Novel method for concentrating electrodialysis membranes with energetic ionic compounds

Abstract

The application belongs to the technical field of compound concentration, and particularly relates to a novel method for concentrating electro-dialysis membrane of energetic ionic compounds, which comprises the following effective steps: first, preparing a water solution of the energetic ionic compound to be concentrated; then, assembling an electro-dialysis membrane stack according to the types of anions and cations of the energetic ionic compound to be concentrated, and installing the electro-dialysis membrane stack into an electro-dialysis membrane filtering device; selecting an electrolyte and adding the electrolyte into the electro-dialysis membrane filtering device; adding the water solution of the energetic ionic compound to be concentrated into a feed liquid storage tank of the electro-dialysis membrane stack, and electrifying to form an electric field to concentrate the water solution, and obtain a primary concentrated solution; and secondarily concentrating the primary concentrated solution of the energetic ionic compound, and finally obtaining a concentrated solution of the energetic ionic compound after the concentration is completed. The application realizes high-efficiency concentration of small-molecular-weight energetic ionic compounds such as ammonium salt or hydrazine salt by using the electro-dialysis membrane concentration method, and has the characteristics of simple operation, low energy consumption, high efficiency, safety and environmental protection, and is suitable for large-scale popularization and use.

Description

Technical Field

[0001] This invention belongs to the field of compound concentration technology, and particularly relates to a novel method for electrodialysis membrane concentration of energetic ionic compounds. Background Technology

[0002] Energetic ionic compounds are currently the main new type of energetic materials. Energetic ionic compounds typically refer to compounds with a nitrogen content of 20% or more. They generally possess high heat of formation and contain strong oxidizing or explosive groups, making them prone to rapid decomposition, combustion, or explosion. Their decomposition products are clean nitrogen gas, hence the term "green energetic materials," and they are widely used in applications such as explosives, propellants, gunpowder, and detonators.

[0003] Energetic compounds typically contain one or more N-N single bonds or O-O bonds, exhibiting high decomposition activity. A representative group is the hydrazine group, while other groups include amino, nitro, and dinitramide groups. Common energetic compounds include ammonium dinitramide (ADN) and hydrazine nitrate (HN).

[0004] In the 1970s, the Soviet Union first synthesized ADN. Currently, the main inorganic method for synthesizing ADN involves nitrifying aminosulfonates with a mixed acid-sulfur mixture, followed by neutralization with ammonia or potassium hydroxide. For example, US Patent No. US2008226533 discloses a method for preparing ADN, specifically using a large amount of organic solvent for extraction, vacuum concentration, and finally crystallization. Chinese Patent No. CN113336241B discloses a method for preparing and separating ADN using column chromatography; however, column chromatography requires a large amount of solvent and has a low feed concentration, resulting in relatively high production costs, which cannot meet the needs of practical applications.

[0005] Of course, in existing technologies, membrane filtration is used to remove impurity salts from the ADN reaction solution, or electrodialysis is used to directly synthesize ADN, which can solve the problem of inorganic salt residue. However, this also results in low feed concentration and the need for concentration. In addition, the synthesis of HN is generally carried out under inert solvent conditions due to the violent reaction between strong acids and strong bases. However, the use of organic solvents leads to complex post-processing. The preparation of HN by low-concentration acid-base reaction is an effective method to control the reaction rate and ensure safety, but it also faces the problem of low feed concentration and the need for concentration.

[0006] Currently, common methods for concentrating aqueous solutions of energetic ionic compounds include evaporation and membrane filtration. However, in actual production and processing, the evaporation method has high energy consumption and is not suitable for low-concentration solutions. While the membrane filtration method is suitable for concentrating low-concentration solutions, it is also affected by osmotic pressure to some extent, which prevents the concentration ratio from meeting the requirements. Therefore, we provide a new electrodialysis membrane concentration method for energetic ionic compounds that has low energy consumption and can achieve a high concentration ratio. Summary of the Invention

[0007] This invention addresses the technical problems existing in the concentration process of low-concentration energetic ionic compounds described above, and proposes a novel electrodialysis membrane concentration method for energetic ionic compounds that is rationally designed, simple in structure, unique in principle, and can effectively increase the concentration of ammonium salts or hydrazine salts.

[0008] To achieve the above objectives, the technical solution adopted by this invention is a novel method for electrodialysis membrane concentration of energetic ionic compounds, comprising the following effective steps:

[0009] a. First, prepare an aqueous solution of the energetic ionic compound to be concentrated and set aside for later use;

[0010] b. Based on the type of anions and cations of the energetic ion compounds to be concentrated, assemble the electrodialysis membrane stack and install it into the electrodialysis membrane filtration device for later use;

[0011] c. Select an electrolyte and add it to the electrodialysis membrane filtration device;

[0012] d. Add the aqueous solution of the energetic ionic compound to be concentrated into the feed tank of the electrodialysis membrane stack, apply electricity to form an electric field for concentration, and obtain a preliminary concentrated solution;

[0013] e. The initial concentrated solution of the energetic ion compound is concentrated a second time. After the concentration is completed, the final concentrated solution of the energetic ion compound is obtained.

[0014] In step d, after the electric field is formed, the anions of the energetic ion compound enter the concentrate compartment through the anion exchange membrane, and the cations of the energetic ion compound enter the concentrate compartment through the cation exchange membrane for preliminary concentration. In step e, during the secondary concentration of the preliminary concentrate of the energetic ion compound, the anions and cations enter the concentrate compartment through the anion exchange membrane and the cation exchange membrane, respectively, until the concentration is completed, and finally the concentrated solution of the energetic ion compound is obtained.

[0015] Preferably, in step a, the concentration of the energetic ion compound is 0.5-15%, and the cation of the energetic ion compound is one of ammonium, hydrazine, or metal ions, and the anion of the energetic ion compound is one of nitrate or dinitramide, and both the cation and anion are small molecular weight groups with a molecular weight of less than 300 Daltons.

[0016] Preferably, in step b, the electrodialysis membrane stack is composed of anion exchange membranes, cation exchange membranes, or bipolar membranes. The combination of the electrodialysis membrane stacks includes cation exchange membrane / anion exchange membrane / cation exchange membrane / anion exchange membrane / cation exchange membrane, anion exchange membrane / cation exchange membrane / anion exchange membrane / cation exchange membrane / anion exchange membrane and bipolar membrane / cation exchange membrane / anion exchange membrane / bipolar membrane.

[0017] Preferably, in step c, the electrolyte selected is one of the aqueous solutions of sodium nitrate, ammonium nitrate, sodium chloride, ammonium sulfate, ammonium chloride, or sodium sulfate, and the concentration of the electrolyte is 2%.

[0018] Preferably, in step d, the applied voltage is 10-200V, the charging current is 1-100A, and the concentration of the obtained preliminary concentrate is 5-25%.

[0019] Preferably, in step e, a secondary concentration is performed by a liquid-pouring operation. The liquid-pouring operation refers to using the preliminary concentrate as both the concentrate supply liquid and the concentrate receiving liquid. In other words, the concentrate supply liquid corresponds to the dilute liquid, and the concentrate receiving liquid corresponds to the concentrated liquid.

[0020] Preferably, in step e, the secondary concentration refers to the electrodialysis membrane being electro-concentrated. Specifically, the voltage applied during the secondary concentration process is 10-200V, the charging current is 1-100A, and the concentration of the final concentrated solution containing energetic ion compounds is 15-50%.

[0021] Compared with the prior art, the advantages and positive effects of the present invention are as follows:

[0022] 1. This invention provides a novel electrodialysis membrane concentration method for energetic ionic compounds. It utilizes an electric field and an ion exchange membrane to achieve high-concentration concentration of low-concentration energetic ionic compounds, featuring low energy consumption, high efficiency, and safety and environmental friendliness. Furthermore, this electrodialysis membrane concentration method allows for continuous concentration increases through liquid reversal, thus providing a highly efficient method for concentrating low-concentration feed solutions. This achieves efficient concentration of low-concentration energetic ionic compounds, pioneering a new method for concentrating energetic ionic compounds, broadening new directions for their preparation, and providing a reliable guarantee for optimizing the synthesis methods of energetic ionic compounds. Attached Figure Description

[0023] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the following description of the embodiments will be briefly introduced. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0024] Figure 1 A schematic diagram of a novel electrodialysis membrane concentration method for energetic ionic compounds;

[0025] Figure 2 This is a schematic diagram illustrating the working principle of energetic ion compound concentration under the first electrodialysis membrane stack combination method, where M... + A represents a cation. - Indicates anion;

[0026] Figure 3 This is a schematic diagram illustrating the working principle of energetic ion compound concentration under the second electrodialysis membrane stack combination method, where M... + A represents a cation. - Indicates anion;

[0027] Figure 4 This is a schematic diagram illustrating the working principle of energetic ion compound concentration under the third electrodialysis membrane stack combination method, where M... + A represents a cation. - It represents anion. Detailed Implementation

[0028] To better understand the above-mentioned objectives, features, and advantages of the present invention, the present invention will be further described below in conjunction with the accompanying drawings and embodiments. It should be noted that, unless otherwise specified, the embodiments and features described in these embodiments can be combined with each other.

[0029] Numerous specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways than those described herein, and therefore the invention is not limited to the specific embodiments disclosed in the following specification.

[0030] Example 1, such as Figure 1 The embodiment shown provides a novel method for electrodialysis membrane concentration of energetic ionic compounds:

[0031] First, the energetic ionic compound intermediate KDN was prepared into a 5% (w / w) aqueous solution for later use.

[0032] according to Figure 2The electrodialysis membrane stack is assembled as shown and installed into the electrodialysis membrane filtration device. The maximum voltage of the device is set to 13V and the maximum current to 3A, ready for use. Of course, for the technical solutions provided in this embodiment, especially for the anion exchange membrane and cation exchange membrane, either self-made or commercially available ion exchange membranes are acceptable. After the above steps are completed, the preliminary preparation work is finished.

[0033] Then, 1.5 L of the KDN solution to be concentrated was added to the prepared electrodialysis membrane filtration system. A 2% potassium sulfate aqueous solution was selected as the electrolyte, and 0.2 L of pure water was used as the KDN receiving solution. The temperature was controlled at 5°C, and concentration was initiated by applying electricity. During the concentration process: metal ions K... + DN moves towards the concentration chamber through the cation membrane towards the negative electrode. - K moves towards the positive electrode through the anion membrane and enters the concentration chamber. + and DN - The mixture was mixed to obtain a KDN concentrate, and the final concentration of the initial KDN concentrate obtained in the concentration chamber reached 20%.

[0034] Using 20% ​​KDN as both concentrate and dilute solutions, a second concentration was achieved via electrodialysis membrane, resulting in a final KDN concentration of 33% in the concentrate.

[0035] Example 2, as Figure 1 The embodiment shown provides a novel method for electrodialysis membrane concentration of energetic ionic compounds:

[0036] First, prepare a 5% (w / w) aqueous solution of the energetic ion compound hydrazine nitrate (HN) for later use;

[0037] according to Figure 3 The electrodialysis membrane stack is assembled as shown and installed into the electrodialysis membrane filtration device. The maximum voltage of the device is set to 13V and the maximum current to 3A, ready for use. Of course, for the technical solutions provided in this embodiment, especially for the anion exchange membrane and cation exchange membrane, either self-made or commercially available ion exchange membranes are acceptable. After the above steps are completed, the preliminary preparation work is finished.

[0038] Then, 1.5L of the HN solution to be concentrated was added to the prepared electrodialysis membrane filtration system. A 2% sodium nitrate aqueous solution was selected as the electrolyte, and 0.2L of pure water was selected as the HN receiving solution. The temperature was controlled at 5°C, and the concentration was started by applying electricity. During the concentration process, hydrazine ions moved from the cation membrane to the negative electrode and entered the concentration chamber, while nitrate ions moved from the anion membrane to the positive electrode and entered the concentration chamber. The hydrazine ions and nitrate ions mixed to obtain the HN solution. Finally, the initial concentration of the HN concentrate obtained in the concentration chamber reached 13%.

[0039] Using 13% HN as both concentrate and dilute solutions, a second concentration was achieved via electrodialysis membrane, resulting in a final concentrate with an HN concentration of 22%.

[0040] Example 3, as Figure 1 The embodiment shown provides a novel method for electrodialysis membrane concentration of energetic ionic compounds:

[0041] First, prepare an aqueous solution of the energetic ionic compound dinitramide ammonium (ADN) with a mass fraction of 5% for later use;

[0042] according to Figure 4 The electrodialysis membrane stack is assembled as shown and installed into the electrodialysis membrane filtration device. The maximum voltage of the device is set to 16V and the maximum current to 3A, ready for use. Of course, for the technical solutions provided in this embodiment, especially for the anion exchange membrane and cation exchange membrane, either self-made or commercially available ion exchange membranes are acceptable. After the above steps are completed, the preliminary preparation work is finished.

[0043] Then, 1.5L of the above-mentioned ADN solution to be concentrated was added to the prepared electrodialysis membrane filtration system. A 2% sodium sulfate aqueous solution was selected as the electrolyte and 0.2L of pure water was selected as the ADN receiving solution. The temperature was controlled at 5°C, and the concentration was started by applying electricity. During the concentration process, ammonium ions moved from the cation membrane to the negative electrode and entered the concentration chamber, while dinitramide ions moved from the anion membrane to the positive electrode and entered the concentration chamber. The ammonium ions and dinitramide ions mixed to obtain ADN. Finally, the concentration of the preliminary ADN concentrate obtained in the concentration chamber reached 15%.

[0044] A 15% ADN solution was used as both the concentrate and dilute solution for secondary concentration via electrodialysis membrane, resulting in a final ADN concentration of 28% in the concentrate.

[0045] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any other way. Any person skilled in the art may make changes or modifications to the above-disclosed technical content to create equivalent embodiments for application in other fields. However, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A novel method for electrodialysis membrane concentration of energetic ionic compounds, characterized in that, The following are the effective steps: a. First, prepare an aqueous solution of the energetic ionic compound to be concentrated and set aside for later use; b. Based on the type of anions and cations of the energetic ion compounds to be concentrated, assemble the electrodialysis membrane stack and install it into the electrodialysis membrane filtration device for later use; c. Select an electrolyte and add it to the electrodialysis membrane filtration device; d. Add the aqueous solution of the energetic ionic compound to be concentrated into the feed tank of the electrodialysis membrane stack, apply electricity to form an electric field for concentration, and obtain a preliminary concentrated solution; e. The initial concentrated solution of the energetic ion compound is concentrated a second time. After the concentration is completed, the final concentrated solution of the energetic ion compound is obtained. In step a, the concentration of the energetic ion compound is 0.5-15%, and the cation of the energetic ion compound is one of ammonium, hydrazine or metal ion, and the anion of the energetic ion compound is one of nitrate or dinitramide, and the cation and anion are small molecular weight groups with a molecular weight of less than 300 Daltons. In step e, a secondary concentration is performed using a liquid-pouring operation, wherein the liquid-pouring operation uses the initially concentrated liquid as both the concentrated supply liquid and the concentrated receiving liquid.

2. The novel method for electrodialysis membrane concentration of energetic ionic compounds according to claim 1, characterized in that, In step b, the electrodialysis membrane stack is composed of anion exchange membranes, cation exchange membranes, or bipolar membranes. The combination of the electrodialysis membrane stack includes cation exchange membrane / anion exchange membrane / cation exchange membrane / anion exchange membrane / cation exchange membrane, anion exchange membrane / cation exchange membrane / anion exchange membrane / cation exchange membrane / anion exchange membrane and bipolar membrane / cation exchange membrane / anion exchange membrane / bipolar membrane.

3. The novel method for electrodialysis membrane concentration of energetic ionic compounds according to claim 2, characterized in that, In step c, the selected electrolyte is one of sodium nitrate, ammonium nitrate, sodium chloride, ammonium sulfate, ammonium chloride, or an aqueous solution of sodium sulfate, and the concentration of the electrolyte is 2%.

4. The novel method for electrodialysis membrane concentration of energetic ionic compounds according to claim 3, characterized in that, In step d, the applied voltage is 10-200V, the charging current is 1-100A, and the concentration of the obtained preliminary concentrate is 5-25%.

5. The novel method for electrodialysis membrane concentration of energetic ionic compounds according to claim 4, characterized in that, In step e, the voltage applied during the secondary concentration process is 10-200V, the charging current is 1-100A, and the concentration of the final obtained concentrated solution of energetic ionic compounds is 15-50%.

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