CN1137507A - Solid state emulsified compound granular explosive and its preparation method - Google Patents

Solid state emulsified compound granular explosive and its preparation method Download PDF

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Publication number
CN1137507A
CN1137507A CN 96104685 CN96104685A CN1137507A CN 1137507 A CN1137507 A CN 1137507A CN 96104685 CN96104685 CN 96104685 CN 96104685 A CN96104685 A CN 96104685A CN 1137507 A CN1137507 A CN 1137507A
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China
Prior art keywords
latex
explosive
porous
agent
oil
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CN 96104685
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CN1045428C (en
Inventor
璩世杰
孙长寿
方祖烈
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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Priority to CN96104685A priority Critical patent/CN1045428C/en
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
    • C06B47/14—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase comprising a solid component and an aqueous phase
    • C06B47/145—Water in oil emulsion type explosives in which a carbonaceous fuel forms the continuous phase
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
    • C06B31/28—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
    • C06B31/285—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with fuel oil, e.g. ANFO-compositions

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

This explosive is composed of porous granular ammonium oil granules as granule nucle and emulsoid which can be solidified at temp. below 60-70 deg.C and used as external water-proofing layer. Said emulsoid is made of ammonium nitrate, sodium nitrate, sodium dodecyl sulfate, water, emulsifying agent, paraffin wax, ceresin wax and crosslinking agent and senitizing agent, and the porous granular ammonium oil is composed of porous granular ammonium nitrate and diesel oil. When preparing, the porous granular ammonium oil is passed through preheating treatment, then mixed with emulsoid uniformly, and stirred 1-3 times so as to obtain the invented product.

Description

Solid state emulsified compound granular explosive and manufacture method thereof
Solid state emulsified compound granular explosive and manufacture method thereof belong to the explosive class.
In the civil blast engineering, particularly at underground mine, in order to improve the operating efficiency of blast hole projectile filling, and guarantee charging quality, adopt pneumatic loading mechanical means (as the pneumatic loading device) replace manual in the big gun hole filling powder type explosive or granular ammonium nitrate-fuel oil mixture not rare at home and abroad.But the water repelling property of these two kinds of explosives can not satisfy actual requirement far away.And the former is easy to cause the back powder phenomenon, pollutes the working face air, harmful workers ' health, and the latter then is only applicable to the wide aperture explosion.
Present widely used emulsion explosive is fat shape dope, and water resisting property is good, but is not suitable for charge pneumatic machinery.And be the pyrotechnic composition that major ingredient mixes with porous and granular ammonium oil and conventional emulsion explosive, can not satisfy two basic demands of water repelling property and charge pneumatic machinery simultaneously.
For remedying the existing above-mentioned deficiency of industrial explosive, the explosive worker has carried out many explorations both at home and abroad.U.S. Atlas gunpowder company (Atlas Powder Co) has developed a kind of with the grainy emulsified explosive (US Patent 4,525,225) of ammoniumper chlorate (weight percent is 25～41%) as grain nuclear and sensitizing agent in 1985.But, remove its ammoniumper chlorate composition and belong to the high sensitivity material, be unfavorable for that the water repelling property of this explosive and blast performance all do not have concrete introduction outside the safety.
Yunnan Province of China province Dongchuan Mining Administration is mixed porous particulated ammonium oil explosive with the paste emulsion explosive of using as adhesion agent, a kind of " explosive mixture " that be called " granulated emulsion explosive for rocks " (CN1031362A, 1989) that contain perchlorate and single chmical compound explosive have been invented.But the water repelling property of this kind explosive how, and the size of emulsion explosive proportion there is no concrete introduction to the influence of charge pneumatic machinery.
The people such as Sanders of ICI Australia holding transaction company limited have introduced in the patent (AU9062187) of nineteen ninety announcement latex and porous and granular ammonium oil, aluminium powder, hollow microspheres with solid have been puddled a kind of grainy emulsified explosive that forms, its blast performance is good, be suitable for mechanized charging, but patent specification also lacks the introduction to its water repelling property.Because explosive contains this high responsive component of sodium perchlorate, be unfavorable for the safety of producing and using in addition.
The object of the present invention is to provide a kind of novel explosive, guaranteeing that explosion properties satisfies general requirement and do not use under the prerequisite of high sensitivity component, makes its water resisting property good, and is suitable for charge pneumatic machinery.
Solid state emulsified compound granular explosive of the present invention is by being composited through certain mixing technique as the porous and granular ammonium oil of grain nuclear with as the latex that covers anti-water layer outward.Wherein latex also is a kind of emulsion explosive, and it is made up of disperse phase, external phase and a spot of sensitizing agent.Disperse phase contains ammonium nitrate, SODIUMNITRATE, sodium lauryl sulphate and water; External phase is made of emulsifying agent, cross linking agent, paraffin and ceresine.Sensitizing agent is aluminium powder or SULPHUR POWDER.Latex component proportioning is as follows:
Ammonium nitrate: a kind of oxygenant.Consumption accounts for the 72-80% of latex gross weight.
SODIUMNITRATE: a kind of oxygenant, can reduce the disperse phase fusing point.Consumption accounts for the 6-12% of latex gross weight.
Sodium lauryl sulphate: use as crystalline form properties-correcting agent, purpose is to control dissolving--the crystallization balance of inorganic oxidant salts such as ammonium nitrate in the disperse phase.Consumption is about 0.15% of latex gross weight.
Water: consumption is the 2.7-3.0% of latex gross weight.
Emulsifying agent: with the polyisobutene succinimide is the polymer compound emulsifying agent of major ingredient, is suitable for high temperature emulsification.Consumption is the 1.5-2.2% of latex gross weight.
Cross linking agent: a kind of carboxylic-acid substance, it also is a kind of combustible agent preferably, and has certain emulsifying capacity.What the present invention used is a kind of stearic acid, better because of its toughness, and the curing that is beneficial to latex is with stable, thus the anti-outlet capacity of raising latex, and its molecular formula is C 18H 30O 2, consumption is 1.6～2.2% of a latex gross weight.
Hundred waxes, ceresine: good for guaranteeing that latex solidifies, should not select for use fluent meterial as combustible agent.Paraffin and ceresine are solid-state or accurate solid matter at normal temperatures, and the consumption of the two accounts for 1.8～2.2% and 0.10～0.15% of latex gross weight respectively.
Sensitizing agent: aluminium powder or SULPHUR POWDER, in order to improve the Sensitivity to Primary Explosion of explosive.When using SULPHUR POWDER, its consumption is 0.0～1.8% of a latex gross weight.
More than the summation of all kinds of components be 100% (weight).
Porous and granular ammonium oil used in the present invention is made of ammonium nitrate and diesel oil, and the weight percent of the two is respectively 94～96% and 4～6%.
The making method of solid state emulsified compound granular explosive can be divided into the preparation of latex and porous and granular ammonium oil and the synthetic granulation processing two portions of the two.It is basic identical to prepare latex required equipment and conventional emulsion explosive, but because the difference on component selection and the proportioning, the preparation technology parameter difference is bigger.Concrete steps are: in proportion ammonium nitrate, SODIUMNITRATE, water and sodium lauryl sulphate are heated to 125～135 ℃, make it fusing and form disperse phase; Simultaneously with paraffin, ceresine heat fused, add cross linking agent and emulsifying agent again and continue to be heated to 120～130 ℃ and make it whole fusings, form external phase; External phase, disperse phase are mixed stirring 6～10 minutes with sensitizing agent, stir maximum line velocity and be advisable, make required latex with 16～20m/s.The preparation of porous and granular ammonium oil is very simple, and ammonium nitrate and diesel oil are mixed in proportion, and stirring gets final product.Because diesel oil is unfavorable for the stable of latex, must deposit certain hour so that diesel oil fully immerses in the ammonium nitrate granule, can use.
In the preparation latex, the porous and granular ammonium oil preheating that immersion oil is good, temperature when making its temperature near the latex discharging, the temperature difference is controlled at below 20～40 ℃, make latex in the two mixing process and after even cooling curing, guarantee the unlikely too early crystallization of oxygenant salt in the latex and destroy the internal structure of latex.When latex preparation finishes, promptly mix and stir with porous and granular ammonium oil, be the timed interval to stir 1～3 time again with 1～3 hour afterwards, in order to avoid the medicine body condenses.The general final explosive product that after 8 hours, promptly obtains being solid-state form of spherical particles.According to the difference that can require water resistance of explosive, the part by weight of latex and porous glue prilled ammonium oil can change between 20～40% and 60～80% respectively, and the latex ratio increases, and then water resistance of explosive can be with corresponding raising.
The invention has the advantages that: solid state emulsified blasting explosive package is overlayed on porous and granular ammonium oil particles surface, solved the water resisting property and two basic problems of conveying free-running property of calming the anger of explosive simultaneously, be suitable for makeup medicine operation of pneumatic loading plant machinery and water-hole blasting and use.
Embodiment one:
The prescription of used latex is as follows:
Composition weight percent (%)
Emulsifying agent 2.17
Paraffin 2.17
Ceresine 0.10
Cross linking agent 1.80
Ammonium nitrate 77.67
SODIUMNITRATE 11.50
Sodium lauryl sulphate 0.14
SULPHUR POWDER 1.80
Water 2.78
The latex that will make in above prescription stirs in 1: 3 ratio fusion with the porous and granular ammonium oil that is preheated to 65 ℃, stirs once every two hours afterwards again, promptly makes solid state emulsified compound granular explosive.Explosive property sees Table one.
Embodiment two
Latex formula:
Composition weight percent (%)
Emulsifying agent 1.98
Paraffin 2.00
Ceresine 0.10
Cross linking agent 1.98
Ammonium nitrate 79.00
SODIUMNITRATE 10.30
Sodium lauryl sulphate 0.15
SULPHUR POWDER 1.80
Water 2.71
To stir with being preheated to of the ratio fusion of about 80 ℃ porous and granular ammonium oil in the latex of above formulation, stirred once every one and a half hours afterwards, promptly make solid state emulsified compound granular explosive behind the stirring secondary in 2: 3.Explosive property sees Table one.
Embodiment three
Latex formula:
Composition weight percent (%)
Emulsifying agent 2.10
Paraffin 2.10
Ceresine 0.16
Cross linking agent 2.10
Ammonium nitrate 79.90
SODIUMNITRATE 9.96
Sodium lauryl sulphate 0.15
SULPHUR POWDER 0.64
Water 2.89
To stir with being preheated to of the ratio fusion of about 75 ℃ porous and granular ammonium oil in the latex that above prescription is made, stirred once every 2 hours afterwards, stir secondary, promptly make solid state emulsified compound granular explosive in 3: 8.Explosive property sees Table one.
Table 1 solid state emulsified compound granular explosive fundamental property
Embodiment One Two Three Remarks
Mode of appearance Spheroidal particle The minimum part of spheroidal particle is Powdered Spheroidal particle
Charge density (g/cm 3) ????1.15 ????1.25 ??1.18
Energy detonates The single-shot detonator The single-shot detonator The 100g primer [cartridge Φ 40mm steel tube confinement condition
Gap distance (cm) ????10 ????12 ??8
Explosion velocity (m/s) ????3200 ????3450 ??2800
Water repelling property By force Stronger By force The propagation of explosion that detonates after the immersion one and half is well strong for water repelling property

Claims (4)

1, a kind of solid state emulsified compound granular explosive, it is characterized in that it by as the porous and granular ammonium oil of grain nuclear and as cover anti-water layer outward and when being lower than 60～70 ℃ the solidified latex form; Porous and granular ammonium oil is formed through uniform mixing by ammonium nitrate and the diesel oil that weight percent is respectively 94-96% and 4-6%; Latex is made up of disperse phase, external phase and a spot of sensitizing agent.
Its disperse phase component and proportioning are:
Composition per-cent (%)
Ammonium nitrate 72～80
SODIUMNITRATE 6～12
Sodium lauryl sulphate 0.14～0.16
Water 2.7～3.0
Its external phase component and proportioning are:
Emulsifying agent 1.5～2.2
Cross linking agent 1.6～2.2
Paraffin 1.8～2.2
Ceresine 0.10～0.15
And
Sensitizing agent 0.1～2.0
Above each component ratio all is weight percentage, and each component is accumulated as 100% (weight).
2, explosive according to claim 1 is characterized in that the emulsifying agent in the latex is to be the polymer compound emulsifying agent of main component with the polyisobutene succinimide; Sensitizing agent is SULPHUR POWDER or aluminium powder; Cross linking agent is a kind of stearic acid, and its molecular formula is C 18H 36O 2
3, explosive according to claim 1 and 2 is characterized in that the weight percent of latex and porous and granular ammonium oil is 20～40% and 60～80%.
4, a kind of manufacturing is characterized in that the disperse phase of latex is heated to 125～135 ℃ of dissolving fusings as method of filling explosive as described in claim 1 or 2 or 3, forms disperse phase liquid; The external phase of latex is heated to 120～130 ℃ of fusings, form external phase liquid, these two kinds of liquid are mixed with sensitizing agent and quick the stirring 6～10 minutes, maximum line velocity 16～20m/s, make it to be emulsified into latex, in the preparation latex, porous and granular ammonium oil is carried out thermal pretreatment, the temperature when making its temperature near the latex discharging, the temperature difference is controlled at below 20～40 ℃ and is advisable; Then rapidly with the latex and the porous and granular ammonium oil mixing and stirring that prepare, and with 1～3 hour is the timed interval to repeat to stir 1～3 time, promptly makes solid state emulsified compound granular explosive.
CN96104685A 1996-04-19 1996-04-19 Solid state emulsified compound granular explosive and its preparation method Expired - Fee Related CN1045428C (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1303042C (en) * 2004-07-29 2007-03-07 国营云南包装厂 High-energy powdery ammonium nitrate explosive with no sibium, and preparation method
CN100357233C (en) * 2006-04-14 2007-12-26 安徽盾安化工集团有限公司 High-strength emulsified explosive and production process thereof
CN101323551B (en) * 2007-06-12 2011-04-06 辽宁红山化工股份有限公司 Rock powdery emulsifying ammonium nitrate fuel explosive and preparing process thereof
CN101323552B (en) * 2007-06-12 2011-04-06 辽宁红山化工股份有限公司 Coal mine admissible powdery emulsifying ammonium nitrate fuel explosive and preparing process thereof
CN103193565A (en) * 2013-04-10 2013-07-10 南京理工大学 Porous granulated ammonium oil explosive and preparation method thereof
CN108484342A (en) * 2018-04-04 2018-09-04 安徽理工大学 A kind of high temperature resistant Blasting In Geotechnical ammonium nitrate-fuel oil mixture
CN108586174A (en) * 2018-04-03 2018-09-28 安徽理工大学 A kind of high temperature resistant Blasting In Geotechnical emulsion and high temperature resistant emulsifying ammonium nitrate fuel explosive
CN111747804A (en) * 2020-06-22 2020-10-09 铜陵雷鸣双狮化工有限责任公司 Emulsion explosive and production process thereof
CN114773133A (en) * 2022-04-02 2022-07-22 山西同德化工股份有限公司 Rock oil emulsion explosive for top hole charging

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102675005B (en) * 2012-05-28 2014-10-08 广东宏大爆破股份有限公司 Emulsion explosive used in deep water blasting and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0238210A3 (en) * 1986-03-14 1989-05-24 Imperial Chemical Industries Plc Solid explosive composition
AU625792B2 (en) * 1989-09-05 1992-07-16 Orica Explosives Technology Pty Ltd Cap-sensitive water-in-oil emulsion explosive composition
CN1027637C (en) * 1991-06-14 1995-02-15 华东工学院 Emulsified powdered nitramon and its making method

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1303042C (en) * 2004-07-29 2007-03-07 国营云南包装厂 High-energy powdery ammonium nitrate explosive with no sibium, and preparation method
CN100357233C (en) * 2006-04-14 2007-12-26 安徽盾安化工集团有限公司 High-strength emulsified explosive and production process thereof
CN101323551B (en) * 2007-06-12 2011-04-06 辽宁红山化工股份有限公司 Rock powdery emulsifying ammonium nitrate fuel explosive and preparing process thereof
CN101323552B (en) * 2007-06-12 2011-04-06 辽宁红山化工股份有限公司 Coal mine admissible powdery emulsifying ammonium nitrate fuel explosive and preparing process thereof
CN103193565A (en) * 2013-04-10 2013-07-10 南京理工大学 Porous granulated ammonium oil explosive and preparation method thereof
CN103193565B (en) * 2013-04-10 2015-01-14 南京理工大学 Porous granulated ammonium oil explosive and preparation method thereof
CN108586174A (en) * 2018-04-03 2018-09-28 安徽理工大学 A kind of high temperature resistant Blasting In Geotechnical emulsion and high temperature resistant emulsifying ammonium nitrate fuel explosive
CN108484342A (en) * 2018-04-04 2018-09-04 安徽理工大学 A kind of high temperature resistant Blasting In Geotechnical ammonium nitrate-fuel oil mixture
CN111747804A (en) * 2020-06-22 2020-10-09 铜陵雷鸣双狮化工有限责任公司 Emulsion explosive and production process 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
CN114773133A (en) * 2022-04-02 2022-07-22 山西同德化工股份有限公司 Rock oil emulsion explosive for top hole charging

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