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WO1998024739A1 - Matiere explosive a usage non militaire, notamment pour travaux dans des mines - Google Patents

Matiere explosive a usage non militaire, notamment pour travaux dans des mines Download PDF

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Publication number
WO1998024739A1
WO1998024739A1 PCT/EP1997/006620 EP9706620W WO9824739A1 WO 1998024739 A1 WO1998024739 A1 WO 1998024739A1 EP 9706620 W EP9706620 W EP 9706620W WO 9824739 A1 WO9824739 A1 WO 9824739A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
ammonium nitrate
explosive
explosive according
approximately
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.)
Ceased
Application number
PCT/EP1997/006620
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German (de)
English (en)
Inventor
Alexsander Vasielewich Bojew
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.)
APPENZELLER ALBERT
Original Assignee
APPENZELLER ALBERT
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 APPENZELLER ALBERT filed Critical APPENZELLER ALBERT
Publication of WO1998024739A1 publication Critical patent/WO1998024739A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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

Definitions

  • the invention relates to an explosive for civil, in particular mining purposes, with granulated ammonium nitrate and at least one carbon compound, in particular mineral oil and / or mineral oil products.
  • Such an explosive belongs to the ammonium nitrate explosives. These are handling-safe mixtures of granulated ammonium nitrate as an oxidizing agent and carbon compounds as a fuel. They are mainly used as rock explosives. A well-known example of generic explosives are so-called ANFO explosives. The common short name ANFO stands for Engl. "ammonium nitrate plus fuel oil”. These explosives contain absorbed liquid carbon compounds as fuel in the ammonium nitrate granules, the so-called prills. An emulsifier is also needed to prevent e.g. Mineral oil and ammonium nitrate e.g. under
  • Sensitizers can of course also be added to compensate for these disadvantages. It is known e.g.
  • An explosive of the generic type is known from British Patent 1,440,038. It contains 1-17% by weight of nitropropane and 1-17% by weight of an alkanol with 1 to 5 carbon atoms as fuel. The total content of these two substances is 10-18% by weight. With this explosive, a loading density of 1.1 to 1.55 g / cm 3 can be achieved. Although it has satisfactory explosive properties, it is relatively expensive and the components are difficult to meter in terms of their oxygen balance.
  • Another explosive is known from French patent specification 2 135 224. It is a water-containing explosive, the sensitivity of which is based on the addition of heavy metal salts or heavy metal oxides in the order of 0.1 to 5% by weight Weight of the emulsion is increased. Suitable additives are, for example, chlorides, nitrates, chlorites, sulfites, chromium, iron, cobalt, nickel or copper oxides and mixtures of two or more of these constituents. The disadvantage of this is that this explosive still has a relatively low detonation speed of 2,400 to 2,800 m / s with loading densities of 0.78 to 0.85 g / cm 3 . This results in unsatisfactory blasting properties and high costs.
  • the object of the invention is to increase the explosive properties, in particular the sensitivity and the explosive force, of a generic explosive in a simple and inexpensive manner.
  • the solution is that at least one of the following substances is added as a further constituent or constituents:
  • ammonium nitrate particles with a grain size of at most about 2 mm;
  • Used oil and / or heavy petroleum distillates such as Asphalt tar or masut not only increase the loading density and sensitivity of the explosive according to the invention, but also act as emulsifiers. So you no longer need additional, usually expensive emulsifiers.
  • waste oil as a fuel is also particularly environmentally friendly.
  • the waste oil burns without residue at the temperatures and pressures that occur during the detonation.
  • the minimum is around 1.5-2.5% by weight for moist ammonium nitrate, regardless of the type and chemical composition of the oil.
  • Mixtures with about 5-7% by weight of mineral oil, mineral oil products and / or waste oil and up to about 0.5% by weight of other combustible additives are preferred.
  • the addition of finely divided ammonium nitrate increases the packing density, thus the loading density and also the explosiveness, because this goes hand in hand with an increase in the interfaces between the actual explosive and the fuel.
  • the particle size is no more than about 2.0 mm.
  • the proportion of these particles should be at least about 10% by weight. About 15-25% by weight is preferred.
  • the semolina also acts as a sensitizer. This effect is due to its porosity.
  • Ground semolina has both open and closed pores. Air is enclosed in the closed pores, which like the air bubbles described below act as a sensitizing and initiating Additive works.
  • the open pores cause the semolina to soak up with mineral oil and waste oil, for example. This intimate connection leads to a clean and complete combustion.
  • the air acts both as an oxidizing agent and as a sensitizing and initiating additive.
  • the expansion of the air during the explosion increases the speed of the shock wave and the normal gas volume because there are more gaseous substances from the outset.
  • the expanding shock wave hits the enclosed air bubbles. These are then pressed together. This greatly increases the pressure and temperature in the air bubbles until the bubbles themselves explode.
  • the high temperatures also act as igniters for further reactions of the ammonium nitrate with the fuel. This takes place on a miniature scale in many finely divided air bubbles, so that the effects add up.
  • the air bubbles are introduced pneumatically. Pneumatic loading of the borehole is an easy way to add air to the explosives.
  • the explosive pressed into the borehole then contains finely divided air bubbles enclosed in the cavities.
  • If the added carbon compound is liquid, e.g. Diesel oil or other mineral oil then also contains air bubbles. It is, so to speak, "foamed".
  • the air can of course also be introduced with all other conceivable pneumatic devices, for example when patroning.
  • the explosive according to the invention has an explosive force that is at least 20% higher than that of explosives of the generic type.
  • the attainable Loading density is 0.8 to 1.5 g / cm 3 .
  • This explosive is particularly inexpensive, but like the dynamite that is dangerous to handle or the ANFO explosives mixed with expensive additives, it is suitable for blowing up particularly dense rock. Compared to conventional explosives, which are comparable in price, the effort for drilling the boreholes and the loading volume are significantly reduced.
  • the explosives according to the invention can be produced with high productivity and economy directly on site and loaded into the blast holes.
  • the explosives can also be produced with a cartridge and placed in the boreholes.
  • the waste oil can, for example. at least about 30% by weight carbon, at least about 5% by weight hydrogen, at least about 1% by weight sulfur, at least about 0.1% by weight? Alcohols, esters and / or asphaltenes, at least about 0.2% by weight of carboxylic acids and / or hydroxy-carboxylic acids and / or oxo-carboxylic acids, at least about 0.5% by weight of oil resins and / or at least about 0.3% by weight Contain metal oxides. It is also possible to replace all or part of the usual mineral oil component with used oil or heavy distillates. This further increases the loading density and sensitivity and strengthens the emulsifier effect. Instead, waste oil or heavy distillates can be added to the explosive according to the invention.
  • the explosives according to the invention can also be mixed with further additives.
  • oxidizing agents for adjusting the oxygen balance such as granulated ammonium nitrate, in particular with a density of approximately 1.45 to 1.65 g / cm 3 and a bulk density of approximately 0.85 to 0.95 cm 3 .
  • This is important, for example, for underground explosions. Explosives with a negative oxygen balance would remove oxygen from the environment, which is undesirable and even dangerous underground. This effect does not occur with blasting over days.
  • Other fuels such as mineral oil or mineral oil products can also be added. Powdery particles of one or more metals, metal salts and / or metal oxides can also be added.
  • the addition of a saturated solution of ammonium nitrate in water has also proven useful, in particular in an amount of about 5% by weight or more.
  • oxygen balance denotes the oxygen content of an explosive, more precisely, that amount of oxygen in% by weight which is released when the explosive is completely converted (positive oxygen balance) or is additionally required for the complete conversion. The closer this value is to zero, i.e. the more balanced the oxygen balance, the more effective the explosive.
  • the heat of detonation is the thermal energy released during the explosion, calculated from the difference between the formation energies of the explosive or the components of the explosive mixture and the formation energies of the reaction products.
  • the normal gas volume is the total volume of the gases generated when the explosives are completely converted, based on 0 ° C and 1.013 bar.
  • the work force or the working capacity of the explosive can be calculated from the heat of detonation and normal gas volume.
  • the loading density is the ratio of the weight of the explosive to the volume of the explosion space. The greater the loading density, the greater the explosiveness and the Explosive power, the lower the detonation ability.
  • the detonation speed is the speed in m / s at which the detonation proceeds in the explosive.
  • the explosiveness or impact pressure is the product of loading density, specific explosion pressure in the shock wave and detonation speed of the explosive.
  • a first embodiment of the present invention contains about 6 to 7% by weight of a mixture of waste oil and / or heavy distillates with diesel oil in a ratio of about 1: 1, about 20% by weight of ammonium nitrate with a particle size of 2.0 mm and about 74 % By weight of ammonium nitrate prills. An emulsifier is not required. Prepared boreholes are filled with this pourable mixture.
  • the mixture In the case of pneumatic filling, the mixture is compressed in the borehole and compressed air in the form of finely divided air bubbles is added at the same time.
  • the mineral oil mixture is "foamed", so to speak.
  • the pressure of the compressed air should exceed the hydrostatic pressure in water-filled boreholes. The higher the boost pressure, the more it is possible to dispense with part of the ammonium nitrate prills. You will then be ground during transport.
  • the achievable loading density is observed from 0.8 to 1.5 g / cm 3 compared to the achievable loading density of 0.8-0.9 g / cm 3 with conventional pourable explosives of the ANFO type.
  • the detonation speed of a typical ANFO charge is approximately 2.5-3.0 at a charge density of 0.9 g / cm 3 km / s.
  • the detonation speed of the explosive according to the invention with the above-mentioned composition is observed at a loading density of approximately 1.2 g / cm 3 and approximately 3-3.6 km / s. This results in excellent blasting behavior, in particular high explosiveness and satisfactory work ability.
  • Bone semolina as mentioned above, is an effective sensitizer.
  • Some basic types of the explosives according to the invention are listed below by way of example: Subsequent addition of about 2% by weight of used oil and / or masut and / or asphalt tar to conventional ANFO explosives gives a free-flowing, inexpensive explosive charge with an achievable loading density of about 1.15 to 1.2 g / cm 3 . The detonation speed is more than 2200 m / s.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

L'invention concerne une matière explosive à usage non militaire, notamment pour travaux dans des mines, comprenant du nitrate d'ammonium sous forme granulée et au moins un composé carbone, notamment de l'huile minérale et/ou des produits d'huile minérale, l'autre ou les autres constituant(s) ajouté(s) étant au moins une des substances suivantes: au moins approximativement 2 % en poids d'huile usée et/ou des fractions lourdes de la distillation de pétrole brut et/ou de leurs dérivés avec une forte proportion de composés hydrocarbures de poids moléculaire élevé, saturés avec de l'oxygène; au moins approximativement 10 % en poids de particules de nitrate d'ammonium d'une grosseur de grain d'au plus approximativement 2 mm; au moins approximativement 1 % en poids de grenaille osseuse moulue d'une grosseur de grain comprise approximativement entre 2 et 4 mm; au moins approximativement 1 % en volume de bulles d'air introduites pneumatiquement, de manière que ladite matière explosive présente une masse volumique comprise 0,8 à 1,5 g/cm<3>. Cette matière explosive s'utilise pour faire exploser des roches denses et est simultanément économique, car la sensibilité et la force explosive sont augmentées avec des moyens simples et avantageux.
PCT/EP1997/006620 1996-11-30 1997-11-27 Matiere explosive a usage non militaire, notamment pour travaux dans des mines Ceased WO1998024739A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1996149763 DE19649763A1 (de) 1996-11-30 1996-11-30 Sprengstoff für zivile, insbesondere bergmännische Zwecke
DE19649763.9 1996-11-30

Publications (1)

Publication Number Publication Date
WO1998024739A1 true WO1998024739A1 (fr) 1998-06-11

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1997/006620 Ceased WO1998024739A1 (fr) 1996-11-30 1997-11-27 Matiere explosive a usage non militaire, notamment pour travaux dans des mines

Country Status (2)

Country Link
DE (1) DE19649763A1 (fr)
WO (1) WO1998024739A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101851142A (zh) * 2010-05-18 2010-10-06 中国神华能源股份有限公司 苏丹红在铵油炸药制备中应用及相应铵油炸药和制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2480519B1 (fr) * 2009-09-23 2013-10-23 Ael Mining Services Limited Procede de fabrication d'un explosif
JP7646571B2 (ja) * 2019-06-07 2025-03-17 シーエムティーイー ディベロップメント リミテッド スリープタイムが改善された過酸化水素に基づく火薬

Citations (12)

* Cited by examiner, † Cited by third party
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US3180773A (en) * 1962-12-26 1965-04-27 Trojan Powder Co Water-resistant explosive compositions
US3394038A (en) * 1967-04-25 1968-07-23 Commercial Solvents Corp Method of producing ammonium nitrate explosive compositions having high package densities
US3781180A (en) * 1970-05-18 1973-12-25 Ici Australia Ltd Ammonium nitrate-fuel oil composition containing ammonium nitrate prills of different porosity,hardness,and density
US4111727A (en) * 1977-09-19 1978-09-05 Clay Robert B Water-in-oil blasting composition
US4161142A (en) * 1977-09-26 1979-07-17 Southern Explosives Corporation Blasting booster and methods
US4404050A (en) * 1982-09-29 1983-09-13 C-I-L Inc. Water-in-oil emulsion blasting agents containing unrefined or partly refined petroleum product as fuel component
US4475965A (en) * 1983-10-24 1984-10-09 Standard Oil Company (Indiana) Shale oil explosives
GB2140404A (en) * 1983-05-12 1984-11-28 Du Pont Stable an/emulsion explosives and emulsion for use therein
US4585496A (en) * 1985-03-11 1986-04-29 E. I. Du Pont De Nemours And Company Method of producing high-density slurry/prill explosives in boreholes and product made thereby
GB2192627A (en) * 1986-07-14 1988-01-20 Aeci Ltd Explosive
EP0256669A2 (fr) * 1986-08-05 1988-02-24 Exxon Chemical Patents Inc. Agents de sautage secs à base de nitrate d'ammonium
US5397405A (en) * 1992-04-01 1995-03-14 Peace Recovery Systems Ltd. Explosive composition comprising waste oil, ammonium nitrate and lignite

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GB1338616A (en) * 1971-05-03 1973-11-28 Ici Ltd Slurry explonsive composition
GB1440038A (en) * 1974-04-27 1976-06-23 Post J R Explosive compositions
US4216040A (en) * 1979-01-19 1980-08-05 Ireco Chemicals Emulsion blasting composition
DE3066625D1 (en) * 1979-11-05 1984-03-22 Ici Plc Slurry explosive composition and a method for the preparation thereof
JPS59156991A (ja) * 1983-02-24 1984-09-06 日本化薬株式会社 油中水滴型エマルジヨン爆薬
GB2156799B (en) * 1984-03-21 1987-12-16 Ici Plc Emulsion explosive
IN166325B (fr) * 1985-10-15 1990-04-14 Du Pont
DE3712488C1 (en) * 1987-04-13 1988-05-05 Dynamit Nobel Ag Use of silicone oils in water-in-oil emulsion explosives, and silicone oil-containing water-in-oil emulsion explosives having reduced surface tackiness
US4940497A (en) * 1988-12-14 1990-07-10 Atlas Powder Company Emulsion explosive composition containing expanded perlite

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3180773A (en) * 1962-12-26 1965-04-27 Trojan Powder Co Water-resistant explosive compositions
US3394038A (en) * 1967-04-25 1968-07-23 Commercial Solvents Corp Method of producing ammonium nitrate explosive compositions having high package densities
US3781180A (en) * 1970-05-18 1973-12-25 Ici Australia Ltd Ammonium nitrate-fuel oil composition containing ammonium nitrate prills of different porosity,hardness,and density
US4111727A (en) * 1977-09-19 1978-09-05 Clay Robert B Water-in-oil blasting composition
US4161142A (en) * 1977-09-26 1979-07-17 Southern Explosives Corporation Blasting booster and methods
US4404050A (en) * 1982-09-29 1983-09-13 C-I-L Inc. Water-in-oil emulsion blasting agents containing unrefined or partly refined petroleum product as fuel component
GB2140404A (en) * 1983-05-12 1984-11-28 Du Pont Stable an/emulsion explosives and emulsion for use therein
US4475965A (en) * 1983-10-24 1984-10-09 Standard Oil Company (Indiana) Shale oil explosives
US4585496A (en) * 1985-03-11 1986-04-29 E. I. Du Pont De Nemours And Company Method of producing high-density slurry/prill explosives in boreholes and product made thereby
GB2192627A (en) * 1986-07-14 1988-01-20 Aeci Ltd Explosive
EP0256669A2 (fr) * 1986-08-05 1988-02-24 Exxon Chemical Patents Inc. Agents de sautage secs à base de nitrate d'ammonium
US5397405A (en) * 1992-04-01 1995-03-14 Peace Recovery Systems Ltd. Explosive composition comprising waste oil, ammonium nitrate and lignite

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101851142A (zh) * 2010-05-18 2010-10-06 中国神华能源股份有限公司 苏丹红在铵油炸药制备中应用及相应铵油炸药和制备方法

Also Published As

Publication number Publication date
DE19649763A1 (de) 1998-06-04

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