CN101618866A - Method for preparing nickel hydrazine azide - Google Patents
Method for preparing nickel hydrazine azide Download PDFInfo
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- CN101618866A CN101618866A CN200810122840A CN200810122840A CN101618866A CN 101618866 A CN101618866 A CN 101618866A CN 200810122840 A CN200810122840 A CN 200810122840A CN 200810122840 A CN200810122840 A CN 200810122840A CN 101618866 A CN101618866 A CN 101618866A
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- nickel
- hydrazine
- azide
- solution
- nickel hydrazine
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Abstract
The invention discloses a method for preparing nickel hydrazine azide. The method comprises: taking soluble nickel salts as base solution; using acetic acid to adjust the pH of the formed base solution; using graphite as modified additives of medicaments; adding sodium nitride solution and hydrazine hydrate solution to the base solution dropwise to perform chemical combination; preserving heat, cooling, leaching, washing, dehydrating and drying; and obtaining a finished product of nickel hydrazine azide. The method is simple in pH control, and buffer solution consisting of weak acid and weak-acid salts ensures stable pH, longer effectiveness and the unicity of medicament composition, and significantly improves explosion initiation capacity, so the buffer solution is more suitable to be used as a primary explosive. By adopting nickel acetate as raw material, a small quantity of nickel hydrazine nitrate substances which are formed by use of nitrates and result in worse or unstable pharmaceutical performance can be avoided. Dropping and time difference ensure the complete reaction of sodium nitride and high yield of nickel hydrazine azide.
Description
Technical field
The present invention relates to a kind of preparation method of priming explosive, particularly a kind of preparation method of nickel hydrazine azide compound.
Background technology
Current, the medicament that is used as priming explosive has lead azoimide (LA), lead styphnate (LTNR), dinitrodiazophenol (DDNP), perchloric acid carbohydrazide cadmium (GTG) and nickel hydrazine nitrate (NHN).The two kinds of medicaments in back are with nickel hydrazine azide, belong to that contain can title complex together.Their power size sequence is: LA＞GTG＞NHN＞DDNP＞LTNR, and the flame sensitivity order is just in contrast.Be in lead azoimide, perchloric acid carbohydrazide cadmium and the lead styphnate at two, in actual applications, or need the filling priming charge because of flame sensitivity is too low, or Yin Weili is little and can't use separately.Simultaneously, exist that the lead azoimide mechanical sensitivity is very high, lead styphnate static sparking sensitivity is too high, the nickel hydrazine nitrate initiation power is on the weak side and dinitrodiazophenol is made problems such as waste water serious environment pollution.Although take the way of co-precipitation, attempt realizes the complementation of performance, and the coprecipitation primary explosive (DS) such as lead azoimide and lead styphnate formation obtains certain effect, and the deficiency that the sensitivity aspect is exposed still exists.
Nickel hydrazine azide has than excellent comprehensive performances as a kind of energy title complex that contains.The most outstanding performance is that flame sensitivity is fabulous, and detonating capability is big, and free-running property is good, does not dye.Also have performances such as mechanical sensitivity is low, accumulation of static electricity is little, the static sparking sensitivity is low, fast light, withstand voltage, non-hygroscopic simultaneously.In extensive trial production, shown competent fully civilian priming explosive, can be assemblied in the Engineering detonator of all size, and on military little detonator, attempted having adapted to the growth requirement of firer's device of new generation medicament as the high-power priming explosive.
Prior art such as nickel hydrazine azide, its preparation method and be raw material with nickelous nitrate, sodium nitride and hydrazine hydrate as the purposes (number of patent application is 200510095639.3) of priming explosive, nickelous nitrate and sodium nitride are made into aqueous mixture, hydrazine hydrate is made into ethanolic soln, form two kinds of dropping liquids, make end liquid with 50mL water or mother liquor again, 50 ℃ of following dropwise reaction liquid, the reinforced time is 50min, generates the synneusis nickel hydrazine azide in the reaction process.Then be technological processs such as cooling, discharging, washing, dehydration and drying.
In above-mentioned preparation process, the subject matter of existence is: (1) nickelous nitrate and sodium nitride mix, and discharge HN easily because of acidity is higher
3Poisonous gas pollutes and injures environment and personnel; (2) mixed solution of nickelous nitrate and sodium nitride, can form spawn when long slightly storage period, has influence on the feasibility and the reasonableness of technology therefrom, and cause line clogging easily; (3) the pH value of chemical combination process is unstable, causes the inconsistent of pharmacy quality.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing nickel hydrazine azide, its reactive mode is more rationally feasible, and the performance of medicament is then further optimized, and operation is also comparatively simple with control.
The technical solution that realizes the object of the invention is: a kind of method for preparing nickel hydrazine azide, with soluble nickel salt as end liquid, adjust the pH value with acetic acid in the liquid of the formed end, and make the modified materials of medicament with graphite, sodium nitride solution and hydrazine hydrate solution are added drop-wise to respectively and carry out combination reaction in the end liquid, be incubated then, cooling, suction filtration, washing, dehydration, drying, obtain the nickel hydrazine azide finished product.
The present invention compared with prior art, its remarkable advantage: the control method of (1) pH value is simple, and the buffered soln of forming by weak acid and salt of weak acid, more make the pH value stabilization, validity is more lasting, guaranteed the unicity that medicament is formed, its detonating capability also significantly improves, and uses as priming explosive thereby be more suitable for it; (2) select for use nickel acetate to do raw material, can avoid using nitrate and a small amount of nickel hydrazine nitrate material of forming, cause powder performance variation or instability; (3) owing to drip and the time difference, guarantee the sodium nitride complete reaction, nickel hydrazine azide yield height; (4) add graphite and can reduce the accumulation of static electricity of medicament and its static sparking sensitivity, mechanical sensitivity reduces simultaneously, has improved security; (5) detonating capability of medicament obviously improves, and the limit explosive quantity of shellac granulation RDX is reduced to 25mg by original 50mg, and detonating capability increases 2.0 times.
Below in conjunction with accompanying drawing the present invention is described in further detail.
Description of drawings
Accompanying drawing is the schema of method for preparing nickel hydrazine azide of the present invention.
Embodiment
In conjunction with the accompanying drawings, method for preparing nickel hydrazine azide of the present invention, with soluble nickel salt as end liquid, adjust the pH value with acetic acid in the liquid of the formed end, and make the modified materials of medicament with graphite, sodium nitride solution and hydrazine hydrate solution are added drop-wise to respectively and carry out combination reaction in the end liquid, are incubated then, cooling, suction filtration, washing, dehydration, drying, obtain the nickel hydrazine azide finished product.Choosing water miscible nickel salt, nitride and hydrazine hydrate, is end liquid with the acidifying nickel salt solution, and adding graphite is performance improver; With nitride and hydrazine hydrate solution,, suitably joining in the end liquid under the chemical combination temperature in two-tube reinforced mode; In reaction process because the suitably containment of acidity, make nucleus generation with grow up, reach comparatively ideal matching status; Simultaneously, the sodium salt that reaction generates with the acetic acid that exists, forms slightly acidic buffered soln, has avoided the generation of alkaline matter, also helps growing up, reuniting of small-crystalline.Through reaction fully, obtained the nickel hydrazine azide product of even glomerocryst state.After suction filtration, washing, drying, become easily wandering crystal grain, satisfy actual service requirements.
The solubility nickel acetate of metering is dissolved in an amount of pure water, after the filtration this nickel salt solution is placed in the combination apparatus, and measure quantitative acetum, pour combination apparatus into, add the graphite of charging capacity 1% again; Open water-bath and make it to heat up, and start stirring; Cofabrication sodium nitride solution and hydrazine hydrate solution are poured in the feed hopper respectively after the filtration.Treat that temperature rises to 50 ℃～70 ℃ scope in the combination apparatus, sodium azide solution and hydrazine hydrate solution can be added in the combination apparatus in the lump.Keep uniform feed rate, the reinforced time of control sodium nitride solution is about 30min～35min, and the reinforced time of hydrazine hydrate solution is about 45min～50min; After adding, feed liquid needs to continue reaction 6min～10min; To the combination apparatus cooling, feed temperature is reduced to below 45 ℃, promptly carries out operations such as discharging, suction filtration, washing, dehydration, drying, finally obtains finished product then.
Embodiment 1: in conjunction with Fig. 1, and specifications of raw materials and requirement: hydrazine hydrate (N
2H
4H
2O) AR, nickel acetate (NiAc
24H
2O) CP, sodium nitride (NaN
3) CP, graphite 1000 orders, acetic acid (HAc) CP, ethanol (C
2H
5OH) CP, key instrument and equipment: electric blender; Powerstat; Thermostatic water-circulator bath; Tall form beaker (combination apparatus) 400mL, volume pump, B Φ 65mm; Filter flask 1000mL, water-bath baking oven, water circulation type vacuum pump.
By raw material feed ratio (mass ratio) be: Ni (Ac)
24H
2O: NaN
3: N
2H
4H
2O=1.76: 1: 0.80, take by weighing nickel acetate 12.3g, with the dissolving of 160mL pure water, change over to after the filtration in the combination apparatus, add 4.0mL acetic acid and 100mg graphite again; Take by weighing the 7.0g sodium nitride again and measure the 6.0mL hydrazine hydrate, all dissolve and dilute, put into small beaker after the filtration separately with the 30mL pure water, standby.Reaction unit is installed, has been demarcated volume pump.Heating makes end liquid be warming up to 50 ℃ in water bath with thermostatic control, starts agitator simultaneously, and regulating voltage is to suitable whipped state.By volume pump, drip sodium nitride and hydrazine hydrate solution slowly, evenly, exactly, the reinforced time of control sodium nitride is 30min ± 5min, and the reinforced time of hydrazine hydrate is 45min ± 5min.The reinforced back constant temperature that finishes stirs 10min, carries out water-cooled to 35 then ℃ with bottom discharge.
The above-mentioned product that makes B suction filtration, and washing 2～3 times embathes 1 time with 95% ethanol again.Drain and be placed in the drying tray, dry under the room temperature, put into 55 ℃～60 ℃ water-bath baking ovens again, more than the dry 6h.
The gained nickel hydrazine azide is the cyan glomerocryst, and the particle that is between 49 μ m～95 μ m accounts for more than 67% of total particle number, adopts graduated cylinder and funnel method, and the apparent density that records nickel hydrazine azide is 0.58g/cm
3～0.63g/cm
3
Impact sensitivity: 10kg hammer, the 55cm drop height, 20 samples record blast percentage ratio.
Measured performance perameter sees the following form.
Friction sensitivity: 70 ° of pivot angles, 1.23MPa, 20 samples record blast percentage ratio.
The accumulation of static electricity data
Embodiment 2: by raw material feed ratio (mass ratio) be: Ni (Ac)
24H
2O: NaN
3: N
2H
4H
2O=1.76: 1: 0.80, take by weighing nickel acetate 14g, with the dissolving of 120mL pure water, change over to after the filtration in the combination apparatus, add 3.5mL acetic acid and 100mg graphite again; Take by weighing the 7.0g sodium nitride again and measure the 6.0mL hydrazine hydrate, dissolve and dilute with 90mL and 60mL pure water respectively, put into small beaker after the filtration separately, standby.Reaction unit is installed, has been demarcated volume pump.Heating makes end liquid be warming up to 70 ℃ in water bath with thermostatic control, starts agitator simultaneously, and regulating voltage is to suitable whipped state.By volume pump, drip sodium nitride and hydrazine hydrate solution slowly, evenly, exactly, the reinforced time of control sodium nitride is 30min ± 5min, and the reinforced time of hydrazine hydrate is 45min ± 5min.The reinforced back constant temperature that finishes stirs 6min, carries out water-cooled to 35 then ℃ with bottom discharge.
Embodiment 3: by raw material feed ratio (mass ratio) be: Ni (Ac)
24H
2O: NaN
3: N
2H
4H
2O=1.76: 1: 0.80, take by weighing nickel acetate 12.3g, with the dissolving of 120mL pure water, change over to after the filtration in the combination apparatus, add 3.5mL acetic acid and 100mg graphite again; Take by weighing the 7.0g sodium nitride again and measure the 5.6mL hydrazine hydrate, dissolve and dilute with 30mL and 30mL pure water respectively, put into small beaker after the filtration separately, standby.Reaction unit is installed, has been demarcated volume pump.Heating makes end liquid be warming up to 65 ℃ in water bath with thermostatic control, starts agitator simultaneously, and regulating voltage is to suitable whipped state.By volume pump, drip sodium nitride and hydrazine hydrate solution slowly, evenly, exactly, the reinforced time of control sodium nitride is 30min ± 2min, and the reinforced time of hydrazine hydrate is 45min ± 2min.The reinforced back constant temperature that finishes stirs 6min, carries out water-cooled to 35 then ℃ with bottom discharge.
The above-mentioned product that makes B suction filtration, and washing 2～3 times embathes 1 time with 95% ethanol again.Drain and be placed in the drying tray, dry under the room temperature, put into 55 ℃～60 ℃ water-bath baking ovens again, more than the dry 6h.
The gained nickel hydrazine azide is the darkcyan glomerocryst, and the particle that is between 66 μ m～102 μ m accounts for more than 65% of total particle number, adopts graduated cylinder and funnel method, and the apparent density that records nickel hydrazine azide is 0.62g/cm
3～0.71g/cm
3, under high chemical combination temperature and rare reaction soln, it is big that particle becomes, and apparent density also increases, but yield can descend about 4%.
After tested, the big density of nickel hydrazine azide is 2.12g/cm
3, than nickel hydrazine nitrate (2.139g/cm
3) slightly smaller.Moisture absorption weightening finish behind the 72h is 0.019%, and is close with lead styphnate, so its water absorbability is equally very little.
Application is as priming explosive, and the 5s bursting point that records is 193 ℃～194 ℃, and 50% feature height of getting angry that measures with common safety fuse is 46.3cm.Impact sensitivity: 10kg drops hammer, the 55cm drop height, and the blast percentage ratio that measures 20 samples is 35%, and the 50% feature drop height of getting angry is 66.1cm; Friction sensitivity: 70 ° of pivot angles, the 1.23MPa gauge pressure, the blast percentage ratio that measures 20 samples is 10%, is lower than respectively to pacify very much explosive and KD priming explosive.The static sparking sensitivity: press the WJ1869-89 standard, dose 20mg, electric capacity 2000pF, series resistance 0, voltage 25kV, discharging gap 0.18mm, point is flat; T=23 ℃, RH=48%.25 blast percentage ratio is 0 as a result.Limit explosive quantity to the granulation hexogen: 20mg during the iron strengthening cap, 25mg during the aluminium strengthening cap.The resistance to pressure of nickel hydrazine azide is fine, and pressure " killing " phenomenon do not occur when 80MPa.
Claims (7)
1, a kind of method for preparing nickel hydrazine azide, it is characterized in that soluble nickel salt as end liquid, adjust the pH value with acetic acid in the liquid of the formed end, and make the modified materials of medicament with graphite, sodium nitride solution and hydrazine hydrate solution are added drop-wise to respectively and carry out combination reaction in the end liquid, be incubated then, cooling, suction filtration, washing, dehydration, drying, obtain the nickel hydrazine azide finished product.
2, method for preparing nickel hydrazine azide according to claim 1 is characterized in that: soluble nickel salt is nickel acetate or nickelous nitrate.
3, method for preparing nickel hydrazine azide according to claim 1 is characterized in that: the dropping time of sodium nitride solution is 30 ± 5min, and the dropping time of hydrazine hydrate solution is 45 ± 5min, and both have 50% time difference.
4, according to the method for preparing nickel hydrazine azide of claim 1, it is characterized in that: graphite modified additive granularity is below 10 μ m.
5, method for preparing nickel hydrazine azide according to claim 1 is characterized in that: mass ratio feeds intake: Ni (Ac)
24H
2O: NaN
3: N
2H
4H
2O=1.7～2.0: 1: 0.80～1.0.
6, method for preparing nickel hydrazine azide according to claim 1 is characterized in that: soaking time: 6min～10min, cooling temperature≤45 ℃ are washed ethanol dehydration 1 time, 55 ℃～60 ℃ of drying temperatures, time of drying 〉=6h 2～3 times.
7, method for preparing nickel hydrazine azide according to claim 1 is characterized in that: temperature of reaction is 50 ℃～70 ℃.
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|---|---|---|---|
| CN200810122840A CN101618866A (en) | 2008-07-01 | 2008-07-01 | Method for preparing nickel hydrazine azide |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659491A (en) * | 2012-03-28 | 2012-09-12 | 南京理工大学 | Novel energetic base material prepared from porous material and preparation method thereof |
| CN104502337A (en) * | 2014-12-30 | 2015-04-08 | 山东艾孚特科技有限公司 | Method for quantitatively detecting various components in sodium azide aqueous-phase synthesis mother solution |
| US11535575B2 (en) | 2016-07-11 | 2022-12-27 | Dynitec Gmbh | Lead-free initiating agents or initiating agent mixtures |
-
2008
- 2008-07-01 CN CN200810122840A patent/CN101618866A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659491A (en) * | 2012-03-28 | 2012-09-12 | 南京理工大学 | Novel energetic base material prepared from porous material and preparation method thereof |
| CN104502337A (en) * | 2014-12-30 | 2015-04-08 | 山东艾孚特科技有限公司 | Method for quantitatively detecting various components in sodium azide aqueous-phase synthesis mother solution |
| CN104502337B (en) * | 2014-12-30 | 2017-02-22 | 山东艾孚特科技有限公司 | Method for quantitatively detecting various components in sodium azide aqueous-phase synthesis mother solution |
| US11535575B2 (en) | 2016-07-11 | 2022-12-27 | Dynitec Gmbh | Lead-free initiating agents or initiating agent mixtures |
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Open date: 20100106 |