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

Use of a sensitizing composition for an explosive Download PDF

Info

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
Authority
EP
European Patent Office
Prior art keywords
use according
microspheres
composition
emulsion
base emulsion
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.)
Not-in-force
Application number
EP10801092.7A
Other languages
German (de)
French (fr)
Other versions
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
Original Assignee
AEL Mining Services Ltd
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=43778196&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2396288(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by AEL Mining Services Ltd filed Critical AEL Mining Services Ltd
Priority to PL10801092T priority Critical patent/PL2396288T3/en
Publication of EP2396288A1 publication Critical patent/EP2396288A1/en
Application granted granted Critical
Publication of EP2396288B1 publication Critical patent/EP2396288B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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.

Landscapes

  • 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

Family

ID=43778196

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10801092.7A Not-in-force EP2396288B1 (en) 2009-11-12 2010-10-21 Use of a sensitizing composition for an explosive

Country Status (10)

Country Link
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)

* Cited by examiner, † Cited by third party
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
ZA201201554B (en) 2012-11-28
CL2011003032A1 (en) 2012-07-06
AU2010319979A1 (en) 2011-10-13
PE20121143A1 (en) 2012-08-27
RS53094B (en) 2014-06-30
MA33151B1 (en) 2012-03-01
PL2396288T3 (en) 2014-04-30
WO2011060455A1 (en) 2011-05-19
EP2396288A1 (en) 2011-12-21
BRPI1010269A2 (en) 2018-02-27

Similar Documents

Publication Publication Date Title
US4394198A (en) Water-in-oil emulsion explosive composition
US3456589A (en) High pressure explosive compositions and method using hollow glass spheres
JPS6214518B2 (en)
AU2015337861B2 (en) Explosive composition and method of delivery
CA1160052A (en) Low water emulsion explosive compositions optionally containing inert salts
AU2012286593A1 (en) Improved explosive composition
AU2017376827A1 (en) Explosives based on hydrogen peroxide and conventional oxidisers
EP2396288B1 (en) Use of a sensitizing composition for an explosive
US3985593A (en) Water gel explosives
IE841675L (en) Slurry explosives with high strength hollow spheres
US6027588A (en) Method of manufacture of emulsion explosives
US20200216369A1 (en) Explosive compositions with reduced fume
KR20080083920A (en) Water-in-oil emulsion explosive
AU2607688A (en) Methods and compositions related to emulsified gassing agents for sensitizing explosive compositions
EP0598115B1 (en) W/o emulsion explosive composition
AU2016217971A1 (en) Water-based explosive suspension
CA2032239C (en) Shock-resistant, low density emulsion explosive
AU9141801A (en) Blasting method for reducing nitrogen oxide fumes
CN104151115A (en) Easy-to-sensitize compound emulsifying agent and preparation method thereof
JPH1112075A (en) Water-in-oil type emulsion explosive composition
JP2009057258A (en) Ammonium nitrate oil explosive
JP4570218B2 (en) Water-in-oil emulsion explosive
JP3342711B2 (en) Explosive composition
EP4086237A1 (en) Composition for forming a hydrogen peroxide based emulsion explosive
WO2022233952A1 (en) Composition for forming an explosive comprising an emulsion of hydrogen peroxide and an oil type fuel

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20110916

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

17Q First examination report despatched

Effective date: 20120807

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20130503

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

INTG Intention to grant announced

Effective date: 20131022

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 644492

Country of ref document: AT

Kind code of ref document: T

Effective date: 20140115

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602010012447

Country of ref document: DE

Effective date: 20140206

REG Reference to a national code

Ref country code: NO

Ref legal event code: T2

Effective date: 20131211

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20131211

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 644492

Country of ref document: AT

Kind code of ref document: T

Effective date: 20131211

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131211

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131211

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131211

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131211

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131211

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131211

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140411

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131211

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131211

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131211

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140411

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131211

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131211

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131211

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602010012447

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131211

26N No opposition filed

Effective date: 20140912

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20140923

Year of fee payment: 5

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602010012447

Country of ref document: DE

Effective date: 20140912

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131211

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602010012447

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131211

Ref country code: LU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141021

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150501

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141031

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141031

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20150630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141021

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NO

Payment date: 20151005

Year of fee payment: 6

Ref country code: FI

Payment date: 20151019

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20151019

Year of fee payment: 6

Ref country code: RS

Payment date: 20151019

Year of fee payment: 6

Ref country code: SE

Payment date: 20151027

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131211

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20151021

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131211

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140312

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131211

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131211

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20151021

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20101021

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131211

REG Reference to a national code

Ref country code: NO

Ref legal event code: MMEP

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20161021

Ref country code: NO

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20161031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170515

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20161022

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20161021

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131211

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131211