CN113336241B - Method for separating and preparing ammonium dinitramide as high-energy oxidant - Google Patents
Method for separating and preparing ammonium dinitramide as high-energy oxidant Download PDFInfo
- Publication number
- CN113336241B CN113336241B CN202110772450.2A CN202110772450A CN113336241B CN 113336241 B CN113336241 B CN 113336241B CN 202110772450 A CN202110772450 A CN 202110772450A CN 113336241 B CN113336241 B CN 113336241B
- Authority
- CN
- China
- Prior art keywords
- adn
- crude product
- water
- purity
- dinitramide
- 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
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
The invention belongs to the technical field of ammonium dinitramide purification application, and particularly relates to a method for separating and preparing ammonium dinitramide as a novel high-energy oxidant. The method comprises the following effective steps: firstly, adding a reversed-phase chromatography filler into a chromatography column for later use; taking sulfamic acid ammonia as a raw material, and synthesizing by a mixed acid method to obtain an ADN crude product for later use; adding water into the ADN-containing crude product synthesized by the mixed acid method to a constant volume, and pumping the ADN-containing crude product into a chromatographic column system at a flow rate to perform sampling; washing the loaded ADN crude product chromatographic column with purified water; after washing, eluting the loaded ADN crude product chromatographic column by using methanol/water, ethanol/water, acetonitrile/water or acetone/water; detecting and analyzing the elution process by High Performance Liquid Chromatography (HPLC), and collecting high-purity ADN fraction; and concentrating the collected high-purity ADN fraction, and crystallizing at low temperature to obtain a high-purity ADN product. The method is simple and has an operation scheme. Safe and reliable and no pollutant is produced, and the method is suitable for large-scale popularization and use.
Description
Technical Field
The invention belongs to the technical field of ammonium dinitramide purification application, and particularly relates to a method for separating and preparing ammonium dinitramide as a high-energy oxidant.
Background
The ammonium dinitramide is ADN, which has the characteristics of high oxygen content and large heat of formation, so that the ammonium dinitramide can be used as an explosive and is often used as an oxidizer of a solid propellant. Compared with ammonium perchlorate, ammonium dinitramide does not contain chlorine in the molecular structure, combustion products are smokeless, the concealment of missile launching can be improved, and the environmental pollution is reduced. The specific flushing and the characteristic speed of ammonium dinitramide are respectively 2003N s/kg and 1282.6m/s which are much higher than those of ammonium perchlorate. Ammonium perchlorate is replaced by ammonium dinitramide, the thrust of the spaceflight booster can be increased by 14 percent, and the load can be increased by 4t each time of launching. However, the initial decomposition temperature of ADN is low (127 ℃), and the improvement of thermal stability becomes a key problem in order to apply ADN to a propellant.
The neutron diffraction technology can be used for exploring the internal structure and defects of a substance, hydrogen in the ammonium dinitramide molecule is replaced by deuterium, the influence of the hydrogen on the neutron diffraction signal-to-noise ratio is avoided, and the substance structure of the deuterium-substituted ammonium dinitramide is represented more accurately. Furthermore, by replacing hydrogen with deuterium, the bond energy of the molecule will also increase and the energy properties of the ammonium dinitramide will thus also increase. It can be seen that the successful synthesis of the ammonium perhydrogenated dinitramide has great promotion effect on the future safe utilization in scientific research and military fields.
The existing ammonium dinitramide preparation is mainly a mixed acid nitration method proposed by Langlet in 1997, and the method adopts mixed acid as a nitrating agent to nitrate ammonium sulfamate, so as to finally obtain ammonium dinitramide. The intermediate product HN (NO2)2 of the method is unstable under acidic conditions and can be gradually decomposed, and the next neutralization operation can be carried out only when the concentration of HN (NO2)2 in the solution reaches the maximum value through continuous sampling and measurement, so the operation process is complicated; in addition, a large amount of nitrate and sulfate byproducts are generated in the synthesis process of the method and are difficult to remove, so that the separation and purification of ADN are difficult, a high-purity ADN product cannot be obtained by various separation and purification methods, the currently adopted purification method is high in production cost, a large amount of solid or liquid wastes are generated, and the environmental pollution is serious.
Disclosure of Invention
Aiming at the technical problems existing in the ADN purification, the invention provides a method for separating and preparing ammonium dinitramide which is a high-energy oxidant, has reasonable design, simple structure and simple method and can effectively improve the ADN purity.
In order to achieve the above object, the technical scheme adopted by the invention is that the invention provides a method for separating and preparing ammonium dinitramide as high-energy oxidant, which comprises the following effective steps:
a. firstly, adding a reversed-phase chromatography filler into a chromatography column for later use;
b. taking sulfamic acid ammonia as a raw material, and synthesizing by a mixed acid method to obtain an ADN crude product for later use;
c. adding water into the ADN-containing crude product synthesized by the mixed acid method to a constant volume, and pumping the ADN-containing crude product into a chromatographic column system at a flow rate to perform sampling;
d. washing the loaded ADN crude product chromatographic column with purified water;
e. after washing, eluting the loaded ADN crude product chromatographic column by using methanol/water, ethanol/water, acetonitrile/water or acetone/water;
f. detecting and analyzing the elution process by High Performance Liquid Chromatography (HPLC), and collecting high-purity ADN fraction;
g. and concentrating the collected high-purity ADN fraction, and crystallizing at low temperature to obtain a high-purity ADN product.
In the step a, the reversed-phase chromatography packing is PS/DVB reverse-phase packing or silica gel bonded C18 \ C8 packing.
Preferably, in the step c, the upper amount ratio of the ADN crude product to the reversed phase filler is 5-20%.
Preferably, in the step d, the chromatographic column is washed with twice the volume of purified water of the chromatographic column.
Preferably, the purified water contains acetic acid.
Preferably, in the step a, the reverse-phase chromatography packing is a packing with a particle size of 10-150 um, and the reverse-phase chromatography packing is a 40um reverse-phase chromatography packing with a uniform particle size.
Preferably, in the step e, the elution is performed at a flow rate of 2 to 4 column volumes per minute.
Compared with the prior art, the invention has the advantages and positive effects that,
1. the invention provides a method for separating and preparing ammonium dinitramide as a high-energy oxidant, which effectively separates ADN and salt in an ADN crude product by utilizing the adsorptive difference of ADN and salt impurities on chromatographic packing and a chromatographic principle, solves the problem of complicated purification procedures of the existing ADN, and is simple and has an operation scheme. Safe and reliable and no pollutant is produced, and the method is suitable for large-scale popularization and use.
Detailed Description
In order that the above objects, features and advantages of the present invention can be more clearly understood, the present invention will be further described with reference to the following examples. It should be noted that the embodiments and features of the embodiments of the present application may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those specifically described herein, and thus the present invention is not limited to the specific embodiments of the present disclosure.
Example 1 this example provides a process for the isolation of the high energy oxidant ammonium dinitramide
200G reverse phase chromatography packing PS/DVB (SKN 10P) packing is firstly loaded into a 500ml chromatographic column, the column is pressed by 2000ml purified water to prepare sample loading, and the flow rate of the purified water entering the column is 2000 ml/H. Dispersed polymer chromatographic packing (PS/DVB) packing is prepared by taking styrene/divinylbenzene (PS/DVB) or acrylate polymer as a matrix through a patent technology, and covers the chromatographic fields of normal phase, reverse phase, ion exchange, affinity, size exclusion and the like. The specific surface area and the particle size and the pore diameter distribution of the series of products are accurately controlled, so that the series of products have stronger selectivity and can meet various separation and purification requirements from laboratory analysis and test to pilot plant test and industrial scale production. The novel column has the advantages of sphericity, uniform particle size height, high resolution ratio of easily packed columns, no fragment and small particle, clean product, capability of effectively avoiding the problems of sieve plate blockage and the like, high mechanical strength, strong pH stability, convenience for online cleaning, long service life, optimized pore diameter structure, low back pressure, large loading capacity and strong selectivity.
Then, adding water into the crude product containing 7.54 g of ADN synthesized by the mixed acid method to fix the volume to 100ml, and pumping the crude product into a column chromatography system at a feeding flow rate of 500ml/H per hour for sampling.
The loaded chromatographic column is washed by 1000ml of purified water, and the washing speed is 500 ml/H. The purpose of such steps is to remove the salt impurities of the crude ADN.
Then, the column after washing with purified water was eluted with 10% methanol aqueous solution, and such steps were carried out in order to collect ADN by eluting it collectively, and fractions with a purity of more than 95% were combined by HPLC for every 50ml fractions.
Then, the components with the purity of more than 95 percent are concentrated, and low-temperature water phase static crystallization is carried out at 4 ℃ to obtain 6.91 g of ADN product with the purity of 99.5 percent, and the total yield is 91.64 percent.
Example 2 this example provides a method for the isolation and preparation of the high energy oxidant ammonium dinitramide
Firstly, 200G and 40um end-capped C18 reversed-phase chromatographic packing is filled into a 400ml chromatographic column, 1500ml of water is used for column pressing to prepare sample loading, the flow rate of purified water entering the column is 1000ml/H, the grain diameter of the packing is 10-150 um, and 40um reversed-phase packing with uniform grain diameter is preferred. In this embodiment, the 40um filler is selected mainly in consideration of low price, low cost, low column packing requirement, low requirement on column packing equipment and simple operation.
Then adding water into the ADN crude product which is synthesized by a mixed acid method and contains 7.21 g to fix the volume to 100ml, and pumping the ADN crude product into a column chromatography system at a feeding flow rate of 500ml/H per hour for sampling;
the loaded chromatographic column is washed by 800ml of purified water, and the washing speed is 150 ml/H.
Eluting the column with 10% ethanol water solution, detecting one fraction per 50ml by HPLC, and mixing fractions with purity higher than 95%.
Finally, the fractions with a purity greater than 95% were concentrated and subjected to low temperature aqueous phase static crystallization at 4 ℃ to give 4.02 g of ADN product with a purity of 99.2% in a total yield of 55.7% (this yield is not too low or normal).
Example 3 this example provides a method for the isolation and preparation of the high energy oxidant ammonium dinitramide
Firstly, 200G, 40um end-capped C18 reversed-phase chromatographic packing is filled into a 400ml chromatographic column, 1500ml water is used for column pressing to prepare sample loading, and the flow rate of purified water entering the column is 1000 ml/H;
then adding water into the ADN crude product which is synthesized by a mixed acid method and contains 7.67 g to fix the volume to 100ml, and pumping the ADN crude product into a column chromatography system at a feeding flow rate of 500ml/H per hour for sampling;
the loaded column was then washed with 800ml of purified water (containing 0.5% o acetic acid) at a rate of 150 ml/H. The main purpose of the addition of acetic acid is to improve the separation of ADN from impurities.
Eluting the column with 10% methanol (containing 0.5 ‰ acetic acid) water solution, adding acetic acid into methanol to elute ADN from the column, collecting, detecting one fraction per 50ml by HPLC, and mixing fractions with purity higher than 95%.
The components with the purity of more than 95 percent are concentrated, and low-temperature water phase static crystallization is carried out at 4 ℃ to obtain 6.77 g of ADN product with the purity of 99.2 percent, and the total yield is 88.2 percent.
Example 3 this example provides a method for the isolation and preparation of the high energy oxidant ammonium dinitramide
Firstly, filling 2000G reversed-phase chromatographic filler SKN10P filler into a 5000ml chromatographic column, and performing column pressing with 20L of purified water to prepare sample loading, wherein the flow rate of the purified water entering the column is 20L/H;
adding water into a crude product containing 79.50 g of ADN synthesized by a mixed acid method to a constant volume of 1000ml, and pumping the crude product into a column chromatography system at a feeding flow rate of 5000ml/H per hour for sampling;
the loaded column was washed with 10L of purified water at a rate of 5L/H.
Eluting the column with 10% methanol water solution, detecting one fraction per 500ml by HPLC, and mixing the fractions with purity higher than 95%.
The components with the purity of more than 95 percent are concentrated, and low-temperature water phase static crystallization is carried out at 4 ℃ to obtain 75.48 g of ADN product with the purity of 99.9 percent, and the total yield is 94.94 percent.
The above description is only a preferred embodiment of the present invention, and not intended to limit the present invention in other forms, and any person skilled in the art may apply the above modifications or changes to the equivalent embodiments with equivalent changes, without departing from the technical spirit of the present invention, and any simple modification, equivalent change and change made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the technical spirit of the present invention.
Claims (7)
1. The method for separating and preparing the ammonium dinitramide as the high-energy oxidant is characterized by comprising the following effective steps of:
a. firstly, adding a reversed-phase chromatography filler into a chromatography column for later use;
b. taking sulfamic acid ammonia as a raw material, and synthesizing by a mixed acid method to obtain an ADN crude product for later use;
c. adding water into the ADN-containing crude product synthesized by the mixed acid method to a constant volume, and pumping the ADN-containing crude product into a chromatographic column system at a flow rate to perform sampling;
d. washing the loaded ADN crude product chromatographic column with purified water;
e. after washing, eluting the loaded ADN crude product chromatographic column by using methanol/water, ethanol/water, acetonitrile/water or acetone/water;
f. detecting and analyzing the elution process by High Performance Liquid Chromatography (HPLC), and collecting high-purity ADN fraction;
g. concentrating the collected high-purity ADN fraction, crystallizing at low temperature to obtain high-purity ADN product,
in the step a, the reversed-phase chromatography packing is PS/DVB reverse-phase packing or silica gel bonded C18 \ C8 packing.
2. The method for the separation and preparation of ammonium dinitramide as high-energy oxidant of claim 1, wherein in step c, the ratio of ADN crude product to reversed phase filler is 5-20%.
3. The method for separating and preparing ammonium dinitramide as high-energy oxidant according to claim 2, wherein in step d, the chromatographic column is washed with twice the volume of purified water.
4. The method for preparing dinitramide ammonium according to claim 3, wherein said purified water contains acetic acid.
5. The method for separating and preparing dinitramide ammonium according to claim 4, wherein in step a, the reverse phase chromatography packing is 10-150 um.
6. The method for separating and preparing dinitramide ammonium according to claim 5, wherein in step e, elution is carried out at a flow rate of 2-4 column volumes per minute.
7. The method for separating and preparing ammonium dinitramide according to claim 5, wherein in step a, the reverse phase chromatographic packing is 40um reverse phase chromatographic packing with uniform particle size.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110772450.2A CN113336241B (en) | 2021-07-08 | 2021-07-08 | Method for separating and preparing ammonium dinitramide as high-energy oxidant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110772450.2A CN113336241B (en) | 2021-07-08 | 2021-07-08 | Method for separating and preparing ammonium dinitramide as high-energy oxidant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113336241A CN113336241A (en) | 2021-09-03 |
| CN113336241B true CN113336241B (en) | 2022-04-01 |
Family
ID=77483004
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110772450.2A Active CN113336241B (en) | 2021-07-08 | 2021-07-08 | Method for separating and preparing ammonium dinitramide as high-energy oxidant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113336241B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6136115A (en) * | 1997-07-02 | 2000-10-24 | Cordant Technologies Inc. | Thermally-stabilized prilled ammonium dinitramide particles, and process for making the same |
| MY117780A (en) * | 1998-03-26 | 2004-08-30 | Du Pont | A process for continuous hydrogenation of adiponitrile |
| CN106552443A (en) * | 2016-03-09 | 2017-04-05 | 北京博康健基因科技有限公司 | A kind of dress column method of reversed phase chromatography post |
| CN109134170A (en) * | 2018-09-27 | 2019-01-04 | 西南科技大学 | The method for preparing super-hydrophobic spherical diamide ammonium based on interfacial tension |
| CN109694044A (en) * | 2018-12-21 | 2019-04-30 | 湖北航天化学技术研究所 | A kind of preparation method of Zoamix azanol |
| CN112834673A (en) * | 2019-11-22 | 2021-05-25 | 中国科学院大连化学物理研究所 | Method for quantitatively analyzing ammonium dinitramide in ammonium dinitramide aqueous solution or solid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2884244B1 (en) * | 2005-04-12 | 2007-07-06 | Snpe Materiaux Energetiques Sa | OBTAINING AMMONIUM DINITROAMIDIDE CRYSTALS (DNA); DNA CRYSTALS AND ENERGY COMPOSITES CONTAINING THEM. |
-
2021
- 2021-07-08 CN CN202110772450.2A patent/CN113336241B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6136115A (en) * | 1997-07-02 | 2000-10-24 | Cordant Technologies Inc. | Thermally-stabilized prilled ammonium dinitramide particles, and process for making the same |
| MY117780A (en) * | 1998-03-26 | 2004-08-30 | Du Pont | A process for continuous hydrogenation of adiponitrile |
| CN106552443A (en) * | 2016-03-09 | 2017-04-05 | 北京博康健基因科技有限公司 | A kind of dress column method of reversed phase chromatography post |
| CN109134170A (en) * | 2018-09-27 | 2019-01-04 | 西南科技大学 | The method for preparing super-hydrophobic spherical diamide ammonium based on interfacial tension |
| CN109694044A (en) * | 2018-12-21 | 2019-04-30 | 湖北航天化学技术研究所 | A kind of preparation method of Zoamix azanol |
| CN112834673A (en) * | 2019-11-22 | 2021-05-25 | 中国科学院大连化学物理研究所 | Method for quantitatively analyzing ammonium dinitramide in ammonium dinitramide aqueous solution or solid |
Non-Patent Citations (1)
| Title |
|---|
| Comparative evaluation of purity of green energetic material (ammonium dinitramide) depending on refining method;Wooram Kim et al.;《Korean J. Chem. Eng.》;20171231;第34卷(第6期);第1693-1698页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113336241A (en) | 2021-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1320122C (en) | Process for extracting xylose and xylitol from a xylose mother liquor or a xylose digest | |
| US20090120878A1 (en) | Separation of a mixture of polyhydric alcohols | |
| CN106632542B (en) | Preparation method of cimicidin glycoside and 5-O-methylvisammioside reference substance | |
| CN101987815B (en) | Purification process for preparing high-purity coenzyme Q10 | |
| CN101570497A (en) | Method for purifying high-purity organic solvent acetonitrile for research | |
| CN109705176A (en) | The isolation and purification method of one boar gangliosides | |
| CN113336241B (en) | Method for separating and preparing ammonium dinitramide as high-energy oxidant | |
| CN101759537B (en) | Method for producing HPLC-grade acetone | |
| CN112569912A (en) | Flexible metal organic framework material and preparation method and application thereof | |
| CN108169399B (en) | Method for separating impurities in ethyl demethylaminothiazolyloximate crude product | |
| CN1312155C (en) | Method for separating and purifying 9-nitro camptothecin | |
| US9108897B2 (en) | Method for desorbing and regenerating butanol-adsorbing hydrophobic macroporous polymer adsorbent | |
| CN102432489B (en) | Method for preparing capsicine monomer and dihydrocapsaicin std monomer | |
| Wang et al. | Chromatographic separation of cytidine triphosphate from fermentation broth of yeast using anion‐exchange cryogel | |
| CN106831943B (en) | Method for purifying transdermal peptide at low cost | |
| CN112724185A (en) | Preparation method of gastrodin impurity | |
| CN105037452B (en) | A kind of process for purification of quick preparation high-purity Fondaparinux sodium | |
| CN114113357A (en) | Etimicin starting material gentamicin C1aIs detected by | |
| CN104030935B (en) | A kind of method of reversed-phase resin purifying capsaicin monomer | |
| CN108569690B (en) | Method for removing radioactive elements in nuclear power waste water by using functionalized graphene material | |
| CN102093214A (en) | Method for preparing Buddledin A | |
| CN1704405A (en) | Method for analyzing and separating preparation of Huperzine A and Huperzine B | |
| CN112079886A (en) | Method for improving purity of xylose and arabinose by chromatographic separation | |
| Hill et al. | Frontal chromatographic techniques in preparative chromatography | |
| Ding et al. | Nitrogen isotope enrichment for nitride fuel by using hybrid chemical exchange process |
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 |