CN108003047B - Iminodisuccinic acid chelated metal salt - Google Patents
Iminodisuccinic acid chelated metal salt Download PDFInfo
- Publication number
- CN108003047B CN108003047B CN201711218425.XA CN201711218425A CN108003047B CN 108003047 B CN108003047 B CN 108003047B CN 201711218425 A CN201711218425 A CN 201711218425A CN 108003047 B CN108003047 B CN 108003047B
- Authority
- CN
- China
- Prior art keywords
- iminodisuccinic acid
- metal
- metal salt
- salt
- raw material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D3/00—Calcareous fertilisers
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D5/00—Fertilisers containing magnesium
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
- C05D9/02—Other inorganic fertilisers containing trace elements
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses an iminodisuccinic acid chelated metal salt, which belongs to the field of green fertilizers and is used for supplementing metal trace elements to crops or soil, wherein the iminodisuccinic acid chelated metal salt comprises a product of reaction of iminodisuccinic acid or iminodisuccinic acid type salt and a raw material containing metal elements, and the raw material containing the metal elements is one or a mixture of more of metal simple substances, oxides, hydroxides, carbonates or alkali carbonates; the invention can obviously improve the content and the utilization rate of the active ingredients of the chelated fertilizer, all the contained ingredients can be completely metabolized and absorbed by plants and can also be degraded by soil microorganisms, and the invention has the advantages of high stability, good safety, no environmental residue and low content of ineffective salt, can effectively avoid soil calcification and hardening, and reduces the packaging, transportation and use costs.
Description
Technical Field
The invention relates to a chelating agent, in particular to a chelated metal salt containing metal trace elements, which belongs to the field of green fertilizers and is used for supplementing metal trace elements to crops or soil.
Background
The plant growth and development essential elements are 16 in total, wherein the major elements comprise carbon, hydrogen, nitrogen, phosphorus and potassium, and the secondary elements and the trace elements comprise calcium, magnesium, sulfur, iron, zinc, manganese, steel, boron, molybdenum and chlorine. With the development of modern science, the application of the fertilizer makes a great contribution to agricultural production increase, so that the yield of agricultural products per unit area is greatly increased, however, unbalanced fertilization also causes crises of modern agriculture, and serious harm is caused to environmental resources and human health. Firstly, the application of a large amount of nitrogen, phosphorus and potassium fertilizers plays a great role in promoting the growth of plants, the plants absorb metal trace elements contained in soil while growing in a large amount, but the content of the metal trace elements in the soil is limited and the metal trace elements are often not supplemented in place, so that the metal trace elements are difficult to fully meet the growth needs of crops, and the crop metabolism is hindered, the nutrient content of agricultural products is unbalanced, the quality is reduced, the taste is changed and the like. Secondly, fertilizers containing macroelements of nitrogen, phosphorus and potassium can precipitate trace metal elements in soil, so that the trace metal elements are immobilized and inactivated, are difficult to be absorbed and utilized by plants, and cause environmental pollution such as soil hardening, granular structure destruction, microorganism reduction and the like. Therefore, the application of metal trace element fertilizers or the improvement of the activity of metal trace elements in soil has become a common recognition in the industry.
Because plants are difficult to absorb and utilize trace metal elements existing in the form of inorganic salt, and soil pollution can be caused by directly applying the metal inorganic salt, the metal trace elements are generally protected by an organic complexing agent to form a relatively stable water-soluble state, so that the compatibility among fertilizers can be ensured, and the absorption utilization rate of the plants on the metal trace elements is improved. The traditional complexing agent is ethylenediaminetetraacetate (abbreviated as EDTA in english). Although the ethylenediamine tetraacetate has good capability of complexing metal ions, the ethylenediamine tetraacetate cannot be absorbed and utilized by crops and cannot be degraded by soil microorganisms, so that the problem of environmental pollution is caused.
The capability of the iminodisuccinate for complexing metal ions is equivalent to that of EDTA (ethylene diamine tetraacetic acid), the iminodisuccinate can be completely absorbed by crops, the utilization efficiency of metal trace elements is higher, and the iminodisuccinate is a green degradable environment-friendly complexing agent. The patent CN200310102834.5 discloses chelated plant micronutrients prepared by metathesis of sodium or potassium iminodisuccinate with metal salts, however their complex production process results in ineffective salt components (sodium or potassium salt form of inorganic or organic anions). The application of the chelate fertilizer can increase unnecessary salt in the soil, for example, the sulfate radical is easy to cause calcification and hardening of the soil and influence the growth of crops; chloride ions have a corrosive effect on equipment and are not suitable for avoiding chlorine crops; nitrate radicals have strong oxidation effect, so that the storage and transportation dangerousness is increased; in addition, the ineffective salt can reduce the content of the effective components of the product, and the cost of the product in the processes of packaging, transportation and use is increased by about 15%.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the iminodisuccinic acid chelated metal salt, which has the advantages of high content of effective components, high efficiency of absorption and utilization by plants, capability of being degraded by microorganisms in soil, high stability, good safety, no environmental residue and no ineffective salt component, capability of avoiding soil hardening, and reduction of packaging, transportation and use costs.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the iminodisuccinic acid chelated metal salt comprises a product of reaction of iminodisuccinic acid or iminodisuccinic acid type salt and a raw material containing metal elements, wherein the raw material containing the metal elements is one or a mixture of more of simple metal substances, oxides, hydroxides, carbonates and basic carbonates.
The technical scheme of the invention is further improved as follows: the molar ratio of hydrogen to potassium or sodium in the iminodisuccinic acid salt is greater than 3: 1.
The technical scheme of the invention is further improved as follows: the metal element is any one or a mixture of more of copper, iron, zinc, calcium, magnesium, manganese and cobalt.
The technical scheme of the invention is further improved as follows: the content of metal ions in the iminodisuccinic acid chelated metal salt is 12-18%.
The technical scheme of the invention is further improved in that the preparation method comprises the following steps:
a. enabling an aqueous solution of iminodisuccinate or iminodisuccinate type salt to pass through ion exchange resin to obtain iminodisuccinate;
b. adding iminodisuccinic acid and a raw material containing metal elements into water, heating to 40-80 ℃, and reacting for 2-8 h;
c. and after the reaction is finished, filtering, concentrating and crystallizing the liquid, centrifuging to obtain solid crystals, and drying to obtain the finished product of the iminodisuccinic acid chelated metal salt.
The technical scheme of the invention is further improved as follows: the concentration of the imino disuccinate or the aqueous solution of the imino disuccinate is 8-15%; the ion exchange resin is strong acid type cation exchange resin.
The technical scheme of the invention is further improved as follows: the molar ratio of the iminodisuccinic acid to the raw material containing the metal element is 1: 0.25-1.
The technical scheme of the invention is further improved as follows: the mass ratio of the total mass of the iminodisuccinic acid and the raw material containing the metal element to the water is 1: 5-10.
The technical scheme of the invention is further improved as follows: the iminodisuccinic acid chelating metal salt is compounded with a compound containing aluminum, chromium, nickel, tin, vanadium or molybdenum elements.
The technical scheme of the invention is further improved as follows: the iminodisuccinic acid chelating metal salt is added with any one or a mixture of several of a surfactant, a binder, a wetting agent or a stabilizer.
Due to the adoption of the technical scheme, the invention has the technical progress that:
the iminodisuccinic acid chelated metal salt provided by the invention obviously improves the content and the utilization rate of active ingredients, all the contained ingredients can be completely metabolized and absorbed by plants, and can also be degraded by soil microorganisms, and the iminodisuccinic acid chelated metal salt has the advantages of high stability, good safety, no environmental residue and no ineffective salt ingredient, can effectively avoid soil calcification and hardening, and reduces the packaging, transportation and use costs.
The invention uses iminodisuccinic acid or iminodisuccinic acid type salt to react with raw material containing metal element to obtain chelated metal salt and water. Compared with the double decomposition reaction of iminodisuccinate and metal salt, the reaction system of the invention has no introduction of ineffective anions such as chloride ions, sulfate ions or nitrate ions, and the like, so that no ineffective salt component is generated, the compound of the metal trace element in the reactant is any one or mixture of a simple substance, an oxide, a hydroxide or a metal organic compound, and the final product is all the effective components capable of being absorbed and degraded biologically.
The invention does not contain invalid salt components, has the advantages of good safety, no corrosiveness, wide applicability, capability of avoiding soil calcification and hardening and the like, and the obtained product does not contain any corrosive components such as chloride ions and phosphate ions, so that the corrosive damage of the chloride ions to containers made of metal materials such as stainless steel and the like can be effectively avoided, the selection range of the materials of the containers in the processes of processing, transportation and use is wider, and the use is more convenient. Meanwhile, the application range of the chelated metal salt as a fertilizer is also enlarged, so that the chelated metal salt can be suitable for crops avoiding chlorine, such as tobacco, sweet potatoes, potatoes and the like. In addition, the product does not contain nitrate radical with strong oxidability and carcinogenicity, thereby improving the safety of the product, avoiding the risk of explosion, reducing the requirements on storage and transportation conditions and reducing the harm to health. The product does not contain sulfate radicals and carbonate ions, so that the problem that the soil is calcified and hardened because the sulfate radicals and the carbonate ions are easily combined with calcium ions and the like in the soil is solved, the problem that the absorption of metal trace elements is hindered because the sulfate radicals and the carbonate ions are combined with manganese ions to form precipitates is also avoided, and the problems that the nozzle is easily blocked or scaled and the like because the sulfate radicals and the carbonate ions are easily formed precipitates with calcium and magnesium ions in water in the spray irrigation process are solved.
The product of the invention does not contain sodium ions or potassium ions, thereby avoiding adding unnecessary potassium and sodium elements into the soil in the process of applying the chelate fertilizer, preventing the soil salinization from being aggravated, or preventing the adverse effects of excessive potassium and sodium on the growth of plants, particularly avoiding crops with potassium or sodium taboos. The iminodisuccinic acid used in the invention is obtained by treating an iminodisuccinic acid salt or an aqueous solution of iminodisuccinic acid salt with cation exchange resin. The sodium cation exchange resin with saturated adsorption can be regenerated by sulfuric acid or hydrochloric acid to convert the hydrogen cation exchange resin for repeated recycling. In general, the iminodisuccinate is more stable in nature and is more easily purchased, and the synthesis reaction is in the form of directly generating salt under alkaline environment. The invention uses hydrogen type strong acid cation exchange resin to exchange the cation of imino disuccinate, such as sodium and potassium ion, with hydrogen ion to obtain imino disuccinic acid.
The invention can solve the problem of lack of metal trace elements in soil, provide supplement of trace nutrient elements for plants, improve disease resistance of the plants, enable fruits to have better taste, nutritive value and appearance, and have good effects of improving seed setting rate, seed plumpness and the like. Because nitrogen, phosphorus and potassium fertilizers are commonly used in agriculture at present and supplement of metal trace elements is insufficient, the metal trace elements needed after plant growth is promoted are correspondingly increased, and the needs are difficult to meet only by taking the metal trace elements from soil. The invention contains metal trace elements required by plant growth, such as any one or mixture of more of copper, iron, zinc, calcium, magnesium, manganese and cobalt, and can be further compounded with substances containing aluminum, chromium, nickel, tin, vanadium or molybdenum elements. Although the content of the elements in the plant body is very small, the elements play an important role in the growth and metabolism of the plant organism and have some special physiological functions.
The invention applies the metal trace elements required by plants into soil in the form of chelated metal salts, and is beneficial to improving the absorption and utilization rate of the metal trace elements. The trace metal elements and the chelating agent iminodisuccinic acid form the chelating microelement fertilizer after being complexed, the problem that inorganic metal ions react with other components to generate precipitates or are fixed and inactivated when being directly applied to soil can be avoided, the effective components of the chelating microelement fertilizer are relatively stable in the soil, can be better absorbed and utilized by plants, cannot cause soil pollution, and can be completely degraded by organisms.
The preparation method disclosed by the invention is simple in process and suitable for industrial production, compared with the traditional method, the content of metal elements is high, the content of metal ions in the product is 12-18%, the purity of the product reaches 99.5-99.8%, the purity of active ingredients in the product is improved, the components of invalid salts are removed, the variety and the using amount of fertilizers applied to soil are favorably and accurately controlled, metal trace elements can be supplemented to crops more specifically, the waste and abuse of the fertilizers are reduced, and the packaging, transportation and use costs are reduced.
The chelated metal salt can be in a solid or liquid state, can be prepared into preparations with different dosage forms by adding different additives, and can select proper dosage forms according to different field conditions and fertilization requirements. The invention can also be compounded with other fertilizers to form a mixed fertilizer, or directly mixed and applied in the fertilizing process. According to the demand conditions of soil and crops for different metal trace elements and major elements (such as nitrogen, phosphorus and potassium), the chelated metal salt disclosed by the invention can be matched with other fertilizers, or the chelated fertilizers containing different metal trace elements can be matched and matched according to a proper proportion, so that accurate fertilization is realized, the effectiveness and the utilization rate of fertilization are improved, and the requirements of environmental protection are better met.
Detailed Description
The following are some specific embodiments of the present invention for further detailed description.
The metal-containing compound is a product of reaction of iminodisuccinic acid or iminodisuccinic acid salt and a raw material containing metal elements, wherein the molar ratio of hydrogen to potassium or sodium in the iminodisuccinic acid salt is more than 3:1, the raw material containing the metal elements is one or a mixture of more of simple metal substances, oxides, hydroxides, carbonates or basic carbonates, and the contained metal elements are one or a mixture of more of copper, iron, zinc, calcium, magnesium, manganese and cobalt.
The preparation method of the iminodisuccinic acid chelated metal salt comprises the following steps:
a. treating an aqueous solution of 8-15% iminodisuccinate or iminodisuccinate salt with strong acid type cation exchange resin to obtain iminodisuccinate;
b. sequentially adding iminodisuccinic acid and a raw material containing a metal element into a reaction kettle filled with pure water, wherein the molar ratio of the iminodisuccinic acid to the raw material containing the metal element is 1: 0.25-1, when the iminodisuccinic acid is independently reacted with a certain raw material containing the metal element, when the iminodisuccinic acid is 1 equivalent, the copper-containing raw material, the magnesium-containing raw material and the zinc-containing raw material are 1 equivalent, the manganese-containing raw material is 0.5 equivalent, and the iron-containing raw material is 0.25 equivalent, the reaction is most complete, and finally, the mass ratio of the total mass of the iminodisuccinic acid and the raw material containing the metal element to water is 1: 5-10, wherein the raw material containing the metal element is an analytical purity standard, and the water is purified water, fully mixing the reactants and heating to 40-80 ℃ for reaction for 2-8 hours;
c. and after the reaction is finished, filtering, removing filter residues, concentrating the liquid part until crystallization occurs, centrifuging water to obtain solid crystals, and drying the crystals to obtain the iminodisuccinic acid chelated metal salt.
After the iminodisuccinic acid chelated metal salt is prepared, the iminodisuccinic acid chelated metal salt can be compounded with a compound containing aluminum, chromium, nickel, tin, vanadium or molybdenum according to a certain proportion. Meanwhile, any one or a mixture of several of a surfactant, a binder, a wetting agent or a stabilizer can be added into the iminodisuccinic acid chelating metal salt or the iminodisuccinic acid chelating metal salt compounded with other compounds.
Example 1
An iminodisuccinic acid chelated metal salt is prepared by the following steps:
a. treating the aqueous solution of iminodisuccinic acid sodium salt with the concentration of 8% by strong acid type cation exchange resin to obtain iminodisuccinic acid;
b. sequentially adding iminodisuccinic acid and CuO into a reaction kettle filled with pure water, wherein the molar ratio of the iminodisuccinic acid to the CuO is 1:1, the mass ratio of the total mass of the iminodisuccinic acid to the CuO to the water is 1:5, fully mixing the raw materials, heating to 40 ℃, and reacting for 2 hours;
c. and after the reaction is finished, filtering, removing filter residues, concentrating the liquid part until crystallization occurs, centrifuging water to obtain solid crystals, and drying the crystals to obtain the iminodisuccinic acid chelated metal salt.
Examples 2 to 4
Examples 2 to 4 were the same as example 1 in terms of the reaction procedure, and the types and contents of the reaction raw materials and the process conditions were as shown in Table 1 below. Wherein "concentration" represents the mass concentration of the aqueous solution of the imino disuccinate or imino disuccinate in step a, "mass ratio" is the mass ratio of the total mass of the imino disuccinate to the metal element-containing raw material to water in step b, "temperature" is the temperature of heating in step b, and "time" is the time of reaction in step b.
TABLE 1
In order to better verify the superiority of the invention in the fertilization effect, the iminodisuccinic acid chelated metal salt obtained in examples 1-4 of the invention is used for product detection, and the same product detection is carried out by using several existing metal chelated salt products in the market as a control group, wherein the control group 1 is Cu-IDHA, the control group 2 is Fe-IDHA and the control group 3 is Mn-IDHA, which are all produced by ADOB company, and the products of the control group are also applied to field tests. Each group was subjected to the component detection and analysis using the same weight (1kg) of the sample, and the specific detection results are shown in Table 2 below. Wherein "metal" represents the sum of the mass percentages of trace metal elements contained in the metal chelate salt (excluding potassium and sodium), "ineffective salt" represents the sum of the mass percentages of ineffective anions contained in the metal chelate salt (such as sulfate, nitrate, chloride, phosphate, etc.), and "potassium and sodium" represent the sum of the mass percentages of potassium and sodium ions.
TABLE 2
As can be seen from the results in Table 2, in the metal salts chelated with iminodisuccinic acid in the examples 1 to 4, the content of trace metal elements is 13 to 18%, no invalid salt, potassium and sodium are contained, and the product purity can reach 99.65% on average, while the content of trace metal elements in the metal salts chelated in the comparison group is only 9 to 10%, the content of invalid salt is 12 to 13%, the content of potassium and sodium is 8 to 8.5%, and the product purity is only 79.2%.
Field test
The chelated metal salts prepared in the embodiments 1-4 of the invention are used for field test, and the same test treatment, sampling detection and analysis are carried out by using several kinds of chelated metal salt products existing in the market as a control group, and the detection results are shown in the following table 3.
TABLE 3
As can be seen from the results in Table 3, the volume weight of the soil in examples 1 to 4 was 1.14g/cm on average3While the average value of the control group reaches 1.24g/cm3In examples 1-4, the average yield was 485 kg/mu, which is higher than the average yield of 446 kg/mu in the control group.
The results show that the imino disuccinic acid chelated metal salt prepared by the method has high metal content, is beneficial to supplement metal trace elements for crops or soil, does not contain invalid salt components, effectively avoids soil hardening, can reduce soil volume weight and improve crop yield.
Claims (4)
1. An iminodisuccinic acid chelated metal salt, characterized in that: the material containing the metal element is a mixture of several of simple metal substances, oxides, hydroxides and carbonates, the simple metal substances are any one or a mixture of several of Fe and Zn, and the oxides are CuO and Fe2O3、Fe3O4、ZnO、CaO、MoO3The carbonate is CaCO3、MgCO3、ZnCO3、CaHCO3Mixing the above components;
the content of metal ions in the iminodisuccinic acid chelated metal salt is 12-18%;
the preparation method of the iminodisuccinic acid chelated metal salt comprises the following steps:
a. enabling an aqueous solution of iminodisuccinate or iminodisuccinate type salt to pass through ion exchange resin to obtain iminodisuccinate;
b. adding iminodisuccinic acid and a raw material containing metal elements into water, heating to 40-80 ℃, and reacting for 2-8 h;
c. filtering after the reaction is finished, concentrating and crystallizing the liquid, centrifuging to obtain solid crystals, and drying to obtain a finished product of the iminodisuccinic acid chelated metal salt;
the concentration of the imino disuccinate or the aqueous solution of the imino disuccinate is 8-15%; the ion exchange resin is strong acid type cation exchange resin;
the molar ratio of the iminodisuccinic acid to the raw material containing the metal element is 1: 0.25-1.
2. The chelating metal salt of iminodisuccinic acid according to claim 1, wherein: the mass ratio of the total mass of the iminodisuccinic acid and the raw material containing the metal element to the water is 1: 5-10.
3. The chelating metal salt of iminodisuccinic acid according to claim 1, wherein: the iminodisuccinic acid chelating metal salt is compounded with a compound containing aluminum, chromium, nickel, tin, vanadium or molybdenum elements.
4. The chelating metal salt of iminodisuccinic acid according to claim 1, wherein: the iminodisuccinic acid chelating metal salt is added with any one or a mixture of several of a surfactant, a binder, a wetting agent or a stabilizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711218425.XA CN108003047B (en) | 2017-11-28 | 2017-11-28 | Iminodisuccinic acid chelated metal salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711218425.XA CN108003047B (en) | 2017-11-28 | 2017-11-28 | Iminodisuccinic acid chelated metal salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108003047A CN108003047A (en) | 2018-05-08 |
| CN108003047B true CN108003047B (en) | 2021-05-07 |
Family
ID=62054392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711218425.XA Active CN108003047B (en) | 2017-11-28 | 2017-11-28 | Iminodisuccinic acid chelated metal salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108003047B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009149748A (en) * | 2007-12-19 | 2009-07-09 | Lion Corp | Bleaching assistant and method for manufacturing bleaching assistant particle |
| CN104591901A (en) * | 2015-01-29 | 2015-05-06 | 石家庄德天科技有限公司 | Application of imino disuccinate as fertilizer synergist |
-
2017
- 2017-11-28 CN CN201711218425.XA patent/CN108003047B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009149748A (en) * | 2007-12-19 | 2009-07-09 | Lion Corp | Bleaching assistant and method for manufacturing bleaching assistant particle |
| CN104591901A (en) * | 2015-01-29 | 2015-05-06 | 石家庄德天科技有限公司 | Application of imino disuccinate as fertilizer synergist |
Non-Patent Citations (2)
| Title |
|---|
| 绿色螯合剂亚氨基二琥珀酸的合成及螯合性能;吴长彧 等;《化学工业与工程》;20070331;第24卷(第2期);第7-10页 * |
| 绿色螯合剂亚氨基二琥珀酸的性能及应用研究进展;石莹莹;《河南化工》;20151231;第32卷(第6期);第121-124页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108003047A (en) | 2018-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102190521B (en) | Water-soluble fertilizer containing humic acid chelating multielement and preparation method thereof | |
| CN102807416A (en) | All-nutritional compound type liquid fertilizer for being sprayed to plant leaf surfaces and preparation method thereof | |
| CN104829342B (en) | A kind of method of allantoin waste water production composite fertilizer | |
| CN100546948C (en) | Plant source disease-resistant foliage fertilizer and preparation method thereof | |
| CN103011941A (en) | Production method of compound fertilizer | |
| CN108586100A (en) | A kind of foliar fertilizer and preparation method thereof | |
| CN101148372B (en) | Method for producing liquid fertilizer by using pharmaceutical factory waste liquid | |
| CN102040424A (en) | Fulvic acid potassium chelating fertilizer | |
| CN1122319A (en) | Active nutrient liquid fertilizer and its preparing method | |
| CN1634806A (en) | High-iron full-complex broad spectrum foliar fertilizer and method for making same | |
| CN104496695A (en) | Special efficient compound fertilizer for chernozem | |
| CN104892395B (en) | Preparation method of ammonia manganese citrate | |
| CN109438266B (en) | Environment-friendly iminodisuccinic acid chelated metal salt | |
| CN113214020A (en) | Zinc-selenium nutrient solution for plants and preparation method thereof | |
| CN106892723A (en) | A kind of boron-rich foliar fertilizer and preparation method thereof | |
| CN108003047B (en) | Iminodisuccinic acid chelated metal salt | |
| CN101717308A (en) | Preparation method of high -efficiency total nutrient organic liquid fertilizer | |
| Mortvedt | Micronutrient fertilizers and fertilization practices | |
| US20240164385A1 (en) | A synergistic plant growth stimulant composition comprising potassium mono/diformate and metal ion compounds to enhanced metabolic activities in plants | |
| CN103664417A (en) | Humic acid, boron and magnesium chelated insecticide-fertilizer and preparation method thereof | |
| CN113845386A (en) | High-tower humic acid type compound fertilizer and preparation method thereof | |
| CN107652094A (en) | The Water soluble fertilizer of a kind of balanced type containing humic acid and preparation method thereof | |
| US6383247B1 (en) | Micronutrient-containing leaf fertilizer based on magnesium sulfate and process for its production | |
| AU3505899A (en) | Liquid concentrate | |
| CN111393208A (en) | Zinc-rich rice liquid fertilizer and application method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20180508 Assignee: Hebei Xieli Chemical Co.,Ltd. Assignor: HEBEI XIETONG ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Contract record no.: X2021130000017 Denomination of invention: A chelated metal salt of Iminodisuccinic acid Granted publication date: 20210507 License type: Common License Record date: 20210914 |