press, 2015). The results were shown in Table 1. Table 1: Effect of the chelating carriers of the present invention on growth and activity of crop roots Item Treatment CK A B C Fresh weight of root (g) 1.26 1.88 2.16 1.94 Root activity ([g/g-h) 582 824 852 830
The absorption capacity of crop roots was an important factor in determining fertilizer utilization. As can be seen from Table 1, compared with the control, the fresh weight and activity of the wheat root treated with sample A, B or C were increased by an average of 58.2% and 4 3 .5%, respectively. Test Example 2: Effect of the alkaline liquid fertilizer of the micronutrient zinc of the present invention on growth and zinc utilization of Brassicachinensis L. Test samples: Zinc sulfate heptahydrate was mixed with the chelating carriers prepared in Example 1, 2 or 4 in a weight ratio of 1:50 respectively to obtain the alkaline liquid fertilizers of the micronutrient zin of the present invention. These samples were marked as Ai, B1, or C 1
, respectively. Zinc sulfate heptahydrate and water in a weight ratio 1:50 were used as control, marked as CK. Test method: 4 kg air-dried soil screened through a 2 mm sieve was mixed evenly with a base fertilizer and put in a polypropylene pot with a height of 225 mm and a diameter of 225 mm. Fertilizer and application rate: the base fertilizer was composed of 1.66 g urea (N 46.2%), 1.11 g diammonium phosphate (18-46-0) and 1.11 g potassium sulfate (K20 500%). 10 seeds of Brassica chinensis L. were sown in each pot. The final singling of seedlings was conducted at the three-leaf stage, and three plants were left in each pot. Each treatment was repeated 6 times. Application methods of test fertilizers: foliar spray or irrigation with water. The seedlings were sprayed at the four-leaf stage. The spray dosage was 20 mL/pot once, and the spray was repeated once every 7 days. There were 5 times of spray conducted during the culture. The Brassica chinensis L. was harvested on day 5 after the last foliar spay. Irrigation with water was carried out in an application amount and management the same as those with spray. Measurement method: The fresh weight of harvested plant was measured, and quality indicators of Vc, soluble sugar and the like were determined with two fresh leaves per plant according to the standard methods described in Experimental Guide for Plant Physiology (South China University of Technology Press, 2015). The rest was subjected to fixation at 105°C for half an hour, dried, and weighed to obtain the amount of the biomass; and then crushed and measured with an atomic absorption spectrophotometry according to Analysis Method for Soil Agrochemistry (China Agricultural Science and Technology Press, 1999) to determine the total zinc content of the plant. The utilization rate of zinc was calculated according to the following formula: utilization rate of zinc=(zinc content of aboveground partxfresh weight of aboveground part)/amount of zinc appliedx100%. Test results were listed in Table 2 and Table 3.
Table 2: Effect of spraying application of different zinc fertilizers on growth, quality and utilization rate of zinc of Brassica chinensis L. Treatment Fresh weight (g/pot) Vc (mg/100 g) Soluble sugar (mg/g) Utilization rate of zinc (%) CK 108.72 43.27 2.36 11.6 Ai 151.22 92.07 4.70 17.4 B1 158.70 66.20 8.37 20.3 C1 142.07 82.80 7.89 19.6
As can be seen from Table 2, compared with CK, foliar spray with the alkaline liquid fertilizer of the micronutrient zinc of the present invention increased the fresh weight, Vc content, soluble sugar content and utilization rate of zinc of Brassica chinensis L. by an average of 38.6%, 85.7%, 196% and 64.6%, respectively. Table 3: Effect of irrigation with different zinc fertilizers on growth, quality and utilization rate of zinc of Brassica chinensis L. Treatment Fresh weight (g/pot) Vc (mg/100 g) Soluble sugar (mg/g) Utilization rate of zinc(%) CK 110.55 89.67 7.73 4.61 Ai 128.69 94.40 10.99 6.31 B1 154.57 98.93 8.40 7.49 C1 190.98 109.13 13.25 6.36
As can be seen from Table 3, compared with CK, the irrigation with the alkaline liquid fertilizer of the micronutrient zinc of the present invention increased the fresh weight, Vc content, soluble sugar content and utilization rate of zinc of Brassica chinensis L. by an average of 43.0%, 12.4%, 40.8% and 45.8%, respectively. It can be seen that, the alkaline liquid fertilizers of secondary and micronutrients prepared in the present invention can significantly increase crop root activity, aboveground biomass, utilization rate of microelement, and improve crop quality.

Claims (5)

  1. What is claimed is: 1. A chelating carrier for secondary and micronutrients, wherein the chelating carrier comprises 100 parts by weight of alcohol amine, 2-10 parts by weight of choline, 1-5 parts by weight of polyamine, 20-60 parts by weight of amino acid and 1,000 parts by weight of solvent; wherein the solvent comprises 10-100 parts by weight of ethylene glycol or glycerin, 2-10 parts by weight of phenol and 1,000 parts by weight of water; wherein the alcohol amine is one or more selected from monoethanolamine, diethanolamine, triethanolamine and N methyldiethanolamine, the choline is one or more selected from choline, acetylcholine or choline chloride, the polyamine is one or more selected from putrescine, spermidine or spermine, and the amino acid is one or more selected from lysine, arginine, methionine or omithine; wherein a weight ratio of the ethylene glycol or the glycerin to the phenol to the water is (10-75):(2 8):1,000, and a weight ratio of the alcohol amine to the choline to the polyamine to the amino acid is 100:(3-8):(2-4):(20-50); or a weight ratio of the ethylene glycol or the glycerin to the phenol to the water is (20-75):(3-8):1,000, and a weight ratio of the alcohol amine to the choline to the polyamine to the amino acid is 100:(3-8):(2-4):(30-50).
  2. 2. Use of the chelating carrier according to claim 1 in preparation of an alkaline liquid fertilizer of secondary and micronutrients.
  3. 3. An alkaline liquid fertilizer of secondary and micronutrients, prepared by the following steps: A. Solvent preparation dissolving 10-100 parts by weight of ethylene glycol or glycerin and 2-10 parts by weight of phenol in 1,000 parts by weight of water, stirring and mixing evenly to obtain the solvent; B. Preparation of an alkaline chelating carrier dissolving 100 parts by weight of alcohol amine, 2-10 parts by weight of choline and 1-5 parts by weight of polyamine in 1,000 parts by weight of the solvent obtained in step A, mixing evenly, heating to 60-80°C, then adding 20-60 parts by weight of amino acid, stirring for dissolution, cooling, and adjust pH above 8.0 by using an aqueous potassium pyrophosphate solution to obtain a chelating carrier; C. Preparation of an alkaline liquid fertilizer of secondary and micronutrients mixing a water-soluble salt of secondary and micronutrients of calcium, magnesium, zinc, manganese, copper or iron with the chelating carrier obtained in step B in a weight ratio of 1:(1 100) and dissolving to obtain the alkaline liquid fertilizer of secondary and micronutrients.
  4. 4. The alkaline liquid fertilizer of secondary and micronutrients according to claim 3, wherein the aqueous potassium pyrophosphate solution has a concentration of 1-5 mol/L.
  5. 5. The alkaline liquid fertilizer of secondary and micronutrients according to claim 4, wherein the water-soluble salt of calcium is calcium nitrate or calcium chloride; the water soluble salt of magnesium is magnesium nitrate or magnesium chloride; the water-soluble salt of zinc is zinc sulfate or zinc chloride; the water-soluble salt of manganese is manganese sulfate or manganese chloride; the water-soluble salt of copper is copper sulfate or copper chloride; the water-soluble salt of iron is ferrous sulfate or ammonium ferrous sulfate.
    Institute of Agricultural Resources and Regional Planning, Chinese Academy of Agricultural Sciences
    Patent Attorneys for the Applicant/Nominated Person SPRUSON&FERGUSON
AU2020102034A 2020-08-28 2020-08-28 Chelating carrier for secondary and micronutrients and use thereof Ceased AU2020102034A4 (en)

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