阅读说明：本技术 一种超细球形硝酸肼镍的制备方法 (Preparation method of superfine spherical nickel hydrazine nitrate ) 是由 朱顺官 陈世勇 张琳 李燕 易镇鑫 袁彬 李晨 于 2020-04-30 设计创作，主要内容包括：本发明公开了一种超细球形硝酸肼镍的方法,属于化学合成材料技术领域,该方法将氨水引入到硝酸肼镍的合成中,通过在一定温度反应初始的底液中加入氨水后,将配置好的硝酸镍溶液和水合肼溶液在规定的时间内按照一定的速度进行双管滴加进料,在一定的反应温度下进行充分的反应,加料完毕后继续保温反应,最后进行冷却抽滤烘干即可得到超细球形硝酸肼镍。本发明提出的制备方法不仅能够得到超细的硝酸肼镍,其直径为5μm左右,同时制备出的硝酸肼镍由传统方法的聚晶状态转变为单晶颗粒的球形状态。本发明的制备工艺简单易于控制,得到的产品性能同传统工艺得到的聚晶硝酸肼镍在一定方面得到很大的改善。(The invention discloses a method for preparing superfine spherical nickel hydrazine nitrate, which belongs to the technical field of chemical synthesis materials. The preparation method provided by the invention can obtain superfine nickel hydrazine nitrate, the diameter of the superfine nickel hydrazine nitrate is about 5 mu m, and the prepared nickel hydrazine nitrate is converted into a spherical state of single crystal particles from a polycrystalline state of a traditional method. The preparation process is simple and easy to control, and the performance of the obtained product is greatly improved in a certain aspect compared with that of polycrystalline nickel hydrazine nitrate obtained by the traditional process.)

1. A method for preparing superfine spherical nickel hydrazine nitrate is characterized in that nickel nitrate and hydrazine hydrate are respectively dropped into a base solution which contains ammonia water and is kept at a certain temperature, and then the steps of heat preservation, cooling, discharging, washing, dehydration and drying are carried out; in the synthesis process, ammonia water is added into the base solution, nickel nitrate reacts with the ammonia water to generate a nickel-ammonia complex, and then under the action of strong alkali hydrazine hydrate, nickel ions are dissociated and react with hydrazine hydrate to obtain superfine spherical nickel hydrazine nitrate of single crystal particles.

2. The method for preparing nickel hydrazine nitrate according to claim 1, wherein the base solution is 3.2-6.2 wt% ammonia water solution.

3. The method for preparing nickel hydrazine nitrate according to claim 1, wherein the prepared nickel nitrate solution and hydrazine hydrate solution are fed with nickel hydrazine nitrate firstly for 1-2 min and then fed simultaneously.

4. The method for preparing nickel hydrazine nitrate according to claim 1, wherein the base solution is ammonia water, the temperature is kept at 40-50 ℃, the feeding is completed within 30-35 min, and the nickel nitrate solution is preferably fed first.

5. The method for preparing nickel hydrazine nitrate according to claim 1, wherein the mass concentration of the nickel nitrate is 4-7%, and the mass concentration of the hydrazine hydrate is 3-6%.

6. The method for preparing nickel hydrazine nitrate according to claim 1, wherein after the feeding is finished, the reaction is kept for 20min to ensure the reaction to be fully carried out.

Technical Field

The invention relates to a preparation method of superfine spherical nickel hydrazine nitrate, belonging to the technical field of chemical synthesis materials.

Background

Nickel hydrazine nitrate is a complex initiating explosive, has good compatibility and vacuum stability, has better impact sensitivity than lead azide and lead stevens acid, has flame sensitivity equivalent to that of lead stevens acid, has simple preparation process, can recycle mother liquor, has less wastewater pollution, and has been widely applied to military and civil use. It not only can be used for detonator charging and as ignition head agent, but also is a good nickel catalyst.

Compare in plumbous initiating explosive of azide, nickel hydrazine nitrate is first there is the higher problem of friction sensitivity, these problems probably are the glomerocryst state with the crystal and have very big relation, because ordinary nickel hydrazine nitrate under the glomerocryst state is the nickel hydrazine nitrate of quasi-sphere still, the crystal granule surface is rough not smooth, crystal surface defect is more, this can lead to the crystal to receive when amazing such as friction, accumulate the heat more easily, in addition nickel hydrazine nitrate phase limit dose is bigger than, power is less, when filling as the detonator, required dose is bigger.

In order to solve the problems of nickel hydrazine nitrate, firstly, the nickel hydrazine nitrate can be spheroidized by a spheroidizing method to form spherical particles with smooth surfaces, so that the friction sensitivity can be reduced, but the literature reported for spheroidizing the nickel hydrazine nitrate shows that crystal particles obtained by crystallization by introducing ultrasonic waves are uniform in crystals, but the spheroidization degree is not high, and the crystal surfaces are still rough. In addition, existing problems can be improved in a refining mode, experiments prove that the superfine initiating explosive has the characteristics of improved combustion rate, high output performance, changed sensitivity, changed detonation mechanism, faster detonation wave propagation and the like, has important application in the fields of explosive logic networks, propellants, laser initiation and the like, and the research on the aspect of nickel hydrazine nitrate is not carried out so far.

Disclosure of Invention

The invention aims to provide a preparation method of superfine spherical nickel hydrazine nitrate.

The technical solution implemented by the invention is as follows:

a process for preparing superfine spherical nickel hydrazine nitrate,

the method comprises the following specific steps: adding the prepared base solution with a certain concentration into a chemical combination device, heating to the temperature required by the reaction, adding nickel nitrate and hydrazine hydrate solution under the stirring state, and then performing heat preservation, cooling, discharging, washing, dehydration and drying to obtain spherical superfine nickel hydrazine nitrate.

Furthermore, the base solution with a certain concentration is 3.2% -6.2% of ammonia water solution, the heating rate of the base solution is high, and the volatilization of the ammonia water is reduced.

Further, when the temperature of the base solution is raised to 40-50 ℃, feeding the nickel nitrate solution and the hydrazine hydrate solution in a double-tube dropwise adding mode, wherein after the nickel nitrate is fed for 1-2 min, the two solutions are fed simultaneously.

Furthermore, the temperature of the whole reaction process should be controlled to be 40-50 ℃, the feeding time of the nickel nitrate solution and the hydrazine hydrate solution should be controlled to be 30-35 min, and the nickel nitrate solution is preferably fed first.

Further, the nickel nitrate solution is prepared by dissolving a solid of nickel nitrate in a solvent to prepare an aqueous solution having a concentration of 4 to 7% by mass.

Further, the preparation method of the hydrazine hydrate solution is to dissolve the liquid of the hydrazine hydrate into deionized water to prepare an aqueous solution with the concentration of 3 to 6 percent (mass).

Further, after the feeding is finished, the reaction time is kept for about 20 min.

Compared with the existing hydrazine nickel nitrate synthesis method, the preparation method has the following remarkable advantages:

1. according to the invention, the characteristics of ammonia water as a complexing agent are utilized, and a nickel-ammonia complex is formed with nickel nitrate firstly, so that the speed of the whole crystallization process is reduced, and the spherical superfine nickel hydrazine nitrate in a single crystal state with the diameter of 5 micrometers is obtained; 2. the friction sensitivity and the electrostatic sensitivity of the prepared superfine spherical hydrazine nickel nitrate are greatly improved, and the process is simple and easy to control.

Drawings

FIG. 1 is a flow chart of the preparation method of the superfine spherical nickel hydrazine nitrate.

FIG. 2 shows polycrystalline hydrazine nickel nitrate crystals obtained by a conventional hydrazine nickel nitrate preparation method.

FIG. 3 is a diagram of ultrafine spherical nickel hydrazine nitrate crystals prepared by the invention.

Detailed Description

The invention will be described in more detail below with reference to the accompanying drawing 1 and examples.

Example 1

(1) 4ml of ammonia water with the content of 25% -28% is measured and added into 100ml of deionized water, and the mixture is injected into a chemical combination device after being stirred evenly.

(2) Weighing 4g of nickel nitrate hexahydrate, and dissolving the nickel nitrate hexahydrate in 60ml of deionized water to prepare 6.25% nickel nitrate solution; 4ml of hydrazine hydrate with the concentration of 85 percent is measured and dissolved in 60ml of deionized water to prepare 5.2 percent hydrazine hydrate solution.

(3) The feeding speeds of the nickel nitrate solution and the hydrazine hydrate solution are respectively calibrated by adopting two peristaltic pumps. Nickel nitrate: 2ml/min, hydrazine hydrate: 1.8 ml/min.

(4) And opening the water bath heating device and the stirrer, quickly heating the base solution to 40 ℃, then starting feeding, feeding the nickel nitrate for 1min, and then simultaneously feeding the nickel nitrate and the nickel nitrate.

(5) Heating in water bath to control the temperature of the whole reaction process at 40-50 ℃, continuing to perform heat preservation reaction for 20min after the house is finished, cooling, filtering, washing with water, and drying to obtain the superfine spherical nickel hydrazine nitrate.

Example 2

(1) 4ml of ammonia water with the content of 25% -28% is measured and added into 100ml of deionized water, and the mixture is injected into a chemical combination device after being stirred evenly.

(2) Weighing 4g of nickel nitrate hexahydrate, and dissolving the nickel nitrate hexahydrate in 100ml of deionized water to prepare a 3.85% nickel nitrate solution; hydrazine hydrate with the concentration of 80 percent is measured and 6ml is dissolved in 100ml deionized water to prepare hydrazine hydrate solution with the concentration of 4.4 percent.

(3) The feeding speeds of the nickel nitrate solution and the hydrazine hydrate solution are respectively calibrated by adopting two peristaltic pumps. Nickel nitrate: 3.3ml/min, hydrazine hydrate: 3.3 ml/min.

(4) And opening the water bath heating device and the stirrer, quickly heating the base solution to 40 ℃, then starting feeding, and feeding the nickel nitrate and the nickel nitrate simultaneously after feeding for 2 min.

(5) Heating in water bath to control the temperature of the whole reaction process at 40-50 ℃, continuing to perform heat preservation reaction for 20min after the house is finished, cooling, filtering, washing with water, and drying to obtain the superfine spherical nickel hydrazine nitrate.

Testing

The preparation method of the invention can not only obtain the superfine nickel hydrazine nitrate with the diameter of about 5 mu m, but also ensure that the crystal is spherical. In addition, the obtained crystal is changed into a single crystal state from a polycrystalline state obtained by a conventional method, the problem of high friction sensitivity of the medicament is well solved, the specific surface area is increased, the combustion rapidity is improved, and the crystal can be used for combustion speed regulation of energetic materials, ignition powder, cold flame pyrotechnic charge and the like.

The test results were as follows:

(1) testing a carbon film bridge ignition head: selecting 40 carbon film bridges of 9.5-10.5 omega, respectively dipping the superfine spherical nickel hydrazine nitrate and the common polycrystalline nickel hydrazine nitrate into 20 ignition heads, igniting under the ignition condition of 9V-68 mu F, fully igniting when the superfine spherical nickel hydrazine nitrate is used as an ignition head medicament, and only half of the superfine spherical nickel hydrazine nitrate is in ignition when the conventional nickel hydrazine nitrate is used as an ignition head medicament.

(2) And (3) testing laser sensitivity: respectively selecting superfine spherical nickel hydrazine nitrate and conventional nickel hydrazine nitrate as laser ignition agents, wherein nearly half of conventional nickel hydrazine nitrate can not be ignited in 30 samples under the same condition under the laser with the wavelength of 1.06um, and the ignited samples can be ignited only after multiple laser ignitions; the ultrafine spherical nickel hydrazine nitrate can be basically delivered by one laser ignition.