CN112759424B - Amino acid water-soluble fertilizer and preparation method thereof - Google Patents
Amino acid water-soluble fertilizer and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C11/00—Other nitrogenous fertilisers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C277/08—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups of substituted guanidines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
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Abstract
The invention discloses an amino acid water-soluble fertilizer and a preparation method thereof. The invention chelates the multi-nitrogen amino acid containing at least two N atoms with metal ions by using a high-pressure microwave method to prepare the amino acid water-soluble fertilizer, thereby improving the bioavailability of the multi-nitrogen amino acid metal chelate; the bioavailability is further improved by further adding a second nitrogen-containing compound. The amino acid water-soluble fertilizer disclosed by the invention does not contain toxic compounds and heavy metals required by non-life activities, is safe and environment-friendly, and the synthesized multi-nitrogen amino acid metal chelate has high activity in plants and is fast in transportation. The preparation method disclosed by the invention is simple in steps, short in time consumption, free of high-cost equipment and beneficial to popularization and application of the amino acid water-soluble fertilizer.
Description
Technical Field
The invention relates to the technical field of water-soluble fertilizers, and particularly relates to an amino acid water-soluble fertilizer and a preparation method thereof.
Background
The water-soluble fertilizer is a water-soluble fertilizer, which is a multi-element compound type quick-acting fertilizer capable of being completely dissolved in water. The application modes mainly comprise 3 modes: the fertilizer is applied along with water, cultivated by nutrient solution and sprayed on leaf surfaces, and has the advantages of controllable formula, high absorption efficiency and the like. The amino acid water-soluble fertilizer is a liquid or solid water-soluble fertilizer prepared by taking free amino acid as a main body and adding a proper amount of trace elements such as copper, iron, manganese, zinc, boron and molybdenum or calcium according to a proportion required by the growth of plants. With the continuous deepening of understanding of people on the defects of the fertilizer and the enhancement of environmental protection consciousness, the amino acid water-soluble fertilizer with the advantages of improving the utilization rate of the fertilizer, increasing both production and income, improving the quality, protecting the environment and the like has great development opportunities.
However, the existing mixed fertilizer of amino acids and trace elements prepared by adopting a mixing mode has the problem of low bioavailability of metal elements, and the problem of further improving the bioavailability of the metal elements in the water-soluble fertilizer of amino acids is a problem to be solved in the field.
Disclosure of Invention
The invention aims to provide an amino acid water-soluble fertilizer and a preparation method thereof, wherein the amino acid and the metal element are chelated by adopting a high-pressure microwave method, so that the chelation rate of the amino acid and the metal element is improved; the amino acid containing at least two N atoms is selected to be chelated with the metal element, so that the bioavailability of the metal element by the crops is improved, and the bioavailability of the metal element by the crops can be further improved by adding the second nitrogen-containing compound.
In order to achieve the purpose, the invention provides the following technical scheme:
one of the technical schemes of the invention is as follows: providing an amino acid water-soluble fertilizer, which comprises a chelate compound consisting of multi-nitrogen amino acid and metal elements; wherein the molar ratio of the polynitrogen amino acid to the metal element is (2-4): 1.
Preferably, the components of the amino acid water-soluble fertilizer also comprise a second nitrogen-containing compound, wherein the mass ratio of the second nitrogen-containing compound to the multi-nitrogen amino acid is (1-2): 1.
Preferably, the multi-nitrogen amino acid is an amino acid containing at least two N atoms; the metal element is one or more of zinc, magnesium, calcium and manganese.
Preferably, the amino acid containing at least two N atoms is one or more of arginine, histidine and lysine.
Preferably, the second nitrogen-containing compound is urea and/or ammonium nitrate.
The second technical scheme of the invention is as follows: the preparation method of the amino acid water-soluble fertilizer comprises the following steps:
dissolving the multi-nitrogen amino acid in water, adding soluble metal salt, adjusting the pH value to 5.0-6.0, and performing microwave treatment under a high pressure condition to obtain the liquid amino acid water-soluble fertilizer.
Preferably, the liquid amino acid water-soluble fertilizer is spray-dried to prepare the solid amino acid water-soluble fertilizer.
The third technical scheme of the invention is as follows: the preparation method of the amino acid water-soluble fertilizer containing the second nitrogen-containing compound comprises the following steps:
dissolving the multi-nitrogen amino acid in water, adding soluble metal salt, adding acid to adjust the pH value of the solution to 5.0-6.0, performing microwave treatment under a high pressure condition, and adding a second nitrogen-containing compound to prepare the liquid amino acid water-soluble fertilizer.
Preferably, the liquid amino acid water-soluble fertilizer is spray-dried to prepare the solid amino acid water-soluble fertilizer.
Preferably, the mass ratio of the multi-nitrogen amino acid to the water is 1 (4-8); the acid is citric acid; the pressure under the high pressure condition is 3-4 MPa.
The higher solid-liquid ratio can obviously improve the mass transfer driving force, but when the solid-liquid ratio is too high, the subsequent treatment difficulty is increased, and the raw materials are wasted.
Preferably, the microwave treatment is performed in a segmented microwave treatment mode, wherein the microwave treatment is performed under the conditions that the treatment is performed for 5-10 min under the power of 300-350W, and then the treatment is performed for 2-5 min under the power of 500-600W.
The fourth technical scheme of the invention is as follows: the amino acid water-soluble fertilizer is applied as a foliar fertilizer.
Preferably, the amino acid water-soluble fertilizer is added with water to be prepared into a proper concentration, and is applied once in a young sprout period and a current bud period and applied 3-4 times in a fruiting period when being applied to fruit trees; the crops are picked for many times, and the application is carried out once in the young sprout period and the early flower bud period respectively, and the application is carried out once every second round after the crops are picked; the fertilizer is applied to short-period vegetable crops once in a seedling stage and once after 10-12 days.
The invention has the following beneficial technical effects:
the synthesized multi-nitrogen amino acid metal chelate has high activity and fast transportation in crops by selecting the multi-nitrogen amino acid and soluble metal salt for chelation. When the amino acid water-soluble fertilizer is used for foliage application, the amino acid water-soluble fertilizer can be quickly absorbed by plants, the utilization rate of the amino acid water-soluble fertilizer is improved, the yield and the income are increased, and the quality of crops can be improved. Meanwhile, the amino acid water-soluble fertilizer provided by the invention does not contain toxic compounds and heavy metals required by non-life activities, and is safe and environment-friendly.
The invention adopts a reduced pressure microwave method to synthesize the multi-nitrogen amino acid metal chelate, and compared with the traditional water system synthesis method, the microwave method has higher metal chelating rate. Under the action of a microwave electromagnetic field, polar molecules are changed from the original thermal motion state to the alternative arrangement orientation according to the direction of the electromagnetic field, and the activity of metal ions is greatly improved under the action of the microwave electromagnetic field in the microwave treatment process; theoretically, the higher the microwave power is, the stronger the metal ion activity is, but the long-time high-power microwave can damage the amino acid molecular structure, so that the invention adopts segmented microwave treatment, under the low-power microwave condition, free metal ions and amino acid molecules are firstly chelated, and then the short-time high-power microwave is switched, so as to further promote the chelation of the free metal ions and the amino acid; the high-pressure treatment is adopted, so that the activity of water molecules can be greatly improved in the microwave treatment process, the chelation of metal ions and amino acid can be hindered, the activity of water molecules can be effectively inhibited under the high-pressure condition in the short-time microwave treatment, and the chelation rate of the amino acid and the metal ions can be improved.
The method provided by the invention has the advantages of simple steps, short time consumption and no need of high-cost equipment, and is favorable for popularization and application of the amino acid water-soluble fertilizer.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
Mixing arginine and water according to the mass ratio of 1:5, and stirring until the arginine is completely dissolved; adding zinc sulfate, wherein the molar ratio of the zinc sulfate to the arginine is 1:3, and stirring until the zinc sulfate is completely dissolved; adjusting the pH value of the solution to 5.5 by using citric acid, pressurizing microwave treatment equipment to maintain the internal pressure at 3-4 MPa, performing microwave treatment for 10min under the power of 300W after the pressure is stable, performing microwave treatment for 2min under the power of 600W, taking out and cooling to obtain the liquid amino acid water-soluble fertilizer.
And (3) spray drying the liquid amino acid water-soluble fertilizer to obtain the solid amino acid water-soluble fertilizer.
Example 2
Mixing histidine with water according to the mass ratio of 1:4, and stirring until the histidine is completely dissolved; adding calcium nitrate, wherein the molar ratio of the calcium nitrate to the histidine is 1:2, and stirring until the calcium nitrate is completely dissolved; adjusting the pH value of the solution to 5.0 by using citric acid, pressurizing microwave treatment equipment to maintain the internal pressure at 3-4 MPa, performing microwave heating for 5min under the power of 350W after the pressure is stable, performing microwave treatment for 5min under the power of 500W, taking out and cooling to obtain the liquid amino acid water-soluble fertilizer.
And (3) spray drying the liquid amino acid water-soluble fertilizer to obtain the solid amino acid water-soluble fertilizer.
Example 3
Mixing lysine and water according to the mass ratio of 1:8, and stirring until the lysine is completely dissolved; adding zinc sulfate, wherein the molar ratio of the zinc sulfate to the lysine is 1:4, and stirring until the zinc sulfate is completely dissolved; adjusting the pH value of the solution to 6.0 by using citric acid, pressurizing microwave treatment equipment to maintain the internal pressure at 3-4 MPa, after the pressure is stable, carrying out microwave heating for 8min under the power of 320W, carrying out microwave treatment for 4min under the power of 550W, taking out, cooling, adding urea, wherein the mass ratio of the urea to the lysine is 1:1, and uniformly stirring to obtain the liquid amino acid water-soluble fertilizer.
And (3) spray drying the liquid amino acid water-soluble fertilizer to obtain the solid amino acid water-soluble fertilizer.
Example 4
Mixing arginine and water according to the mass ratio of 1:5, and stirring until the arginine is completely dissolved; adding zinc sulfate, wherein the molar ratio of the zinc sulfate to the arginine is 1:3, and stirring until the zinc sulfate is completely dissolved; adjusting the pH value of the solution to 5.5 by using citric acid, pressurizing microwave treatment equipment to maintain the internal pressure at 3-4 MPa, performing microwave heating for 10min under the power of 300W after the pressure is stable, performing microwave treatment for 2min under the power of 600W, taking out, cooling, adding urea, wherein the mass ratio of the urea to the lysine is 2:1, and uniformly stirring to obtain the liquid amino acid water-soluble fertilizer.
And (3) spray drying the liquid amino acid water-soluble fertilizer to obtain the solid amino acid water-soluble fertilizer.
Comparative example 1
The difference from example 1 is that no pressurization treatment is performed during the production process, and the other conditions are the same as example 1.
Comparative example 2
Compared with the example 1, the difference is that the microwave treatment adopts one-stage microwave treatment, the condition is changed to treatment for 12min under the power of 300W, and other conditions are the same as the example 1.
Comparative example 3
Compared with the example 1, the difference is that the microwave treatment adopts one-stage microwave treatment, the condition is changed to treatment for 12min under the power of 600W, and other conditions are the same as the example 1.
Comparative example 4
Mixing glycine and water according to the mass ratio of 1:5, and stirring until the glycine is completely dissolved; adding zinc sulfate, wherein the molar ratio of the zinc sulfate to the glycine is 1:3, and stirring until the zinc sulfate is completely dissolved; adjusting the pH value of the solution to 5.5 by using citric acid, pressurizing microwave treatment equipment to maintain the internal pressure at 3-4 MPa, performing microwave heating for 10min under the power of 300W after the pressure is stable, performing microwave treatment for 2min under the power of 600W, taking out and cooling to obtain the liquid amino acid water-soluble fertilizer.
And (3) spray drying the liquid amino acid water-soluble fertilizer to obtain the solid amino acid water-soluble fertilizer.
Comparative example 5
Mixing leucine with water according to the mass ratio of 1:5, and stirring until the leucine is completely dissolved; adding zinc sulfate, wherein the molar ratio of the zinc sulfate to the leucine is 1:3, and stirring until the zinc sulfate is completely dissolved; adjusting the pH value of the solution to 5.5 by using citric acid, pressurizing microwave treatment equipment to maintain the internal pressure at 3-4 MPa, performing microwave heating for 10min under the power of 300W after the pressure is stable, performing microwave treatment for 2min under the power of 600W, taking out and cooling to obtain the liquid amino acid water-soluble fertilizer.
And (3) spray drying the liquid amino acid water-soluble fertilizer to obtain the solid amino acid water-soluble fertilizer.
The effect test is carried out on the amino acid water-soluble fertilizer prepared in the above examples and comparative examples:
(1) the amino acid chelating rates of example 1 and comparative examples 1 to 3 were determined by the following method:
determination of total amount of metal in amino acid metal chelate:
precisely transferring 10ml of the liquid amino acid water-soluble fertilizer into a 100ml volumetric flask, fixing the volume and shaking up. Precisely transferring 20ml into a 200ml conical flask, adding 50ml of distilled water, dropwise adding 2-3 drops of PAN indicator, and adding EDTA standard solution (with the concentration of c)0) Titrating, wherein the color of the solution is faded from purple red to be a titration endpoint, and recording the volume (V) of the EDTA standard solution consumed0)。
Determination of chelated metal in amino acid metal chelate:
precisely transferring 10ml of liquid amino acid water-soluble fertilizer into a 100ml beaker, heating and concentrating until the fertilizer is dried, adding 50ml of absolute ethyl alcohol, heating in a water bath, fully stirring, centrifuging, dissolving the precipitate in water, transferring into a 100ml volumetric flask, fixing the volume, and shaking up. Precisely transferring 20ml into a 200ml conical flask, adding 50ml of distilled water, dropwise adding 2-3 drops of PAN indicator, and adding EDTA standard solution (with the concentration of c)1) Titrating, wherein the color of the solution is faded from purple red to be a titration endpoint, and recording the volume (V) of the EDTA standard solution consumed1)。
The calculation formula of the chelating rate of the metal elements is as follows:
the zinc chelation rate of example 1 was determined to be 98.6% by the above test method; the zinc chelation rate of comparative example 1 was 91.2%; the zinc chelation rate of comparative example 2 was 86.5%; the zinc chelation rate of comparative example 3 was 65.6%. According to the measurement result, the high-pressure microwave method provided by the invention is short in time consumption, the chelation rate of the amino acid and the metal ions is high, and the chelation rate of the comparative example 3 is far lower than that of the comparative example 2 because the molecular structure of the amino acid is damaged by long-time high-power microwave treatment, so that the chelation rate is greatly reduced.
(2) Effect of amino acid Water-soluble fertilizers prepared in comparative examples 1 to 4 and comparative examples 4 to 5 on yield and quality of oranges
In a certain sugar orange garden (the planting density is about 75 plants/mu) in the south, 7 fields with the size of 1 mu are selected as test lands, the amino acid water-soluble fertilizers prepared in examples 1-4 and comparative examples 4-5 are prepared into an aqueous solution with the zinc content of 400ppm, a zinc sulfate and arginine mixed aqueous solution with the zinc content of 400ppm and the arginine content of 0.32% is prepared as a control group and respectively applied to four test lands, the application time is that foliar spraying is carried out once respectively in the young sprout period and the bud period of the oranges, foliar spraying is carried out 3 times in the fruiting period, and the spraying amount is 30 liters per mu.
70 orange trees are randomly selected from 7 test sites for picking, the weight of the picked sugar oranges is counted, and the results are shown in table 1.
TABLE 1 orange Tree yields
| Serial number | Picking weight (kg) of 70 orange trees | Average yield per orange tree (kg) |
| Control group | 6881 | 98.3 |
| Example 1 | 10920 | 156.0 |
| Example 2 | 10492 | 149.6 |
| Example 3 | 12061 | 172.3 |
| Example 4 | 12642 | 180.6 |
| Comparative example 2 | 8645 | 123.5 |
| Comparative example 3 | 8421 | 120.3 |
As can be seen from Table 1, the yields of examples 1 to 4 and comparative examples 4 to 5 to which the amino acid chelated zinc was applied were significantly higher than those of the control group to which the zinc sulfate-arginine mixed fertilizer was applied; the yields of the groups of examples 1 to 4 to which the zinc amino acid chelate was applied were significantly higher than those of the groups of comparative examples 2 to 3 to which the zinc amino acid chelate was applied; the yields of the groups of examples 3-4 with the addition of the second nitrogen-containing compound are significantly higher than the groups of examples 1-2 without the addition of the second nitrogen-containing compound.
ICP is utilized to measure the zinc content in the leaves and fruits of 7 orange trees selected as test sites after the oranges are picked, and the measurement results are shown in Table 2.
TABLE 2 ICP determination of Zinc content in orange leaves and fruits
| Serial number | Zinc content (ppm) in leaves | Zinc content (ppm) in fruit |
| Control group | 20.32 | 18.62 |
| Example 1 | 22.32 | 32.13 |
| Example 2 | 22.16 | 31.68 |
| Example 3 | 20.02 | 36.03 |
| Example 4 | 19.35 | 36.57 |
| Comparative example 2 | 24.90 | 26.12 |
| Comparative example 3 | 24.52 | 25.56 |
As can be seen from Table 2, the fruits of the groups 3 to 4 to which the zinc amino acid chelate with the addition of the second nitrogen-containing compound was applied had the highest zinc content, followed by the groups 1 to 2 to which the zinc amino acid chelate with the polyaza was applied, followed by the groups 4 to 5 to which the zinc amino acid chelate with the monoaza was applied, and the control group had the lowest. The zinc-containing foliage spray fertilizer shows that the multi-nitrogen amino acid chelated zinc is transported in the plant body most rapidly and is better than the single-nitrogen amino acid chelated zinc, and the bioavailability is highest; compared with common soluble zinc salt, the amino acid chelated zinc transport is obviously higher; in addition, the addition of a second nitrogen-containing compound also facilitates zinc transport in plants.
The above point was also demonstrated in combination with the zinc content in the leaves of citrus trees, in comparative examples 4-5, in which zinc mononitrogenated amino acid was applied, the zinc content in the leaves was significantly higher than in examples 1-4, in which zinc polynitrogenated amino acid was applied, but the zinc content in the leaves of the comparative examples was not much different from that of examples 3-4, which was caused by the fact that the zinc content in the leaves was not high and the zinc content in the fruits was low because of the low absorption rate due to the simple use of soluble zinc salt mixed with polynitrogenated amino acid. In addition, the zinc content in the leaves of the groups 3-4 added with the second nitrogen-containing compound is higher than that in the groups 1-2, which proves that the addition of the second nitrogen-containing compound promotes the transportation of the zinc absorbed by the plants through the leaves.
The bioavailability of the zinc amino acid chelate is higher than that of the zinc amino acid chelate, and the zinc amino acid chelate is probably more similar to the enzyme form in the plant body in structure compared with the zinc amino acid chelate, so that the transport speed in the plant body is higher, and the bioavailability is higher.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (5)
1. The preparation method of the amino acid water-soluble fertilizer is characterized by comprising the following steps:
dissolving poly-nitrogen amino acid in water, adding soluble metal salt, adjusting the pH value to 5.0-6.0, and performing microwave heating under a high-pressure condition to obtain a liquid amino acid water-soluble fertilizer;
the multi-nitrogen amino acid is an amino acid containing at least two N atoms;
the metal element in the soluble metal salt is one or more of zinc, magnesium, calcium and manganese;
the molar ratio of the polynitrogen amino acid to the metal elements in the soluble metal salt is (2-4) to 1;
the mass ratio of the polynitrogen amino acid to the water is 1 (4-8); the pressure under the high-pressure condition is 3-4 MPa;
the microwave treatment adopts segmented microwave treatment, and the conditions are that the microwave treatment is firstly carried out for 5-10 min under the power of 300-350W, and then the microwave treatment is carried out for 2-5 min under the power of 500-600W.
2. The preparation method of the amino acid water-soluble fertilizer is characterized by comprising the following steps:
dissolving multi-nitrogen amino acid in water, adding soluble metal salt, adding acid to adjust the pH value of the solution to 5.0-6.0, performing microwave treatment under a high pressure condition, and adding a second nitrogen-containing compound to prepare a liquid amino acid water-soluble fertilizer;
the multi-nitrogen amino acid is an amino acid containing at least two N atoms;
the metal element in the soluble metal salt is one or more of zinc, magnesium, calcium and manganese;
the molar ratio of the polynitrogen amino acid to the metal elements in the soluble metal salt is (2-4) to 1;
the second nitrogen-containing compound is urea and/or ammonium nitrate;
the mass ratio of the second nitrogen-containing compound to the multi-nitrogen amino acid is (1-2) to 1;
the mass ratio of the polynitrogen amino acid to the water is 1 (4-8); the pressure under the high-pressure condition is 3-4 MPa;
the microwave treatment adopts segmented microwave treatment, and the conditions are that the microwave treatment is firstly carried out for 5-10 min under the power of 300-350W, and then the microwave treatment is carried out for 2-5 min under the power of 500-600W.
3. The method for preparing the amino acid water-soluble fertilizer as claimed in claim 1 or 2, wherein the prepared liquid amino acid water-soluble fertilizer is spray-dried to prepare a solid amino acid water-soluble fertilizer.
4. An amino acid water-soluble fertilizer prepared by the preparation method according to any one of claims 1 to 3.
5. The use of the amino acid water-soluble fertilizer as claimed in claim 4 as a foliar fertilizer.
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| CN1284766C (en) * | 2003-12-29 | 2006-11-15 | 江南大学 | Solid phase synthesis process of amino acid chelate adopting airflow synergizing microwave technology |
| CN103833566A (en) * | 2012-11-26 | 2014-06-04 | 青岛宝依特生物制药有限公司 | Method for preparing high-purity lysine trace element chelate compound |
| CN104609944A (en) * | 2014-12-30 | 2015-05-13 | 成都新柯力化工科技有限公司 | Special slow release water soluble fertilizer for rubber tree and preparation method thereof |
| CN107098770A (en) * | 2017-06-26 | 2017-08-29 | 福州大学化肥催化剂国家工程研究中心 | A kind of chelating amino acids zinc fertilizer and preparation method thereof |
| CN107986876A (en) * | 2017-12-20 | 2018-05-04 | 崔凯 | A kind of organic granular Water soluble fertilizer and preparation method thereof |
| CN107867896A (en) * | 2017-12-21 | 2018-04-03 | 中南林业科技大学 | A kind of special chelated microelements water-soluble fertilizer of oil tea and preparation method thereof |
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