EP2396288B1 - Use of a sensitizing composition for an explosive - Google Patents

Use of a sensitizing composition for an explosive Download PDF

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Publication number
EP2396288B1
EP2396288B1 EP10801092.7A EP10801092A EP2396288B1 EP 2396288 B1 EP2396288 B1 EP 2396288B1 EP 10801092 A EP10801092 A EP 10801092A EP 2396288 B1 EP2396288 B1 EP 2396288B1
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EP
European Patent Office
Prior art keywords
use according
microspheres
composition
emulsion
base emulsion
Prior art date
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Not-in-force
Application number
EP10801092.7A
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German (de)
French (fr)
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EP2396288A1 (en
Inventor
Charl Vermaak
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.)
AEL Mining Services Ltd
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AEL Mining Services Ltd
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Priority to PL10801092T priority Critical patent/PL2396288T3/en
Publication of EP2396288A1 publication Critical patent/EP2396288A1/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
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/002—Sensitisers or density reducing agents, foam stabilisers, crystal habit modifiers
    • C06B23/003—Porous or hollow inert particles

Definitions

  • This invention relates generally to a sensitizing composition for use with slurry and emulsion explosives (hereinafter collectively referred to as explosives) to provide sensitization through density reduction.
  • explosives slurry and emulsion explosives
  • base emulsion is used to refer to a water-in-oil emulsion comprising an inorganic oxidizer salt solution, for example ammonium nitrate, as a discontinuous phase and an organic fuel as a continuous phase.
  • an inorganic oxidizer salt solution for example ammonium nitrate
  • a base emulsion component of an emulsion explosive typically has a density in a range 1.3 to 14 g/cc. At these densities, the base emulsion is not "cap sensitive" i.e. it is too dense, and therefore too insensitive, to be detonated to explode by the initiating shock produced by a blasting cap.
  • a density reducing agent is added to reduce the density typically to within a range 0.9 to 1.1 g/cc.
  • a density reducing agent may be chemical agent for example sodium nitrite, which chemically reacts with the base emulsion to produce density reducing gas bubbles, it may be a mechanical agent, such as a hollow or solid microsphere, or it may be a combination of a chemical and a mechanical agent.
  • microspheres used in a density reducing context is isobutane plastic enclosed micro-balloons, each with a particle diameter in a range 10-150 ⁇ m.
  • Microspheres provide an advantage, over gas bubbles created by a chemical agent, in that they do not coalesce to reduce the sensitivity of the emulsion, and their density reducing effect can be more accurately predicted due to their relatively regular unit dimensions.
  • this advantage is somewhat mitigated by handling difficulties, due to their small particulate size. Consequently, the microspheres easily can become airborne, creating a dust problem, exacerbated in an underground location, and a respiratory irritant.
  • the invention at least partially addresses the aforementioned problems.
  • surfactant and "emulsifier” (hereinafter the terms are used interchangeably) are used to describe an organic compound that exhibits an amphiphilic characteristic, meaning it has both hydrophobic and hydrophilic properties, which enables a surfactant compound to interface between a hydrophobic organic compound and an aqueous solution to form an emulsion.
  • the invention provides the use of a sensitizing composition to sensitize a base emulsion which includes a carrier emulsion, of a liquid non-polar organic fuel, a surfactant and an aqueous solution, and a plurality of microspheres suspended in the carrier emulsion.
  • Sensitizing compositions using gassing agents are known from WO 2008/026124 and WO 89/02881 .
  • the organic fuel may a mineral oil, a vegetable oil or a wax.
  • the surfactant may be any suitable surfactant, for example an SMO (sorbutan mono oleate) or PIBSA (polyisobutylene succinic anhydride) based surfactant.
  • SMO sulfur-sorbutan mono oleate
  • PIBSA polyisobutylene succinic anhydride
  • the aqueous solution may include one or more compounds selected from a group of inorganic salts consisting of ammonium, alkali and alkaline earth metal nitrates, chlorates and perchlorates and a group of organic compounds consisting of organic nitrates, for example MMAN (monomethyl ammonium nitrate), and organic chlorides.
  • a group of inorganic salts consisting of ammonium, alkali and alkaline earth metal nitrates, chlorates and perchlorates
  • organic compounds consisting of organic nitrates, for example MMAN (monomethyl ammonium nitrate), and organic chlorides.
  • the aqueous solution may contain at least calcium nitrate.
  • the aqueous solution is a solution of calcium nitrate and a perchlorate salt, for example sodium perchlorate.
  • the sensitizing composition may contain the following components in the following concentration ranges: (a) calcium nitrate: 40 - 80 % (m/m); (b) water: 15 - 45 % (m/m); and (c) the carrier emulsion and the surfactant: 4 - 20% (m/m).
  • the microspheres may be either solid, for example polystyrene spheres or beads of vermiculite, or hollow, for example gas filled micro-balloons of glass, plastic, a resinous material or a carbonaceous material.
  • the microspheres are isobutane filled plastic micro-balloons of the type manufactured by Akzo Nobel.
  • the microspheres may be present in the sensitizing composition in a range 0.5% - 10%. Preferably the range is 1% - 4% (m/m). More preferably 2% (m/m) of the sensitizing composition comprises microspheres.
  • the average diameter of the microspheres may be in a range 20-160 ⁇ m. Preferably the range is 60-80 ⁇ m.
  • the density of the sensitizer composition may be in a range 0.3 to 1.05 g/cc.
  • the sensitizing composition may include a chemical gassing agent, for example sodium nitrite, to provide gas bubbles in the composition which are functionally supplementary to the microspheres.
  • a chemical gassing agent for example sodium nitrite
  • the invention further provides a method of producing an explosive composition which includes the steps of:
  • explosive composition is used hereinafter to refer to a composition which has been diluted to within a density range of 0.4 - 1.35 g/cc, and thus is sensitized to detonate when initiated, either by booster or cap initiation.
  • the base emulsion may have a density above 1.28 g/cc.
  • the mass ratio of base emulsion to sensitizing composition is 80:20.
  • the organic fuel of the base emulsion and the organic fuel of the sensitizing composition may be the same.
  • the inorganic oxidizer salt solution of the base emulsion includes ammonium nitrate (AN) whilst the aqueous solution of the sensitizing composition includes at least one salt or compound from the following: an ammonium, alkali or alkali earth metal nitrate, chlorate or perchlorate, an organic nitrate and an organic chloride.
  • AN ammonium nitrate
  • the aqueous solution of the sensitizing composition includes at least one salt or compound from the following: an ammonium, alkali or alkali earth metal nitrate, chlorate or perchlorate, an organic nitrate and an organic chloride.
  • the aqueous solution includes calcium nitrate.
  • AN may be excluded from the aqueous solution to render the solution thermodynamically stable relatively to the base emulsion.
  • an explosive mixture 10 is produced from the combination of a base emulsion 12 and a sensitizing composition 14 which is in accordance with the present invention.
  • the base emulsion 12 can be any inorganic oxidizer salt solution 16 and organic fuel 18 combination, with a density in a range 1.3 to 1.4 g/cc, emulsified with a suitable emulsifier 20.
  • the sensitizing composition 14 comprises a carrier emulsion 22 of a fuel phase 24 and an aqueous phase 26 to which is added the plastic or glass micro-balloons 28.
  • the fuel phase 24 is a mixture of an organic hydrocarbon fuel 30, for example a mineral oil, and surfactant 32 such as PIBSA and/or SMO.
  • the aqueous phase 26 is an aqueous solution of calcium nitrate.
  • another oxidizer salt for example sodium perchlorate, can be included in the aqueous solution.
  • the sensitizing composition 14 contains the following components in the following concentrations: (a) calcium nitrate: 64 % (m/m); (b) water: 20 % (m/m); (c) the fuel phase: 14 % (m/m); and (d) micro-balloons: 2% (m/m).
  • the sensitizing composition 14 is mixed with the base emulsion 12, in situ, in the mass ratio (sensitizing composition to base emulsion) of 20:80, to produce the explosive mixture which has a density within the range 0.9 to 1.1 g/cc.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Air Bags (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Paints Or Removers (AREA)

Description

    BACKGROUND OF THE INVENTION
  • This invention relates generally to a sensitizing composition for use with slurry and emulsion explosives (hereinafter collectively referred to as explosives) to provide sensitization through density reduction.
  • The term "base emulsion" is used to refer to a water-in-oil emulsion comprising an inorganic oxidizer salt solution, for example ammonium nitrate, as a discontinuous phase and an organic fuel as a continuous phase.
  • A base emulsion component of an emulsion explosive typically has a density in a range 1.3 to 14 g/cc. At these densities, the base emulsion is not "cap sensitive" i.e. it is too dense, and therefore too insensitive, to be detonated to explode by the initiating shock produced by a blasting cap.
  • To sensitize the base emulsion, to a cap sensitive composition, a density reducing agent is added to reduce the density typically to within a range 0.9 to 1.1 g/cc.
  • A density reducing agent may be chemical agent for example sodium nitrite, which chemically reacts with the base emulsion to produce density reducing gas bubbles, it may be a mechanical agent, such as a hollow or solid microsphere, or it may be a combination of a chemical and a mechanical agent.
  • An example of the microspheres used in a density reducing context is isobutane plastic enclosed micro-balloons, each with a particle diameter in a range 10-150 µm.
  • Microspheres provide an advantage, over gas bubbles created by a chemical agent, in that they do not coalesce to reduce the sensitivity of the emulsion, and their density reducing effect can be more accurately predicted due to their relatively regular unit dimensions. However this advantage is somewhat mitigated by handling difficulties, due to their small particulate size. Consequently, the microspheres easily can become airborne, creating a dust problem, exacerbated in an underground location, and a respiratory irritant.
  • The invention at least partially addresses the aforementioned problems.
    • SUMMARY OF INVENTION
  • The terms "surfactant" and "emulsifier" (hereinafter the terms are used interchangeably) are used to describe an organic compound that exhibits an amphiphilic characteristic, meaning it has both hydrophobic and hydrophilic properties, which enables a surfactant compound to interface between a hydrophobic organic compound and an aqueous solution to form an emulsion.
  • The invention provides the use of a sensitizing composition to sensitize a base emulsion which includes a carrier emulsion, of a liquid non-polar organic fuel, a surfactant and an aqueous solution, and a plurality of microspheres suspended in the carrier emulsion. Sensitizing compositions using gassing agents are known from WO 2008/026124 and WO 89/02881 .
  • The organic fuel may a mineral oil, a vegetable oil or a wax.
  • The surfactant may be any suitable surfactant, for example an SMO (sorbutan mono oleate) or PIBSA (polyisobutylene succinic anhydride) based surfactant.
  • The aqueous solution may include one or more compounds selected from a group of inorganic salts consisting of ammonium, alkali and alkaline earth metal nitrates, chlorates and perchlorates and a group of organic compounds consisting of organic nitrates, for example MMAN (monomethyl ammonium nitrate), and organic chlorides.
  • The aqueous solution may contain at least calcium nitrate. Preferably the aqueous solution is a solution of calcium nitrate and a perchlorate salt, for example sodium perchlorate.
  • The sensitizing composition may contain the following components in the following concentration ranges:
    (a) calcium nitrate: 40 - 80 % (m/m);
    (b) water: 15 - 45 % (m/m); and
    (c) the carrier emulsion and the surfactant: 4 - 20% (m/m).
  • The microspheres may be either solid, for example polystyrene spheres or beads of vermiculite, or hollow, for example gas filled micro-balloons of glass, plastic, a resinous material or a carbonaceous material. Preferably, the microspheres are isobutane filled plastic micro-balloons of the type manufactured by Akzo Nobel.
  • The microspheres may be present in the sensitizing composition in a range 0.5% - 10%. Preferably the range is 1% - 4% (m/m). More preferably 2% (m/m) of the sensitizing composition comprises microspheres.
  • The average diameter of the microspheres may be in a range 20-160µm. Preferably the range is 60-80µm.
  • The density of the sensitizer composition may be in a range 0.3 to 1.05 g/cc.
  • Optionally, the sensitizing composition may include a chemical gassing agent, for example sodium nitrite, to provide gas bubbles in the composition which are functionally supplementary to the microspheres.
  • The invention further provides a method of producing an explosive composition which includes the steps of:
    1. (a) providing a base emulsion;
    2. (b) providing a sensitizing composition which includes a carrier emulsion, of a liquid non-polar organic fuel, a surfactant and an aqueous solution, and a plurality of microspheres suspended in the carrier emulsion; and
    3. (c) mixing the base emulsion with the sensitizing composition in a respective mass ratio in the range 90:10 to 50:50 to form the explosive composition.
  • The term "explosive composition" is used hereinafter to refer to a composition which has been diluted to within a density range of 0.4 - 1.35 g/cc, and thus is sensitized to detonate when initiated, either by booster or cap initiation.
  • The base emulsion may have a density above 1.28 g/cc.
  • Preferably, the mass ratio of base emulsion to sensitizing composition is 80:20.
  • The organic fuel of the base emulsion and the organic fuel of the sensitizing composition may be the same.
  • Preferably, the inorganic oxidizer salt solution of the base emulsion includes ammonium nitrate (AN) whilst the aqueous solution of the sensitizing composition includes at least one salt or compound from the following: an ammonium, alkali or alkali earth metal nitrate, chlorate or perchlorate, an organic nitrate and an organic chloride.
  • Preferably the aqueous solution includes calcium nitrate. AN may be excluded from the aqueous solution to render the solution thermodynamically stable relatively to the base emulsion.
    • BRIEF DESCRIPTION OF THE DRAWING
  • The invention is further described by way of example with reference to the accompanying drawing which schematically illustrates the process steps in the production of an explosive mixture from the combination of a base emulsion and a sensitizing composition which is in accordance with the present invention.
    • DESCRIPTION OF PREFERRED EMBODIMENT
  • With reference to. Figure 1, an explosive mixture 10 is produced from the combination of a base emulsion 12 and a sensitizing composition 14 which is in accordance with the present invention.
  • The base emulsion 12, as hereinabove generally defined, can be any inorganic oxidizer salt solution 16 and organic fuel 18 combination, with a density in a range 1.3 to 1.4 g/cc, emulsified with a suitable emulsifier 20.
  • The sensitizing composition 14 comprises a carrier emulsion 22 of a fuel phase 24 and an aqueous phase 26 to which is added the plastic or glass micro-balloons 28.
  • The fuel phase 24 is a mixture of an organic hydrocarbon fuel 30, for example a mineral oil, and surfactant 32 such as PIBSA and/or SMO.
  • The aqueous phase 26 is an aqueous solution of calcium nitrate. Optionally, another oxidizer salt for example sodium perchlorate, can be included in the aqueous solution.
  • The sensitizing composition 14 contains the following components in the following concentrations:
    (a) calcium nitrate: 64 % (m/m);
    (b) water: 20 % (m/m);
    (c) the fuel phase: 14 % (m/m); and
    (d) micro-balloons: 2% (m/m).
  • The sensitizing composition 14 is mixed with the base emulsion 12, in situ, in the mass ratio (sensitizing composition to base emulsion) of 20:80, to produce the explosive mixture which has a density within the range 0.9 to 1.1 g/cc.

Claims (14)

  1. Use of a composition in the form of an emulsion containing the following components in the following concentration ranges (a) calcium nitrate: 40 - 80 % (m/m); (b) waster: 15 - 45 % (m/m); (c) a liquid non-polar organic fuel and a surfactant: 4 - 20% (m/m); (d) microspheres: 0,5-10% (m/m);
    (a) and (b) being present as an aqueous solution and having a densitiy in a range 0.3 to 1.05 g/cc as a sensitizing composition to sensitize a base emulsion comprising a water-in-oil emulsion comprising an inorganic oxidizer salt solution as a discontinous phase and an organic fuel as a continous phase.
  2. Use according to claim 1, wherein the organic fuel is a mineral oil, a vegetable oil or a wax.
  3. Use according to claim 1 or 2, wherein the surfactant is a sorbitan mono oleate (SMO) or polyisobutylene succinic anhydride (PIBSA) based surfactant.
  4. Use according to any one of claims 1 to 3 wherein the aqueous solution includes, in addition to calcium nitrate, one or more compounds selected from a group of inorganic salts consisting of ammonium, alkali and alkaline earth metal nitrates, chlorates and perchlorates and a group of organic compounds consisting of organic nitrates and organic chlorides.
  5. Use according to claim 4, wherein the aqueous solution includes a solution of calcium nitrate and a perchlorate salt.
  6. Use according to any one of claims 1 to 5, wherein the microspheres are either solid or hollow.
  7. Use according to claim 6, wherein the solid microspheres are polystyrene spheres or beads of vermiculite.
  8. Use according to claim 6, wherein the hollow microspheres are gas-filled micro-balloons of glass, plastic, or a resinous or carbonaceous material.
  9. Use according to claim 8, wherein the microspheres are isobutane filled plastic micro-balloons.
  10. Use according to any one of claims 1 to 9, wherein the average diameter of the microspheres is in a range 20-160µm.
  11. A method of producing an explosive composition which includes the steps of:
    (a) providing a base emulsion;
    (b) providing a sensitizing composition according to anyone of claims 1 to 10; and
    (c) mixing the base emulsion with the sensitizing composition in a respective mass ratio in the range 90:10 to 50:50 to form the explosive composition.
  12. A method according to claim 11, wherein the base emulsion has a density above 1.28 g/cc.
  13. A method according to claim 11 or 12, wherein the mass ratio of base emulsion to sensitizing composition is 80:20.
  14. A method according to any of claims 11 to 13, wherein the base emulsion includes ammonium nitrate (AN) and the aqueous solution of the sensitizing composition includes calcium nitrate.
EP10801092.7A 2009-11-12 2010-10-21 Use of a sensitizing composition for an explosive Not-in-force EP2396288B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL10801092T PL2396288T3 (en) 2009-11-12 2010-10-21 Use of a sensitizing composition for an explosive

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ZA200907945 2009-11-12
PCT/ZA2010/000062 WO2011060455A1 (en) 2009-11-12 2010-10-21 A sensitizing composition for an explosive

Publications (2)

Publication Number Publication Date
EP2396288A1 EP2396288A1 (en) 2011-12-21
EP2396288B1 true EP2396288B1 (en) 2013-12-11

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EP (1) EP2396288B1 (en)
AU (1) AU2010319979A1 (en)
BR (1) BRPI1010269A2 (en)
CL (1) CL2011003032A1 (en)
MA (1) MA33151B1 (en)
PE (1) PE20121143A1 (en)
PL (1) PL2396288T3 (en)
RS (1) RS53094B (en)
WO (1) WO2011060455A1 (en)
ZA (1) ZA201201554B (en)

Families Citing this family (2)

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Publication number Priority date Publication date Assignee Title
CN102910992A (en) * 2012-10-24 2013-02-06 雅化集团三台化工有限公司 Process for physical sensitization of emulsion explosive by using resin microsphere
FR3021313B1 (en) * 2014-05-20 2016-06-17 Nitrates & Innovation EXPLOSIVE CARTRIDGE PRODUCT OBTAINED FROM MIXTURE OF EMULSION AND POLYSTYRENE BALLS

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2096590A (en) * 1981-03-23 1982-10-20 Ireco Chemicals Water-in-oil emulsion blasting agent

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1262973A (en) * 1969-04-01 1972-02-09 Atlas Chem Ind Blasting composition
US3773573A (en) * 1970-10-15 1973-11-20 Dow Chemical Co Explosive composition containing monocellular thermoplastic globules and method of preparing same
SE451196B (en) * 1985-12-23 1987-09-14 Nitro Nobel Ab PROCEDURE FOR PREPARING A TYPE OF WATER-IN-OIL EMULSION EXPLOSION AND AN OXIDATION COMPOSITION FOR USING THE PROCEDURE
WO1989002881A1 (en) * 1987-09-30 1989-04-06 Mining Services International Corporation Methods and compositions related to emulsified gassing agents for sensitizing explosive compositions
AU598162B2 (en) * 1987-11-18 1990-06-14 Dyno Nobel Asia Pacific Limited Binding additive for explosive compositions
ZW13990A1 (en) * 1989-09-05 1992-06-10 Ici Australia Operations Explosive composition
US5470407A (en) * 1993-05-25 1995-11-28 Nelson Brothers, Inc. Method of varying rate of detonation in an explosive composition
CA2163682A1 (en) * 1995-11-24 1997-05-25 Arun Kumar Chattopadhyay Microemulsion and oil soluble gassing system
US5670739A (en) * 1996-02-22 1997-09-23 Nelson Brothers, Inc. Two phase emulsion useful in explosive compositions
PE20080896A1 (en) * 2006-08-29 2008-08-21 African Explosives Ltd EXPLOSIVE SYSTEM THAT HAS A BASIC EMULSION AND A SENSITIZING SOLUTION

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2096590A (en) * 1981-03-23 1982-10-20 Ireco Chemicals Water-in-oil emulsion blasting agent

Also Published As

Publication number Publication date
PL2396288T3 (en) 2014-04-30
ZA201201554B (en) 2012-11-28
BRPI1010269A2 (en) 2018-02-27
CL2011003032A1 (en) 2012-07-06
AU2010319979A1 (en) 2011-10-13
WO2011060455A1 (en) 2011-05-19
PE20121143A1 (en) 2012-08-27
EP2396288A1 (en) 2011-12-21
RS53094B (en) 2014-06-30
MA33151B1 (en) 2012-03-01

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