CN101618866A - Method for preparing nickel hydrazine azide - Google Patents

Method for preparing nickel hydrazine azide Download PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
nickel
hydrazine
azide
solution
nickel hydrazine
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.)
Pending
Application number
CN200810122840A
Other languages
Chinese (zh)
Inventor
朱顺官
李燕
张琳
牟景艳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing University of Science and Technology
Original Assignee
Nanjing University of Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nanjing University of Science and Technology filed Critical Nanjing University of Science and Technology
Priority to CN200810122840A priority Critical patent/CN101618866A/en
Publication of CN101618866A publication Critical patent/CN101618866A/en
Pending legal-status Critical Current

Links

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

Method for preparing nickel hydrazine azide
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 ℃.
CN200810122840A 2008-07-01 2008-07-01 Method for preparing nickel hydrazine azide Pending CN101618866A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN200810122840A CN101618866A (en) 2008-07-01 2008-07-01 Method for preparing nickel hydrazine azide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN200810122840A CN101618866A (en) 2008-07-01 2008-07-01 Method for preparing nickel hydrazine azide

Publications (1)

Publication Number Publication Date
CN101618866A true CN101618866A (en) 2010-01-06

Family

ID=41512291

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200810122840A Pending CN101618866A (en) 2008-07-01 2008-07-01 Method for preparing nickel hydrazine azide

Country Status (1)

Country Link
CN (1) CN101618866A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
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

Cited By (3)

* Cited by examiner, † Cited by third party
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

Similar Documents

Publication Publication Date Title
CN103254026B (en) Compact aluminum-containing explosive and preparation method thereof
CN104447144B (en) Superhigh temperature petroleum perforation charge plastic bonded explosive and preparation method thereof
CN106116995B (en) A kind of method that aqueous suspension prepares press fitting aluminum composition modeling powder
CN102584507A (en) Special composite oil phase for high-temperature sensitized and emulsified explosive production process
US20140178292A1 (en) Hydrogen-storage-material
CN101618866A (en) Method for preparing nickel hydrazine azide
CN108163855A (en) A kind of method for preparing ultracapacitor activated carbon
CN101823926A (en) Preparation process of emulsion explosive
CN1970514A (en) Nickel hydrazine azide, its preparation method and uses as explosive ignitor
CN105152824A (en) Safe ignition powder and preparation method thereof
CN103333034A (en) Nano nickel oxide coated modified boron fuel and preparation methods thereof
CN105440070A (en) 1,1'-dihydro-5,5'-bistetrazole-lead coordination polymer and preparation method thereof
Zhou et al. Antistatic modification of lead styphnate and lead azide for surfactant applications
CN103396279B (en) A kind of rock type low temperature agglomeration resistance modified ammonium nitrate-fuel oil explosive and preparation method thereof
CN102173973A (en) Igniter for gas generator of safety gasbag and preparation method thereof
CN101857516B (en) Micro-pore firework powder capable with improved fire ignition and transfer properties and preparation method thereof
CN102219626B (en) Additive used for fireworks medicament pelletizing process and adding method thereof
CN103319291B (en) A kind of preparation method of green priming explosive nitrine hydrazine copper
CN102746074A (en) Method for sensitizing explosives
CN107473914A (en) A kind of high energy is pressed insensitive booster explosive and preparation method
CN102659080A (en) Novel method for preparing lithium aluminum hydride
CN111875456A (en) Preparation method of MTNP/TNAZ eutectic mixture
CN206902200U (en) A kind of system for improving iron ore sintering mixture ventilation
CN100483807C (en) Method for preparing plus plate material of lithium ion battery by combustion method
CN102643214B (en) The preparation method of the big crystal grain of Vorinostat I crystal form and preparation

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Open date: 20100106