阅读说明：本技术 一种α-AlH3浮选方法及其应用 (alpha-AlH 3 flotation method and application thereof ) 是由 李磊 刘明珠 杜芳 黄丹椿 汪慧思 张思 邱贤平 胡翔 陶博文 顾健 胡建江 于 2019-09-12 设计创作，主要内容包括：本发明涉及一种α-AlH_3浮选方法及其应用,属于含能材料技术领域。本发明利用α晶型和非α晶型AlH_3不同的理化性质、表面吸附特性、晶体形貌特性等固有性质,借助超声波的分离提纯功能,采用特定的浮选液,实现了AlH_3中α晶型和非α晶型AlH_3高效分离,得到了高品质α晶型AlH_3和非α晶型。通过撞击感度和摩擦感度实验,验证了分离得到的高品质α晶型AlH_3在复合高能固体推进剂中应用的安全性。本发明的高品质α晶型AlH_3氢含量高,基于高品质α晶型AlH_3的高能推进剂的药浆感度低。(The invention relates to an alpha-AlH 3 flotation method and application thereof, belonging to the technical field of energetic materials, wherein the method utilizes inherent properties such as different physicochemical properties, surface adsorption properties and crystal morphology properties of alpha crystal form AlH 3 and non-alpha crystal form AlH 3 , and utilizes the separation and purification functions of ultrasonic waves and adopts specific flotation liquid to realize the efficient separation of alpha crystal form AlH 3 and non-alpha crystal form AlH 3 in AlH 3 , so as to obtain high-quality alpha crystal form AlH 3 and non-alpha crystal form.)

1. An alpha-AlH ₃ flotation method, characterized in that the method comprises the following steps:

S1, dispersing the AlH ₃ crude product in a flotation solution to form a suspension A;

S2: ultrasonically crushing the suspension A by using an ultrasonic crusher, and then stirring to obtain a suspension B;

and S3, pouring the suspension B into a separating funnel, standing and layering, marking the lower-layer solid as C and the upper-layer suspension as D, separating the lower-layer solid C from the upper-layer suspension D, washing, filtering and vacuum drying the lower-layer solid C, and obtaining the alpha crystal form AlH ₃.

2. The flotation method according to claim 1, wherein in the step S1, the crude AlH ₃ is crude AlH ₃ produced by industrial ether synthesis.

₃3. A flotation method according to claim 1, wherein in step S1, the flotation solution is one or a mixture of two or more of oleic acid, linoleic acid, linolenic acid and arachidonic acid.

4. The flotation method according to claim 1, wherein in the step S1, the mass ratio of the AlH ₃ crude product to the flotation solution is 1: 20-100.

5. The alpha-AlH ₃ flotation method as set forth in claim 1, wherein in the step S2, the ultrasonic pulverization power is 400-2000W, and the ultrasonic pulverization time is 30-1800S.

6. The alpha-AlH ₃ flotation method as set forth in claim 1, wherein the stirring speed is 200-1500r/min and the stirring time is 30-300min in step S2.

7. an alpha-AlH ₃ flotation method according to claim 1, wherein the standing time in step S3 is 2-72 hours.

₃8. a flotation method according to claim 1, wherein the solvent used for washing in step S3 is cyclohexane, n-hexane or ethyl acetate.

9. An alpha-AlH ₃ flotation method according to claim 1, wherein in step S3, the vacuum drying temperature is 30-50 ℃ and the vacuum drying time is 6-48 h.

10. The application of the alpha-AlH ₃ is characterized in that the alpha-AlH ₃ is applied to the field of propellant or explosive energetic materials as fuel.

Technical Field

The invention relates to an alpha-AlH ₃ flotation method and application thereof, belongs to the technical field of energetic materials, and more particularly relates to a high-quality alpha-AlH ₃ applicable to the fields of propellants, explosives or other energetic materials, and a method for improving the applicability of AlH ₃ in the field of energetic materials by utilizing liquid-phase ultrasonic-assisted flotation of the high-quality alpha-AlH ₃.

Background

According to theoretical calculation, AlH ₃ is used to replace aluminum powder, so that the specific impulse of the solid propellant is at least increased to 100N.s.kg ^-1, the temperature of a combustion chamber and the temperature of sprayed gas are lower than that of an aluminum powder-containing propellant, and AlH ₃ releases 10% of the weight of H ₂ in the decomposition process, so that the average molecular weight of the gas is effectively reduced, therefore, AlH ₃ as a high-energy additive of the solid propellant becomes the focus of attention of domestic and foreign researchers.

according to different synthesis methods and reaction conditions, the obtained unsolvated AlH ₃ has 7 different crystal forms, namely alpha, alpha ', beta, gamma, delta, epsilon and zeta, each crystal form AlH ₃ has a fixed atom arrangement mode, so that the crystal forms have unique thermodynamic properties, and practice proves that all separated crystal forms are most stable, namely the crystal forms alpha-AlH ₃, beta-AlH ₃ and gamma-AlH ₃ can be converted into the crystal forms alpha-AlH ₃ at 91.0 ℃ and 100.7 ℃ respectively, but the thermodynamic properties of the crystal forms are unstable at normal temperature, the decomposition speed of the crystal forms is far greater than that of the crystal forms alpha-AlH ₃, while the crystal forms alpha', delta, epsilon and zeta cannot be converted into the crystal forms alpha, the thermal stability is poor, a small amount of non-alpha crystal forms exist in the crystal forms, so that the thermal stability of the crystal forms is remarkably reduced.

In the early 60's of the 20 th century, the application of AlH ₃ in military affairs was evaluated by American military, and the results show that AlH ₃ is poor in stability, releases hydrogen during storage, not only reduces the energy of an energetic material, but also affects the preparation process and safety performance of the energetic material.

Just as in the above-mentioned process for synthesizing AlH ₃ by using an ether method, because the α -crystal AlH ₃ is sensitive to the factors such as the purity of raw materials, the moisture content, the use and proportion of a cosolvent, the type and amount of a crystallization additive, etc. during synthesis, non- α -crystal AlH ₃ often appears, and α', β, γ crystal forms are taken as main crystal forms, and the occurrence of the crystal forms has different degrees of influence on the thermodynamic stability and safety of an AlH ₃ product under the room-temperature storage condition.

Disclosure of Invention

the invention solves the technical problems that the defects of the prior art are overcome, and provides an alpha-AlH ₃ flotation method and application thereof, wherein the method is a method for separating alpha crystal form AlH ₃ and non-alpha crystal form AlH ₃ and other impurities in AlH ₃ produced industrially, and can improve the purity and stability of the alpha crystal form in AlH ₃ to obtain high-quality alpha-AlH ₃, further reduce the mechanical sensitivity of a system after the alpha crystal form is mixed with propellant common components, and realize the practical application of the alpha crystal form in a high-energy solid propellant.

The technical solution of the invention is as follows:

An alpha-AlH ₃ flotation method, comprising the steps of:

S1, dispersing the AlH ₃ crude product in a flotation solution to form a suspension A;

S2, ultrasonically crushing the suspension A by using an ultrasonic crusher to separate the surface of the alpha crystal form AlH ₃ in the AlH ₃ crude product from the adsorbed non-alpha crystal form AlH ₃ and other impurities, and then stirring to fully react the AlH ₃ crude product with the flotation solution to form a suspension B;

And S3, pouring the suspension B into a separating funnel, standing to naturally settle and stratify, recording the lower-layer solid as C and the upper-layer suspension as D, separating the lower-layer solid C from the upper-layer suspension D, washing, filtering and vacuum drying the lower-layer solid C to obtain alpha crystal form AlH ₃, and performing suction filtration, washing and vacuum drying on the upper-layer suspension D to obtain non-alpha crystal form AlH ₃ and other impurity compounds.

In the step S1, the crude AlH ₃ is crude AlH ₃ produced by an industrial ether synthesis method;

In the step S1, the flotation solution is one or a mixture of more than two of oleic acid, linoleic acid, linolenic acid and arachidonic acid;

In the step S1, the mass ratio of the AlH ₃ crude product to the flotation solution is 1: 20-100;

In the step S2, the ultrasonic crushing power is 400-2000W, and the ultrasonic crushing time is 30-1800S;

In the step S2, the stirring speed is 200-1500r/min, and the stirring time is 30-300 min;

In the step S3, the standing time is 2-72 h;

In the step S3, the solvent used for washing is cyclohexane, n-hexane or ethyl acetate;

In the step S3, the vacuum drying temperature is 30-50 ℃, and the vacuum drying time is 6-48 h.

an application of alpha-AlH ₃, alpha-AlH ₃ is used as fuel in the field of energetic materials such as propellant, explosive and the like.

Compared with the prior art, the invention has the advantages that:

(1) The AlH ₃ post-treatment based on industrial production does not influence the preparation process of industrial production, the separation technology is simple and efficient, and the industrial capacity is continuous.

(2) The treatment process effectively reduces the content of non-alpha crystal form AlH ₃, not only improves the stability of AlH ₃, but also improves the hydrogen content of AlH ₃ due to the removal of non-alpha crystal form AlH ₃ and other impurities, and has the advantage of remarkably improving or maintaining the H content of AlH ₃ compared with a desensitization method for introducing other substances.

(3) The high-quality AlH ₃ has applicability in the field of energetic materials such as solid propellants, explosives and the like.

(4) the effects before and after flotation are evaluated by adopting an H content and impact sensitivity instrument and a friction sensitivity instrument of AlH ₃ slurry, and the H content of AlH ₃ and the sensitivity of AlH ₃ sample-based high-quality alpha-AlH ₃ and non-alpha crystal-type AlH ₃ high-energy propellant slurry are respectively tested.

(5) According to the invention, the inherent properties such as different physicochemical properties, surface adsorption properties and crystal morphology properties of alpha crystal form AlH ₃ and non-alpha crystal form AlH ₃ are utilized, the separation and purification functions of ultrasonic waves are utilized, and a specific flotation solution is adopted, so that the alpha crystal form AlH ₃ and the non-alpha crystal form AlH ₃ are efficiently separated, and the high-quality alpha crystal form AlH ₃ and the non-alpha crystal form are obtained.

(6) A high-quality alpha-AlH ₃ flotation method is characterized in that AlH ₃ crude products prepared by an industrial ether synthesis method are used as starting raw materials, and AlH ₃ and AlH ₃ in non-alpha crystal form and other impurities in the industrial AlH ₃ crude products are separated by a liquid-phase ultrasonic auxiliary flotation method at normal temperature to obtain high-quality alpha-AlH ₃.

Drawings

FIG. 1 is an SEM image of crude AlH ₃;

FIG. 2 is an SEM image of alpha crystalline form AlH ₃;

Fig. 3 is an SEM image of non-alpha crystalline AlH ₃.

Detailed Description

A high-quality alpha-AlH ₃ flotation method aims at the fact that non-alpha-crystal-form AlH ₃ and other impurities often appear in an AlH ₃ crude product prepared by an industrial ether synthesis method, and utilizes the physicochemical properties and surface morphology difference of different crystal-form AlH ₃, and a higher ultrasonic stripping effect of an ultrasonic crusher is adopted to separate the non-alpha-crystal-form AlH ₃ adsorbed on the surface of alpha-crystal-form AlH ₃ from the other impurities.

A high-quality alpha-AlH ₃ flotation method comprises the following steps:

S1, preparing AlH ₃ into a suspension A at normal temperature, specifically, placing a crude AlH ₃ prepared by an industrial ether synthesis method into a beaker, preparing AlH ₃ -flotation liquid slurry with the mass ratio of 1: 20-1: 100, and stirring for a certain time to completely wet AlH ₃ to obtain the suspension A;

S2, ultrasonically crushing the suspension A for a certain time by using an ultrasonic crusher at a certain power to separate non-alpha crystal form AlH ₃ and other impurities on the surface of alpha crystal form AlH ₃ in the AlH ₃ crude product, and then stirring for a certain time at a certain speed to enable the AlH ₃ and a flotation solvent to fully react to form a suspension B;

And S3, pouring the suspension B into a separating funnel, standing for a certain time to allow the suspension B to naturally settle and stratify, recording a lower-layer solid as C and an upper-layer suspension as D, separating the C and the D, and respectively performing suction filtration, washing and vacuum drying to obtain high-quality alpha-AlH ₃, non-alpha crystal form AlH ₃ and other impurities.

The solvent used in the step S1 is one or two of oleic acid, linoleic acid, linolenic acid and arachidonic acid.

In the step S1, the stirring speed is 200r/min-1500r/min, and the preferred stirring speed is 400r/min-800 r/min.

the ultrasonic power used in the step S2 is 400W-2000W, and the ultrasonic mode may be one time of long time ultrasonic or multiple times of short time ultrasonic.

The ultrasonic time of the step S2 is 30S-1800S, and the preferable ultrasonic time is 120S-600S.

in the step S2, the stirring speed is 200r/min-1500r/min, the preferred stirring speed is 400r/min-1000r/min, the stirring time is 10min-360min, and the preferred stirring time is 30min-120 min.

the standing time in the step S3) is 2-72h, and the preferable time is 6-24 h.

The solvent used for washing in the step S3 is cyclohexane, n-hexane, ethyl acetate and the like, the vacuum drying temperature is 30-50 ℃, and the vacuum heat preservation time is 6-48 h.

the application of high-quality alpha-AlH ₃ in propellants and explosives is provided.

The following examples are provided to better illustrate the effects of the present invention, but the present invention is not limited to the following examples.