CN114349628A - Preparation method and application of citric acid complex of manganese - Google Patents
Preparation method and application of citric acid complex of manganese Download PDFInfo
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- CN114349628A CN114349628A CN202111508793.4A CN202111508793A CN114349628A CN 114349628 A CN114349628 A CN 114349628A CN 202111508793 A CN202111508793 A CN 202111508793A CN 114349628 A CN114349628 A CN 114349628A
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Abstract
The invention provides a preparation method and application of a citric acid complex of manganese, and relates to the technical field of organic metal salt preparation. The method comprises the following steps: dissolving soluble manganese salt and citric acid in water under inert atmosphere to prepare a mixed solution, adding ammonia water for reaction, and dehydrating the obtained reaction solution to obtain the catalyst. The method uses soluble manganese salt as a raw material, can prepare the manganese citrate and the ammonium salt in one step, has no toxicity and harm on the product, can be absorbed and utilized by plants, has simple preparation process, and can better ensure the safety compared with the existing preparation method.
Description
Technical Field
The invention relates to the technical field of organic metal salt preparation, in particular to a preparation method and application of a citric acid complex of manganese.
Background
The manganese citrate is a trace element supplement, can be used as a fertilizer or a plant nutrition regulator, and has a certain application in the fields of agriculture and forestry. The existing manganese citrate is generally prepared by reacting manganese carbonate with citric acid, and the reaction equation is as follows:
3MnCO3+2C6H8O7→Mn3(C6H5O7)2+3CO2+3H2O
however, impurities such as other metal ions are easily introduced in the industrial preparation process of the manganese carbonate, certain harmfulness exists, the impurities are difficult to remove from the product, and the application of the manganese citrate in the fertilizer is seriously influenced.
In order to solve the above problems, manganese carbonate needs to be purified, or manganese carbonate with higher purity needs to be prepared separately, which increases the process complexity.
Disclosure of Invention
The present invention is directed to solving at least one of the above problems in the prior art. Therefore, the invention provides a preparation method of a manganese citric acid complex, which avoids the defect that manganese carbonate is needed to be used as a raw material, can prepare manganese citrate and ammonium salt in one step, wherein the manganese citrate is used as a manganese supplement, the ammonium citrate is used as a nitrogen fertilizer, the product is nontoxic and harmless, can be absorbed and utilized by plants, and has simple preparation process and considerable application value.
The invention also provides a citric acid complex of manganese prepared by the preparation method.
The invention also provides application of the citric acid complex of manganese prepared by the preparation method.
The first aspect of the present invention provides a method for preparing a citric acid complex of manganese, comprising the steps of:
and dissolving the soluble manganese salt and citric acid in water under an inert atmosphere to prepare a mixed solution, adding ammonia water for reaction, and dehydrating the obtained reaction solution to obtain the catalyst.
Taking manganese chloride as an example, the general equation of the reaction is as follows:
3MnCl2+6NH3+2C6H8O7→Mn3(C6H5O7)2+6NH4Cl
the preparation method of the manganese citric acid complex at least has the following beneficial effects:
soluble manganese salt and citric acid are dissolved in water to prepare a mixed solution, wherein the citrate is used as a coordination center and can form a complex with manganese ions, so that ammonia added later is favorably combined with hydrogen ions to generate ammonium ions. Compared with ammonium ions, the manganese ions have small steric hindrance and higher charge amount, are easier to complex with citrate radicals, and further promote the formation of a manganese citrate complex along with the generation of the ammonium ions. The manganese complex and the ammonium salt in the obtained product are respectively used as a manganese supplement and a nitrogen fertilizer, can be absorbed and utilized by plants, and can be directly used as a fertilizer or a fertilizer additive.
According to the preparation method disclosed by the invention, the soluble manganese salt is used as the raw material, the quality of the raw material is higher, and the safety of the product can be better ensured.
According to the preparation method, the manganese content in the product can reach 18.5 wt% and the nitrogen content can reach more than 10 wt% based on the raw material proportion of reaction equivalent, and the fertilizer effect is better.
The preparation method disclosed by the invention is simple in process, strong in operability, convenient for batch production and significant in application value.
According to some embodiments of the invention, before the adding ammonia, the method further comprises: and aging the mixed solution to facilitate the complexation of the citric acid and the manganese. Optionally, the aging time is 1h or more. Optionally, the stirring treatment can be performed fully before the aging, and the stirring time can be more than 0.5 h.
According to some embodiments of the invention, the soluble manganese salt is manganese chloride or manganese sulfate.
According to some embodiments of the present invention, the ammonia water is added dropwise, which facilitates the combination of ammonia and hydrogen ions and reduces the volatilization of ammonia.
According to some embodiments of the invention, the concentration of the aqueous ammonia is no more than 10 wt%.
According to some embodiments of the invention, the reaction is carried out under heated conditions, further the temperature of the reaction is between 30 ℃ and 90 ℃, further between 40 ℃ and 70 ℃.
According to some embodiments of the invention, the soluble manganese salt and citric acid are in a molar ratio of less than 1.5: 1.
According to some embodiments of the invention, the molar ratio of the soluble manganese salt to ammonia in the aqueous ammonia is less than 0.5:1, further less than 0.4: 1.
According to some embodiments of the invention, the means of dewatering is evaporation or centrifugation.
According to some embodiments of the invention, the inert atmosphere is a nitrogen atmosphere.
The second aspect of the present invention provides a citric acid complex of manganese prepared by the above preparation method.
The manganese citric acid complex prepared by the preparation method of the invention at least has the following beneficial effects:
the citric acid complex of manganese has the highest manganese content of 18.5 wt% and the lowest nitrogen content of 10 wt%, and has high fertilizer effect. The manganese content and the nitrogen content can be regulated and controlled by relatively excessive citric acid and ammonia, and simultaneously ammonium citrate can be formed by doping, can play the roles of a complexing agent and a pH regulator, can be used for complexing heavy metal ions, regulating the pH value of soil and the like, is a common soil conditioner, and improves the application range of the product.
According to some embodiments of the invention, the manganese citrate complex has a manganese content of 18.5 wt% or less and a nitrogen content of 10 wt% or more.
The third aspect of the invention provides the application of the manganese citric acid complex prepared by the preparation method as a fertilizer or a fertilizer additive or a soil conditioner.
The fertilizer can be a single fertilizer or a compound fertilizer and can be divided into soil topdressing and foliar fertilizer according to the use scene.
The effects of the soil conditioner include, but are not limited to, soil pH adjustment or heavy metal pollution remediation.
The fertilizer additive may be a manganese supplement.
In a fourth aspect of the present invention, there is provided a fertilizer comprising the citric acid complex of manganese prepared by the above-mentioned preparation method.
In a fifth aspect of the present invention, there is provided a fertilizer additive comprising the citric acid complex of manganese prepared by the above preparation method.
In a sixth aspect of the present invention, there is provided a soil conditioner comprising the citric acid complex of manganese prepared by the above-mentioned preparation method.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Provided is a method for preparing a citric acid complex of manganese, comprising the steps of:
(1) deoxidizing deionized water, dissolving manganese chloride (pink powder) and citric acid in the deionized water according to the molar ratio of 1:0.8 in the nitrogen atmosphere, stirring for 1 hour, and aging for 2 hours;
(2) keeping inert atmosphere, heating the solution obtained in the step (1) to 60 ℃, dropwise adding ammonia water with the mass fraction of 8% under the stirring action, controlling the total usage amount of ammonia in the ammonia water to be 4 times of the mole number of manganese chloride, and stirring for half an hour after dropwise adding is finished;
(3) and (3) dehydrating the reaction solution obtained in the step (2) to obtain white powder, wherein the white powder indicates that manganese in the raw material forms a complex with citric acid.
Example 2
Provided is a method for preparing a citric acid complex of manganese, comprising the steps of:
(1) deoxidizing deionized water, dissolving manganese chloride (pink powder) and citric acid in the deionized water according to the molar ratio of 1:0.7 in the nitrogen atmosphere, stirring for 1 hour, and aging for 2 hours;
(2) keeping inert atmosphere, heating the solution obtained in the step (1) to 50 ℃, dropwise adding ammonia water with the mass fraction of 10% under the stirring action, controlling the total dosage of ammonia in the ammonia water to be 3.5 times of the mole number of manganese chloride, and stirring for half an hour after dropwise adding;
(3) and (3) dehydrating the reaction solution obtained in the step (2) to obtain white powder, wherein the white powder indicates that manganese in the raw material forms a complex with citric acid.
Example 3
The application of the citric acid complex of manganese as a fertilizer is provided, wherein the fertilizer can be a single fertilizer or a compound fertilizer. The addition amount of the fertilizer is easily determined according to the contents of manganese and nitrogen in the complex and the combination of soil conditions and crop types.
Besides, the citric acid complex can be used as a fertilizer additive or a soil conditioner and has the functions of supplementing manganese elements or regulating soil properties.
Test example
The method is used for testing the manganese nitrogen content and the pH value of the citric acid complex, wherein the manganese content is determined by adopting an atomic absorption spectrum, and the nitrogen content is determined by adopting a Kjeldahl method. The test results are shown in table 1.
TABLE 1
While the preferred embodiments of the present invention have been described in detail, it will be understood by those skilled in the art that the foregoing and various other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention.
Claims (10)
1. A method for preparing a citric acid complex of manganese, comprising the steps of:
dissolving soluble manganese salt and citric acid in water under inert atmosphere to prepare a mixed solution, adding ammonia water for reaction, and dehydrating the obtained reaction solution to obtain the catalyst.
2. The method of claim 1, wherein the soluble manganese salt is manganese chloride or manganese sulfate.
3. The method of claim 1, further comprising, prior to the addition of the ammonia water: and aging the mixed solution.
4. The method of claim 1, wherein the ammonia water is added dropwise.
5. The method of claim 1, wherein the concentration of the aqueous ammonia is not more than 10 wt%.
6. The method of preparing the citric acid complex of manganese according to claim 1, wherein said reaction is carried out under heating, further, the temperature of said reaction is 30-90 ℃.
7. The method of claim 1, wherein the soluble manganese salt and citric acid are present in a molar ratio of less than 1.5: 1.
8. The method of claim 1, wherein the soluble manganese salt and ammonia in aqueous ammonia are present in a molar ratio of less than 0.5: 1.
9. The citric acid complex of manganese produced by the production method according to any one of claims 1 to 8.
10. Use of the citric acid complex of manganese according to claim 9 as a fertilizer or a fertilizer additive or a soil amendment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111508793.4A CN114349628A (en) | 2021-12-10 | 2021-12-10 | Preparation method and application of citric acid complex of manganese |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111508793.4A CN114349628A (en) | 2021-12-10 | 2021-12-10 | Preparation method and application of citric acid complex of manganese |
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| Publication Number | Publication Date |
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| CN114349628A true CN114349628A (en) | 2022-04-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111508793.4A Withdrawn CN114349628A (en) | 2021-12-10 | 2021-12-10 | Preparation method and application of citric acid complex of manganese |
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- 2021-12-10 CN CN202111508793.4A patent/CN114349628A/en not_active Withdrawn
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Application publication date: 20220415 |
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