CN105218283B - A kind of gluey emulsion of high explosion velocity type and preparation method thereof - Google Patents
A kind of gluey emulsion of high explosion velocity type and preparation method thereof Download PDFInfo
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- CN105218283B CN105218283B CN201510525967.6A CN201510525967A CN105218283B CN 105218283 B CN105218283 B CN 105218283B CN 201510525967 A CN201510525967 A CN 201510525967A CN 105218283 B CN105218283 B CN 105218283B
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Abstract
The invention discloses a kind of gluey emulsion of high explosion velocity type, the gluey emulsion of high explosion velocity type includes following components：Primary oxidant, cooxidant, reducing agent, water, additive, emulsifying agent, sensitizer, thickener, density adjuster, crystalline form modifying agent, waterproofing agent, stabilizer；The present invention have also been devised a kind of preparation method of the gluey emulsion of high explosion velocity type, and the emulsion has formula simple novel, and raw material sources are extensive, manufacturing process is simple, with low cost, high explosion velocity, storage is stable, the technical indicator of the obtained gluey emulsion of high explosion velocity type：Explosion velocity（m/s）：4700 5000m/s, brisance：17 19mm, explosive density：1.0‑1.2g/cm3, storage stability >=10 month, impact sensitivity, friction sensitivity are ≤8%.
Description
Technical field
The present invention relates to a kind of emulsion and preparation method thereof, and in particular to a kind of gluey emulsion of high explosion velocity type and
Its preparation method, belongs to explosive manufacturing technology field.
Background technology
Emulsion is that developed recently is more rapid and the aqueous commercial explosive of widely used class ammonium nitrate class, and it is with mistake
Saturation inorganic oxidizer aqueous solution is dispersed phase, and the hydrocarbon oils immiscible with water is continuous phase, by emulsifying technology
Aqueous oxidizing agent solution is uniformly densely scattered in fuel tank continuous media in the form of fine droplet, water-in-oil type is formed（W/
O）Gluey emulsion, emulsion has excellent explosion property and water repelling property, by universal weight in commercial explosive circle
Depending on and carry out substantial amounts of research in succession, emulsion is rapidly developed and is widely used in engineering explosion, emulsion life
Nontoxic pollution-free during production, and security is preferable during transport, storage, use, simultaneously because it is in spy of fluidised form
Point, in constructing at the scene, load, pump it is convenient, it has also become China civil explosive material industry gives priority to product.
By years of researches and development, emulsion explosives technology has obtained significant progress, either formula, performance, survey
In terms of examination, or in production technology, equipment and automatically control aspect etc. and achieve significant achievement, but with the hair in epoch
Exhibition, the continuous expansion of production scale and application field, the production of emulsion and use still have many difficult points to be solved
Problem and emerging specific demand, the explosive issue of such as emulsion, the current emulsion used in engineering
Not enough, explosion velocity is slow for explosion property, it is impossible to reach the requirement of explosion in short time moment, researches and develops a kind of higher emulsification of explosion velocity
Explosive turns into those skilled in the art's technical problem urgently to be resolved hurrily.
The content of the invention
The technical problems to be solved by the invention are that the shortcoming existed for above prior art proposes a kind of high explosion velocity
Type glue emulsion and preparation method thereof, the emulsion is simple novel with formula, and extensively, manufacturing process is simple for raw material sources
Single, with low cost, high explosion velocity, storage is stable.
The present invention solve above technical problem technical scheme be：
A kind of gluey emulsion of high explosion velocity type, the gluey emulsion of high explosion velocity type includes with the following group according to the mass fraction
Point：
Primary oxidant：50-60 parts, cooxidant：8-11 parts, reducing agent：5-9 parts, water：10-18 parts, additive：
0.5-1.5 parts, emulsifying agent：4-6 parts, sensitizer：7-9 parts, thickener：0.5-0.8 parts, density adjuster：0.5-1 parts, crystalline form
Modifying agent：1-2 parts, waterproofing agent：1-3 parts, stabilizer：0.1-0.5 parts；
Primary oxidant includes following components by weight percentage：Ferric nitrate：35-45%, manganese nitrate：25-35%, nitric acid
Zinc：15-18%, calcium nitrate：10-15%, above each component sum is 100%；
Reducing agent includes following components according to the mass fraction：1-2 parts of paraffin, vaseline：1.5-2.0 part, machine oil：0.5-
0.8 part, stearic acid：1-3 parts, diesel oil：1-1.2 part；
Cooxidant is ammonium nitrate；Additive is ammonium perchlorate；Emulsifying agent is nonionic surfactant containing triazine ring；
Sensitizer is natrium nitrosum；Thickener is one in diatomite, sodium bentonite, polyurethane, polyvinyl alcohol or polyacrylamide
Kind；Density adjuster is expanded perlite；Crystalline form modifying agent is dodecyl sodium sulfate；Waterproofing agent is stearic acid；Stabilizer is
One kind in urea, nitric acid and sodium chloride；
The technical scheme that further limits of the present invention as：
In the foregoing gluey emulsion of high explosion velocity type, the preparation of emulsifying agent nonionic surfactant containing triazine ring, specifically
Comprise the following steps：
（1）0.2mol Cyanuric Chloride is added into 500ml four-hole bottle, toluene is added into four-hole bottle to Cyanuric Chloride
Be dissolved to it is transparent, ice bath maintain temperature be slowly added dropwise at 1-3 DEG C, under agitation 0.12mol fatty amine toluene solution carry out
Reaction solution is moved into separatory funnel after reaction, reaction result, stratification, organic layer uses hydrochloric acid, sodium acid carbonate and saturation respectively
Sodium-chloride water solution is washed successively, is then dried with anhydrous sodium sulfate, and concentration cooling separates out white solid, finally uses
Normal heptane is recrystallized to give the chloro- 1,3,5- s-triazine of intermediate 2- fat amidos -4,6- two；
（2）The poly glycol monomethyl ether and toluene for taking 0.03mol are put into three-necked flask, are heated under the protection of nitrogen
100-110 DEG C, toluene reacts 10-12h with enough metallic sodiums are added after water, until solution is changed into dark brown, as sodium alkoxide is molten
Liquid is stored for future use；
Take step（1）Intermediate 2- fat amidos -4,6- bis- chloro- 1 of middle preparation, 3,5- s-triazine 0.015mol are added
Into the alcohol sodium solution prepared, under nitrogen protection, it is warming up to 40-50 DEG C and is reacted, suction filtration after reaction bonded, gained
Filtrate revolving removes toluene, spontaneously dries obtain emulsifying agent nonionic surfactant containing triazine ring at room temperature.
In the foregoing gluey emulsion of high explosion velocity type, the performance of emulsifying agent nonionic surfactant containing triazine ring is as follows：
Critical micelle concentration is that the surface tension under 0.162-0.171g/L, critical micelle concentration is 31.5-31.9mN/m, and cloud point is
65-72 DEG C, emulsifying ability is 18.5-20.5min.
In the foregoing gluey emulsion of high explosion velocity type, the gluey emulsion of high explosion velocity type includes with the following group according to the mass fraction
Point：
Primary oxidant：50 parts, cooxidant：11 parts, reducing agent：9 parts, water：15 parts, additive：0.5 part, emulsifying agent：
6 parts, sensitizer：8 parts, thickener：0.6 part, density adjuster：0.8 part, crystalline form modifying agent：1.5 part, waterproofing agent：It is 1 part, stable
Agent：0.3 part, wherein：
Primary oxidant includes following components by weight percentage：Ferric nitrate：35 %, manganese nitrate：35%, zinc nitrate：15%,
Calcium nitrate：15%, above each component sum is 100%；
Reducing agent includes following components according to the mass fraction：2 parts of paraffin, vaseline：2.0 parts, machine oil：0.8 part, 18
Acid：3 parts, diesel oil：1.2 part.
In the foregoing gluey emulsion of high explosion velocity type, the gluey emulsion of high explosion velocity type includes with the following group according to the mass fraction
Point：
Primary oxidant：60 parts, cooxidant：8 parts, reducing agent：5 parts, water：10 parts, additive：1.5 parts, emulsifying agent：4
Part, sensitizer：7 parts, thickener：0.8 part, density adjuster：0.5 part, crystalline form modifying agent：2 parts, waterproofing agent：3 parts, stabilizer：
0.5 part, wherein：
Primary oxidant includes following components by weight percentage：Ferric nitrate：45%, manganese nitrate：25%, zinc nitrate：18%,
Calcium nitrate：12%, above each component sum is 100%；
Reducing agent includes following components according to the mass fraction：1 part of paraffin, vaseline：1.5 parts, machine oil：0.5 part, 18
Acid：1 part, diesel oil：1 part.
In the foregoing gluey emulsion of high explosion velocity type, the gluey emulsion of high explosion velocity type includes with the following group according to the mass fraction
Point：
Primary oxidant：55 parts, cooxidant：9 parts, reducing agent：7 parts, water：18 parts, additive：0.9 part, emulsifying agent：5
Part, sensitizer：9 parts, thickener：0.5 part, density adjuster：1 part, crystalline form modifying agent：1 part, waterproofing agent：2 parts, stabilizer：
0.1 part, wherein：
Primary oxidant includes following components by weight percentage：Ferric nitrate：42%, manganese nitrate：31%, zinc nitrate：17%,
Calcium nitrate：10%, above each component sum is 100%；
Reducing agent includes following components according to the mass fraction：1 part of paraffin, vaseline：1.5 parts, machine oil：0.5 part, 18
Acid：3 parts, diesel oil：1 part.
The present invention have also been devised a kind of preparation method of the gluey emulsion of high explosion velocity type, specifically include following steps：
（1）Primary oxidant, cooxidant and water are accurately weighed with balance, the aqueous phase with interlayer and agitating device is put into
In dissolving tank, heating-up temperature is 80-90 DEG C, and mixing speed is controlled in 100-200r/min, makes primary oxidant, cooxidant complete
Portion dissolves, and ie in solution is in clear shape, and 10-20min is stood in 80-85 DEG C of constant temperature, aqueous phase solution is made and through filter
Filtering is stand-by；
（2）Reducing agent and emulsifying agent are accurately weighed with balance, another oil phase fusing with interlayer and agitating device is put into
In tank, 85-100 DEG C is heated to, mixing speed control obtains oil phase liquid and passed through in 150-200 r/min, insulation 8-11min
Filter device filtering stand-by；
（3）The agitating device in aqueous phase dissolved tank is adjusted, it is 150-180 r/min to control mixing speed, then by step
（2）In the slow mode at the uniform velocity of the oil phase liquid for preparing be added in the aqueous phase dissolved tank for being formed with aqueous phase solution, after adding
The mixing speed for adjusting agitating device is 300-380 r/min, stirs 10-13min, obtains emulsion matrix；
（4）By step（3）In obtained emulsion matrix be cooled to 45-55 DEG C, emulsion matrix will be delivered in sensitizing machine, so
Sensitizer is added in sensitizing machine and is sensitized afterwards, sensitizing temperature is 70-80 DEG C, is sensitized 30-60s, add in activation process additive,
Thickener, density adjuster, crystalline form modifying agent, waterproofing agent and stabilizer, and be uniformly mixed be cooled to room temperature discharging；
（5）By step（4）In discharging dress up powder stick with charging machine, bar nest mouthful of sealing with wax is stained with powder stick two, produces high explosion velocity
Type glue emulsion finished product.
The technical scheme that further limits of the present invention as：
In the foregoing gluey emulsion of high explosion velocity type, the technical indicator of the obtained gluey emulsion of high explosion velocity type：Explosion velocity
（m/s）：4700-5000m/s, brisance：17-19mm, explosive density：1.0-1.2g/cm3, storage stability >=10 month are hit
Sensitivity, friction sensitivity are ≤8%.
The beneficial effects of the invention are as follows：
Emulsifying agent plays an important role in the formation of emulsion and stability, and emulsion process can consider in drop week
Enclose to form steady and continuous phase film, the effect of emulsifying agent is the surface Gibbs free energys for expanding drop, improve oil phase content and be conducive to
The storage stability of emulsified bases is improved, but the content of water is not bright to the storage stability of emulsified bases to a certain extent
Development is rung, and with the raising of concentration of metal ions, its storage stability is decreased obviously；Species, quality and the concentration pair of emulsifying agent
Quality, granular size and explosion property of emulsification system etc. have the emulsifying agent used in significant impact, the present invention to contain triazine ring
The backbone structure of nonionic surfactant is close with reducing agent structure, or similar, increases both affinities, their institute's shapes
Into interface film strength and tightness degree must increase, stability of emulsion enhancing, the stability of emulsifying agent directly affects breast
Change the stability of explosive, enhance the stability of the emulsion of the present invention, it is ensured that security, the interfacial film shape of emulsion
It is vital for the stability of explosive and the rate of release of energy into critical condition.
Density adjuster is added in the present invention, density adjuster is control explosive density, improves the pass of its detonation sensitivity
Key component, the present invention applies the hot spot-effect of sensitization bubble to improve emulsion detonation susceptibility, i.e., in process of dynamite substrate
Interior addition density adjuster, makes it produce substantial amounts of micro-bubble inside explosive, is adjusted or controlled with playing with sensitization bubble
The purpose of explosive density processed, the present invention produces sensitization bubble by adding density adjuster, and this method is reliable, simple, warp
Ji, density domination is more accurate,
The reducing agent of the present invention is made up of paraffin, vaseline, machine oil, stearic acid and diesel oil, the stable chemical performance of paraffin,
It is solid-state under normal temperature, with higher toughness and less penetrability, viscosity is relatively low after high temperature melting, has to reducing agent good
Viscosity adjustment effect, the oil film of formation closely has preferable toughness and water-resistance；Machine oil calorific value is high, with paraffin compatibility
It is good, also there is good viscosity adjustment effect to reducing agent.
The crystalline form modifying agent added in the present invention is dodecyl sodium sulfate, and dodecyl sodium sulfate can exist with emulsifying agent
Mixed micellazation is formed in solution, the hydrophobic effect of the C-H bond of two kinds of surface active agent ions is easier to form micelle, and in solution
Adsorption, reduces surface tension, has broken the dissolving crystallized of supersaturated nitrate and balanced each other, and balance is moved to dissolving direction
It is dynamic, make the reduction of its crystallization point.
Ammonium perchlorate is with the addition of in the present invention, ammonium perchlorate can increase the quick-fried heat of emulsion, quick-fried temperature and explosion velocity, reduced
Its quick-fried appearance so that the explosive parameters for the emulsion prepared reach good value, improve the explosion property of explosive.
Embodiment
Embodiment 1
The present embodiment provides a kind of high explosion velocity type gluey emulsion, and the gluey emulsion of high explosion velocity type is according to the mass fraction
Including following components：
Primary oxidant：50 parts, cooxidant ammonium nitrate：11 parts, reducing agent：9 parts, water：15 parts, additive perchloric acid
Ammonium：0.5 part, emulsifying agent nonionic surfactant containing triazine ring：6 parts, sensitizer natrium nitrosum：8 parts, thickener Na-bentonite
Soil：0.6 part, density adjuster expanded perlite：0.8 part, crystalline form modifying agent dodecyl sodium sulfate：1.5 parts, waterproofing agent is stearic
Acid：1 part, stabilizer urea：0.3 part, wherein：
Primary oxidant includes following components by weight percentage：Ferric nitrate：35 %, manganese nitrate：35%, zinc nitrate：15%,
Calcium nitrate：15%, above each component sum is 100%；
Reducing agent includes following components according to the mass fraction：2 parts of paraffin, vaseline：2.0 parts, machine oil：0.8 part, 18
Acid：3 parts, diesel oil：1.2 part.
The preparation of emulsifying agent nonionic surfactant containing triazine ring, specifically includes following steps：
（1）0.2mol Cyanuric Chloride is added into 500ml four-hole bottle, toluene is added into four-hole bottle to Cyanuric Chloride
Be dissolved to transparent, ice bath maintains temperature at 1 DEG C, be slowly added dropwise under agitation 0.12mol fatty amine toluene solution carry out it is anti-
Should, reaction solution is moved into separatory funnel after reaction result, stratification, organic layer uses hydrochloric acid, sodium acid carbonate and saturation chlorine respectively
Change sodium water solution to be washed successively, be then dried with anhydrous sodium sulfate, concentration cooling separates out white solid, finally with just
Heptane is recrystallized to give the chloro- 1,3,5- s-triazine of intermediate 2- fat amidos -4,6- two；
（2）The poly glycol monomethyl ether and toluene for taking 0.03mol are put into three-necked flask, are heated under the protection of nitrogen
110 DEG C, toluene reacts 10h with enough metallic sodiums are added after water, until solution is changed into dark brown, as sodium alkoxide solution storage is standby
With；
Take step（1）Intermediate 2- fat amidos -4,6- bis- chloro- 1 of middle preparation, 3,5- s-triazine 0.015mol are added
Into the alcohol sodium solution prepared, under nitrogen protection, it is warming up to 40 DEG C and is reacted, suction filtration after reaction bonded, the filter of gained
Liquid revolving removes toluene, spontaneously dries obtain emulsifying agent nonionic surfactant containing triazine ring at room temperature；
The performance of emulsifying agent nonionic surfactant containing triazine ring is as follows：Critical micelle concentration is 0.171g/L, critical
Surface tension under micellar concentration is 31.5mN/m, and cloud point is 65 DEG C, and emulsifying ability is 18.5min.
The preparation method of the above-mentioned gluey emulsion of high explosion velocity type, specifically includes following steps：
（1）Primary oxidant, cooxidant ammonium nitrate and water are accurately weighed with balance, is put into interlayer and agitating device
Aqueous phase dissolved tank in, heating-up temperature be 80 DEG C, mixing speed control in 150r/min, make primary oxidant, cooxidant nitre
Sour ammonium all dissolves, and ie in solution is in clear shape, and 10min is stood in 85 DEG C of constant temperature, aqueous phase solution is made and through filter
Filtering is stand-by；
（2）Reducing agent and emulsifying agent nonionic surfactant containing triazine ring are accurately weighed with balance, another carry is put into
In the oil phase melting pot of interlayer and agitating device, 100 DEG C are heated to, mixing speed control is obtained in 180 r/min, insulation 8min
Oil phase liquid simultaneously filters stand-by through filter；
（3）The agitating device in aqueous phase dissolved tank is adjusted, it is 150r/min to control mixing speed, then by step（2）In
The slow mode at the uniform velocity of oil phase liquid prepared is added in the aqueous phase dissolved tank for being formed with aqueous phase solution, and regulation is stirred after adding
The mixing speed for mixing device is 350r/min, stirs 13min, obtains emulsion matrix；
（4）By step（3）In obtained emulsion matrix be cooled to 45 DEG C, emulsion matrix will be delivered in sensitizing machine, then
Sensitizer natrium nitrosum is added in sensitizing machine and is sensitized, sensitizing temperature is 75 DEG C, is sensitized adding additive in 45s, activation process
Ammonium perchlorate, thickener sodium bentonite, density adjuster expanded perlite, crystalline form modifying agent dodecyl sodium sulfate, waterproof
Agent stearic acid and stabilizer urea, and be uniformly mixed be cooled to room temperature discharging；
（5）By step（4）In discharging dress up powder stick with charging machine, bar nest mouthful of sealing with wax is stained with powder stick two, produces high explosion velocity
Type glue emulsion finished product；
The technical indicator of the obtained gluey emulsion of high explosion velocity type：Explosion velocity（m/s）：4700m/s, brisance：18mm, explosive
Density：1.0g/cm3, storage stability >=10 month, impact sensitivity, friction sensitivity are ≤8%.
Embodiment 2
The present embodiment provides a kind of high explosion velocity type gluey emulsion, and the gluey emulsion of high explosion velocity type is according to the mass fraction
Including following components：
Primary oxidant：60 parts, cooxidant ammonium nitrate：8 parts, reducing agent：5 parts, water：10 parts, additive ammonium perchlorate：
1.5 parts, emulsifying agent nonionic surfactant containing triazine ring：4 parts, sensitizer natrium nitrosum：7 parts, thickener polyurethane：0.8
Part, density adjuster expanded perlite：0.5 part, crystalline form modifying agent dodecyl sodium sulfate：2 parts, waterproofing agent stearic acid：3 parts,
Stabilizer nitric acid：0.5 part, wherein：
Primary oxidant includes following components by weight percentage：Ferric nitrate：45%, manganese nitrate：25%, zinc nitrate：18%,
Calcium nitrate：12%, above each component sum is 100%；
Reducing agent includes following components according to the mass fraction：1 part of paraffin, vaseline：1.5 parts, machine oil：0.5 part, 18
Acid：1 part, diesel oil：1 part；
The preparation of emulsifying agent nonionic surfactant containing triazine ring, specifically includes following steps：
（1）0.2mol Cyanuric Chloride is added into 500ml four-hole bottle, toluene is added into four-hole bottle to Cyanuric Chloride
Be dissolved to transparent, ice bath maintains temperature at 2 DEG C, be slowly added dropwise under agitation 0.12mol fatty amine toluene solution carry out it is anti-
Should, reaction solution is moved into separatory funnel after reaction result, stratification, organic layer uses hydrochloric acid, sodium acid carbonate and saturation chlorine respectively
Change sodium water solution to be washed successively, be then dried with anhydrous sodium sulfate, concentration cooling separates out white solid, finally with just
Heptane is recrystallized to give the chloro- 1,3,5- s-triazine of intermediate 2- fat amidos -4,6- two；
（2）The poly glycol monomethyl ether and toluene for taking 0.03mol are put into three-necked flask, are heated under the protection of nitrogen
100 DEG C, toluene reacts 11h with enough metallic sodiums are added after water, until solution is changed into dark brown, as sodium alkoxide solution storage is standby
With；
Take step（1）Intermediate 2- fat amidos -4,6- bis- chloro- 1 of middle preparation, 3,5- s-triazine 0.015mol are added
Into the alcohol sodium solution prepared, under nitrogen protection, it is warming up to 45 DEG C and is reacted, suction filtration after reaction bonded, the filter of gained
Liquid revolving removes toluene, spontaneously dries obtain emulsifying agent nonionic surfactant containing triazine ring at room temperature；
The performance of emulsifying agent nonionic surfactant containing triazine ring is as follows：Critical micelle concentration is 0.162g/L, critical
Surface tension under micellar concentration is 31.9mN/m, and cloud point is 72 DEG C, and emulsifying ability is 20.5min.
The preparation method of the above-mentioned gluey emulsion of high explosion velocity type, specifically includes following steps：
（1）Primary oxidant, cooxidant ammonium nitrate and water are accurately weighed with balance, is put into interlayer and agitating device
Aqueous phase dissolved tank in, heating-up temperature be 90 DEG C, mixing speed control in 100r/min, make primary oxidant, cooxidant nitre
Sour ammonium all dissolves, and ie in solution is in clear shape, and 20min is stood in 80 DEG C of constant temperature, aqueous phase solution is made and through filter
Filtering is stand-by；
（2）Reducing agent and emulsifying agent nonionic surfactant containing triazine ring are accurately weighed with balance, another carry is put into
In the oil phase melting pot of interlayer and agitating device, 85 DEG C are heated to, mixing speed control is obtained in 150 r/min, insulation 11min
Oil phase liquid simultaneously filters stand-by through filter；
（3）The agitating device in aqueous phase dissolved tank is adjusted, it is 180 r/min to control mixing speed, then by step（2）In
The slow mode at the uniform velocity of oil phase liquid prepared is added in the aqueous phase dissolved tank for being formed with aqueous phase solution, and regulation is stirred after adding
The mixing speed for mixing device is 300r/min, stirs 10min, obtains emulsion matrix；
（4）By step（3）In obtained emulsion matrix be cooled to 55 DEG C, emulsion matrix will be delivered in sensitizing machine, then
Sensitizer natrium nitrosum is added in sensitizing machine and is sensitized, sensitizing temperature is 70 DEG C, is sensitized adding additive in 30s, activation process
Ammonium perchlorate, thickener polyurethane, density adjuster expanded perlite, crystalline form modifying agent dodecyl sodium sulfate, waterproofing agent are hard
Resin acid and stabilizer nitric acid, and be uniformly mixed be cooled to room temperature discharging；
（5）By step（4）In discharging dress up powder stick with charging machine, bar nest mouthful of sealing with wax is stained with powder stick two, produces high explosion velocity
Type glue emulsion finished product；
The technical indicator of the obtained gluey emulsion of high explosion velocity type：Explosion velocity（m/s）：5000m/s, brisance：17mm, explosive
Density：1.1g/cm3, storage stability >=10 month, impact sensitivity, friction sensitivity are ≤8%.
Embodiment 3
The present embodiment provides a kind of high explosion velocity type gluey emulsion, and the gluey emulsion of high explosion velocity type is according to the mass fraction
Including following components：
Primary oxidant：55 parts, cooxidant ammonium nitrate：9 parts, reducing agent：7 parts, water：18 parts, additive ammonium perchlorate：
0.9 part, emulsifying agent nonionic surfactant containing triazine ring：5 parts, sensitizer natrium nitrosum：9 parts, thickener diatomite：0.5
Part, density adjuster expanded perlite：1 part, crystalline form modifying agent dodecyl sodium sulfate：1 part, waterproofing agent stearic acid：2 parts, surely
Determine agent sodium chloride：0.1 part, wherein：
Primary oxidant includes following components by weight percentage：Ferric nitrate：42%, manganese nitrate：31%, zinc nitrate：17%,
Calcium nitrate：10%, above each component sum is 100%；
Reducing agent includes following components according to the mass fraction：1 part of paraffin, vaseline：1.5 parts, machine oil：0.5 part, 18
Acid：3 parts, diesel oil：1 part；
The preparation of emulsifying agent nonionic surfactant containing triazine ring, specifically includes following steps：
（1）0.2mol Cyanuric Chloride is added into 500ml four-hole bottle, toluene is added into four-hole bottle to Cyanuric Chloride
Be dissolved to transparent, ice bath maintains temperature at 3 DEG C, be slowly added dropwise under agitation 0.12mol fatty amine toluene solution carry out it is anti-
Should, reaction solution is moved into separatory funnel after reaction result, stratification, organic layer uses hydrochloric acid, sodium acid carbonate and saturation chlorine respectively
Change sodium water solution to be washed successively, be then dried with anhydrous sodium sulfate, concentration cooling separates out white solid, finally with just
Heptane is recrystallized to give the chloro- 1,3,5- s-triazine of intermediate 2- fat amidos -4,6- two；
（2）The poly glycol monomethyl ether and toluene for taking 0.03mol are put into three-necked flask, are heated under the protection of nitrogen
105 DEG C, toluene reacts 12h with enough metallic sodiums are added after water, until solution is changed into dark brown, as sodium alkoxide solution storage is standby
With；
Take step（1）Intermediate 2- fat amidos -4,6- bis- chloro- 1 of middle preparation, 3,5- s-triazine 0.015mol are added
Into the alcohol sodium solution prepared, under nitrogen protection, it is warming up to 50 DEG C and is reacted, suction filtration after reaction bonded, the filter of gained
Liquid revolving removes toluene, spontaneously dries obtain emulsifying agent nonionic surfactant containing triazine ring at room temperature；
The performance of emulsifying agent nonionic surfactant containing triazine ring is as follows：Critical micelle concentration is 0.169g/L, critical
Surface tension under micellar concentration is 31.7mN/m, and cloud point is 68 DEG C, and emulsifying ability is 19.5min.
The preparation method of the above-mentioned gluey emulsion of high explosion velocity type, specifically includes following steps：
（1）Primary oxidant, cooxidant ammonium nitrate ammonium nitrate and water are accurately weighed with balance, is put into interlayer and stirs
In the aqueous phase dissolved tank for mixing device, heating-up temperature is 85 DEG C, and mixing speed is controlled in 100r/min, makes primary oxidant, auxiliary oxygen
Agent ammonium nitrate all dissolves, and ie in solution is in clear shape, and 15min is stood in 82 DEG C of constant temperature, and aqueous phase solution is made and passes through
Filter device filtering stand-by；
（2）Reducing agent and emulsifying agent nonionic surfactant containing triazine ring are accurately weighed with balance, another carry is put into
In the oil phase melting pot of interlayer and agitating device, 91 DEG C are heated to, mixing speed control obtains oil in 200r/min, insulation 9min
Phase liquid simultaneously filters stand-by through filter；
（3）The agitating device in aqueous phase dissolved tank is adjusted, it is 165 r/min to control mixing speed, then by step（2）In
The slow mode at the uniform velocity of oil phase liquid prepared is added in the aqueous phase dissolved tank for being formed with aqueous phase solution, and regulation is stirred after adding
The mixing speed for mixing device is 380r/min, stirs 11min, obtains emulsion matrix；
（4）By step（3）In obtained emulsion matrix be cooled to 50 DEG C, emulsion matrix will be delivered in sensitizing machine, then
Sensitizer natrium nitrosum is added in sensitizing machine and is sensitized, sensitizing temperature is 80 DEG C, is sensitized adding additive in 60s, activation process
Ammonium perchlorate, thickener diatomite, density adjuster expanded perlite, crystalline form modifying agent dodecyl sodium sulfate, waterproofing agent are hard
Resin acid and stabilizer sodium chloride, and be uniformly mixed be cooled to room temperature discharging；
（5）By step（4）In discharging dress up powder stick with charging machine, bar nest mouthful of sealing with wax is stained with powder stick two, produces high explosion velocity
Type glue emulsion finished product；
The technical indicator of the obtained gluey emulsion of high explosion velocity type：Explosion velocity（m/s）：4900m/s, brisance：19mm, explosive
Density：1.2g/cm3, storage stability >=10 month, impact sensitivity, friction sensitivity are ≤8%.
In addition to the implementation, the present invention can also have other embodiment.All use equivalent substitution or equivalent transformation shape
Into technical scheme, all fall within the protection domain of application claims.
Claims (8)
1. a kind of gluey emulsion of high explosion velocity type, it is characterised in that：The gluey emulsion of high explosion velocity type presses mass fraction
Meter includes following components：
Primary oxidant：50-60 parts, cooxidant：8-11 parts, reducing agent：5-9 parts, water：10-18 parts, additive：0.5-1.5
Part, emulsifying agent：4-6 parts, sensitizer：7-9 parts, thickener：0.5-0.8 parts, density adjuster：0.5-1 parts, crystalline form modifying agent：
1-2 parts, waterproofing agent：1-3 parts, stabilizer：0.1-0.5 parts；
Described primary oxidant includes following components by weight percentage：Ferric nitrate：35-45%, manganese nitrate：25-35%, nitre
Sour zinc：15-18%, calcium nitrate：10-15%, above each component sum is 100%；
Described reducing agent includes following components according to the mass fraction：1-2 parts of paraffin, vaseline：1.5-2.0 part, machine oil：0.5-
0.8 part, stearic acid：1-3 parts, diesel oil：1-1.2 part；
Described cooxidant is ammonium nitrate；Described additive is ammonium perchlorate；Described emulsifying agent is non-containing triazine ring
Ionic surface active agent；Described sensitizer is natrium nitrosum；Described thickener be diatomite, sodium bentonite, polyurethane,
One kind in polyvinyl alcohol or polyacrylamide；Described density adjuster is expanded perlite；Described crystalline form modifying agent is
Dodecyl sodium sulfate；Described waterproofing agent is stearic acid；Described stabilizer is one kind in urea, nitric acid and sodium chloride.
2. the gluey emulsion of high explosion velocity type according to claim 1, it is characterised in that：The emulsifying agent is non-containing triazine ring
The preparation of ionic surface active agent, specifically includes following steps：
(1) 0.2mol Cyanuric Chloride is added into 500ml four-hole bottle, toluene to Cyanuric Chloride is added into four-hole bottle and is dissolved
Extremely transparent, the toluene solution for the fatty amine that 0.12mol is slowly added dropwise at 1-3 DEG C, under agitation for ice bath maintenance temperature is reacted,
Reaction solution is moved to separatory funnel by reaction after terminating, and stratification, organic layer uses hydrochloric acid, sodium acid carbonate and saturated sodium-chloride respectively
The aqueous solution is washed successively, is then dried with anhydrous sodium sulfate, and concentration cooling separates out white solid, finally uses normal heptane
It is recrystallized to give the chloro- 1,3,5- s-triazine of intermediate 2- fat amidos -4,6- two；
(2) poly glycol monomethyl ether and toluene for taking 0.03mol are put into three-necked flask, and 100- is heated under the protection of nitrogen
110 DEG C, toluene reacts 10-12h with enough metallic sodiums are added after water, until solution is changed into dark brown, as alcohol sodium solution is stored up
Deposit standby；
The intermediate 2- fat amidos -4,6- bis- chloro- 1 prepared in step (1) are taken, 3,5- s-triazine 0.015mol are added to system
In the alcohol sodium solution got ready, under nitrogen protection, it is warming up to 40-50 DEG C and is reacted, reaction terminates rear suction filtration, the filtrate of gained
Revolving removes toluene, spontaneously dries obtain emulsifying agent nonionic surfactant containing triazine ring at room temperature.
3. the gluey emulsion of high explosion velocity type according to claim 1, it is characterised in that：Described emulsifying agent contains triazine ring
The performance of nonionic surfactant is as follows：Critical micelle concentration is the surface under 0.162-0.171g/L, critical micelle concentration
Tension force is 31.5-31.9mN/m, and cloud point is 65-72 DEG C, and emulsifying ability is 18.5-20.5min.
4. the gluey emulsion of high explosion velocity type according to claim 1, it is characterised in that：The high explosion velocity type glue emulsification
Explosive includes following components according to the mass fraction：
Primary oxidant：50 parts, cooxidant：11 parts, reducing agent：9 parts, water：15 parts, additive：0.5 part, emulsifying agent：6 parts,
Sensitizer：8 parts, thickener：0.6 part, density adjuster：0.8 part, crystalline form modifying agent：1.5 parts, waterproofing agent：1 part, stabilizer：
0.3 part, wherein：
Described primary oxidant includes following components by weight percentage：Ferric nitrate：35%, manganese nitrate：35%, zinc nitrate：
15%, calcium nitrate：15%, above each component sum is 100%；
Described reducing agent includes following components according to the mass fraction：2 parts of paraffin, vaseline：2.0 parts, machine oil：0.8 part, 18
Acid：3 parts, diesel oil：1.2 part.
5. the gluey emulsion of high explosion velocity type according to claim 1, it is characterised in that：The high explosion velocity type glue emulsification
Explosive includes following components according to the mass fraction：
Primary oxidant：60 parts, cooxidant：8 parts, reducing agent：5 parts, water：10 parts, additive：1.5 parts, emulsifying agent：4 parts,
Sensitizer：7 parts, thickener：0.8 part, density adjuster：0.5 part, crystalline form modifying agent：2 parts, waterproofing agent：3 parts, stabilizer：0.5
Part, wherein：
Described primary oxidant includes following components by weight percentage：Ferric nitrate：45%, manganese nitrate：25%, zinc nitrate：
18%, calcium nitrate：12%, above each component sum is 100%；
Described reducing agent includes following components according to the mass fraction：1 part of paraffin, vaseline：1.5 parts, machine oil：0.5 part, 18
Acid：1 part, diesel oil：1 part.
6. the gluey emulsion of high explosion velocity type according to claim 1, it is characterised in that：The high explosion velocity type glue emulsification
Explosive includes following components according to the mass fraction：
Primary oxidant：55 parts, cooxidant：9 parts, reducing agent：7 parts, water：18 parts, additive：0.9 part, emulsifying agent：5 parts,
Sensitizer：9 parts, thickener：0.5 part, density adjuster：1 part, crystalline form modifying agent：1 part, waterproofing agent：2 parts, stabilizer：0.1
Part, wherein：
Described primary oxidant includes following components by weight percentage：Ferric nitrate：42%, manganese nitrate：31%, zinc nitrate：
17%, calcium nitrate：10%, above each component sum is 100%；
Described reducing agent includes following components according to the mass fraction：1 part of paraffin, vaseline：1.5 parts, machine oil：0.5 part, 18
Acid：3 parts, diesel oil：1 part.
7. the preparation method of the gluey emulsion of high explosion velocity type as claimed in claim 1, it is characterised in that：The emulsion
Preparation method specifically includes following steps：
(1) primary oxidant, cooxidant and water are accurately weighed with balance, the aqueous phase dissolved with interlayer and agitating device is put into
In tank, heating-up temperature is 80-90 DEG C, and mixing speed is controlled in 100-200r/min, makes primary oxidant, cooxidant all molten
Solution, ie in solution is in clear shape, and 10-20min is stood in 80-85 DEG C of constant temperature, and aqueous phase solution is made and is filtered through filter
It is stand-by；
(2) reducing agent and emulsifying agent are accurately weighed with balance, are put into another oil phase melting pot with interlayer and agitating device,
85-100 DEG C is heated to, mixing speed control obtains oil phase liquid and through filter in 150-200r/min, insulation 8-11min
Filtering is stand-by；
(3) agitating device in regulation aqueous phase dissolved tank, it is 150-180r/min to control mixing speed, then by step (2)
The slow mode at the uniform velocity of oil phase liquid prepared is added in the aqueous phase dissolved tank for being formed with aqueous phase solution, and regulation is stirred after adding
The mixing speed for mixing device is 300-380r/min, stirs 10-13min, obtains emulsion matrix；
(4) emulsion matrix obtained in step (3) is cooled to 45-55 DEG C, emulsion matrix is delivered in sensitizing machine, then will be quick
Agent is added in sensitizing machine and is sensitized, and sensitizing temperature is 70-80 DEG C, is sensitized adding additive, thickening in 30-60s, activation process
Agent, density adjuster, crystalline form modifying agent, waterproofing agent and stabilizer, and be uniformly mixed be cooled to room temperature discharging；
(5) powder stick is dressed up into the discharging in step (4) with charging machine, powder stick two is stained with bar nest mouthful of sealing with wax, produces high explosion velocity type glue
Shape emulsion finished product.
8. the preparation method of the gluey emulsion of high explosion velocity type according to claim 7, it is characterised in that：Obtained height is quick-fried
The technical indicator of the gluey emulsion of fast type：Explosion velocity：4700-5000m/s, brisance：17-19mm, explosive density：1.0-1.2g/
cm3, storage stability >=10 month, impact sensitivity, friction sensitivity are ≤8%.
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| CN105753617A (en) * | 2016-05-20 | 2016-07-13 | 宜兴市阳生化工有限公司 | Gelatinous emulsion explosive for drilling shaft and preparation method of gelatinous emulsion explosive |
| CN105753614A (en) * | 2016-05-20 | 2016-07-13 | 宜兴市阳生化工有限公司 | Gel-type emulsified explosive and preparation method thereof |
| CN107353173A (en) * | 2017-07-28 | 2017-11-17 | 宜兴市阳生化工有限公司 | A kind of high explosion velocity Blasting in deep water gluey emulsion and preparation method thereof |
| CN107353174A (en) * | 2017-07-28 | 2017-11-17 | 宜兴市阳生化工有限公司 | A kind of high stability photoface exploision emulsion and preparation method thereof |
| CN108586167A (en) * | 2018-05-07 | 2018-09-28 | 宜兴市阳生化工有限公司 | A kind of high rigidity emulsion and its preparation process |
| CN110668906A (en) * | 2019-10-22 | 2020-01-10 | 江西国泰龙狮科技有限责任公司 | Emulsion explosive sensitizing agent and foaming agent thereof |
| CN111747804B (en) * | 2020-06-22 | 2021-03-16 | 铜陵雷鸣双狮化工有限责任公司 | Emulsion explosive and production process thereof |
| CN111925260A (en) * | 2020-07-31 | 2020-11-13 | 宜兴市阳生化工有限公司 | High-viscosity colloidal explosive |
| CN116217311B (en) * | 2022-12-19 | 2024-03-15 | 本溪钢铁（集团）矿业有限责任公司 | Method for debugging and sensitization of emulsion explosive formula by using Gibbs function variable |
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| CN101805237A (en) * | 2010-03-30 | 2010-08-18 | 宜兴市阳生化工有限公司 | Production method of emulsified explosive |
| CN103724143A (en) * | 2013-12-31 | 2014-04-16 | 宜兴市阳生化工有限公司 | Rock powdery civil emulsion explosive and production process thereof |
| CN104311374A (en) * | 2014-10-20 | 2015-01-28 | 宜兴市阳生化工有限公司 | Novel sensitization bubble carrier colloidal emulsion explosive and preparation method thereof |
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| CN101805237A (en) * | 2010-03-30 | 2010-08-18 | 宜兴市阳生化工有限公司 | Production method of emulsified explosive |
| CN103724143A (en) * | 2013-12-31 | 2014-04-16 | 宜兴市阳生化工有限公司 | Rock powdery civil emulsion explosive and production process thereof |
| CN104311374A (en) * | 2014-10-20 | 2015-01-28 | 宜兴市阳生化工有限公司 | Novel sensitization bubble carrier colloidal emulsion explosive and preparation method thereof |
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