CN114436814A - Preparation method of ammonium citrate - Google Patents
Preparation method of ammonium citrate Download PDFInfo
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- CN114436814A CN114436814A CN202210048507.9A CN202210048507A CN114436814A CN 114436814 A CN114436814 A CN 114436814A CN 202210048507 A CN202210048507 A CN 202210048507A CN 114436814 A CN114436814 A CN 114436814A
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- ammonium citrate
- carbon dioxide
- hydrate
- citric acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of ammonium citrate. The method comprises the following steps: adding ammonium bicarbonate into a citric acid solution with the surface covered with a hydrate promoter at a temperature of not higher than 10 ℃ and a pressure of more than 4.5MPa, collecting a water phase part after reaction, and concentrating and crystallizing to obtain the ammonium citrate. The method skillfully utilizes the principle of the hydrate, controls the environment of a reaction system, adds a hydrate promoter to promote carbon dioxide generated by the reaction to form the hydrate and enter a solid phase part, directly collects the carbon dioxide after collecting a liquid water phase part, avoids the diffusion of the carbon dioxide, can more conveniently recycle and treat the carbon dioxide converted into the solid phase, and avoids the problem of the escape of the carbon dioxide.
Description
Technical Field
The invention belongs to the technical field of citrate preparation, and particularly relates to a preparation method of ammonium citrate.
Background
Ammonium citrate (Ammonium ferri citrate), also known as triammonium citrate, is a white deliquescent powder or crystal, readily soluble in water. The method is mainly used for chemical analysis, industrial water treatment, metal surface cleaning (petroleum pipeline cleaning), ceramic dispersing agent, permeation aid, detergent raw material and soil conditioner components, and is also used in the industries of medicine, electronics and the like. The method is used as a chemical reagent in analytical chemistry, such as determination of phosphate in fertilizer, determination of phosphate and effective phosphoric acid in fertilizer. The electroplating industry is used as a cyanide-free plating complexing agent. The mechanical industry is used to formulate rust inhibitors. Used as buffering agent and emulsifier in food industry.
Currently, ammonium citrate is generally prepared by performing neutralization reaction on citric acid and ammonium bicarbonate through the working procedures of activated carbon decolorization, sulfide impurity removal, filtration, vacuum concentration, crystallization, drying and the like. The process will generate a large amount of carbon dioxide waste gas emissions during the neutralization process, and carbon dioxide is considered to be the main greenhouse gas harmful to the global environment.
Statements in this background are not admitted to be prior art to the present disclosure.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a preparation method of ammonium citrate, which can reduce the emission of carbon dioxide.
According to one aspect of the invention, a method for preparing ammonium citrate is provided, which comprises the following steps:
adding ammonium bicarbonate into a citric acid solution with the surface covered with a hydrate promoter at a temperature of not higher than 10 ℃ and a pressure of more than 4.5MPa, collecting a water phase part after reaction, and concentrating and crystallizing to obtain the ammonium citrate.
According to a preferred embodiment of the present invention, at least the following advantages are provided: the method skillfully utilizes the principle of the hydrate, controls the environment of a reaction system, adds a hydrate promoter to promote carbon dioxide generated by the reaction to form the hydrate and enter a solid phase part, directly collects the carbon dioxide after collecting a liquid water phase part, avoids the diffusion of the carbon dioxide, can more conveniently recycle and treat the carbon dioxide converted into the solid phase, and avoids the problem of the escape of the carbon dioxide.
In some embodiments of the invention, the hydrate promoter comprises at least one of tetrahydrofuran, cyclohexane, or n-tetradecane. The hydrate accelerant such as tetrahydrofuran, n-tetradecane or n-tetradecane is adopted, so that not only can the hydrate formation be promoted, but also the carbon dioxide can be prevented from escaping by covering the surface of the water phase. Tetrahydrofuran and cyclohexane are used as promoters, and can be converted into a gas phase in advance in the crystallization process due to low boiling point, so that impurities are prevented from entering. In addition, cyclohexane or n-tetradecane is insoluble in water, and it is separated directly from water into two phases.
In some preferred embodiments of the invention, the hydrate accelerant is added in an amount no greater than 50% by volume of the citric acid solution.
In some preferred embodiments of the invention, the hydrate accelerant is added in an amount no greater than 30% by volume of the citric acid solution.
In some embodiments of the invention, the preparation method further comprises adding sodium hydroxide to the solid phase fraction obtained after the reaction and raising the temperature to above 10 ℃ or lowering the pressure to below 4.5 MPa. The decomposition of the hydrate is promoted by changing the conditions, and the carbon dioxide is recycled.
In some embodiments of the invention, the reaction is carried out with stirring.
In some preferred embodiments of the present invention, the stirring speed is 400 to 500 rpm. The reaction is carried out under stirring to increase the reaction rate.
In some embodiments of the invention, the hydrate promoter comprises tetrahydrofuran and the temperature of the concentrating is greater than 66 ℃.
In some embodiments of the invention, the hydrate promoter comprises cyclohexane and the temperature of the concentrating is greater than 83 ℃.
The concentration temperature is controlled above the boiling point of the hydrate promoter to facilitate direct separation of the hydrate promoter from the target product.
Drawings
FIG. 1 is a schematic view of a preparation process in embodiments 1 to 7 of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention. The test methods used in the examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are commercially available reagents and materials unless otherwise specified.
In the description of the present invention, the meaning of a plurality is one or more, the meaning of a plurality is two or more, and the above, below, exceeding, etc. are understood as excluding the present numbers, and the above, below, within, etc. are understood as including the present numbers. If the first and second are described for the purpose of distinguishing technical features, they are not to be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
In the description of the present invention, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Example 1
In this example, ammonium citrate is prepared, as shown in fig. 1, and the specific process is as follows: dissolving 1kg of citric acid (with purity of 99.9% after decolorization by activated carbon and removal of sulfide) in water to prepare a citric acid aqueous solution with a mass percentage concentration of 20%, and adding tetrahydrofuran with a volume amount of 10% of the citric acid aqueous solution into the citric acid aqueous solution to obtain a mixed solution. The mixture was left at 4 ℃ and sodium bicarbonate (added below the liquid level) was added in an amount of 3.2 times the amount of the citric acid substance. After the addition, the system is placed in a closed reaction container with the pressure of 5 MPa. After 15h of reaction, the liquid phase was concentrated to supersaturation in vacuo at 70 ℃ (vapor during recovery was collected with water), cooled for crystallization and dried. The purity of ammonium citrate in the prepared product is detected to be 98%.
And (3) mixing the reacted solid-phase hydrate part with sodium hydroxide, controlling the temperature to be 15 ℃, and recycling the carbon dioxide to avoid the carbon dioxide from diffusing into the air.
Detection shows that no carbon dioxide escapes during the experiment process.
Example 2
The embodiment prepares the ammonium citrate, and the specific process is as follows: dissolving 1kg of citric acid (with purity of 99.9% after decolorization by activated carbon and removal of sulfide) in water to prepare a citric acid aqueous solution with a mass percentage concentration of 20%, and adding cyclohexane with a volume amount of 10% of the citric acid aqueous solution into the citric acid aqueous solution to obtain a mixed solution. The mixture was left at 4 ℃ and sodium bicarbonate (added below the liquid level) was added in an amount of 3.2 times the amount of the citric acid substance. After the addition, the system is placed in a closed reaction container with the pressure of 5 MPa. After 15h of reaction, the liquid phase was separated by a separatory funnel, and the aqueous phase was concentrated under vacuum at 88 ℃ and then cooled to crystallize and dried. The purity of ammonium citrate in the prepared product is detected to be 99.7%.
And (3) mixing the reacted solid-phase hydrate part with sodium hydroxide, controlling the temperature to be 15 ℃, and recycling the carbon dioxide to avoid the carbon dioxide from diffusing into the air.
Detection shows that no carbon dioxide escapes during the experiment process.
Example 3
The embodiment prepares the ammonium citrate, and the specific process is as follows: dissolving 1kg of citric acid (with purity of 99.9% after activated carbon decolorization and sulfide impurity removal) in water to prepare a citric acid aqueous solution with mass percentage concentration of 20%, and adding n-tetradecane with volume amount of 10% of the citric acid aqueous solution into the citric acid aqueous solution to obtain a mixed solution. The mixture was left at 4 ℃ and sodium bicarbonate (added below the liquid level) was added in an amount of 3.2 times the amount of the citric acid substance. After the addition, the system is placed in a closed reaction container with the pressure of 5 MPa. After 15h of reaction, the liquid phase was separated by a separatory funnel, and the aqueous phase was concentrated under vacuum at 88 ℃, cooled, crystallized and dried. The purity of ammonium citrate in the prepared product is detected to be 99%.
And (3) mixing the reacted solid-phase hydrate part with sodium hydroxide, controlling the temperature to be 15 ℃, and recycling the carbon dioxide to avoid the carbon dioxide from diffusing into the air.
Detection shows that no carbon dioxide escapes during the experiment process.
Example 4
The embodiment prepares the ammonium citrate, and the specific process is as follows: dissolving 1kg of citric acid (with purity of 99.9% after decolorization by activated carbon and removal of sulfide) in water to prepare a citric acid aqueous solution with a mass percentage concentration of 20%, and adding tetrahydrofuran with a volume amount of 20% of the citric acid aqueous solution into the citric acid aqueous solution to obtain a mixed solution. The mixture was left at 4 ℃ and sodium bicarbonate (added below the liquid level) was added in an amount of 3.2 times the amount of the citric acid substance. After the addition, the system is placed in a closed reaction container with the pressure of 5 MPa. After 10 hours of reaction, the liquid phase was separated by a separatory funnel, and the aqueous phase was concentrated under vacuum at 70 ℃ and then cooled to crystallize and dried. The purity of the ammonium citrate in the prepared product is detected to be 97.9%.
And (3) mixing the reacted solid-phase hydrate part with sodium hydroxide, controlling the temperature to be 15 ℃, and recycling the carbon dioxide to avoid the carbon dioxide from diffusing into the air.
Detection shows that no carbon dioxide escapes during the experiment process.
Example 5
The embodiment prepares the ammonium citrate, and the specific process is as follows: dissolving 1kg of citric acid (with purity of 99.9% after decolorization by activated carbon and removal of sulfide) in water to prepare a citric acid aqueous solution with a mass percentage concentration of 20%, and adding tetrahydrofuran with a volume amount of 30% of the citric acid aqueous solution into the citric acid aqueous solution to obtain a mixed solution. The mixture was left at 4 ℃ and sodium bicarbonate (added below the liquid level) was added in an amount of 3.2 times the amount of the citric acid substance. After the addition, the system is placed in a closed reaction container with the pressure of 5 MPa. After 6h of reaction, the liquid phase was separated by a separatory funnel, and the aqueous phase was concentrated under vacuum at 70 ℃ and then cooled to crystallize and dried. The purity of ammonium citrate in the prepared product is detected to be 98.1%.
And (3) mixing the reacted solid-phase hydrate part with sodium hydroxide, controlling the temperature to be 15 ℃, and recycling the carbon dioxide to avoid the carbon dioxide from diffusing into the air.
Detection shows that no carbon dioxide escapes during the experiment process.
Example 6
The embodiment prepares the ammonium citrate, and the specific process is as follows: dissolving 1kg of citric acid (with purity of 99.9% after decolorization by activated carbon and removal of sulfide) in water to prepare a citric acid aqueous solution with a mass percentage concentration of 20%, and adding tetrahydrofuran with a volume amount of 40% of the citric acid aqueous solution into the citric acid aqueous solution to obtain a mixed solution. The mixture was left at 4 ℃ and sodium bicarbonate (added below the liquid level) was added in an amount of 3.2 times the amount of the citric acid substance. After the addition, the system is placed in a closed reaction container with the pressure of 5 MPa. After 18h of reaction, the liquid phase was separated by a separatory funnel, and the aqueous phase was concentrated under vacuum at 88 ℃ and then cooled to crystallize and dried. The purity of the ammonium citrate in the prepared product is detected to be 97.9%.
And (3) mixing the reacted solid-phase hydrate part with sodium hydroxide, controlling the temperature to be 15 ℃, and recycling the carbon dioxide to avoid the carbon dioxide from diffusing into the air.
Detection shows that no carbon dioxide escapes during the experiment process.
Example 7
The embodiment prepares the ammonium citrate, and the specific process is as follows: dissolving 1kg of citric acid (with purity of 99.9% after activated carbon decolorization and sulfide impurity removal) in water to prepare a citric acid aqueous solution with a mass percentage concentration of 20%, and adding tetrahydrofuran with a volume amount of 10% of the citric acid aqueous solution into the citric acid aqueous solution to obtain a mixed solution. The mixture was left at 4 ℃ and sodium bicarbonate (added below the liquid level) was added in an amount of 3.2 times the amount of the citric acid substance. After the addition, the system is placed in a closed reaction container with the pressure of 5 MPa. After the reaction was carried out for 12 hours with stirring at 400rpm, the liquid phase was separated by a separatory funnel, and the aqueous phase was concentrated under vacuum at 88 ℃ and then cooled to crystallize and dried. The purity of the ammonium citrate in the prepared product is detected to be 97.9%.
And (3) mixing the reacted solid-phase hydrate part with sodium hydroxide, controlling the temperature to be 15 ℃, and recycling the carbon dioxide to avoid the carbon dioxide from diffusing into the air.
Detection shows that no carbon dioxide escapes during the experiment process.
Comparative example 1
The embodiment prepares the ammonium citrate, and the specific process is as follows: 1kg of citric acid (with purity of 99.9 percent after being decolored by active carbon and removed by sulfide) is dissolved in water to prepare a citric acid aqueous solution with mass percentage concentration of 20 percent. The mixture was left at 4 ℃ and sodium bicarbonate (added below the liquid level) was added in an amount of 3.2 times the amount of the citric acid substance. After the addition, the system is placed in a closed reaction container with the pressure of 5 MPa. After 36 hours of reaction, the liquid phase was separated by a separatory funnel, and the aqueous phase was concentrated under vacuum at 88 ℃ and then cooled to crystallize and dried. The purity of ammonium citrate in the prepared product is detected to be 98%.
And (3) mixing the reacted solid-phase hydrate part with sodium hydroxide, controlling the temperature to be 15 ℃, and recycling the carbon dioxide to avoid the carbon dioxide from diffusing into the air.
It was determined that there was some escape of carbon dioxide during the experiment (about 15% of the total carbon dioxide was escaped, calculated according to the equation).
The reaction termination time in the above examples and comparative examples was controlled such that the reaction was terminated when no citric acid was detected by spot inspection. The reaction principle is shown as the following formula:
comparing examples 1-7 with comparative example 1, it can be seen that the use of the hydrate accelerant immiscible with water is more beneficial to obtaining high-purity ammonium citrate in the later period. Compared with a reaction system without the hydrate accelerant, the reaction time can be obviously shortened by the scheme provided by the invention, the addition amount of the hydrate accelerant is increased to a certain extent, the carbon dioxide can be promoted to be converted into the hydrate, the reaction is promoted to move rightwards more quickly, and the reaction time is favorably shortened. The scheme of the invention can better prevent the diffusion of the carbon dioxide, and simultaneously, the carbon dioxide is converted into solid substances by skillfully utilizing the hydrate forming process to prevent the diffusion of the carbon dioxide, so the operation is simple and convenient, and the effect is good. Tetrahydrofuran, cyclohexane or n-tetradecane is added as a hydrate promoter, which can be separated well from water in the solution, thus allowing the product to have a higher purity.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (9)
1. A preparation method of ammonium citrate is characterized by comprising the following steps: the method comprises the following steps:
adding ammonium bicarbonate into a citric acid solution with the surface covered with a hydrate promoter at a temperature of not higher than 10 ℃ and a pressure of more than 4.5MPa, collecting a water phase part after reaction, and concentrating and crystallizing to obtain the ammonium citrate.
2. The method of preparing ammonium citrate as set forth in claim 1, characterized in that: the hydrate accelerant comprises at least one of tetrahydrofuran, cyclohexane, or n-tetradecane.
3. The method of preparing ammonium citrate as set forth in claim 1, characterized in that: the addition volume amount of the hydrate accelerant is not more than 50% of the volume of the citric acid solution.
4. The method of preparing ammonium citrate as set forth in claim 3, characterized in that: the addition volume amount of the hydrate accelerant is not more than 30% of the volume of the citric acid solution.
5. The method for the preparation of ammonium citrate according to any of the claims 1 to 4, characterized in that: the preparation method also comprises the steps of adding sodium hydroxide into the solid phase part obtained after the reaction, and increasing the temperature to be more than 10 ℃ or reducing the pressure to be less than 4.5 MPa.
6. The method for the preparation of ammonium citrate according to any of the claims 1 to 4, characterized in that: the reaction is carried out with stirring.
7. The method of preparing ammonium citrate as set forth in claim 6, characterized in that: the stirring speed is 400-500 rpm.
8. The method for the preparation of ammonium citrate according to any of the claims 1 to 4, characterized in that: the hydrate promoter comprises tetrahydrofuran, and the temperature of the concentration is higher than 66 ℃.
9. The method for the preparation of ammonium citrate according to any of the claims 1 to 4, characterized in that: the hydrate promoter comprises cyclohexane and the temperature of the concentration is above 83 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202210048507.9A CN114436814A (en) | 2022-01-17 | 2022-01-17 | Preparation method of ammonium citrate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210048507.9A CN114436814A (en) | 2022-01-17 | 2022-01-17 | Preparation method of ammonium citrate |
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| CN114436814A true CN114436814A (en) | 2022-05-06 |
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| CN202210048507.9A Withdrawn CN114436814A (en) | 2022-01-17 | 2022-01-17 | Preparation method of ammonium citrate |
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