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WO2013013272A1 - Composition explosive améliorée - Google Patents

Composition explosive améliorée Download PDF

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Publication number
WO2013013272A1
WO2013013272A1 PCT/AU2012/000890 AU2012000890W WO2013013272A1 WO 2013013272 A1 WO2013013272 A1 WO 2013013272A1 AU 2012000890 W AU2012000890 W AU 2012000890W WO 2013013272 A1 WO2013013272 A1 WO 2013013272A1
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WO
WIPO (PCT)
Prior art keywords
composition
sensitiser
gas
composition according
explosive
Prior art date
Application number
PCT/AU2012/000890
Other languages
English (en)
Inventor
Miguel ARAOS
Original Assignee
Cmte Development Limited
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
Priority claimed from AU2011903076A external-priority patent/AU2011903076A0/en
Application filed by Cmte Development Limited filed Critical Cmte Development Limited
Priority to CA2842822A priority Critical patent/CA2842822C/fr
Priority to AU2012286593A priority patent/AU2012286593B2/en
Publication of WO2013013272A1 publication Critical patent/WO2013013272A1/fr
Priority to ZA2014/01430A priority patent/ZA201401430B/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B43/00—Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00
    • 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

Definitions

  • the present invention relates to an improved explosive composition. More particularly, the invention relates to a peroxide-based explosive composition which provides several advantages over the prior art, such as a reduction in the production of toxic nitrogen oxides ( ⁇ ) in the after-blast fumes.
  • the invention has been developed primarily for use as a hydrogen peroxide-based explosive composition for use in mining applications and will be described hereinafter with reference to this application. However, it will be appreciated that the invention is not limited to this particular field of use.
  • AN ammonium nitrate
  • AN alkaline and/or alkaline earth nitrate salts
  • Most explosives of this type rely on the energetic reaction of nitrogen compounds incorporated within the explosive to provide the necessary explosive power.
  • AN which is a strong oxidiser, has been used as the base of commerci al explosives for at least the last 50-60 years.
  • Slurries can also be blended with ANFO depending on the characteristics of the ground being blasted.
  • Slurries also typical ly include solid sensitisers (aluminium and high explosives such as TNT, RDX, efc) to enable the slurry to detonate and to minimise misfires.
  • Watergels have similar compositions to slurries, however, crosslinkers can be added to enhance the water resistance of the product. Watergels can be aerated or gassed with bubbles chemically generated in situ or mixed with glass/plastic miaospheresto lower the density, improve sensitivity and change the levels of energy delivered to the ground being blasted.
  • Emulsions can also be blended with ANFO in different ratios
  • Watergels can be aerated, gassed with bubbles chemically generated in situ or mixed with glass plastic microspheres to lower the density, improve sensitivity velocity of detonation (VOD) and changethe levelsof energy delivered to theground being blasted.
  • VOD velocity of detonation
  • any explosive composition which can be substituted for an AN-based explosive is insensitive to misfires and is not desensitised by wet blast holes
  • any AN substitute is a sustainable raw material which has a relatively low carbon footprint, and which can be manufactured relatively easily and preferably near the actual mine site to minimise transport issues.
  • any AN substitute can be produoed on an as- needs basis to minimise the need for stockpiling and to increase safety.
  • any AN substitute can be used in slurry or in emulsion form so that existing equipment can be used, and when in slurry form or is emulsified such that the viscosity enables pumping without difficulty. It would also be ideal if there are no onerous regulatory requirements for such a substitute, thereby reducing administrative costs It would also be preferable for the explosive compostion to be cross linkable in- situXo increase viscosity down the blast hole. Despite of the advances on the types of composition that can be manufactured from ammonium nitrate, one of the disadvantages is that during the detonation NO x fumes can be generated, due to the presence of nitrogen compounds in the explosive composition (from nitrates).
  • HP hydrogen peroxide
  • Shanley US Patent No. 2,452,074
  • HP was mixed with glycerol and water, and initiated with a detonator.
  • US ⁇ 74 teaches that to achieve detonation the explosive compositions can only contain up to 52 wt% water.
  • I n 1962 a. patent was granted to Baker (US Patent No. 3,047,441) in which HP was mixed with a range of different combustibles (wood products, hulls, metals, etc). Mixtures of HP and gelforming materials (corn starch) were also disclosed. The mixtures were sensitive to detonation with No. 6 blasting caps, but no velocities of detonation (VOD) were disclosed.
  • VOD velocities of detonation
  • the present invention relates to an explosive which substantially avoids the release of unwanted ⁇ fumes upon detonation into the atmosphere surrounding the blasting ate.
  • a preferred objective of the present invention is to reduce and preferably eliminate nitrogen contaning ingredients from the explosive composition. It will be appreciated that with little or no nitrogen present in the explosive virtually no ⁇ is released into the atmosphere, or a substantially reduced amount.
  • the present invention relates to explosives for use in commercial, construction, agriculture, mining, and similar fields However, it will be appreciated that the invention could be utilised in other related fields.
  • the present invention provides an explosive composition comprising hydrogen peroxide and a sensitiser, where ' n the sensitiser comprises a compressible material and/or bubbles of gas.
  • the compressible material includes one or more gas-filled voids
  • the composition further includes other additives, such as fuel, water, stabilisers (either thickenersor emulsifiers), asdiscussed further below.
  • additives such as fuel, water, stabilisers (either thickenersor emulsifiers), asdiscussed further below.
  • the composition comprises no components which lead to the production of NOx in the after-blast fumes. However, in other embodiments components are added which result in minimal NOx in the after-blast fumes.
  • oxidiser salts or peroxide derivatives can be used with the invention, either as complete or partial replacements of HP.
  • Non-limiting examples include nitrates salts, perchlorates salts, sodium/potassium peroxide, etc.
  • the preferred concentration of HP in the composition of the invention is between about 25% to 85% by weight.
  • a concentrated HP solution can be sourced (70% w/w) and diluted down to 25% w/w for use in the composition.
  • the HP concentration in the composition is around 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85% (w/w).
  • the HP concentration in the composition is around between about 25 to 30, 30 to 35, 35 to 40, 40 to 45, 45 to 50, 50 to 55, 55 to 60, 60 to 65, 65 to 70, 70 to 75, 75 to 80, or 80 to 85 % (w/w).
  • the present invention relies on sensitisation of a hydrogen peroxide based composition to result in an explosive composition, and to control key factors such as explosive sensitivity, density, velocity of detonation (VOD) and the delivery of the energy.
  • Sensitisation of AN-based explosive compositions is known in the art. In particular, it is known to sensitise by the addition of solid materials, high explosives, and the addition of micro balloons and gas bubbles.
  • sensitisation of peroxide- based compositions is not commonly practiced in the art. Without wishing to be bound by theory, it is believed that because HP in high concentration may detonate as it is relatively unstable to impact or friction, explosive engineers have steered away from its use.
  • the explosive composition of the invention is adapted to retain the sensitiser in a substantially homogenous dispersion. It will be appreciated that a variety of techniques can be utilised to achieve this property, as discussed further below.
  • a minimum concentration of sensitiser is included into the composition to cause it to be explosive.
  • the sensitiser is included in a detonation-sensitive concentration or amount.
  • the sensitiser is also preferably maintained in a detonation-sensitive dispersiorVdistribution throughout the composition.
  • the final density of the composition is controlled into a preferred predetermined explosive range.
  • the final density is controlled with sensitiser to around 1.25 to 1.3 g/ml.
  • the density of the composition is formulated to be around 0.1 , 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 , 1.1 , 1.2, 1.3, or 1.4 g ml.
  • the final density of the composition is formulated to be between around 0.1 to 0.2, 0.2 to 0.3, 0.3 to 0.4, 0.4 to 0.5, 0.5 to 0.6, 0.6 to 0.7, 0.7 to 0.8, 0.8 to 0.9, 0.9 to 1.0, 1.0 to 1.1 , 1.1 to 1.2, 1.2 to 1.3, or 1.3 to 1.4 g/ml.
  • high density additives can specifically be included to increase the density, up to 1.6, 1.7, 1 ,8, 1.9 or 2.0 g/ml .
  • inventive explosive compositions taught herein are more cost effective compared to existing explosive compositions, and are capable of being produced in large quantities to meet the demand from the mining industry.
  • the explosive compositions of the invention utilise HP, which is a sustainably-produced raw material that has a relatively low carbon footprint compared to other types oxidisers used in the art.
  • HP which is a sustainably-produced raw material that has a relatively low carbon footprint compared to other types oxidisers used in the art.
  • the explosive compositions of the invention can also be formulated into slurry or emulsion form. It will also be appreciated that the inventive con ositions of the invention produce reduced amounts of NOx, and in preferred forms of the invention no NOx at all.
  • the explosive compositions of the present invention comprise a discontinuous gaseous component to sensitise the composition. Once the explosive is sensitised, it can be easily initiated by a primer, which as the skilled person will be aware is an explosive which generates a high detonation pressure which then initiates detonation of the sensitised explosive.
  • the gaseous component is incorporated into the compositions of the present invention as fine gas bubbles dispersed throughout the composition. Alternatively, hollow gas-filled compressible particles such as miCTp balloons, or porous particles, or mixtures thereof are included.
  • the discontinuous phase of fine gas bubbles may be incorporated into the compositions of the present invention by mechanical agitation, injection by bubbling the gas through the composition, or by in situ generation of the gas by chemical means.
  • Suitable chemicals for the in situ generation of gas bubbles include HP itself which can be decomposed with Mn salts, yeast, iodide salts, etc ; nitrogen-based compounds such as, for example, sodium nitrite, nitrosoamines such as, for example, N.N'dinitrosopentamethylenetetramine; boron-based compounds such as, for example, sodium borohydride; carbonates such as, for example, sodium carbonate
  • suitable hollow particles include small hollow microspheres of glass and resinous materials such as phenol-formaldehyde, polyvinyl idene chloride)/poly(acrylonitrile) copolymers and ureaformaldehyde -Examples of suitable hollow particles include Q-Cel, Cenospheres, Expancel , 3M , Extendospheres, etc. Exampl es of porous materi al s i ncl ude expanded minerals such as perlite, fly ash or hollow particles that
  • sufficient bubbles and/or hollow particles and/or porous particles are used in the compositions of the present invention to give an explosive composition having a density i n the range of from 0.1 to 1.4 g/cm 3 .
  • bubbles with a range of bubble sizes.
  • the bubbles often have diameters up to 2000 microns and average bubble diameters of less than 50 microns are also common.
  • suitable surfactants bubbles of smaller or larger diameters can be produced.
  • the mean gas bubble diameter in the discontinuous gas phase may be controlled, and bubbles of 50 to 200 microns are possible. It will be appreciated that the bubble size influences the overall density, and if low densities are required large gas bubbles are preferred.
  • the density range is preferably around 0.60 - 1.20 g/ml, and for watergels the density range is preferably between 0.2 - 1.2 g/ml.
  • the gas bubbles are preferably 10 - 100 times larger than the disperse phase droplets. The oily phase is likely to be in contact the gas bubble, whereas the oxidiser (or discontinuous phase) does not.
  • the introduction of gas bubbles can be provided by a variety of techniques, which are all applicable to the present invention.
  • the bubbles may be 'trapped' during the preparation of the explosive composition or by their formation through a chemical reaction.
  • a formulation which uses prota ' n in solution (albumin, collagen, soy protein, etc.) in order to favour the formation of bubbles and their stabilization is described.
  • US Patent No. 3,582,411 describes a watergel explosive formulation which contains a foaming agent of the guar gum type modified by hydroxy groups.
  • 3,678,140 a process for the incorporation of air by means of the use of protein solution is described, by passing the composition through a series of openings at pressures from 40 to 200 psi and simultaneously introducing air through eductors. Incorporation of gas bubbles by means of their generation as a result of a chemical reaction is also described in the following prior art (see for example US Patent No's. 3,706,607; 3,711,345; 3,713,919; 3,770,522; 3,790,415 and 3,886,010).
  • the compressible material is hollow microspheres such as glass or plastic micro balloons, which are suspended in the composition.
  • the microspheres / miCTo balloons contain gas such as pentane, eta
  • the compressible material is a cellular material, such as expanded polystyrene (EPS), polyurethane foam, cotton seeds, expanded pop corn, husks, eta
  • the compressible material is any low density material which has a specific gravity ⁇ 1.0 g cm 3
  • examples of glass balloons can be seen in US Patent No.'s 4,326 " ,900 and 3,447,978, and plastic micro balloons in US Patent No.'s 4,820,361 and 4,547,234.
  • balloons are typically 0.05 mm in diameter and have a bulk density of 100 g/L.
  • Use of expanded polystyrene can be seen for example in US Patent No.'s 5,470,407 and 5,271 ,779.
  • Other types of sensitising materials can be used in the compositions of the invention, eg. TNT, HMX, RDX and aluminium or silicon powder.
  • HP-based watergels can be prepared with either water-miscible or water immiscible fuels.
  • Water-soluble fuels which can be used with the present invention can be selected from the group consisting of: glycerol, sugar, amine nitrates, hexamine and urea
  • Water-insoluble fuels which can be used with the present invention can be selected from the group consisting of: include aliphatic, alicyclic and aromatic compounds and mixtures thereof which are in the liquid state at the formulation temperature.
  • Suitable organic fuels may be chosen from fuel oil, diesel oil, distillate, kerosene, naphtha, waxes, (eg.
  • Preferred organic fuels are liquid hydrocarbons generally referred to as petroleum distillates such as gasoline, kerosene, fuel oils, paraffin oils and vegetable oils or mixture thereof.
  • the water miscible or water-immiscible fuel of the watergel composition of the present invention comprises from 5 to 30% by weight and preferably 10 to 25% by weight of the total composition.
  • the fuel is included in a concentration of about 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50% (w/w).
  • the f uel is incl uded i n a concentration of between about 5 to 10, 10 to 15, 15 to 20, 20 to 25, 25 to 30, 30 to 35, 35 to 40, 40 to 45, or 45 to 50% (w/w).
  • bubbles of gas and materials enclosing gas have a relatively low density, they will tend to migrate towards the surface of the column of explosive if the viscoaty of the HP-based explosive composition is not capable of maintaining the sensitising material homogeneously dispersed throughout. Migration of the sensitising material towards the surface is undesirable as it may render the explosive too insensitive to initiation, and therefore the explosive composition may not deliver the energy and gases needed to break and move the rock as required or even worst, the explosive may undergo a misfire.
  • One way to ameliorate this issue is to formulate the explosive composition into a watergel. These types of compositions can be formulated with different levels of viscosity by using a thickener. Viscosities can be selected to generally retain the sensitising material in a homogeneously dispersed state throughout the composition.
  • the aqueous solution of the compositions of the present invention may comprise thickening agentswhich optionally may be crosslinked.
  • thickening agents when used in the compositions of the present invention, are suitably polymeric materials, especially gum materials typified by the galactomannan gums such as locust bean gum or xantham gum or guar gum or derivatives thereof such as hydroxypropyl guar gum.
  • gums are the so-called biopolymeric gums such as the heteropolysaccharides prepared by the microbial transformation of carbohydrate material, for example the treatment of glucose with a plant pathogen of the genus Xanthomonas typified by Xanthomonas campestris
  • Other useful thickening agents include synthetic polymeric materials and in particular synthetic polymeric materials which are derived, at least in part, from the monomer acrylamide.
  • the thickening agent component of the compositions of the present invention comprises from 0 to 5% by weight of the total composition.
  • the thickening agent when used in the compositions of the present invention, may be crosslinked. It is convenient for this purpose to use conventional crosslinking agents such as zinc chromate or a cBchromate either as a separate entity or as a component of a redox system such as, for example, a mixture of potassium dichromate and potassium antimony tartrate. Salts of Ca, Ti, Sb can also be used as crossl inkers Typically, the crosslinking agent component of the compositions of the present invention comprises from 0 to 0.5% and preferably from 0 to 0.1% by weight of the total composition.
  • conventional crosslinking agents such as zinc chromate or a cBchromate either as a separate entity or as a component of a redox system such as, for example, a mixture of potassium dichromate and potassium antimony tartrate. Salts of Ca, Ti, Sb can also be used as crossl inkers
  • the crosslinking agent component of the compositions of the present invention comprises from 0 to 0.5% and preferably from 0 to 0.
  • HP-based emulsions can be prepared with water-immiscible fuels
  • the water- immiscible organic phase component of the composition of the present invention comprises the continuous "oil" phase of the water-in-oil emula ' on and is the fuel.
  • Suitable organic fuels include aliphatic, alicyclic and aromatic compounds and mixtures thereof which are in the liquid state at the formulation. Suitable organic fuels may be chosen from fuel oil, diesel oil, distillate, kerosene, naphtha, waxes, (&g.
  • organic fuels are liquid hydrocarbons generally referred to as petroleum distillates such as gasoline, kerosene, fuel oils paraffin oils and vegetable oils or mixture thereof.
  • the organic fuel or continuous phase of the HP-based emulsion composition of the present invention comprises from 2 to 20% by weight and preferably 3 to % 20% by weight of the total composition.
  • the organic fuel is i ncl uded i n a concentration of about 2, 4, 6, 8, 10, 12, 14, 16, 18, or 20 % (w/w).
  • the organic fuel is i ncl uded i n a concentration of between about 2 to 4, 4 to 6, 6 to 8, 8 to 10, 10to 12, 12to 14, 14to 16, 16to 18, or 18to 20% (w/w).
  • Emulsifier/Stabiliser Emulsifier/Stabiliser
  • HP-based emulaon compositions are made of a discontinuous phase of oxidising material that isdispersed in a continuous phase of an organic fuel in the presence of one or more emulsifying agents.
  • the emulsifying agent is adapted or chosen to maintan phase separation.
  • the emulsifying agent component of the composition of the present invention may be chosen from the wide range of emulsifying agents known in the art for the preparation of water-in-oil emulsion explosive compositions.
  • emulsifying agents include polyisobutylene succinic anhydride (PIBSA) reacted with amines; other emulsifiers examples are alcohol alkoxylates, phenol alkoxylates, poly(oxyalkylene) glycols, poly(oxyalkylene) fatty acid esters, amine alkoxylates, fatty acid esters of sorbitol and glycerol, fatty acid salts, sorbitan esters, poly(oxyalkylene) sorbitan esters, fatty amine alkoxylates, poly(oxyalkylene) glycol esters, fatty acid amides, fatty acid amide alkoxylates, fatty amines, quaternary amines, alkyloxazoltnes, alkenyloxazolines
  • the preferred emulsifying agents are the 2-alkyl- and 2- alkenyl-4,4'-bis (hydroxymethyl oxazoline, the fatty acid esters of sorbitol, lecithin, copolymers of poly(oxyalkylene) glycols and poly(12-hydroxystearic acid), and mixtures thereof, and particularly sorbitan mono-oleate, sorbitan sesquioleate, 2-oleyl- 4,4'-bis (hydroxymethyl) oxazoline, mixture of sorbitan sesquioleate, lecithin and a copolymer of poly(oxyalkylene glycol and poly (12-hydroxystearic acid), and mixtures thereof.
  • the emulsifying agent component of the composition of the present invention comprises up to 5% by weight of the total composition. Higher proportions of the emulsifying agent may be used and may serve as a supplemental fuel for the composition but in general it is not necessary to add more than 5% by weight of emulsifying agent to achieve the desired effect.
  • One of the advantages of the compositions of the present invention is that stable emulsions can be formed using relatively low levels of emulsifying agent and for reasons of economy it is preferable to keep to amount of emulsifying agent used to the minimum required to have the desired effect.
  • the preferred level of emulsifying agent used is in the range from 0.1 to 2.0% by weight of the total composition.
  • secondary fuels may be incorporated into the compositions of the present invention in addition to the water-immiscible organic fuel phase.
  • secondary fuels include finely divided solids, and water-miscible organic liquids.
  • solid secondary fuels include finely divided materials such as: sulfur; aluminium; and carbonaceous materials such as gilsonite, comminuted coke or charcoal, carbon black, resin acids such as abietic acid, vegetable products such as starch, nut meal, grain meal and wood pulp.
  • the optional secondary fuel component of the compositions of the present invention comprise from 0 to 20% by weight of the total composition.
  • oxidisers can be used to partially replace HP in the HP compositions.
  • examples of such oxidisers are nitrate salts, perchlorate salts, sodium / potassium peroxide, etc.
  • the pH of the emulsion explosive compositions of the present invention is not narrowly critical. However, in general the pH is between 0 and 8 and preferably the pH is between 1 and 6, and may becontrolled by suitable addition of conventional additives, for example inorganic or organic acids and salts
  • HP-based compositions of the present invention may be prepared by a number of methods.
  • the HP-based watergel type compositions may be prepared by combining hydrogen peroxide with water miscible fuels and thickeners until the thickener starts increasing the viscosity of said composition. Once the watergel is formed, solid ingredients (fuels, energy diluting agents, etc) are optionally mixed into said watergel. Finally, sensitising agents are mixed into said watergel capable in an amount capable to sensitise said watergel.
  • the HP-based emulsion type compositions may be prepared by: combining hydrogen peroxide with said water- immiscible organic phase, awater-in-oil emulsifying agent, with rapid mixing to form a water-in-oil emulsion; then mixing until the emulsion is uniform. Once the emulsion is formed, solid ingredients (fuels, energy diluting agents, etc) are optionally mixed into said watergel. Finally, sensitising agents are mixed into said watergel in an amount capable of sensitising said watergel.
  • the viscosity of the HP-based compositions will be discussed in terms of apparent viscosity.
  • apparent viscosity refers to viscosity measure using a Brookfield RVT viscometer, #7 spindle at 50 r.p.m. It is preferred in the process of the present invention that the explosive composition of the water-in-oil emulsion exploave particles have an apparent viscosity greater than 10Pa * s (Pascal * second) prior to the entrainment of gas bubbles.
  • Apparent viscosity is more preferably in the range 10 to 50 Pa * & A more preferred viscosity range for the entrainment of gas bubbles by mechanical mixing is from 10 to 35Pa * s. The range 10 to 25Pa * s provides the most efficient entrainment of gas bubbles by mechanical mixing.
  • energy diluting agents are inert materials that have minimal contribution to the detonation prooess and can be used to replace part of the energetic material in the composition and therefore reduce the energy output of the hydrogen peroxide-based explosive. In some cases these energy diluting agents are able to reduce the density of the HP-based composition without increasing the sensitivity. Examples of these diluents materials are granulated/shredded rubber (from tyres), cotton seeds, saw dust, husk, expanded pop corn, plastic beads, wool meal, saw dust, bagasse, peanut and oat husks, peanut shells etc. US Patent No. 5,409,556 describes some example of these energy reducing agents.
  • the HP-based explosive compositions of the invention comprise the following components: HP:fuel:water in the range between 25%:5%:70% to 73%:11%:16%.
  • Table 1 lists the components of exploa ' ve systems discussed herein and provides typical ranges for each.
  • Table 1 components for explosive systems discussed herein with typical ranges for each. NOTE: it will be appreciated that the volume can be increased by 8x ( * ), and 3x( * * ), respectively.
  • the present invention provides a method of preparing an explosive composition comprising combining hydrogen peroxide and a sensitiser, wherein the sensitiser comprises a compressible material and/or bubbles of gas. It will also be appreciated that the invention relates to a method of preparing an explosive composition comprising combining hydrogen peroxide and one or more compounds which produce a sensitiser.
  • the present invention provides use of an explosive • composition comprising hydrogen peroxide and a sensitiser, wherein the sensitiser comprises a compressible material and/or bubbles of gas.
  • the composition of the invention can be used for many purposes, but in particular to break and move ground i n mi ni ng operations.
  • the present invention provides a sensitised explosive composition comprising hydrogen peroxide and compressible material and/or bubbles of gas.
  • the present invention consists essentially of hydrogen peroxide and a sensitiser, wherein the sensitiser comprises a compressible material and/or bubbles of gas.
  • the present invention consists essentially of hydrogen peroxide, a sensitiser, a thickener and/or crosslinker, wherein the sensitiser comprises a compressible material and/or bubbles of gas.
  • the present invention consists essentially of hydrogen peroxide, asensitiser, fuel, athickener and/or crosslinker, wherein the sensitiser comprises a compressible material and/or bubbles of gas.
  • the present invention consists essentially of hydrogen peroxide, a sensitiser, fuel, surfactant/emulsifier, a thickener and/or crosslinker, wherein the sensitiser comprises a compressible material and or bubbles of gas.
  • Figure 1 is a schematic outlining the preparation of a HP-based watergel explosive composition according to the invention.
  • Figure 2 is a schematic outlining the preparation of a HP-based water-in-oil emulsion explosive composition according to the invention.
  • the terms 'a' , 'an' and 'the' mean One or more' , unless expressly specified otherwise.
  • One or more embodiments' and 'one embodiment' mean 'one or more (but not necessarily all) embodiments of the present invention(s)' unless expressly specif ied otherwise.
  • the term "sensitiser” is meant to define voids that can increase the sensitivity to detonation of energetic materials. [Examples are air bubbles, entrapping air, and material like micro balloons/spheres.
  • the present invention relates to a peroxide-based explosive composition that is preferably prepared as watergel or water-in-oil emulsion, and is sensitised. Typical components for each type of explosive technology are listed in Table 2.
  • Table 2 Typical conponents of the present invention for each type of explosive technology.
  • Watergel explosive compositions made according to the present invention preferably include HP in concentrations between 25 - 64% by weight.
  • oxidisers can be combined with HP, as discussed above
  • HP nitrate salts, perchlorate salts, amine nitrates; sodium potassium peroxide, etc.
  • nitrate salts, perchlorate salts, amine nitrates; sodium potassium peroxide, etc. can be also incorporated in combination with HP.
  • the fuel may be a product of vegetable origin, such as sugars or molasses, alcohols, organic acids, ethers, esters, urea, hexamines,etc.
  • the fuel may be a product derived from crude oil such adiesel, paraffrnic oilsor mineral oil, etc.
  • Other fuels may bea ' lioone oils, eta
  • Secondary fuels may be a solid hydrocarbon, such as coal and recycled plastic waste. It may also be a metallic fuel, such as aluminium / silicon, etc, or gilsonite, comminuted coke or charcoal, carbon black, resin acids such as abietic acid, vegetable products such as starch, nut ' meal, gran meal and wood pulp; or nitrogen compounds such as amides, amines, eta
  • the amount of these fuels materials in the formulation can be adjusted so the HP-based composition has an oxygen balance between 3 and -10 and the HP- based composition can be easily pumped.
  • the preferred fuels are glycerol, sugar, syrup, alcohol, carbon, ground coal, waxes, oils such as corn, cottonseed, olive, peanut, or fatty acid oils
  • an HP-based composition in accordance with the invention it is important that gas bubbles are homogeneously distributed throughout the composition. It is also important that once distributed throughout, the gas bubbles should be maintained in a homogenous distribution throughout the composition , /.a little or no segregation or settling. In accordance with the present invention this may be achieved by formulating the explosive as a stable watergel. Formation of such forms of compositions is conventional in the art and one skilled in the art will be familiar with the various formsthat may be produced. Typically this will involve the use of a thickener that acts on the liquid oxidant component of the composition.
  • thickener is also intended to include gelling agents, crossl inking agents, and the like
  • any conventional thickening agent may be used with the present invention.
  • the thickener may be selected from natural gums, such guar gum, xanthan gum, sodium alginate, carboxymethylcellullose, methylcellulose and the like. Synthetic thickeners, such polyacrylamide, may also be used. Inorganic thickeners, such as fumed silica, clays and car bosi I, may also be used, or a combination thereof.
  • Crosslinkers can also used with the present invention. Thickening agents in combination with crosslinkers can improve the water resistance and mechanical strength of the HP-based explosive. Examples of crosslinkers are those from antimony, calcium, titanium, chromium, borate salts and dichromate salts, etc.
  • Water-in-oil explosive compositions made according to the present invention include hydrogen peroxide in concentration between 25 - 85% by weight. It will also be appreciated that other oxidisers can be combined with HP, as discussed abova For example nitrate salts, perchlorate salts, amine nitrates, sodium / potassium peroxide, etc., can be also incorporated in combination with HP.
  • the fuel can be any fuel such as diesel fuel. Alternatively it can be paraffinic, mineral, olefinic, naphtenic, animal, vegetable, fish and silicone oils Other types of fuels are benzene, toluene, xylenes, asphaltic materials and the likes.
  • Secondary fuels may be a solid hydrocarbon, such as coal and recycled plastic waste,. It may also be a metallic fuel, such as aluminium / s ' lioon, etc, or gilsonite, comminuted coke or charcoal, carbon black, resin acids such as abietic acid, vegetable products such as starch, nut meal, grain meal and wood pulp; or nitrogen compounds such as amides, amines, etc
  • the amount of these fuels materials in the formulation can be adjusted so the HP-based composition has an oxygen balance between 3 and -10 and the HP- based composition can be easily pumped..
  • water-in-oil explosive compositions as the watergel explosive compositions discussed above, namely preferably the gas bubbles are homogeneously distributed throughout the composition.
  • this is achieved by formulating the exploave as a stable water-in-oil emulsion. Formation of emulsified explosives is conventional in the art and one skilled in the art will be familiar with the various forms may be produced. Typically this will involve the use of an emulsif ier, which is adapted to keep the oxidiser dispersed throughout the conti nuous organic phase (fuel).
  • Emulsif iers commonly used in emulsion exploave compositions include sorbitan mono oleate, sorbitan sesquioleate, poly isobutylene succinic anhydrides (PIBSA) and amino derivatives of BSA, ⁇ -lactone and its amino derivatives, fatty acid salts, lecithin, etc.
  • PIBSA poly isobutylene succinic anhydrides
  • sensitising agents include gas bubbles generated in a ' tu or injected a ' r or air/gas entrapped material.
  • sensitising agents include gas bubbles generated in a ' tu or injected a ' r or air/gas entrapped material.
  • a further example of sena ' tisation for hydrogen peroxide-based exploa ' ves is the decomposition in situ of a portion of the hydrogen peroxide with permanganates (or other ions) to form oxygen gas bubbles.
  • Another example to produce gas bubbles is the decomposition of carbonates with acid in situ to form carbon dioxide bubbles.
  • Examples of air entrapped material for sensitisation for hydrogen peroxide-based explosives are glass or plastic mi crobal loons, expanded polystyrene beads, polyurethane foam, etc, as discussed above.
  • Another example of sensitisation is the combination of both gas bubbles (chemically generated and or injected) and air entrapped material.
  • Watergel or water-in-oil HP-based explosive compositions made according to the present invention include sensitisers in concentration between 1 - 800% by volume, (i.e. the volume can be increased by 8x).
  • diluting agents could be used to replace part of the mass of the HP-based composition and thus reduce the energy output. These energy- diluting agents may increase, decrease or not alter the density of the HP-based composition.
  • energy-diluting energy agents are granulated shredded rubber (from tyres), plastic beads, cotton seeds, saw dust, husk, expanded pop corn, plastic beads, wool meal, saw dust, bagasse, peanut and oat husks, peanut shells etc.
  • These diluents material could also be used in combination with sena ' tia ' ng agents to offer more flexibility as far as the performance properties of the HP-based exploave is concerned. Therefore another advantage of the HP-based exploave is that the performance properties of the exploave can be altered to suit the characteristics of the blasting site.
  • Watergel or water-in-oil HP-based explosive compositions made according to the present invention include energy-diluting agents in concentration between 0 - 800% by voluma
  • the use of the additives provides a better control of the density, VOD and energy delivery in the ground being blasted. Therefore an additional advantage of the HP-based explosve is that it could be used i n a range of density between 0.1 g/ml to 1.40 g ml .
  • compositions (weight percent)
  • Table 3 Explosive compositions prepared according to the invention.
  • P3000 isan emulsifier manufactured by Croda chemicals. Detonation testing
  • composition 2 had a density after entrapping air of 0.89 g/ml. A 0.1% by weight (or 25% by volume) of expanded polystyrene, density 4 g L, was mixed into the composition, producing a final density of 0.55 g/ml.
  • composition 3 was mixed with 3.75% of glass micro balloons (GMB) (or 37.5% by volume) from 3M, density 100 g/L.
  • GMB glass micro balloons
  • sample 6 was initiated with a detonator and with a 50 g booster (see Table 5).

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Abstract

L'invention concerne une composition explosive comprenant du peroxyde d'hydrogène et un sensibilisateur, le sensibilisateur comprenant un matériau compressible ayant au moins une cavité remplie de gaz et/ou des bulles de gaz. Le sensibilisateur est compris dans une concentration sensible à la détonation et la composition explosive est de préférence adaptée pour retenir le sensibilisateur dans une dispersion pratiquement homogène. L'invention concerne également un procédé de préparation d'une composition explosive consistant à mélanger du peroxyde d'hydrogène et un sensibilisateur, le sensibilisateur comprenant un matériau compressible et/ou des bulles de gaz, et l'utilisation de ladite composition explosive.
PCT/AU2012/000890 2011-07-27 2012-07-27 Composition explosive améliorée WO2013013272A1 (fr)

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CA2842822A CA2842822C (fr) 2011-07-27 2012-07-27 Composition explosive amelioree renfermant du peroxyde d'hydrogene et unagent sensibilisant
AU2012286593A AU2012286593B2 (en) 2011-07-27 2012-07-27 Improved explosive composition
ZA2014/01430A ZA201401430B (en) 2011-07-27 2014-02-25 Improved explosive composition

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AU2011903076A AU2011903076A0 (en) 2011-07-27 Nitrogen-free explosive composition for blasting

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Cited By (11)

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CN103553852A (zh) * 2013-10-25 2014-02-05 湖北同一石油化工有限公司 一种乳化炸药用乳化剂及其制备方法
WO2016010783A1 (fr) * 2014-07-18 2016-01-21 Senules Jeffrey S Explosif en émulsion infusé de gaz noble
WO2018107213A1 (fr) * 2016-12-12 2018-06-21 Cmte Development Limited Composition explosive améliorée
CN108358733A (zh) * 2018-03-14 2018-08-03 安徽理工大学 一种热膨胀中空微球包覆含能添加剂的方法
US10138720B2 (en) 2017-03-17 2018-11-27 Energy Technology Group Method and system for perforating and fragmenting sediments using blasting material
WO2020085986A1 (fr) * 2018-10-25 2020-04-30 Ab Etken Teknologi Composition explosive sensibilisée, sans danger pour la fabrication et respectueuse de l'environnement
CN114206811A (zh) * 2019-06-07 2022-03-18 Cmte发展有限公司 具有改进的睡眠时间的基于过氧化氢的爆炸物
US11427515B2 (en) 2018-01-29 2022-08-30 Dyno Nobel Inc. Mechanically-gassed emulsion explosives and methods related thereto
EP4086236A1 (fr) 2021-05-05 2022-11-09 Hypex Bio Explosives Technology AB Composition sensibilisante pour émulsions énergétiques de peroxyde d'hydrogène
EP4086237A1 (fr) 2021-05-05 2022-11-09 Hypex Bio Explosives Technology AB Composition de formation d'un explosif en émulsion à base de peroxyde d'hydrogène
EP4086238A1 (fr) 2021-05-05 2022-11-09 Hypex Bio Explosives Technology AB Composition pour former un explosif comprenant une émulsion de peroxyde d'hydrogène et un combustible de type huileux

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WO2008083436A1 (fr) * 2007-01-10 2008-07-17 Newcastle Innovation Limited Procédé de gazage d'explosifs, en particulier à basse température

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US3047441A (en) * 1946-04-08 1962-07-31 American Cyanamid Co Hydrogen peroxide explosives
US4081299A (en) * 1977-02-14 1978-03-28 Imc Chemical Group, Inc. Aqueous explosive slurrie with inorganic peroxide sensitizer
WO2008083436A1 (fr) * 2007-01-10 2008-07-17 Newcastle Innovation Limited Procédé de gazage d'explosifs, en particulier à basse température

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103553852A (zh) * 2013-10-25 2014-02-05 湖北同一石油化工有限公司 一种乳化炸药用乳化剂及其制备方法
WO2016010783A1 (fr) * 2014-07-18 2016-01-21 Senules Jeffrey S Explosif en émulsion infusé de gaz noble
US10494312B2 (en) 2014-07-18 2019-12-03 Jeffrey S. Senules Noble gas infused emulsion explosive
WO2018107213A1 (fr) * 2016-12-12 2018-06-21 Cmte Development Limited Composition explosive améliorée
CN110267929A (zh) * 2016-12-12 2019-09-20 Cmte发展有限公司 改进的爆炸组合物
US10138720B2 (en) 2017-03-17 2018-11-27 Energy Technology Group Method and system for perforating and fragmenting sediments using blasting material
US11143007B2 (en) 2017-03-17 2021-10-12 Energy Technologies Group, Llc Method and systems for perforating and fragmenting sediments using blasting material
US11427515B2 (en) 2018-01-29 2022-08-30 Dyno Nobel Inc. Mechanically-gassed emulsion explosives and methods related thereto
CN108358733A (zh) * 2018-03-14 2018-08-03 安徽理工大学 一种热膨胀中空微球包覆含能添加剂的方法
CN108358733B (zh) * 2018-03-14 2020-07-03 安徽理工大学 一种热膨胀中空微球包覆含能添加剂的方法
AU2019365614B2 (en) * 2018-10-25 2022-10-27 Ab Etken Teknologi A sensitised, safe to manufacture and environmentally friendly explosive composition
WO2020085986A1 (fr) * 2018-10-25 2020-04-30 Ab Etken Teknologi Composition explosive sensibilisée, sans danger pour la fabrication et respectueuse de l'environnement
CN114206811A (zh) * 2019-06-07 2022-03-18 Cmte发展有限公司 具有改进的睡眠时间的基于过氧化氢的爆炸物
EP4086236A1 (fr) 2021-05-05 2022-11-09 Hypex Bio Explosives Technology AB Composition sensibilisante pour émulsions énergétiques de peroxyde d'hydrogène
EP4086237A1 (fr) 2021-05-05 2022-11-09 Hypex Bio Explosives Technology AB Composition de formation d'un explosif en émulsion à base de peroxyde d'hydrogène
EP4086238A1 (fr) 2021-05-05 2022-11-09 Hypex Bio Explosives Technology AB Composition pour former un explosif comprenant une émulsion de peroxyde d'hydrogène et un combustible de type huileux
WO2022233948A1 (fr) 2021-05-05 2022-11-10 Hypex Bio Explosives Technology Ab Composition de formation d'un explosif à émulsion à base de peroxyde d'hydrogène
WO2022233955A1 (fr) 2021-05-05 2022-11-10 Hypex Bio Explosives Technology Ab Composition sensibilisante pour émulsions de peroxyde d'hydrogène énergétiques
WO2022233952A1 (fr) 2021-05-05 2022-11-10 Hypex Bio Explosives Technology Ab Composition de formation d'un explosif comprenant une émulsion de peroxyde d'hydrogène et un carburant de type huile
US20240239722A1 (en) * 2021-05-05 2024-07-18 Hypex Bio Explosives Technology Ab Composition for forming an explosive comprising an emulsion of hydrogen peroxide and an oil type fuel
US20240239720A1 (en) * 2021-05-05 2024-07-18 Hypex Bio Explosives Technology Ab Sensitizing composition for energetic hydrogen peroxide emulsions

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CA2842822A1 (fr) 2013-01-31
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ZA201401430B (en) 2015-10-28
AU2012286593B2 (en) 2017-07-27

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