CA3118770C - Chelating carrier for secondary nutrients and micronutrients and use thereof - Google Patents
Chelating carrier for secondary nutrients and micronutrients and use thereof Download PDFInfo
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- CA3118770C CA3118770C CA3118770A CA3118770A CA3118770C CA 3118770 C CA3118770 C CA 3118770C CA 3118770 A CA3118770 A CA 3118770A CA 3118770 A CA3118770 A CA 3118770A CA 3118770 C CA3118770 C CA 3118770C
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/45—Form not covered by groups C05G5/10 - C05G5/18, C05G5/20 - C05G5/27, C05G5/30 - C05G5/38 or C05G5/40, e.g. soluble or permeable packaging
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C5/00—Fertilisers containing other nitrates
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C5/00—Fertilisers containing other nitrates
- C05C5/04—Fertilisers containing other nitrates containing calcium nitrate
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D3/00—Calcareous fertilisers
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Abstract
Disclosed by the present invention are a chelate carrier for medium/trace nutrient element and use thereof. The chelate carrier for medium/trace nutrient element consists of alkylol amine, choline, polyamine, amino acid and a solvent. The fresh weight and the activity of wheat root systems treated with the chelate carrier are respectively increased by 58.2% and 43.5% on average as compared with those of controls. A trace element zinc alkali liquid fertilizer prepared according to the present invention is capable of remarkably increasing the weights of ground parts of pakchoi and the utilization rate of trace elements, and also has an effect of quality improvement.
Description
CHELATING CARRIER FOR SECONDARY NUTRIENTS AND
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 nutrients and micronutrients, and use thereof.
BACKGROUND
In the last three decades, nitrogen, phosphorus and potassium fertilizers were applied in large quantities to increase crop yields, and cash crops, such as fruit trees and vegetables, were quickly developed because of planting industry restructuring. The above brings about an increasingly serious microelement malnutrition problem for crops, which limits further improvement of crop yield and quality. For secondary nutrient deficiencies, 64% by area of existing cultivated soil has a calcium content below the deficiency threshold, 53% by area of existing cultivated soil has a magnesium content below the deficiency threshold, and 40% by area of existing cultivated soil has a sulfur content below the deficiency threshold; and for micronutrients, 84% by area of existing cultivated soil has a boron content below the deficiency threshold, 31% by area of existing cultivated soil has an iron content below the deficiency threshold, 42% by area of existing cultivated soil has a zinc content below the deficiency threshold, 48% by area of existing cultivated soil has a manganese content below the deficiency threshold, 25% by area of existing cultivated soil has a copper content below the deficiency threshold and 59% by area of existing cultivated soil has a molybdenum content below the deficiency threshold. Compared with the results from the second national soil survey, the soil area of element deficiency almost doubled. Improper fertilization results in a pH reduction of the cultivated soil by 0.85 units, with the area of acidified soil accounting for 21.6% of the total cultivated area. Alkaline fertilizers, especially alkaline liquid fertilizers of secondary nutrients and micronutrients with excellent water solubility are highly desirable for national food safety and agricultural product quality in future.
Conventional secondary nutrients and micronutrients such as calcium, magnesium, copper, zinc, iron and manganese could not show good water solubility unless under acidic conditions, and will precipitate under alkaline conditions, leading to a poor performance and inconvenience for application. Current methods for improving the water solubility of secondary and micronutrients include using chelating materials such as EDTA, organic acids, sugar alcohols, amino acids to improve their effectiveness. Such methods will aggravate the acidify of an acidic soil, and precipitates will occur in the case of alkaline hard water, which result in decreased effectiveness, and block drip irrigation tubes, thereby affecting normal agricultural production.
CN106748096A discloses an alkaline fertilizer prepared from raw materials of secondary nutrients, pine pollen, polyglutamic acid solution, sulfuric acid, ammonium chloride, red potash, Si-Ca-K fertilizer and monoammonium phosphate and the like. CN104876769B
discloses an alkaline silicon-containing fertilizer for ameliorating soil acidification and a preparation method thereof. The fertilizer is prepared from raw materials of potassium silicate, potassium humate, urea, ammonium molybdate, EDTA, diethylaminoethanol hexanoate, compound sodium nitrophenolate, ground phosphate rock, calcium chloride, natural potassium magnesium sulfate fertilizer and mature compost. The fertilizer can improve acidic soil.
discloses a production process for organic chelated microelement fertilizer by extracting humus from lignite, precipitating to obtain a required liquid, adding citric acid or its salts as the organic chelating agent and microelements, adjusting pH to neutral with an acid or base, and drying to obtain the product. CN106146163A discloses a method for producing sugar alcohol chelated secondary elements by adding secondary elements, a sugar alcohol and a solvent to a reactor to carry out the chelation reaction at a certain temperature to obtain the sugar alcohol chelated secondary nutrients. CN105948955A discloses a method for producing a fertilizer containing sugar alcohol chelated microelements by preparing sugar alcohol chelated microelements, and then adding the sugar alcohol chelated microelements to a fertilizer to obtain the fertilizer containing sugar alcohol chelated microelements. However, a chelating carrier for secondary and microelement fertilizers has not been reported in any prior patent applications or documents.
In view of the above, the present invention was accomplished based on plenty of experimental research and analysis aiming at solve the technical problems existing in the prior art.
SUMMARY
[Technical Problem to Be Solved]
An object of the present invention is to provide a chelating carrier for secondary nutrients and micronutrients.
Another object of the present invention is to provide use of the chelating carrier for secondary nutrients and micronutrients.
[Technical Solution]
The present invention is embodied by the following embodiments.
The present invention relates to a chelating carrier for secondary nutrients and micronutrients.
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 nutrients and micronutrients, and use thereof.
BACKGROUND
In the last three decades, nitrogen, phosphorus and potassium fertilizers were applied in large quantities to increase crop yields, and cash crops, such as fruit trees and vegetables, were quickly developed because of planting industry restructuring. The above brings about an increasingly serious microelement malnutrition problem for crops, which limits further improvement of crop yield and quality. For secondary nutrient deficiencies, 64% by area of existing cultivated soil has a calcium content below the deficiency threshold, 53% by area of existing cultivated soil has a magnesium content below the deficiency threshold, and 40% by area of existing cultivated soil has a sulfur content below the deficiency threshold; and for micronutrients, 84% by area of existing cultivated soil has a boron content below the deficiency threshold, 31% by area of existing cultivated soil has an iron content below the deficiency threshold, 42% by area of existing cultivated soil has a zinc content below the deficiency threshold, 48% by area of existing cultivated soil has a manganese content below the deficiency threshold, 25% by area of existing cultivated soil has a copper content below the deficiency threshold and 59% by area of existing cultivated soil has a molybdenum content below the deficiency threshold. Compared with the results from the second national soil survey, the soil area of element deficiency almost doubled. Improper fertilization results in a pH reduction of the cultivated soil by 0.85 units, with the area of acidified soil accounting for 21.6% of the total cultivated area. Alkaline fertilizers, especially alkaline liquid fertilizers of secondary nutrients and micronutrients with excellent water solubility are highly desirable for national food safety and agricultural product quality in future.
Conventional secondary nutrients and micronutrients such as calcium, magnesium, copper, zinc, iron and manganese could not show good water solubility unless under acidic conditions, and will precipitate under alkaline conditions, leading to a poor performance and inconvenience for application. Current methods for improving the water solubility of secondary and micronutrients include using chelating materials such as EDTA, organic acids, sugar alcohols, amino acids to improve their effectiveness. Such methods will aggravate the acidify of an acidic soil, and precipitates will occur in the case of alkaline hard water, which result in decreased effectiveness, and block drip irrigation tubes, thereby affecting normal agricultural production.
CN106748096A discloses an alkaline fertilizer prepared from raw materials of secondary nutrients, pine pollen, polyglutamic acid solution, sulfuric acid, ammonium chloride, red potash, Si-Ca-K fertilizer and monoammonium phosphate and the like. CN104876769B
discloses an alkaline silicon-containing fertilizer for ameliorating soil acidification and a preparation method thereof. The fertilizer is prepared from raw materials of potassium silicate, potassium humate, urea, ammonium molybdate, EDTA, diethylaminoethanol hexanoate, compound sodium nitrophenolate, ground phosphate rock, calcium chloride, natural potassium magnesium sulfate fertilizer and mature compost. The fertilizer can improve acidic soil.
discloses a production process for organic chelated microelement fertilizer by extracting humus from lignite, precipitating to obtain a required liquid, adding citric acid or its salts as the organic chelating agent and microelements, adjusting pH to neutral with an acid or base, and drying to obtain the product. CN106146163A discloses a method for producing sugar alcohol chelated secondary elements by adding secondary elements, a sugar alcohol and a solvent to a reactor to carry out the chelation reaction at a certain temperature to obtain the sugar alcohol chelated secondary nutrients. CN105948955A discloses a method for producing a fertilizer containing sugar alcohol chelated microelements by preparing sugar alcohol chelated microelements, and then adding the sugar alcohol chelated microelements to a fertilizer to obtain the fertilizer containing sugar alcohol chelated microelements. However, a chelating carrier for secondary and microelement fertilizers has not been reported in any prior patent applications or documents.
In view of the above, the present invention was accomplished based on plenty of experimental research and analysis aiming at solve the technical problems existing in the prior art.
SUMMARY
[Technical Problem to Be Solved]
An object of the present invention is to provide a chelating carrier for secondary nutrients and micronutrients.
Another object of the present invention is to provide use of the chelating carrier for secondary nutrients and micronutrients.
[Technical Solution]
The present invention is embodied by the following embodiments.
The present invention relates to a chelating carrier for secondary nutrients and micronutrients.
2 The chelating carrier comprises 100 parts by weight of an alcohol amine, 2-10 parts by weight of a choline, 1-5 parts by weight of a polyamine, 20-60 parts by weight of an amino acid and 1,000 parts by weight of a solvent, where 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.
According to a preferred embodiment of the present invention, the alcohol amine is one or more selected from monoethanolamine, diethanolamine, triethanolamine and N-methyldiethanolamine.
According to another preferred embodiment of the present invention, the choline is one or more selected from choline, acetylcholine and choline chloride.
According to another preferred embodiment of the present invention, the polyamine is one or more selected from putrescine, spermidine and spermine.
According to another preferred embodiment of the present invention, the amino acid is one or more selected from lysine, arginine, methionine and ornithine.
According to another preferred embodiment of the present invention, the weight ratio of ethylene glycol or glycerin to phenol to the water is (10-75) : (2-8) : 1,000, and/or the 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 embodiment of the present invention, the weight ratio of ethylene glycol or glycerin to phenol to the water is (20-75) : (3-8) : 1,000, and/or the 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 nutrients and micronutrients.
According to a preferred embodiment of the present invention, the preparation of an alkaline liquid fertilizer of secondary nutrients and micronutrients includes 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, mixing homogeneously under stifling to obtain the solvent;
B. Preparation of an alkaline chelating carrier dissolving 100 parts by weight of an alcohol amine, 2-10 parts by weight of a choline and 1-5 parts by weight of a polyamine in 1,000 parts by weight of the solvent obtained in step A, mixing homogeneously, heating to a temperature of 60-80 C, then adding 20-60 parts by weight of an amino acid, stirring to dissolve, cooling, and adjusting pH to 8.0 or higher by using an aqueous potassium pyrophosphate solution to obtain an alkaline chelating carrier;
According to a preferred embodiment of the present invention, the alcohol amine is one or more selected from monoethanolamine, diethanolamine, triethanolamine and N-methyldiethanolamine.
According to another preferred embodiment of the present invention, the choline is one or more selected from choline, acetylcholine and choline chloride.
According to another preferred embodiment of the present invention, the polyamine is one or more selected from putrescine, spermidine and spermine.
According to another preferred embodiment of the present invention, the amino acid is one or more selected from lysine, arginine, methionine and ornithine.
According to another preferred embodiment of the present invention, the weight ratio of ethylene glycol or glycerin to phenol to the water is (10-75) : (2-8) : 1,000, and/or the 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 embodiment of the present invention, the weight ratio of ethylene glycol or glycerin to phenol to the water is (20-75) : (3-8) : 1,000, and/or the 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 nutrients and micronutrients.
According to a preferred embodiment of the present invention, the preparation of an alkaline liquid fertilizer of secondary nutrients and micronutrients includes 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, mixing homogeneously under stifling to obtain the solvent;
B. Preparation of an alkaline chelating carrier dissolving 100 parts by weight of an alcohol amine, 2-10 parts by weight of a choline and 1-5 parts by weight of a polyamine in 1,000 parts by weight of the solvent obtained in step A, mixing homogeneously, heating to a temperature of 60-80 C, then adding 20-60 parts by weight of an amino acid, stirring to dissolve, cooling, and adjusting pH to 8.0 or higher by using an aqueous potassium pyrophosphate solution to obtain an alkaline chelating carrier;
3 C. Preparation of an alkaline liquid fertilizer of secondary nutrients and micronutrients mixing a water-soluble salt of calcium, magnesium, zinc, manganese, copper and/or iron as the secondary nutrients and micronutrients 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 nutrients and micronutrients.
According to another preferred embodiment of the present invention, the concentration of the aqueous potassium pyrophosphate solution is 1-5 mol/L.
According to another preferred embodiment 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 will be further described in detail below.
The present invention relates to a chelating carrier for secondary nutrients and micronutrients.
Herein, it will be noted that the chelating carrier for secondary nutrients and micronutrients may be abbreviated as "chelating carrier", and both of them have the same meaning.
The chelating carrier comprises 100 parts by weight of an alcohol amine, 2-10 parts by weight of a choline, 1-5 parts by weight of a polyamine, 20-60 parts by weight of an amino acid and 1,000 parts by weight of a solvent, where the solvent comprises10-100 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 nutrients and micronutrients to form chelates which are soluble under alkaline conditions.
The alcohol amine used in the present invention is one or more selected from monoethanolamine, diethanolamine, triethanolamine and N-methyldiethanolamine.
The alcohol amines are all commercially available, for example, under the trade name "monoethanolamine (MEA)" from Shanghai Minchen Chemical Co., Ltd., and under the trade name "N-methyldiethanolamine (MDEA)" from Zouping County Guoan Chemical Co., Ltd..
In the present invention, the choline in the chelating carrier is mainly used to increase alkalinity of an alkaline liquid fertilizer of secondary nutrients and micronutrients and to enhance the stability of the secondary nutrients and micronutrients in the alkaline liquid fertilizer. Moreover, the choline has a biological activity in promoting synthesis and transportation of photosynthates in crops.
According to another preferred embodiment of the present invention, the concentration of the aqueous potassium pyrophosphate solution is 1-5 mol/L.
According to another preferred embodiment 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 will be further described in detail below.
The present invention relates to a chelating carrier for secondary nutrients and micronutrients.
Herein, it will be noted that the chelating carrier for secondary nutrients and micronutrients may be abbreviated as "chelating carrier", and both of them have the same meaning.
The chelating carrier comprises 100 parts by weight of an alcohol amine, 2-10 parts by weight of a choline, 1-5 parts by weight of a polyamine, 20-60 parts by weight of an amino acid and 1,000 parts by weight of a solvent, where the solvent comprises10-100 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 nutrients and micronutrients to form chelates which are soluble under alkaline conditions.
The alcohol amine used in the present invention is one or more selected from monoethanolamine, diethanolamine, triethanolamine and N-methyldiethanolamine.
The alcohol amines are all commercially available, for example, under the trade name "monoethanolamine (MEA)" from Shanghai Minchen Chemical Co., Ltd., and under the trade name "N-methyldiethanolamine (MDEA)" from Zouping County Guoan Chemical Co., Ltd..
In the present invention, the choline in the chelating carrier is mainly used to increase alkalinity of an alkaline liquid fertilizer of secondary nutrients and micronutrients and to enhance the stability of the secondary nutrients and micronutrients in the alkaline liquid fertilizer. Moreover, the choline has a biological activity in promoting synthesis and transportation of photosynthates in crops.
4 The choline used in the present invention is one or more selected from choline, acetylcholine and choline chloride. The choline is commercially available, for example, under the trade name "choline" from Xi'an Laweiya Biotechnology Co., Ltd., under the trade name "acetylcholine" from He'nan Xingyuan Chemical Products Co., Ltd., and under the trade name "choline chloride" from Wuxi Shengshihongcheng Biotechnology Co., Ltd..
In the chelating carrier of the present invention, if the amount of the choline is less than 2 parts by weight, the effect thereof to increase the stability of the secondary nutrients and micronutrients in the alkaline liquid fertilizer will not be significant; if the amount of the choline is higher than 10 parts by weight, the production cost of the chelating carrier will increase, in the case that the amounts of other components are within the above described ranges. Therefore, it is desirable that the amount of the choline is 2-10 parts by weight, 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, promoting 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 and spermine. The polyamine is commercially available, for example, under the trade name "putrescine" from Shanghai Yihe Biotechnology Co., Ltd., under the trade name "spermidine" from Hubei Wande Chemical Co., Ltd., or under the trade name "spermine" from Qingdao Jieshikang Biotechnology Co., Ltd.
In the chelating carrier of the present invention, if the amount of the polyamine is less than 1 part by weight, the effect of promoting crop growth, improving seed activity and germination and the like will not be significant; if the amount of polyamine is higher than 5 parts by weight, the production cost of the chelating carrier will increase, in the case that the amounts of other components are within the above described ranges. Therefore, it is desirable that the amount of the polyamine is 1-5 parts by weight, 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 the secondary nutrients and micronutrients. The amino acid also participates in synthesis of polyamines in a plant, and improves the stability of the secondary nutrients and micronutrients in the alkaline liquid fertilizer of secondary nutrients and micronutrients.
The amino acid used in the present invention is one or more selected from lysine, arginine, methionine and ornithine. The amino acids are commercially available, for example, under the trade name "lysine" from Xijie (Shenyang) Biotechnology Co., Ltd., under the trade name arginine" from Shandong Dongrun Biotechnology Co., Ltd., under the trade name methionine" from Jiangsu Xinheyuan Biotechnology Co., Ltd., or under the trade name "ornithine" from Jiangsu Caiwei Biotechnology Co., Ltd..
In the chelating carrier of the present invention, if the amount of the amino acid is less than 20 parts by weight, there will be a limited chelating effect due to the low amount of the formed amino acid-organic base chelate; if the amount of the amino acid is higher than 60 parts by weight, the amino acid may precipitate depending on factors such as storage temperature, in the case that the amounts of other components are within the above described ranges. Therefore, it is desirable that the amount of the amino acid is 20-60 parts by weight, preferably 30-50 parts by weight, more preferably 36-42 parts by weight.
Preferably, the 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 comprises10-100 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 as a polyol can promote dissolution of an organic base, and increase the stability and fluidity of the alkaline liquid fertilizer of secondary nutrients and micronutrients. If the amount of ethylene glycol or glycerin is less than 10 parts by weight, the prepared alkaline liquid fertilizer of secondary nutrients and micronutrients will show poor stability. If the amount of ethylene glycol or glycerin is higher than 100 parts by weight, the prepared alkaline liquid fertilizer of secondary nutrients and micronutrients will show a high viscosity, which affects dissolution of the organic base and the secondary nutrients and micronutrients.
Phenol can promote dissolution of the organic base, and further enhance the stability of the secondary nutrients and micronutrients in the alkaline liquid fertilizer of secondary nutrients and micronutrients. If the amount of phenol is less than 2 parts by weight, the effect of improving the stability of the alkaline liquid fertilizer of secondary nutrients and micronutrients will not be significant. If the amount of phenol is higher than 10 parts by weight, the production cost will increase.
Preferably, the weight ratio of ethylene glycol or glycerin to phenol to water is (10-75) :
(2-8) : 1,000, or (20-75) : (3-8) : 1,000.
The present invention also relates to use of the chelating carrier in preparation of an alkaline liquid fertilizer of secondary nutrients and micronutrients.
The preparation of an alkaline liquid fertilizer of secondary nutrients and micronutrients includes the steps as described hereinbelow:
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, mixing homogeneously under stifling to obtain the solvent.
B. Preparation of an alkaline chelating carrier dissolving 100 parts by weight of an alcohol amine, 2-10 parts by weight of a choline and 1-5 parts by weight of a polyamine in 1,000 parts by weight of the solvent obtained in step A, mixing homogeneously, heating to 60-80 C, then adding 20-60 parts by weight of an amino acid, stirring to dissolve, cooling, and adjusting pH to 8.0 or higher 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 description regarding ethylene glycol or glycerin, phenol, alcohol amine, choline, polyamine and amino acid provided hereinabove may be applied here.
C. Preparation of an alkaline liquid fertilizer of secondary nutrients and micronutrients mixing a water-soluble salt of calcium, magnesium, zinc, manganese, copper and/or iron as the secondary nutrients and micronutrients 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 nutrients 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 nutrients and micronutrients in the present invention has the following characteristics:
A. The chelating carrier of the present invention can be used in preparation of an alkaline liquid fertilizer of secondary nutrients and micronutrients.
B. The chelating carrier of the present invention is alkaline, which can regulate the pH of acidic soil.
C. The alkaline liquid fertilizer comprising calcium and/or magnesium chelated by the chelating carrier of the present invention will not precipitate when applied via irrigation or foliar spray with water of high hardness.
D. The alkaline liquid fertilizer of secondary nutrients and micronutrients of the present invention, when used for foliar spray, can promote absorption of the secondary nutrients and micronutrients, improve accumulation of carbon dioxide on foliage of crops, and enhance photosynthesis. When the fertilizer is applied to soil, the secondary nutrients and microelements can also be absorbed by crops. In addition, the 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 nutrients and micronutrients of the present invention can be used in preparation of an alkaline liquid fertilizer of secondary nutrients and micronutrients such that the secondary nutrients and micronutrients are soluble without precipitating even under alkaline conditions to achieve a higher utilization rate.
B. The chelating carrier for secondary nutrients and micronutrients of the present invention is alkaline which can regulate the soil pH of acidic soil.
C. The alkaline liquid fertilizer of secondary nutrients and micronutrients of the present invention will not precipitate when applied via irrigation or foliar spray with water of high hardness.
D. The alkaline liquid fertilizer of secondary nutrients and micronutrients of the present invention, when used for foliar spray, can promote absorption of the secondary nutrients and micronutrients, improve the accumulation of carbon dioxide on foliage of crops, and enhance photosynthesis. In case of foliar spray of Brassica chinensis L. with the alkaline liquid fertilizer of secondary nutrients and micronutrients of the present invention, the fresh weight, vitamin C
(Vc) content, soluble sugar content and zinc utilization rate may be increased by 38.6%, 85.7%, 196% and 64.6% on average respectively, compared with CK.
E. When the alkaline liquid fertilizer of secondary nutrients and micronutrients of the present invention is applied to soil, the secondary nutrients and micronutrients will be absorbed by crops, stimulate growth of root system, improve root activity and promote absorption of the nutrients. In case of irrigation of Brassica chinensis L. with the alkaline liquid fertilizer of secondary nutrients and micronutrients of the present invention, the fresh weight, Vc content, soluble sugar content and zinc utilization rate may be increased by 43.0%, 12.4%, 40.8% and 45.8% on average respectively, compared with CK. In case of irrigation of wheat with the alkaline liquid fertilizer of secondary nutrients and micronutrients of the present invention, the root fresh weight and activity are increased by 58.2% and 43.5% on average respectively, compared with CK.
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 following steps are included.
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, mixed homogeneously under stifling 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 homogeneously 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 following steps are included.
A. Solvent preparation parts by weight of glycerin and 2 parts by weight of phenol were dissolved in 1,000 parts by weight of water, mixed homogeneously under stirring 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 homogeneously and heated to 60 C. Then 20 parts by weight of arginine was added, stifled for dissolution and cooled. A 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 following steps are included.
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, mixed homogeneously under stifling 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 homogeneously 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 following steps are included.
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, mixed homogeneously under stirring 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 homogeneously and heated to 60 C. Then 30 parts by weight of ornithine 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 following steps are included.
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, mixed homogeneously under stifling 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 homogeneously 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, stifled 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 following steps are included.
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, mixed homogeneously under stifling 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 homogeneously 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 following steps are included.
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 homogeneously 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 nutrients and micronutrients with the chelating carrier The following steps are included.
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 homogeneously 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 nutrients and micronutrients.
Example 9 Preparation of an alkaline liquid fertilizer of secondary nutrients and micronutrients with the chelating carrier The following steps are included.
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 homogeneously 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 nutrients and micronutrients.
Example 10 Preparation of an alkaline liquid fertilizer of secondary nutrients and micronutrients with the chelating carrier The following steps are included.
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 homogeneously 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 nutrients 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 nutrients and micronutrients.
Example 11 Preparation of an alkaline liquid fertilizer of secondary nutrients and micronutrients with the chelating carrier The following steps are included.
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 homogeneously 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
In the chelating carrier of the present invention, if the amount of the choline is less than 2 parts by weight, the effect thereof to increase the stability of the secondary nutrients and micronutrients in the alkaline liquid fertilizer will not be significant; if the amount of the choline is higher than 10 parts by weight, the production cost of the chelating carrier will increase, in the case that the amounts of other components are within the above described ranges. Therefore, it is desirable that the amount of the choline is 2-10 parts by weight, 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, promoting 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 and spermine. The polyamine is commercially available, for example, under the trade name "putrescine" from Shanghai Yihe Biotechnology Co., Ltd., under the trade name "spermidine" from Hubei Wande Chemical Co., Ltd., or under the trade name "spermine" from Qingdao Jieshikang Biotechnology Co., Ltd.
In the chelating carrier of the present invention, if the amount of the polyamine is less than 1 part by weight, the effect of promoting crop growth, improving seed activity and germination and the like will not be significant; if the amount of polyamine is higher than 5 parts by weight, the production cost of the chelating carrier will increase, in the case that the amounts of other components are within the above described ranges. Therefore, it is desirable that the amount of the polyamine is 1-5 parts by weight, 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 the secondary nutrients and micronutrients. The amino acid also participates in synthesis of polyamines in a plant, and improves the stability of the secondary nutrients and micronutrients in the alkaline liquid fertilizer of secondary nutrients and micronutrients.
The amino acid used in the present invention is one or more selected from lysine, arginine, methionine and ornithine. The amino acids are commercially available, for example, under the trade name "lysine" from Xijie (Shenyang) Biotechnology Co., Ltd., under the trade name arginine" from Shandong Dongrun Biotechnology Co., Ltd., under the trade name methionine" from Jiangsu Xinheyuan Biotechnology Co., Ltd., or under the trade name "ornithine" from Jiangsu Caiwei Biotechnology Co., Ltd..
In the chelating carrier of the present invention, if the amount of the amino acid is less than 20 parts by weight, there will be a limited chelating effect due to the low amount of the formed amino acid-organic base chelate; if the amount of the amino acid is higher than 60 parts by weight, the amino acid may precipitate depending on factors such as storage temperature, in the case that the amounts of other components are within the above described ranges. Therefore, it is desirable that the amount of the amino acid is 20-60 parts by weight, preferably 30-50 parts by weight, more preferably 36-42 parts by weight.
Preferably, the 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 comprises10-100 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 as a polyol can promote dissolution of an organic base, and increase the stability and fluidity of the alkaline liquid fertilizer of secondary nutrients and micronutrients. If the amount of ethylene glycol or glycerin is less than 10 parts by weight, the prepared alkaline liquid fertilizer of secondary nutrients and micronutrients will show poor stability. If the amount of ethylene glycol or glycerin is higher than 100 parts by weight, the prepared alkaline liquid fertilizer of secondary nutrients and micronutrients will show a high viscosity, which affects dissolution of the organic base and the secondary nutrients and micronutrients.
Phenol can promote dissolution of the organic base, and further enhance the stability of the secondary nutrients and micronutrients in the alkaline liquid fertilizer of secondary nutrients and micronutrients. If the amount of phenol is less than 2 parts by weight, the effect of improving the stability of the alkaline liquid fertilizer of secondary nutrients and micronutrients will not be significant. If the amount of phenol is higher than 10 parts by weight, the production cost will increase.
Preferably, the weight ratio of ethylene glycol or glycerin to phenol to water is (10-75) :
(2-8) : 1,000, or (20-75) : (3-8) : 1,000.
The present invention also relates to use of the chelating carrier in preparation of an alkaline liquid fertilizer of secondary nutrients and micronutrients.
The preparation of an alkaline liquid fertilizer of secondary nutrients and micronutrients includes the steps as described hereinbelow:
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, mixing homogeneously under stifling to obtain the solvent.
B. Preparation of an alkaline chelating carrier dissolving 100 parts by weight of an alcohol amine, 2-10 parts by weight of a choline and 1-5 parts by weight of a polyamine in 1,000 parts by weight of the solvent obtained in step A, mixing homogeneously, heating to 60-80 C, then adding 20-60 parts by weight of an amino acid, stirring to dissolve, cooling, and adjusting pH to 8.0 or higher 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 description regarding ethylene glycol or glycerin, phenol, alcohol amine, choline, polyamine and amino acid provided hereinabove may be applied here.
C. Preparation of an alkaline liquid fertilizer of secondary nutrients and micronutrients mixing a water-soluble salt of calcium, magnesium, zinc, manganese, copper and/or iron as the secondary nutrients and micronutrients 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 nutrients 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 nutrients and micronutrients in the present invention has the following characteristics:
A. The chelating carrier of the present invention can be used in preparation of an alkaline liquid fertilizer of secondary nutrients and micronutrients.
B. The chelating carrier of the present invention is alkaline, which can regulate the pH of acidic soil.
C. The alkaline liquid fertilizer comprising calcium and/or magnesium chelated by the chelating carrier of the present invention will not precipitate when applied via irrigation or foliar spray with water of high hardness.
D. The alkaline liquid fertilizer of secondary nutrients and micronutrients of the present invention, when used for foliar spray, can promote absorption of the secondary nutrients and micronutrients, improve accumulation of carbon dioxide on foliage of crops, and enhance photosynthesis. When the fertilizer is applied to soil, the secondary nutrients and microelements can also be absorbed by crops. In addition, the 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 nutrients and micronutrients of the present invention can be used in preparation of an alkaline liquid fertilizer of secondary nutrients and micronutrients such that the secondary nutrients and micronutrients are soluble without precipitating even under alkaline conditions to achieve a higher utilization rate.
B. The chelating carrier for secondary nutrients and micronutrients of the present invention is alkaline which can regulate the soil pH of acidic soil.
C. The alkaline liquid fertilizer of secondary nutrients and micronutrients of the present invention will not precipitate when applied via irrigation or foliar spray with water of high hardness.
D. The alkaline liquid fertilizer of secondary nutrients and micronutrients of the present invention, when used for foliar spray, can promote absorption of the secondary nutrients and micronutrients, improve the accumulation of carbon dioxide on foliage of crops, and enhance photosynthesis. In case of foliar spray of Brassica chinensis L. with the alkaline liquid fertilizer of secondary nutrients and micronutrients of the present invention, the fresh weight, vitamin C
(Vc) content, soluble sugar content and zinc utilization rate may be increased by 38.6%, 85.7%, 196% and 64.6% on average respectively, compared with CK.
E. When the alkaline liquid fertilizer of secondary nutrients and micronutrients of the present invention is applied to soil, the secondary nutrients and micronutrients will be absorbed by crops, stimulate growth of root system, improve root activity and promote absorption of the nutrients. In case of irrigation of Brassica chinensis L. with the alkaline liquid fertilizer of secondary nutrients and micronutrients of the present invention, the fresh weight, Vc content, soluble sugar content and zinc utilization rate may be increased by 43.0%, 12.4%, 40.8% and 45.8% on average respectively, compared with CK. In case of irrigation of wheat with the alkaline liquid fertilizer of secondary nutrients and micronutrients of the present invention, the root fresh weight and activity are increased by 58.2% and 43.5% on average respectively, compared with CK.
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 following steps are included.
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, mixed homogeneously under stifling 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 homogeneously 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 following steps are included.
A. Solvent preparation parts by weight of glycerin and 2 parts by weight of phenol were dissolved in 1,000 parts by weight of water, mixed homogeneously under stirring 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 homogeneously and heated to 60 C. Then 20 parts by weight of arginine was added, stifled for dissolution and cooled. A 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 following steps are included.
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, mixed homogeneously under stifling 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 homogeneously 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 following steps are included.
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, mixed homogeneously under stirring 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 homogeneously and heated to 60 C. Then 30 parts by weight of ornithine 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 following steps are included.
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, mixed homogeneously under stifling 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 homogeneously 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, stifled 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 following steps are included.
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, mixed homogeneously under stifling 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 homogeneously 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 following steps are included.
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 homogeneously 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 nutrients and micronutrients with the chelating carrier The following steps are included.
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 homogeneously 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 nutrients and micronutrients.
Example 9 Preparation of an alkaline liquid fertilizer of secondary nutrients and micronutrients with the chelating carrier The following steps are included.
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 homogeneously 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 nutrients and micronutrients.
Example 10 Preparation of an alkaline liquid fertilizer of secondary nutrients and micronutrients with the chelating carrier The following steps are included.
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 homogeneously 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 nutrients 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 nutrients and micronutrients.
Example 11 Preparation of an alkaline liquid fertilizer of secondary nutrients and micronutrients with the chelating carrier The following steps are included.
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 homogeneously 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 nutrients and micronutrients.
Example 12 Preparation of an alkaline liquid fertilizer of micronutrients with the chelating carrier The following steps are included.
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 homogeneously 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 fertilizers of secondary nutrients and micronutrients were successfully prepared, with the secondary nutrients and micronutrients being dissolved without precipitation.
II. Test Examples Test Example 1 Effect of the chelating carrier for secondary nutrients 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 used as a control, marked as CK.
Test method:
A 500 mL culture bowl which has a drainage hole at the bottom was filled with the conventionally treated quartz sand such that the surface of the quartz sand was at a distance of 2-3 cm from the edge of the bowl. The test crop was planted in the culture bowl, and six culture bowls with test crop for each treatment were prepared. The test crop was irrigated with 100 mL
nutrient solution every 4 days 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 via TTC according to the 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 wheat roots Item Treatment CK A
Fresh weight of root (g) 1.26 1.88 2.16 1.94 Root activity (ng/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, 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 43.5%
respectively, compared with the control.
Test Example 2 Effect of the alkaline liquid fertilizer of the micronutrient zinc of the present invention on growth and zinc utilization of Brassica chinensis L.
Test samples:
Zinc sulfate heptahydrate was mixed with each of the chelating carriers prepared in Example 1, 2 and 4 in a weight ratio of 1: 50 respectively to obtain the alkaline liquid fertilizers of the micronutrient zinc of the present invention. These samples were marked as Ai, Bi or Ci respectively. A solution of micronutrient zinc prepared from zinc sulfate heptahydrate and water in a weight ratio 1 : 50 was used as a control, marked as CK.
Test method:
4 kg air-dried soil screened through a 2 mm sieve was mixed homogeneously with a base fertilizer and placed 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 50%). Six pots with ten seeds of Brassica chinensis L. being sown in each pot for each treatment were prepared. The final singling of seedlings was conducted at the three-leaf stage, with three plants being left in each pot.
Application of test fertilizers via foliar spray or irrigation with water:
The seedlings were subjected to the foliar spay at the four-leaf stage. The seedlings were sprayed once every 7 days at a dosage of 20 mL/pot per spray and for 5 times in total, and then harvested completely 5 days after the last foliar spay. The Application via irrigation with water was carried out in the same application amount and treatment manner as that described for the foliar spray.
Measurement method:
The fresh weight of harvested plant was measured. The quality in terms of Vc, soluble sugar and the like was 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 remaining part of the plants was subjected to fixation at 105 C
for half an hour and baked, 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 the aboveground part x fresh weight of the aboveground part)/amount of applied zinc x 100%.
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.
Fresh weight Vc (mg/100 Soluble sugar Utilization rate of zinc Treatment (g/pot) g) (mg/g) (%) CK 108.72 43.27 2.36 11.6 A1 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, the fresh weight, Vc content, soluble sugar content and utilization rate of zinc for Brassica chinensis L. were increased by an average of 38.6%, 85.7%, 196% and 64.6% respectively via foliar spray with the alkaline liquid fertilizer of the micronutrient zinc of the present invention, compared with CK.
Table 3: Effect of irrigation with different zinc fertilizers on growth, quality and utilization rate of zinc for Brassica chinensis L.
Fresh weight Vc (mg/100 Soluble sugar Utilization rate of zinc Treatment (g/pot) g) (mg/g) (%) CK 110.55 89.67 7.73 4.61 A1 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, the fresh weight, Vc content, soluble sugar content and utilization rate of zinc for Brassica chinensis L. were increased by an average of 43.0%, 12.4%, 40.8% and 45.8% respectively via irrigation with the alkaline liquid fertilizer of the micronutrient zinc of the present invention, compared with CK.
It can be seen that, the alkaline liquid fertilizers of secondary nutrients and micronutrients prepared in the present invention can significantly increase crop root activity, weight of the aboveground part, utilization rate of microelements, and improve crop quality.
Example 12 Preparation of an alkaline liquid fertilizer of micronutrients with the chelating carrier The following steps are included.
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 homogeneously 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 fertilizers of secondary nutrients and micronutrients were successfully prepared, with the secondary nutrients and micronutrients being dissolved without precipitation.
II. Test Examples Test Example 1 Effect of the chelating carrier for secondary nutrients 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 used as a control, marked as CK.
Test method:
A 500 mL culture bowl which has a drainage hole at the bottom was filled with the conventionally treated quartz sand such that the surface of the quartz sand was at a distance of 2-3 cm from the edge of the bowl. The test crop was planted in the culture bowl, and six culture bowls with test crop for each treatment were prepared. The test crop was irrigated with 100 mL
nutrient solution every 4 days 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 via TTC according to the 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 wheat roots Item Treatment CK A
Fresh weight of root (g) 1.26 1.88 2.16 1.94 Root activity (ng/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, 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 43.5%
respectively, compared with the control.
Test Example 2 Effect of the alkaline liquid fertilizer of the micronutrient zinc of the present invention on growth and zinc utilization of Brassica chinensis L.
Test samples:
Zinc sulfate heptahydrate was mixed with each of the chelating carriers prepared in Example 1, 2 and 4 in a weight ratio of 1: 50 respectively to obtain the alkaline liquid fertilizers of the micronutrient zinc of the present invention. These samples were marked as Ai, Bi or Ci respectively. A solution of micronutrient zinc prepared from zinc sulfate heptahydrate and water in a weight ratio 1 : 50 was used as a control, marked as CK.
Test method:
4 kg air-dried soil screened through a 2 mm sieve was mixed homogeneously with a base fertilizer and placed 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 50%). Six pots with ten seeds of Brassica chinensis L. being sown in each pot for each treatment were prepared. The final singling of seedlings was conducted at the three-leaf stage, with three plants being left in each pot.
Application of test fertilizers via foliar spray or irrigation with water:
The seedlings were subjected to the foliar spay at the four-leaf stage. The seedlings were sprayed once every 7 days at a dosage of 20 mL/pot per spray and for 5 times in total, and then harvested completely 5 days after the last foliar spay. The Application via irrigation with water was carried out in the same application amount and treatment manner as that described for the foliar spray.
Measurement method:
The fresh weight of harvested plant was measured. The quality in terms of Vc, soluble sugar and the like was 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 remaining part of the plants was subjected to fixation at 105 C
for half an hour and baked, 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 the aboveground part x fresh weight of the aboveground part)/amount of applied zinc x 100%.
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.
Fresh weight Vc (mg/100 Soluble sugar Utilization rate of zinc Treatment (g/pot) g) (mg/g) (%) CK 108.72 43.27 2.36 11.6 A1 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, the fresh weight, Vc content, soluble sugar content and utilization rate of zinc for Brassica chinensis L. were increased by an average of 38.6%, 85.7%, 196% and 64.6% respectively via foliar spray with the alkaline liquid fertilizer of the micronutrient zinc of the present invention, compared with CK.
Table 3: Effect of irrigation with different zinc fertilizers on growth, quality and utilization rate of zinc for Brassica chinensis L.
Fresh weight Vc (mg/100 Soluble sugar Utilization rate of zinc Treatment (g/pot) g) (mg/g) (%) CK 110.55 89.67 7.73 4.61 A1 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, the fresh weight, Vc content, soluble sugar content and utilization rate of zinc for Brassica chinensis L. were increased by an average of 43.0%, 12.4%, 40.8% and 45.8% respectively via irrigation with the alkaline liquid fertilizer of the micronutrient zinc of the present invention, compared with CK.
It can be seen that, the alkaline liquid fertilizers of secondary nutrients and micronutrients prepared in the present invention can significantly increase crop root activity, weight of the aboveground part, utilization rate of microelements, and improve crop quality.
Claims (11)
1. A chelating carrier for secondary nutrients and micronutrients, wherein the chelating carrier comprises 100 parts by weight of an alcohol amine, 2-10 parts by weight of a choline, 1-5 parts by weight of a polyamine, 20-60 parts by weight of an amino acid and 1,000 parts by weight of a 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.
2. The chelating carrier according to claim 1, wherein the alcohol amine is at least one of monoethanolamine, diethanolamine, triethanolamine and N-methyldiethanolamine.
3. The chelating carrier according to claim 1 or 2, wherein the choline is at least one of choline, acetylcholine and choline chloride.
4. The chelating canier according to any one of claims 1 to 3, wherein the polyamine is at least one of putrescine, spermidine and spermine.
5. The chelating carrier according to any one of claims 1 to 4, wherein the amino acid is at least one of lysine, arginine, methionine and ornithine.
6. The chelating carrier according to any one of claims 1 to 5, wherein the weight ratio of ethylene glycol or glycerin to phenol to water is (10-75) : (2-8) : 1,000, and/or the weight ratio of the alcohol amine to the choline to the polyamine to the amino acid is 100 : (2-8) : (1-4) :
(20-50).
(20-50).
7. The chelating carrier according to any one of claims 1 to 5, wherein the weight ratio of ethylene glycol or glycerin to phenol to water is (20-75) : (3-8) : 1,000, and/or the weight ratio of the alcohol amine to the choline to the polyamine to the amino acid is 100 : (3-8) : (2-4) :
(30-50).
(30-50).
8. Use of a chelating carrier as defined in any one of claims 1 to 7 in preparation of an alkaline liquid fertilizer of secondary nutrients and micronutrients.
9. The use according to claim 8, wherein the alkaline liquid fertilizer of secondary nutrients and micronutrients is prepared by a process comprising:
A) preparing a solvent by 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, and mixing homogeneously under stirring to obtain the solvent;
B) preparing an alkaline chelating carrier by dissolving 100 parts by weight of an alcohol amine, 2-10 parts by weight of a choline and 1-5 parts by weight of a polyamine in 1,000 parts by weight of the solvent obtained in step A, mixing homogeneously, heating to 60-80 C, then adding 20-60 parts by weight of an amino acid, stifling for dissolution, cooling, and adjust pH
to 8.0 or higher by using an aqueous potassium pyrophosphate solution to obtain a chelating carrier; and C) preparing the alkaline liquid fertilizer of secondary nutrients and micronutrients by mixing a water-soluble salt of calcium, magnesium, zinc, manganese, copper and/or iron as the secondary nutrients and micronutrients 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 nutrients and micronutrients.
A) preparing a solvent by 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, and mixing homogeneously under stirring to obtain the solvent;
B) preparing an alkaline chelating carrier by dissolving 100 parts by weight of an alcohol amine, 2-10 parts by weight of a choline and 1-5 parts by weight of a polyamine in 1,000 parts by weight of the solvent obtained in step A, mixing homogeneously, heating to 60-80 C, then adding 20-60 parts by weight of an amino acid, stifling for dissolution, cooling, and adjust pH
to 8.0 or higher by using an aqueous potassium pyrophosphate solution to obtain a chelating carrier; and C) preparing the alkaline liquid fertilizer of secondary nutrients and micronutrients by mixing a water-soluble salt of calcium, magnesium, zinc, manganese, copper and/or iron as the secondary nutrients and micronutrients 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 nutrients and micronutrients.
10. Use according to claim 9, wherein the aqueous potassium pyrophosphate solution has a concentration of 1-5 mol/L.
11. Use according to claim 9 or 10, 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; and/or the water-soluble salt of iron is ferrous sulfate or ammonium ferrous sulfate.
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