CN111187108A

CN111187108A - Stable sugar alcohol chelated medium-trace element composite liquid fertilizer and preparation method thereof

Info

Publication number: CN111187108A
Application number: CN201811347533.1A
Authority: CN
Inventors: 詹姆斯·T·布里斯托
Original assignee: Rotam Agrochem International Co Ltd
Current assignee: Jiangsu Rotam Chemical Co Ltd; Rotam Agrochem International Co Ltd
Priority date: 2018-11-13
Filing date: 2018-11-13
Publication date: 2020-05-22

Abstract

The invention provides a stable sugar alcohol chelated medium and trace element composite liquid fertilizer and a preparation method thereof, wherein the composite liquid fertilizer comprises the following components in percentage by weight: (1) 5-50% of sugar alcohol chelating medium trace elements by weight of the sugar alcohol; (2) 0.1 to 5 percent of alkali; (3) 5% -30% of alcohol; (4) 5 to 30 percent of water. The invention adopts a one-pot method to completely react various medium and trace elements with sugar alcohol in an alcohol-water solution at a constant temperature of 70-90 ℃, and then a proper amount of alkali is added to obtain the stable sugar alcohol chelated medium and trace element composite liquid fertilizer. The one-pot method has the advantages of simple process, less equipment and low cost for producing the composite liquid fertilizer, and well solves the problem that the medium and trace elements are high in content and are more in elements, so that the compound liquid fertilizer cannot be fully dissolved; the addition of a proper amount of alkali effectively controls the trace element compound liquid fertilizer in the sugar alcohol chelate not to generate precipitates in the long-term storage process, and has good physical and chemical stability.

Description

Stable sugar alcohol chelated medium-trace element composite liquid fertilizer and preparation method thereof

Technical Field

The invention belongs to the field of agricultural production, particularly relates to a liquid fertilizer and a preparation method thereof, and particularly relates to a stable sugar alcohol chelated medium and trace element composite liquid fertilizer and a preparation method thereof.

Background

Calcium and magnesium are important constituent nutrients of plants. Most calcium is present in the cell wall as a structural component that constitutes the cell wall pectin. Calcium has the functions of stabilizing cell membranes, stabilizing cell walls, promoting cell elongation, root growth, osmotic adjustment and the like, and meanwhile, the calcium has poor mobility in plants, so that the calcium deficiency of crops occurs sometimes; when the calcium is deficient, the plant growth is blocked, and the tissue is soft; terminal buds, lateral buds and root tips are easy to rot and die, and young leaves are curled and deformed. Cabbage, Chinese cabbage and lettuce are lack of calcium and have leaf scorch, apple suffers from bitter pit, tomato, pepper and the like suffer from navel rot. Magnesium plays an important role in chloroplast synthesis and photosynthesis in leaves, promotes the activation of phosphatase and glucose-converting enzyme, facilitates the conversion of monosaccharides, and thus plays an important role in carbohydrate metabolism. Crops lack magnesium, chlorophyll is reduced, photosynthesis is weakened, carbohydrate metabolism is hindered, and growth is affected. Magnesium also participates in the formation of fat, and when leguminous crops lack magnesium, the oil content of seeds is reduced. According to chemical measurement, the content of magnesium is higher in crops with more phosphorus, which indicates that magnesium can correspondingly promote the absorption of phosphorus.

Zinc, boron, manganese and copper are important trace elements in plants. In the absence of zinc, the growth of the plants is inhibited, especially the internode growth is seriously inhibited, and the internodal greening or whitening symptoms of the leaves are shown; boron exists in plants in the form of acid radical, participates in a plurality of important physiological activities, and has irreplaceable specific physiological functions. Boron can promote carbohydrate transport and metabolism, promote cell elongation and cell division, and promote the establishment and development of reproductive organs. Boron has various nutritional functions, and boron deficiency mainly shows that stem tip growing points are inhibited, root development is influenced, and reproductive organ development is hindered. Boron-deficient crops often have many typical symptoms, such as rot of sugar beet, flowering but not fruiting of rape, fruit set of apples, etc.

Iron is an important medium element of plants. In plants iron is present on the electron transfer bond of hemoglobin and can be in oxidized or reduced form, i.e. one electron can be reduced or added, in catalytic oxidation-reduction reactions. Iron is not a component of chlorophyll, but in the absence of iron, the lamellar structure of the chloroplast is greatly changed, and in severe cases, the chloroplast is even disintegrated. Iron binds to proteins in various forms in plants and participates in many vital activities as an important electron transporter or catalyst. Iron is a component of ferritin and ferromolybdenum in azotase and plays an extremely important role in biological nitrogen fixation.

Sugar alcohol is polyhydroxy compound, is primary product of photosynthesis, and belongs to functional sugar alcohol. The sugar alcohol complex has low molecular weight, and can be combined with adjuvants such as surfactant and penetrant to easily penetrate into the leaf via the cuticle of the leaf. Sugar alcohol is a good complexing agent for nutrients such as medium and trace elements, can be combined with various nutrient substances to form a stable complex, and is the only substance which can carry mineral nutrients and can be rapidly transported in phloem at present; and the sugar alcohol is a natural extract in plant phloem juice, is non-toxic and has no damage to plants and human bodies. The sugar alcohol is also a natural humectant, has moisture keeping effect, can prevent the medicinal liquid from losing efficacy due to rapid drying of the leaf, and prolongs the time for the leaf to absorb nutrient elements.

CN103588564A discloses a sugar alcohol calcium magnesium zinc boron compound liquid fertilizer and a preparation method and application thereof, wherein sugar alcohol is used for chelating each element to prepare mother liquor and then mixing treatment is carried out. The preparation process needs a plurality of reaction devices for operation, the reaction period is long, the operation is various, and the overall production cost is high.

CN106242759A discloses a method for preparing sugar alcohol chelated medium and trace liquid fertilizer. In the patent, different reaction conditions of two reaction kettles and a chelating agent are adopted to chelate secondary elements and trace elements respectively to obtain a mother liquor, and the mixed mother liquor is subjected to secondary chelating treatment. The preparation process also needs a plurality of reaction devices, and the reaction conditions and the chelating agent are different, thereby bringing great inconvenience to production operation and having higher production cost. Meanwhile, secondary chelation is needed, so that the production energy consumption and the production cost are further increased.

In addition to the problems of long reaction period, complicated operation, high cost and the like in the existing documents, in the existing sugar alcohol chelated medium and trace element compound liquid fertilizer products, particularly high-content and multi-element sugar alcohol chelated compound liquid fertilizer products, precipitates are generated in the long-term storage process, so that the fertilizer efficiency of the sugar alcohol chelated medium and trace element compound liquid fertilizer during fertilization is reduced.

Therefore, how to provide a compound liquid fertilizer which is easy and convenient to operate and has less equipment investment and can avoid the phenomenon of generating precipitates in the long-term storage process becomes a problem to be solved urgently at present.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a stable sugar alcohol chelated medium-trace element composite liquid fertilizer and a preparation method thereof. The preparation method is a one-pot method, the one-pot method has simple process, simple and convenient operation, less required equipment, less equipment investment, less generated waste and low environmental pressure, and meanwhile, the sugar alcohol chelated medium and trace element composite liquid fertilizer provided by the invention has good stability, does not generate precipitation phenomenon even if being stored for a long time and keeps high fertilizer efficiency.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the invention provides a stable sugar alcohol chelated medium and trace element composite liquid fertilizer, which comprises the following components in percentage by weight:

in the sugar alcohol chelated medium and trace element composite liquid fertilizer, the sugar alcohol chelated medium and trace element component refers to a component obtained by chelating medium and trace elements with sugar alcohol; the alkali is added into the composite liquid fertilizer as a raw material component different from the sugar alcohol chelated medium trace element, namely the sugar alcohol chelated medium trace element and the alkali component are independent.

The alkali component is added into the chelated medium and trace element raw material of the sugar alcohol chelate, so that the precipitation phenomenon of the sugar alcohol chelate medium and trace element composite liquid fertilizer can not occur even in the long-term storage process, and the high fertilizer efficiency of the composite liquid fertilizer is maintained.

Wherein, the weight percentage of the trace elements in the sugar alcohol chelation in the liquid compound fertilizer can be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% by weight of the sugar alcohol; the weight percentage of alkali contained in the liquid compound fertilizer can be 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%; the weight percentage of the alcohol contained in the liquid compound fertilizer can be 5%, 10%, 15%, 20%, 25% or 30%; the weight percentage of water contained in the liquid compound fertilizer can be 5%, 10%, 15%, 20%, 25% or 30%. It will be clear to the person skilled in the art that other values not listed in this numerical range are equally applicable.

Preferably, the sugar alcohol is any one or a mixture of at least two of xylitol, sorbitol, mannitol, maltitol, glucitol or lactitol, and typical but non-limiting mixtures include a mixture of xylitol and sorbitol, a mixture of xylitol and mannitol, a mixture of sorbitol, mannitol and maltitol or a mixture of xylitol, sorbitol, mannitol, maltitol, glucitol and lactitol.

Preferably, the base is an organic base or an inorganic base as a stabilizer. That is to say, the alkali component exists as a stabilizer of the sugar alcohol chelated medium-trace element compound liquid fertilizer, and due to the existence of the alkali component, the compound liquid fertilizer can still keep clear and free of precipitation within a high-temperature storage period of 54 ℃ of more than 28 days, so that the fertilizer efficiency of the compound liquid fertilizer is ensured.

Preferably, the base is any one or a mixture of at least two of ethanolamine, ethylenediamine, triethylamine, triethylenediamine, tetramethylethylenediamine, potassium hydroxide, sodium hydroxide, potassium phosphate, potassium monohydrogenphosphate, sodium phosphate, or sodium monohydrogenphosphate, and typical but non-limiting mixtures include a mixture of ethanolamine and ethylenediamine, a mixture of ethanolamine, ethylenediamine and triethylamine, ethylenediamine, triethylamine, and tetramethylethylenediamine, a mixture of ethanolamine, ethylenediamine, triethylamine, triethylenediamine, and tetramethylethylenediamine, a mixture of potassium hydroxide and sodium hydroxide, a mixture of sodium hydroxide, potassium phosphate, and potassium monohydrogen phosphate, a mixture of sodium hydroxide, potassium phosphate, sodium phosphate, and sodium monohydrogen phosphate, a mixture of potassium hydroxide, sodium hydroxide, potassium phosphate, potassium monohydrogen phosphate, sodium phosphate, and sodium monohydrogen phosphate, potassium hydroxide in combination with ethanolamine, potassium hydroxide, sodium hydroxide, ethylenediamine in combination with tetramethylethylenediamine, or potassium phosphate, potassium monohydrogen phosphate, sodium phosphate, ethylenediamine, triethylamine in combination with ethanolamine.

Preferably, the alcohol is any one or a mixture of at least two of ethylene glycol, diethylene glycol, propylene glycol, glycerol, polypropylene glycol, polyethylene glycol or polyglycerol, and typical but non-limiting mixtures include mixtures of ethylene glycol and diethylene glycol, mixtures of ethylene glycol, propylene glycol and glycerol, mixtures of diethylene glycol, glycerol and polypropylene glycol, mixtures of polyethylene glycol, polypropylene glycol, polyglycerol and ethylene glycol or mixtures of ethylene glycol, diethylene glycol, propylene glycol, glycerol, polypropylene glycol, polyethylene glycol and polyglycerol.

Preferably, the medium trace element is any one or a mixture of at least two of calcium, magnesium, boron, iron, zinc, copper or manganese, and typical but non-limiting mixtures include mixtures of calcium and magnesium, mixtures of calcium, magnesium and iron, mixtures of magnesium, zinc, copper and manganese or mixtures of calcium, magnesium, iron, zinc, copper, manganese and boron.

Preferably, the calcium element is derived from a calcium salt, preferably any one or a mixture of at least two of calcium chloride, calcium nitrate, EDTA-calcium, calcium ammonium nitrate, calcium formate or calcium acetate, and typical but non-limiting mixtures include mixtures of calcium chloride and calcium nitrate, calcium nitrate and EDTA-calcium, calcium chloride, calcium ammonium nitrate and calcium formate, calcium nitrate, calcium formate, calcium acetate and EDTA-calcium, or calcium chloride, calcium nitrate, EDTA-calcium, calcium ammonium nitrate, calcium formate and calcium acetate.

Preferably, the magnesium element is derived from a magnesium salt, preferably any one or a mixture of at least two of magnesium chloride, magnesium nitrate, magnesium sulfate, magnesium formate, magnesium acetate or EDTA-magnesium, and typical but non-limiting mixtures include a mixture of magnesium chloride and magnesium nitrate, a mixture of magnesium chloride and magnesium sulfate, a mixture of magnesium nitrate, magnesium formate and magnesium acetate, a mixture of magnesium nitrate, magnesium sulfate, magnesium formate, magnesium acetate and EDTA-magnesium, or a mixture of magnesium chloride, magnesium nitrate, magnesium sulfate, magnesium formate, magnesium acetate and EDTA-magnesium.

Preferably, the iron element is derived from an iron salt, preferably any one or a mixture of at least two of ferric chloride, ferric sulfate, ferric nitrate, ferric formate, ferric acetate or ferric EDTA, and typical but non-limiting mixtures include a mixture of ferric chloride and ferric nitrate, a mixture of ferric chloride and ferric sulfate, a mixture of ferric nitrate, ferric formate and ferric acetate, a mixture of ferric nitrate, ferric sulfate, ferric formate, ferric acetate and ferric EDTA or a mixture of ferric chloride, ferric nitrate, ferric sulfate, ferric formate, ferric acetate and ferric EDTA-iron.

Preferably, the zinc element is derived from a zinc salt, preferably any one or a mixture of at least two of zinc chloride, zinc sulfate, zinc nitrate, zinc formate, zinc acetate or EDTA-zinc, and typical but non-limiting mixtures include a mixture of zinc chloride and zinc nitrate, a mixture of zinc chloride and zinc sulfate, a mixture of zinc nitrate, zinc formate and zinc acetate, a mixture of zinc nitrate, zinc sulfate, zinc formate, zinc acetate and EDTA-zinc or a mixture of zinc chloride, zinc nitrate, zinc sulfate, zinc formate, zinc acetate and EDTA-zinc.

Preferably, the copper element is derived from a copper salt, preferably any one or a mixture of at least two of copper chloride, copper sulfate, copper nitrate, copper formate, copper acetate or EDTA-copper, and typical but non-limiting mixtures include a mixture of copper chloride and copper nitrate, a mixture of copper chloride and copper sulfate, a mixture of copper nitrate, copper formate and copper acetate, a mixture of copper nitrate, copper sulfate, copper formate, copper acetate and EDTA-copper, or a mixture of copper chloride, copper nitrate, copper sulfate, copper formate, copper acetate and EDTA-copper.

Preferably, the manganese element is derived from a manganese salt, preferably any one or a mixture of at least two of manganese chloride, manganese sulfate, manganese nitrate, manganese formate, manganese acetate or EDTA-manganese, and typical but non-limiting mixtures include a mixture of manganese chloride and manganese nitrate, a mixture of manganese chloride and manganese sulfate, a mixture of manganese nitrate, manganese formate and manganese acetate, a mixture of manganese nitrate, manganese sulfate, manganese formate, manganese acetate and EDTA-manganese or a mixture of manganese chloride, manganese nitrate, manganese sulfate, manganese formate, manganese acetate and EDTA-manganese.

Preferably, the boron element is derived from a boron salt, preferably any one or a mixture of at least two of calcium borate, magnesium borate, sodium borate, ferric borate, or manganese borate, and typical but non-limiting mixtures include mixtures of calcium borate and magnesium borate, mixtures of magnesium borate and sodium borate, mixtures of calcium borate, magnesium borate, and ferric borate, or mixtures of calcium borate, magnesium borate, sodium borate, ferric borate, and manganese borate.

It will be clear to those skilled in the art that the mixture of boric acid and at least one of the above-mentioned medium trace element calcium salt, medium trace element magnesium salt, medium trace element iron salt, medium trace element zinc salt, medium trace element copper salt or medium trace element manganese salt also falls within the scope of the present invention.

In a second aspect, the invention provides a preparation method of a stable sugar alcohol chelated medium and trace element composite liquid fertilizer, which comprises the following steps:

(1) completely reacting medium and trace elements with sugar alcohol in an alcohol-water solution by adopting a one-pot method;

(2) and (2) adding alkali into the solution completely reacted in the step (1) to obtain the stable sugar alcohol chelated medium and trace element composite liquid fertilizer.

In the invention, the sugar alcohol chelation of medium and trace elements is realized by adopting a one-pot method, namely, the alcohol solvent is mixed with water to obtain an alcohol-water solution, and all medium and trace element salts and the sugar alcohol are added into the alcohol-water solution together for chelation reaction.

When all the medium and trace element salts and the sugar alcohol are added into the alcohol-water solution, part of the medium and trace element salts are firstly dissolved in the alcohol-water solution to react with part of the sugar alcohol, and the rest undissolved medium and trace element salts are gradually and uniformly dispersed in the alcohol-water solution to be continuously dissolved, so that all the medium and trace element salts and the sugar alcohol are completely chelated, and the one-pot preparation is realized.

By adopting the one-pot method, the invention has the advantages of simple process and less equipment, greatly reduces the cost for producing the composite liquid fertilizer, and solves the problem that the solid content of medium and trace elements is high and the elements are more so that the medium and trace elements cannot be fully dissolved.

According to the invention, the alkali is added into the solution obtained after chelation in the step (1), so that the stability of the sugar alcohol chelated medium and trace element composite liquid fertilizer can be effectively improved, and the stable sugar alcohol chelated medium and trace element composite liquid fertilizer is obtained, and even if the composite liquid fertilizer is stored for more than 28 days at 54 ℃, no precipitate is separated out, and the composite liquid fertilizer is always kept in a clear solution state, and no precipitate is generated.

The sugar alcohol chelated medium and trace element composite liquid fertilizer prepared by the one-pot method has high medium and trace element content, wherein the mass fractions of calcium, magnesium, boron, iron, manganese, zinc and copper can respectively reach 9 wt%, 6 wt%, 0.35 wt%, 5 wt%, 4.5 wt%, 6 wt% and 10 wt% under the condition of simultaneous chelation.

Preferably, the temperature of the reaction in step (1) is 70 to 90 ℃, for example 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃, preferably 75 to 85 ℃.

Preferably, the reaction time is 2-6h, for example, 2h, 3h, 4h, 5h or 6h, and can be selected by those skilled in the art according to the reaction temperature.

Preferably, the one-pot method of step (1) comprises the steps of:

(I) adding alcohol and water into a reaction kettle, heating to 70-90 deg.C, such as 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C or 90 deg.C, stirring at constant temperature;

(II) maintaining the temperature at 70-90 ℃, for example 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃, adding one or more salts of medium and trace elements into the solution of step (I), and stirring for dispersion and/or dissolution;

(III) adding a sugar alcohol to the solution of step (II) and maintaining the temperature at 70 ℃ to 90 ℃, for example 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃, and stirring for 2 to 6 hours, for example 2 hours, 3 hours, 4 hours, 5 hours or 6 hours until the sugar alcohol is fully chelated with the one or more trace elements.

Preferably, after the alkali is added in the step (2), the method further comprises the steps of stirring uniformly and cooling to normal temperature.

As a preferable embodiment of the production method according to the second aspect of the present invention, the production method comprises the steps of:

(I) adding alcohol and water into a reaction kettle, heating to 70-90 ℃, and stirring at constant temperature;

(II) keeping the temperature at 70-90 ℃, adding one or more medium and trace element salts into the solution in the step (I), and stirring to disperse and/or dissolve;

(III) adding sugar alcohol to the solution of step (II), keeping the temperature at 70-90 ℃, and stirring for 2-6 hours until the sugar alcohol is completely chelated with one or more trace elements;

and (IV) adding alkali into the solution completely reacted in the step (III), uniformly stirring, and cooling to normal temperature to obtain the stable sugar alcohol chelated medium and trace element composite liquid fertilizer.

Compared with the prior art, the invention has the beneficial effects that:

(1) the alkali component is added into the chelated medium and trace element raw material of the sugar alcohol chelate, and the alkali component can be used as a stabilizer, so that the provided sugar alcohol chelate medium and trace element composite liquid fertilizer has higher stability, and can keep a clear solution state and have no precipitation even if the liquid fertilizer is stored at 54 ℃ for more than 28 ℃, thereby ensuring the fertilizer efficiency;

(2) the invention adopts a one-pot method to prepare the sugar alcohol chelated medium and trace element liquid compound fertilizer, has the characteristics of simple process and less equipment, greatly reduces the cost for producing the compound liquid fertilizer, and simultaneously solves the problem that the medium and trace element cannot be fully dissolved in alcohol-water solution due to high solid content and more elements.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments.

Example 1

The embodiment provides a preparation method of a stable sugar alcohol chelated medium-trace element composite liquid fertilizer, which comprises the following steps:

(I) adding 150kg of glycerol and 250kg of water into a reaction kettle, heating to 80 ℃, and stirring at constant temperature;

(II) adding 185kg of calcium nitrate, 185kg of magnesium nitrate, 17kg of boric acid, 535kg of ferric sulfate and 63kg of zinc chloride into the solution obtained in the step (I), and stirring at the constant temperature of 80 ℃ for 0.5 hour;

(III) adding 120kg of sorbitol into the solution in the step (II), keeping the temperature at 80 ℃, stirring until the chelation between the calcium, magnesium, boron, iron and zinc and the sorbitol is completed to obtain a clear solution, and stirring at constant temperature for 3.5 hours;

and (IV) adding 15kg of sodium hydroxide into the clear solution obtained in the step (III), stirring for 0.5 hour at 80 ℃, and cooling to normal temperature to obtain the stable sugar alcohol chelated medium and trace element composite liquid fertilizer.

The composite liquid fertilizer prepared by the content detection example 1 contains calcium: 3.01%, magnesium: 2.03%, boron: 0.21%, iron: 4.95%, zinc: 1.98 percent.

Example 2

(I) adding 255kg of propylene glycol and 375kg of water into a reaction kettle, heating to 75 ℃, and stirring at constant temperature;

(II) adding 208kg of calcium chloride, 148kg of magnesium chloride, 25kg of boric acid, 130kg of ferric nitrate and 185kg of copper sulfate into the solution obtained in the step (I), and stirring at the constant temperature of 75 ℃ for 0.5 hour;

(III) adding 150kg of sorbitol into the solution obtained in the step (II), keeping the temperature at 75 ℃, stirring until the chelation between the calcium, magnesium, boron, iron and zinc and the sorbitol is completed to obtain a clear solution, and stirring at constant temperature for 3 hours;

and (IV) adding 22kg of potassium phosphate into the clear solution obtained in the step (III), stirring for 0.5 hour at 75 ℃, and cooling to normal temperature to obtain the stable sugar alcohol chelated medium and trace element composite liquid fertilizer.

Content detection the composite liquid fertilizer of example 2 contains calcium: 5.12%, magnesium: 2.53%, boron: 0.32%, iron: 2.04%, copper: 5.10 percent.

Example 3

(I) adding 140kg of ethylene glycol and 230kg of deionized water into a reaction kettle, heating to 85 ℃, and stirring at constant temperature;

(II) adding 185kg of EDTA-calcium, 450kg of magnesium sulfate, 125kg of manganese sulfate, 86kg of ferric chloride and 132kg of zinc nitrate into the solution obtained in the step (I), and stirring at the constant temperature of 85 ℃ for 0.5 hour;

(III) adding 140kg of xylitol into the solution in the step (II), keeping the temperature at 85 ℃, stirring until the chelation of the calcium, magnesium, manganese, iron and zinc and the xylitol is completed to obtain a clear solution, and stirring at the constant temperature of 85 ℃ for 3 hours;

and (IV) adding 22kg of ethanolamine into the clear solution obtained in the step (III), stirring for 0.5 hour at 85 ℃, and cooling to normal temperature to obtain the stable sugar alcohol chelated medium and trace element composite liquid fertilizer.

Content detection the composite liquid fertilizer of example 3 contains calcium: 1.22%, magnesium: 6.04%, manganese: 3.04%, iron: 2.05%, zinc: 2.00 percent.

Example 4

(I) adding 230kg of diethylene glycol and 180kg of water into a reaction kettle, heating to 70 ℃, and stirring at constant temperature;

(II) adding 415kg of calcium formate, 90kg of magnesium chloride, 27kg of boric acid, 210kg of manganese acetate and 210kg of zinc acetate into the solution obtained in the step (I), and stirring at the constant temperature of 70 ℃ for 0.5 hour;

(III) adding 180kg of mannitol into the solution obtained in the step (II), keeping the temperature at 70 ℃, stirring until the chelation between the calcium, magnesium, boron, iron and zinc and the mannitol is finished to obtain a clear solution, and stirring at the constant temperature of 70 ℃ for 4 hours;

and (IV) adding 15kg of triethylamine into the clear solution obtained in the step (III), stirring for 0.5 hour at 70 ℃, and cooling to normal temperature to obtain the stable sugar alcohol chelated medium and trace element composite liquid fertilizer.

Content detection the sugar alcohol chelated medium and trace element composite liquid fertilizer of example 4 contains calcium: 8.25%, magnesium: 1.45%, boron: 0.31%, manganese: 4.29%, zinc: 4.81 percent.

Example 5

(I) adding 140kg of glycerol and 120kg of water into a reaction kettle, heating to 90 ℃, and stirring at constant temperature;

(II) adding 243kg of calcium formate, 118kg of magnesium sulfate, 17kg of manganese sulfate, 442kg of copper acetate and 253kg of zinc acetate into the solution obtained in the step (I), and stirring at the constant temperature of 90 ℃ for 0.5 hour;

(III) adding 150kg of sorbitol into the solution obtained in the step (II), keeping the temperature at 90 ℃, stirring until the chelation between the calcium, boron, manganese, copper and zinc and the sorbitol is completed to obtain a clear solution, and stirring at the constant temperature of 90 ℃ for 2.5 hours;

and (IV) adding 15kg of ethanolamine into the clear solution obtained in the step (III), stirring for 0.5 hour at 90 ℃, and cooling to normal temperature to obtain the sugar alcohol chelated medium and trace element composite liquid fertilizer.

Content detection the sugar alcohol chelated medium and trace element composite liquid fertilizer of example 5 contains calcium: 4.95%, magnesium: 1.58%, manganese: 0.42%, copper: 9.48%, zinc: 6.02 percent.

Example 6

(I) adding 75kg of polyethylene glycol and 450kg of water into a reaction kettle, heating to 80 ℃, and stirring at constant temperature;

(II) adding 180kg of calcium nitrate, 160kg of magnesium nitrate, 20kg of boric acid and 20kg of manganese chloride into the solution obtained in the step (I), and stirring at a constant temperature of 80 ℃ for 0.5 hour;

(III) adding 450kg of maltitol into the solution in the step (II), keeping the temperature at 80 ℃, stirring until the chelation between the calcium, magnesium, boron and manganese and the maltitol is finished to obtain a clear solution, and stirring for 5 hours at constant temperature;

and (IV) adding 7kg of potassium hydroxide into the clear solution obtained in the step (III), stirring for 0.5 hour at 80 ℃, and cooling to normal temperature to obtain the stable sugar alcohol chelated medium and trace element composite liquid fertilizer.

Content detection the calcium-magnesium-boron-iron-zinc composite liquid fertilizer of example 1 contains calcium: 3.23%, magnesium: 1.92%, boron: 0.26%, manganese: 0.64 percent.

Example 7

(I) adding 450kg of polyglycerol and 75kg of water into a reaction kettle, heating to 80 ℃, and stirring at constant temperature;

(II) adding 22kg of boric acid, 18kg of manganese chloride, 155kg of copper nitrate and 250kg of zinc formate into the solution obtained in the step (I), and stirring at the constant temperature of 80 ℃ for 0.5 hour;

(III) adding 75kg of glucitol into the solution obtained in the step (II), keeping the temperature at 80 ℃, stirring until the chelation between the boron, manganese, copper and zinc and the glucitol is completed to obtain a clear solution, and stirring at the constant temperature of 80 ℃ for 4 hours;

and (IV) adding 45kg of tetramethylethylenediamine into the clear solution obtained in the step (III), stirring for 0.5 hour at the temperature of 80 ℃, and cooling to normal temperature to obtain the sugar alcohol chelated medium and trace element composite liquid fertilizer.

Content detection the sugar alcohol chelated medium and trace element composite liquid fertilizer of example 7 contains boron: 0.36%, manganese: 0.72%, zinc: 9.62%, copper: 4.84 percent.

Example 8

(I) adding 300kg of polypropylene glycol and 150kg of water into a reaction kettle, heating to 80 ℃, and stirring at constant temperature;

(II) adding 40kg of EDTA-calcium, 25kg of magnesium sulfate, 20kg of manganese sulfate, 35kg of ferric chloride and 24kg of zinc nitrate into the solution obtained in the step (I), and stirring at the constant temperature of 80 ℃ for 0.5 hour;

(III) adding 600kg of lactitol into the solution in the step (II), keeping the temperature at 80 ℃, stirring until the chelation of calcium, magnesium, manganese, iron and zinc with the lactitol is completed to obtain a clear solution, and stirring at the constant temperature of 80 ℃ for 5 hours;

and (IV) adding 1.2kg of ethylenediamine into the clear solution obtained in the step (III), stirring for 0.5 hour at the temperature of 80 ℃, and cooling to normal temperature to obtain the stable sugar alcohol chelated medium and trace element composite liquid fertilizer.

Content detection the sugar alcohol chelated medium and trace element composite liquid fertilizer of example 8 contains calcium: 0.33%, magnesium: 0.42%, manganese: 0.61%, iron: 1.01%, zinc: 0.44 percent.

Example 9

(I) adding 75kg of polypropylene glycol and 225kg of water into a reaction kettle, heating to 80 ℃, and stirring at constant temperature;

(II) adding 105kg of copper nitrate, 17kg of boric acid, 90kg of magnesium chloride, 63kg of zinc chloride and 100kg of calcium chloride into the solution obtained in the step (I), and stirring at the constant temperature of 80 ℃ for 0.5 hour;

(III) adding 750kg of sorbitol into the solution in the step (II), keeping the temperature at 80 ℃, stirring until the chelation between the copper, boron, magnesium, zinc and calcium and the sorbitol is completed to obtain a clear solution, and stirring at the constant temperature of 80 ℃ for 2 hours;

and (IV) adding 75kg of potassium monohydrogen phosphate into the clear solution obtained in the step (III), stirring for 0.5 hour at the temperature of 80 ℃, and cooling to normal temperature to obtain the stable sugar alcohol chelated medium and trace element composite liquid fertilizer.

Content detection the sugar alcohol chelated medium and trace element composite liquid fertilizer of example 9 contains calcium: 0.26%, magnesium: 1.51%, copper: 2.38%, zinc: 2%, boron: 0.2 percent.

Comparative example 1

The comparative example provides a preparation method of a sugar alcohol chelated medium and trace element composite liquid fertilizer, and the preparation method is the same as the embodiment 1 except that the sodium hydroxide in the step (IV) is replaced by water with the same mass.

Comparative example 2

The comparative example provides a preparation method of a sugar alcohol chelated medium and trace element composite liquid fertilizer, which is the same as that in example 2 except that potassium phosphate in the step (IV) is replaced by water with the same mass.

Comparative example 3

The comparative example provides a preparation method of a sugar alcohol chelated medium and trace element composite liquid fertilizer, and the preparation method is the same as the embodiment 3 except that the ethanolamine in the step (IV) is replaced by water with the same mass.

Comparative example 4

The comparative example provides a preparation method of a sugar alcohol chelated medium and trace element composite liquid fertilizer, and the preparation method is the same as that in example 4 except that triethylamine in the step (IV) is replaced by water with the same mass.

Comparative example 5

The comparative example provides a preparation method of a sugar alcohol chelated medium and trace element composite liquid fertilizer, and the preparation method is the same as the embodiment 5 except that the ethanolamine in the step (IV) is replaced by water with the same mass.

Comparative example 6

The comparative example provides a preparation method of a sugar alcohol chelated medium and trace element composite liquid fertilizer, which is the preparation method described in example 1 provided by CN 103588564B.

Comparative example 7

The comparative example provides a preparation method of a sugar alcohol chelated medium and trace element composite liquid fertilizer, which is the preparation method described in example 1 provided by CN 106242759A.

The liquid fertilizers prepared in examples 1 to 9 and comparative examples 1 to 7 provided by the invention were subjected to a 54 ℃ heat storage acceleration test, and the test conditions are shown in table 1.

TABLE 1

As can be seen from table 1 above, the liquid fertilizers prepared in examples 1 to 9 exhibited clear solutions and no precipitate formation after storage at 54 ℃ for 14 days and 28 days, whereas comparative examples 1 to 5 exhibited a small amount of precipitate after storage at 54 ℃ for 14 days and all showed significant precipitate formation after storage at 54 ℃ for 28 days. Therefore, compared with the composite liquid fertilizer prepared by using the same amount of water, the stability of the liquid compound fertilizer can be improved, and the generation of precipitates is avoided, so that the stability of the liquid compound fertilizer in the long-term storage process is improved by adding the alkali.

The compound liquid fertilizer prepared in the comparative example 6 also has a small amount of precipitate after being stored at 54 ℃ for 14 days, and obvious precipitate is generated after being stored at 54 ℃ for 28 days. The reason that the caustic alkali added in the comparative example 6 causes the precipitation reaction different from that in the example 1 is that the caustic alkali added in the comparative example 6 is added when the sugar alcohol chelates with the medium trace element, participates in the chelating reaction, and is consumed after the sugar alcohol chelates with the medium trace element, unlike the adding time of the alkali in the present invention, the alkali can be used as a stabilizer by adding the alkali after the sugar alcohol chelates with the medium trace element, thereby reducing and inhibiting the occurrence of side reaction during storage, having a longer storage period, and improving the uniformity and physicochemical stability of the product

The comparative example 7 adopts the multi-step chelating method to prepare the sugar alcohol chelated medium and trace element composite liquid fertilizer, a small amount of precipitate can appear after the sugar alcohol chelated medium and trace element composite liquid fertilizer is stored for 14 days at 54 ℃, and obvious precipitate is generated after the sugar alcohol chelated medium and trace element composite liquid fertilizer is stored for 28 days at 54 ℃.

Field effect test

Test example 1 influence of sugar alcohol chelated calcium-magnesium-boron-iron-zinc composite liquid fertilizer on cucumber

The experiment is carried out in the experimental field of agricultural science research institute in cigarette stage city of Shandong province, the area of an experimental community is 10 square meters, the experiment is designed into 3 treatments, and each treatment is repeated for 3 times.

The experiment set up 3 treatments:

treatment 1: spraying the liquid fertilizer prepared in the example 1 except for conventional fertilization; diluting 1000 times, and spraying once in 10 days.

And (3) treatment 2: spraying and treating 1 equivalent of aqueous solution of calcium nitrate, magnesium nitrate, sodium octaborate tetrahydrate, ferric nitrate and zinc nitrate of calcium, magnesium, boron, iron and zinc elements except conventional fertilization; spraying once in 10 days.

And (3) treatment: besides the conventional fertilization, clear water CK with the same amount as that of the treated fertilizer CK 1 is sprayed, and the fertilizer is sprayed once in 10 days.

The test results are shown in table 2.

TABLE 2

As can be seen from table 2, both treatments 1 and 2 have an effect of promoting the growth and yield of cucumbers, and have significant effects of increasing the stem thickness, the leaf length, the leaf width and the yield of the cucumbers, but the treatment 1, namely the sugar alcohol chelated calcium-magnesium-boron-iron-zinc composite liquid fertilizer of the embodiment 1 of the invention, has a more significant effect of promoting the cucumbers, and is superior to directly applying corresponding nutrient elements to the cucumbers. And treatment 3 only adopts the same amount of clear water, so that the cucumber promoting effect is not obvious.

Test example 2 influence of sugar alcohol chelated calcium-magnesium-boron-iron-zinc composite liquid fertilizer on rice

The experiment is carried out in an agricultural experimental field of Sanjiang, Heilongjiang, the area of an experimental community is 667 square meters, the experiment is designed for 3 treatments, and each treatment is repeated for 3 times.

And (3) treatment 2: except for conventional fertilization, spraying and treating 1 equivalent of aqueous solution of calcium nitrate, magnesium nitrate, sodium octaborate tetrahydrate, ferric nitrate and zinc nitrate of trace elements in calcium, magnesium, boron, iron and zinc; spraying once in 10 days.

The results of the experiment are shown in table 3.

TABLE 3

As can be seen from Table 3, both treatments 1 and 2 have an effect of promoting the yield of rice, and have obvious effects of improving the plant height, thousand seed weight, number of seeds per ear, setting rate and yield of rice, but the treatment 1, namely the sugar alcohol calcium magnesium boron iron zinc compound liquid fertilizer of the embodiment 1 of the invention, has a more obvious effect of promoting rice, and is better than the effect of directly applying corresponding nutrient elements to rice. And treatment 3 only adopts the same amount of clear water, so that the cucumber promoting effect is not obvious.

In conclusion, the one-pot method is simple in process, simple and convenient to operate, less in used equipment and lower in cost of producing the composite liquid fertilizer, the sugar alcohol chelated medium and trace element composite liquid fertilizer prepared by the preparation method provided by the invention contains various medium and trace elements, the soil can be effectively fertilized, and the composite liquid fertilizer has higher stability due to the addition of alkali as a stabilizer, precipitation cannot be caused after long-time storage, and the fertilizer efficiency cannot be reduced.

The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims

1. The stable sugar alcohol chelated medium and trace element composite liquid fertilizer is characterized by comprising the following components in percentage by weight:

2. the compound liquid fertilizer as claimed in claim 1, wherein the sugar alcohol is any one or a mixture of at least two of xylitol, sorbitol, mannitol, maltitol, glucitol or lactitol.

3. The compound liquid fertilizer as claimed in claim 1 or 2, wherein the alkali is an organic alkali and an inorganic alkali as a stabilizer;

preferably, the base is any one or a mixture of at least two of ethanolamine, ethylenediamine, triethylamine, triethylenediamine, tetramethylethylenediamine, potassium hydroxide, sodium hydroxide, potassium phosphate, potassium monohydrogenphosphate, sodium phosphate or sodium monohydrogenphosphate.

4. The compound liquid fertilizer as claimed in any one of claims 1 to 3, wherein the alcohol is any one or a mixture of at least two of ethylene glycol, diethylene glycol, propylene glycol, glycerin, polypropylene glycol, polyethylene glycol or polyglycerol.

5. The compound liquid fertilizer as claimed in any one of claims 1 to 4, wherein the medium trace element is any one or a mixture of at least two of calcium, magnesium, boron, iron, zinc, copper or manganese;

preferably, the calcium element is derived from a calcium salt, preferably any one or a mixture of at least two of calcium chloride, calcium nitrate, EDTA-calcium, calcium ammonium nitrate, calcium formate or calcium acetate;

preferably, the magnesium element is derived from a magnesium salt, preferably any one or a mixture of at least two of magnesium chloride, magnesium nitrate, magnesium sulfate, magnesium formate, magnesium acetate or EDTA-magnesium;

preferably, the iron element is derived from an iron salt, preferably any one or a mixture of at least two of ferric chloride, ferric sulfate, ferric nitrate, ferric formate, ferric acetate or EDTA-iron;

preferably, the zinc element is derived from a zinc salt, preferably any one or a mixture of at least two of zinc chloride, zinc sulfate, zinc nitrate, iron formate, iron acetate or EDTA-zinc;

preferably, the copper element is derived from copper salt, preferably any one or a mixture of at least two of copper chloride, iron sulfate, copper nitrate, copper formate, copper acetate or EDTA-copper;

preferably, the manganese element is derived from manganese salt, preferably any one or a mixture of at least two of manganese chloride, manganese sulfate, manganese nitrate, manganese formate, manganese acetate or EDTA-manganese;

preferably, the boron element is derived from a boron salt and/or boric acid, preferably any one or a mixture of at least two of boric acid, calcium borate, magnesium borate, sodium borate, ferric borate or manganese borate.

6. A preparation method of a stable sugar alcohol chelated medium-trace element composite liquid fertilizer is characterized by comprising the following steps:

7. The method for preparing the compound of claim 6, wherein the temperature of the reaction in the step (1) is 70-90 ℃;

preferably, the reaction time is 2-6 h.

8. The method of claim 6 or 7, wherein the one-pot method of step (1) comprises the steps of:

(III) adding sugar alcohol to the solution of step (II), keeping the temperature at 70-90 ℃, and stirring for 2-6 hours until the sugar alcohol is completely chelated with one or more trace elements.

9. The preparation method according to any one of claims 6 to 8, wherein the step (2) further comprises the steps of stirring uniformly and cooling to normal temperature after adding the alkali.

10. The method according to any one of claims 6 to 9, characterized in that it comprises the steps of: