EP4086237B1 - Composition de formation d'un explosif en émulsion à base de peroxyde d'hydrogène - Google Patents

Composition de formation d'un explosif en émulsion à base de peroxyde d'hydrogène

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Publication number
EP4086237B1
EP4086237B1 EP21172313.5A EP21172313A EP4086237B1 EP 4086237 B1 EP4086237 B1 EP 4086237B1 EP 21172313 A EP21172313 A EP 21172313A EP 4086237 B1 EP4086237 B1 EP 4086237B1
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EP
European Patent Office
Prior art keywords
phase
composition
oils
fuel
emulsion
Prior art date
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EP21172313.5A
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German (de)
English (en)
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EP4086237A1 (fr
EP4086237C0 (fr
Inventor
Thomas GUSTAVSSON
Robert HAKLAND
Stefan Nilsson
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Hypex Bio Explosives Technology AB
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Hypex Bio Explosives Technology AB
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Priority to EP21172313.5A priority Critical patent/EP4086237B1/fr
Application filed by Hypex Bio Explosives Technology AB filed Critical Hypex Bio Explosives Technology AB
Priority to CA3217755A priority patent/CA3217755A1/fr
Priority to US18/289,140 priority patent/US20240217892A1/en
Priority to EP22727840.5A priority patent/EP4334269A1/fr
Priority to PE2023003005A priority patent/PE20242121A1/es
Priority to PCT/EP2022/062007 priority patent/WO2022233948A1/fr
Priority to AU2022268594A priority patent/AU2022268594A1/en
Publication of EP4086237A1 publication Critical patent/EP4086237A1/fr
Priority to CL2023003266A priority patent/CL2023003266A1/es
Priority to ZA2023/11166A priority patent/ZA202311166B/en
Application granted granted Critical
Publication of EP4086237B1 publication Critical patent/EP4086237B1/fr
Publication of EP4086237C0 publication Critical patent/EP4086237C0/fr
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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
    • C06B23/006—Stabilisers (e.g. thermal stabilisers)

Definitions

  • the present invention relates to a composition for forming an emulsion type hydrogen peroxide-based explosive.
  • the invention also relates to a method of preparing such a composition.
  • the composition may be used e.g. in mining, construction and similar applications for rock blasting. However, it will be appreciated that the invention is not limited to this particular field of use.
  • Emulsion explosives are normally water-in-oil type dispersions consisting of a discontinuous aqueous oxidizer phase normally consisting of nitrate salts dissolved in water and a continuous fuel phase consisting of various water insoluble fuels (normally oils) and emulsifiers. The two phases are combined in a continuous or batch mixing process which normally implements pressurized high shear mixing.
  • AN Ammonium nitrate
  • HP Hydrogen peroxide
  • HP is known to be a suitable candidate and prior art research proposes various explosive compositions.
  • HP is nitrate free and decomposes to water and oxygen in the detonation process.
  • the oxidizing properties of HP can also be used as a replacement for traditional nitrate salt oxidizers.
  • the idea of using HP is not new; Baker & Groves where granted a patent for an HP based explosive composition ( US7491279B1 ) and another was granted to Bouillet et. al in 1990 (US4942800A ).
  • the use of the term HP denotes hydrogen peroxide in combination with water in various concentrations combined with known hydrogen peroxide stabilizers such as phosphonic acid.
  • HP is normally solved in water and is normally supplied with phosphonate acids or similar compounds as the stabilizing effects on HP are well known.
  • US patent 8802613B2 (Bonislawski, Lovetro) from 2007 gives an example of the stabilizing characteristics of various phosphonic acids and other compounds when added into the HP solution.
  • HP solutions with varying concentration of such stabilizers are readily available which implies that the HP stabilizer, i.e. phosphonic acid is de-facto added to the explosive via the HP solution.
  • emulsion compositions Another problematic aspect of the emulsion compositions is the process of sensitization. Test show that addition of glass hollow spheres (micro balloons) used as sensitizer for emulsion explosives, tend to quickly destabilize and separate these emulsions. If hydrogen peroxide decomposition catalysts are used as sensitizer, it has been found that controlling the gassed density is very difficult due to the movement capabilities of the catalyst particles inside the emulsion. In practice, such emulsions are not practically applicable due to their inherent instability and sensitization incompatibility.
  • HP The properties of HP are well known. Among the known risks is the peroxide's highly reactive nature in combination with many materials commonly found in the mining and construction industry. HP decomposes to water and oxygen in an exothermic reaction which may lead to explosive type events. This decomposition can be aggressive and occur if impurities with catalytic behaviour enters the solution, in particular, alkaline materials, metals and some organic compounds may cause such reaction.
  • HP solutions over 60%
  • organic fuels such as sugars, alcohols or similar which is the case for water gel type explosives.
  • HP solutions at these pH levels are normally very stable if pure and it is normal that when stored in suitable tanks in cool temperatures the concentration in the solution decreases with no more than 1% annually.
  • Controlling temperature in the HP solution is imperative to safety as a rising temperature destabilizes the peroxide. As the decomposition is exothermic, an increasing temperature could be sign of contamination which may in a worst-case scenario lead to an explosive type event. Therefore, it is important to maintain storage temperature ranges for HP from -20° C to +25° C.
  • HP based explosives in particular water gel type compositions, challenging to handle, use safely, and store.
  • Water gels with high HP concentrations (over 40%) can react aggressively with alkaline, sulfuric or mineral rock types commonly found in blast holes.
  • the risks from the reactive behaviour of the HP itself in combination with catalytic fuels is the main reason why HP based explosives have been discarded as an unsafe alternative and not used in the industry.
  • Ammonium nitrate-based emulsions contain high concentrations of salt dissolved in the discontinuous aqueous phase.
  • AN is highly hydroscopic which allows for high solubility in water.
  • the solubility in water is an endothermic process and proportional to the solution's temperature where a higher temperature increases solubility and possible concentrations (saturation maximum).
  • the potency and performance of the explosive is directly proportional to the concentration of oxidizer available in the aqueous phase. It is therefore desirable to dissolve as much AN as possible to partly allow for a higher oxygen concentration, partly to minimize water content and also to increase density of the emulsion.
  • nitrate-based emulsions use hot AN solution as aqueous oxidizer phase where temperatures of the solution ranges from 60° C to 85° C.
  • other nitrate salts such as sodium or calcium nitrate salts or alkaline salts are added.
  • the solution is saturated at or close to this temperature. This implies that if the temperature of the solution drops under the saturation temperature, crystallization occurs where solid AN salt crystals are formed inside the solution in an amount relative to the change in temperature.
  • the aqueous oxidizer phase must therefore be kept at or above the saturation temperature in the solution storage tank and during the emulsification process, else the emulsion will crystallize which affects quality and performance.
  • crystallization inside process equipment causes clogging in pipes etc. and is a well-known process problem.
  • Heating nitrate solutions and ensuring temperature consistency is complex, expensive and requires high amounts of energy and is in general an operational risk and manufacturing challenge. Therefore, it is desirable to design emulsion explosives compositions which do not exhibit similar crystallization tendencies and which are able to form stable emulsions in a cold process not requiring strict temperature control and heating.
  • Modern bulk emulsion explosives used in the mining and civil industries today are made insensitive to detonation to allow for greater safety during production, transport and storing.
  • the sensitisation process is normally conducted by mechanical agitation of gassing chemicals and emulsion just before the explosive is pumped into the drill hole where the sensitisation (gassing) process evolves and sensitizes the explosive.
  • the emulsions need an addition of a sensitizer to reach detonability.
  • This sensitizer commonly comprises small gas filled voids/bubbles distributed evenly throughout the explosive composition. Upon detonation, these gas voids are compressed and thereby generate high temperatures forming so called "hot-spots" in the explosive.
  • WO2018/1072213A1 discloses an explosive composition wherein the oxidiser-phase comprises hydrogen peroxide, at least one other oxidiser and water.
  • the fuel-phase may comprise an oil mixed with an emulsifier.
  • the explosive composition further comprises a sensitizer which at some embodiments may comprise an aluminium or silicon powder
  • An object of the invention is to offer an explosive composition which significantly improves on the environmental aspects of blasting compared to nitrate based explosives and minimizes or avoids the generation of toxic NO x gas in the post detonation fumes and does not leach any nitrates. Another objective is to offer an emulsion type explosive composition which is easy to manufacture and achieves high stability using cold ingredients. A further object of the invention is to offer an emulsion explosive composition which can be manufactured in a process not requiring heating.
  • the present invention relates to explosives for use in the mining and civil construction industries and similar fields. These examples should not be considered limiting as it can be expected that other fields might be applicable such as underwater blasting, agriculture or oil well blasting.
  • a composition for forming a hydrogen peroxide based emulsion explosive as set out in appended claim 1.
  • the composition comprises a oxidizer-phase comprising at least 15% by weight of hydrogen peroxide and at least 15% by weight of water, a fuel-phase comprising at least one oil type fuel, at least one emulsifier and at least one finely divided solid adsorbent which is included and dispersed in the fuel-phase.
  • the oxidizer-phase is discontinuously dispersed throughout the continuous fuel-phase.
  • HP emulsions made from the teachings of the prior art have been proven to be difficult to emulsify in lower temperatures.
  • One reason for this is the very high viscosities of commercially available emulsifiers.
  • the emulsifier must be heated and solved in a low viscous oil to enable solubility and by extension allow for high contact surface between emulsifier and oil once added to the continuous oil phase. This implies the need to use low viscosity oils which in turn lead to a relatively low viscosity in the emulsion itself.
  • oils and emulsifiers affects the ability to form a stable emulsion at cold temperatures and often, inconsistent stability over time is noted. It is also to be noted that emulsions might exhibit apparent stability but once gassing (chemical or mechanical addition of gas voids or micro balloons) is preformed these emulsions tend to separate and destabilize rapidly.
  • emulsion compositions Another problematic aspect of the known emulsion compositions is the process of sensitization. Test show that addition of hollow spheres (gas filled hollow micro balloons) commonly used as sensitizer for emulsion explosives, tend to quickly destabilize and separate these emulsions. If hydrogen peroxide decomposition catalysts are used as sensitizer, it has been found that controlling the gassed density is very difficult due to the movement capabilities of the catalyst particles inside the emulsion. In practice, such emulsions are not practically applicable due to their inherent instability and sensitization incompatibility.
  • Emulsions are mixtures of two or more liquids which are normally immiscible.
  • Water insoluble fuel (oil) and water-soluble aqueous oxidizer (HP solution) droplets are bonded by a thin film of emulsifier molecules.
  • Such bonding films are normally only a few molecules thick and the de-facto thickness is defined by the molecular structure of the emulsifier.
  • the thickness of the emulsifier bonding film can be assessed to be in the range of molecules thick.
  • Another barrier (film) between the HP and oil droplets may be formed.
  • This barrier which comprises solid particles, are magnitudes thicker than the barrier formed by the emulsifier molecules.
  • the wetting binding of the solid particles between the oil and HP phases are weaker compared to the polar/non-polar binding off the colloidal emulsifier but physically adds a stronger protective film around the droplets. This implies that even if the solid particles add a stronger film, in absence of an emulsifier, they do not offer any improvement in stability as the droplets would not bond effectively and coalescence would occur.
  • the combination of conventional colloidal emulsifiers together with at least one finely divided solid adsorbent significantly increases stability as the droplets are more protected from penetration of possible impurities, additives or reactants such as sharp edges found in glass micro balloons or from the pressure formed by expanding gas in the case of using chemical gassing agents or from edges in the blast hole rock wall.
  • the ability of the solid particles to be wetted by both the oil- and HP phases also allows the particles to homogenize even in cold and highly viscous oil phases and emulsifiers during high shear mixing. It has been seen that such solid adsorbent particles significantly improve the solubility of emulsifiers into oil, even at cold temperatures and as an extension the particles allows for a larger surface area during cold emulsification ensuring effective droplet bonding
  • the composition may further comprise a sensitizer, whereby the composition forms a sensitized emulsion explosive.
  • a sensitized explosive may be formulated to become detonation enabled (explosive) i.e. to be ready to be detonated with traditional initiation means such as a detonator of conventional strength with or without an amplification charge (booster or primer) such as normally used in blasting.
  • the emulsion explosive composition described herein must be sensitized.
  • the preferred method of sensitization for the current invention is the use of gas filled voids by either in-situ generation of bubbles using chemical gassing agents or by adding hollow microspheres (commonly known as glass, plastic or cellulose micro balloons) or by injection of gas.
  • the use of "sensitizer” refers to small bubbles of gas or compressible materials.
  • the sensitizer may be added as a part of a pumping and charging process where the sensitizer is added and dispersed throughout the composition just before the sensitized composition is pumped into a blast hole, or, the sensitizer may be added in a process where the sensitized composition is loaded into a package to be used at a later stage.
  • sensitizer and emulsion composition separate just until the moment of charging ensures that the risk of accidental initiation during production, transporting or handling is minimized. It further allows the operator to control the exact sensitivity or density of the explosive needed for each particular application at the point of use.
  • chemical sensitization should be used where an agent is incorporated into the emulsion explosive close to point of insertion into the drill hole.
  • the agent chemically generates bubbles of gas as a result of a chemical reaction.
  • the bubbles are generated by peroxide decomposition.
  • the generation of gas bubbles are delayed and only generated in-situ of the drill hole.
  • the sensitizer comprises enclosed gas bubbles or voids which are generated inside the explosive composition through a chemical reaction.
  • Such voids are generated by a chemical decomposition process which may be delayed to achieve sensitization of the composition in-situ.
  • the sensitizer comprises enclosed gas bubbles or voids which are mechanically added into the explosive composition.
  • a minimum of sensitizer must be added into the composition to achieve the desired detonability.
  • gas bubbles should be added until the sensitized emulsion explosive reaches a density between 0,4-1,25 grams / cm 3 . If secondary fuels or oxidizers are incorporated it is to be appreciated that the density range may be increased. This density could be higher depending on the base density of the unsensitised emulsion explosive and also based on the density of potential additives such as other oxidizers or secondary fuels.
  • the density is maintained or stabilised as discussed above over an extended period of time, thereby increasing sleep time compared to the explosive composition not including a density stabiliser as discussed herein.
  • a mathematical conversion may be used to convert the required weight of mechanical sensitizers for yielding a certain density into volume, correspondingly, the required amount of the chemical gassing agent to be decomposed into bubbles for yielding a certain density may be converted into volume by a mathematical conversion.
  • the density of the unsensitised composition shall normally always be higher than the sensitized density of the same.
  • the size of the gas bubbles should be between 10-200 micrometre (microns) and preferably larger than the dispersed droplets of the oxidizer phase.
  • Lager bubbles may join forming instabilities in the emulsion matrix.
  • the particle size of the finely divided solid should be less than 10 micrometres, and more preferably less than 2 micrometres in average particle size which has been seen to be close to the oxidizer droplet mean size distribution.
  • the size of the solid adsorbent particles should be in the same range as the range of sizes for the oxidizer droplets. Too large adsorbent particles may hinder the emulsifier's ability to bonding the oil and aqueous droplets. Too small particles may cause full adsorption into an oxidizer droplet which may destabilize the droplet.
  • the finely divided solid adsorbent is included and dispersed in the continuous fuel-phase. This creates a better dispersion of the adsorbent particles. It has been seen that adsorbent particles exhibit clumping behaviour if added to the oxidizer phase. If added into the fuel-phase it has been found that the adsorbent improves emulsification due to the continuous wetting of the oxidizer phase upon emulsification.
  • the solid adsorbent may be added in a concentration between 0.1 to 10% by weight and dispersed into the oil phase together with fuel oils and emulsifiers prior to adding the discontinuous phase.
  • the finely divided solid adsorbent may comprise at least one solid selected from the group consisting of acrylic polymer powders, wheat, potato, rice or corn starch powders, organic gum powders, alginate cross linking powders, fumed silica powder, colloidal silica, silica powder, polymer zein powder, gluten powder, and clay particles.
  • the composition may further comprise a continuous fuel phase and a discontinuous aqueous oxidizer phase having a hydrogen peroxide concentration between 15-85% by weight, preferably between 30-60% by weight, a water content between 15-50% by weight.
  • the oxygen balance between the fuel and oxidizer phases are between -10 and +3% where oxygen balance denotes the selected fuels ability to fully oxidize.
  • Fuel additives may be added to modify the oxygen balance, energy, and detonation temperature and detonation pressure.
  • the oil type fuel may comprise at least one oil selected from the group consisting of mineral oils, aromatic oils, bio-oils, synthetic fuel oils, diesel oils, lubrication oils, kerosene oils, naphtha oils, paraffin oils, chlorinated paraffin oils, , benzene, toluene, polymeric oils, rapeseed oils, coconut oils and fish oils or mixtures thereof.
  • the composition may further comprise a density modifying additive fuel comprising at least one of metal powders such as non-reactive metal powders such as aluminium powder, silica powder, sugars, glycerol, cellulose and alcohols.
  • a density modifying additive fuel comprising at least one of metal powders such as non-reactive metal powders such as aluminium powder, silica powder, sugars, glycerol, cellulose and alcohols.
  • Such an additive fuel may be used to change the energy of the fuel component.
  • the density of the unsensitized explosive composition s in the range of 0,8-1,4 grams per cm 3 .
  • Unsensitized Compositions using secondary oxidizers or secondary fuels may have an unsensitised density up to 1,8.
  • the emulsifier may comprise at least one Polyisobutylene succinic anhydride (PIBSA), PIBSA amine derivatives, PIB-lactone and its amino derivatives, Sorbitan monooleate (SMO), sorbitan sesquioleate, lecithin, alkoxylates, esters combinations, fatty amines, alkyloxazolines, alkenyloxazolines, imidazolines, alkyl-sulfonates, alkylarylsulfonates, alkylsulfosuccinates, alkylphosphates, alkenylphosphates, phosphate esters and mixtures thereof.
  • PIBSA Polyisobutylene succinic anhydride
  • SMO Sorbitan monooleate
  • sorbitan sesquioleate sorbithin
  • alkoxylates esters combinations
  • fatty amines alkyloxazolines
  • alkenyloxazolines imidazolines
  • the concentration of emulsifier in the explosive composition may range from 0,8 - 5% by weight, preferably from 1,1 to 3% by weight.
  • the composition contains less than 1.5% nitrates by weight. More preferably it contains less than 0.5% nitrates by weight.
  • Commonly available emulsifiers often comprise nitrate bearing molecules. When such emulsifiers are used in the composition, they should preferably be selected to minimize the nitrate content in the overall emulsion such that nitrate content may be kept below the preferred or the more preferred limit.
  • viscosity refers to the viscosity measured by using a Brookfield RVT viscometer, #7 spindle at 20 r.p.m.
  • the viscosity of the oil phase during emulsification is relevant for effective droplet bonding, it is therefore preferred that oils, emulsifiers and solid adsorbents are selected and pre-mixed so that the oil phase has an apparent viscosity lower than 25 000 centipoise (cP).
  • the explosive composition of the water-in-oil emulsion explosive have an apparent viscosity greater than 35 000 centipoise (cP) at 25 °C prior to the introduction of the sensitizing gas bubbles. Apparent viscosity is more preferably in the range 60 000 to 120 000 cP.
  • the explosive composition of the invention can be pumped.
  • the viscosity of the unsensitised, emulsion is greater than 60 000 centipoises [cP] to ensure stability in the drill hole and to avoid mass transfer of HP and resulting reactivity.
  • the oxidizer phase should be free of nitrogen, and in one embodiment the oxidizer phase may consist only of hydrogen peroxide and water where the concentration of hydrogen peroxide in the oxidizer phase is no less than 35%.
  • secondary oxidizers such as other peroxide oxidizers such as sodium or potassium peroxide or perchlorates such as potassium perchlorate may be added to the oxidizer phase in combination with the hydrogen peroxide and water solution.
  • concentration of hydrogen peroxide in this embodiment should be no less than 15%.
  • a method of preparing an emulsion type explosive composition comprises
  • the emulsifier and/or the solid absorbent may be added to the fuel-phase prior to forming the emulsion or during the formation of the emulsion.
  • a composition for forming a hydrogen peroxide based emulsion explosive comprises an oxidizer-phase comprising at least 15% by weight of hydrogen peroxide and at least 15% by weight of water which oxidizer-phase is discontinuously dispersed throughout a continuous fuel-phase comprising at least one oil type fuel.
  • the composition further comprises an emulsifier and at least one finely divided solid adsorbent.
  • the composition may be formed by mixing the hydrogen peroxide water solution forming the oxidiser-phase with the fuel-phase in a mixer to thereby create an emulsion with the oxidiser phase being dispersed in the fuel phase.
  • the emulsifier and the solid absorbent should be added to the fuel phase prior to mixing.
  • the emulsifier and/or the solid absorbent may be added during the mixing process for forming the emulsion.
  • the temperature of the oxidiser-phase may be kept at approx. 10-20° C when added to the mixer.
  • the temperature of the fuel-phase may be kept at room temperature.
  • oil fuels having lower viscosity it may be preferable to add heat during the formation of the fuel phase.
  • the fuel phase may be supplied to the emulsification mixer at room temperature or it may be somewhat pre-heated before being supplied to the mixer.
  • the so formed composition becomes detonation enabled and explosive though initiation with conventional means, such a detonator with or without an amplification charge (known as a primer or booster).
  • the sensitizer may be chemically generated though a chemical reaction between a gassing agent added as a part of a pumping process whereby gas bubbles are formed slowly in-situ of the composition once placed in a blast hole.
  • gassing agents which may be used is carbon powder suspended in water.
  • Another example is a mixture of vinegar (CH 3 COOH) and bicarbonate solved in water. When carbon powder suspended in water is used, the suspension will react with the hydrogen peroxide to form oxygen bubbles which act as hot spots in the composition.
  • vinegar and bicarbonate these two substances react with each other to form hot carbon dioxide bubbles acting as hot spots.
  • the sensitizer in the form of solid compressible gas filled micro-balloons is added mechanically and mixed into the composition making the composition detonation enabled immediately.
  • composition can be used for many purposes, but in particular to break and move rock in mining operations.
  • composition it many comprise the types of functional components listed in Table 1; Table 1: Typical types of functional components and ratios of exemplifying compositions Type of functional component Ratios in % by weight of the total composition HP (primary oxidizer) From 15 to 85 Water From 15 to 55 Fuels From 2 to 15 Emulsifiers From 0.5 to 5 Solid adsorbents From 0.01 to 2 Secondary fuels From 0 to 15 Secondary oxidizers From 0 to 50 Additives From 0 to 5;
  • HP primary oxidizer
  • compositions may have the properties listed in Table 2: Table 2: Properties of the exemplifying compositions Properties Value Oxygen balance From -10 to +5 Un-sensitized density From 0.8 to 1,8 Sensitized density From 0.3 to 1,5 Viscosity From 35000 to 120 000 cP Preparation temperature From 5 to 25° C Velocity of detonation 2800-5500 m/s
  • Exemplifying typical substances for each type of functional component are listed in Table 3: Table 3: Exemplifying substances comprised in the compositions Functional component Substance
  • Oxidizers(s) At least 15% Hydrogen peroxide by weight, optionally potassium peroxide/and, or sodium peroxide/ and, or perchlorate salts/and, or chlorate salts.
  • Fuel(s) Water immiscible fuels and optionally water miscible fuels Emulsifiers Emulsifiers containing simultaneously lipophilic and hydrophilic moieties (PIBSA, SMO or the like) Solid adsorbents Finley divided solids which can be adsorbed and wetted at the interface between the two liquid phases to form a film of particles around the dispersed phases.
  • No limiting examples are gums, cross linkers, poly acrylic acids (tradenames Carbopol, carbomer, Utrez, Floset), starches (wheat, corn, rice, potato), polymer zein, fumed silica, colloidal silica, silica powder, titanium dioxide, clay particles.
  • the present invention can be used for a variety of forms of emulsion type explosive compositions provided that the principles of the invention as described herein are observed.
  • the invention is further illustrated with reference to the following examples.
  • a hydrogen peroxide emulsion formulation containing an oil-based fuel phase was calculated and hand made at a preparation temperature of 14°C using a bench drill driven mixer.
  • the oil phase combined one PIBSA type emulsifier and one SMO type emulsifier with a HP and water solution of 49.9% by weight concentration.
  • a mineral oil with density of 0.83 g / cm 3 was selected and combined with the two emulsifiers. 4 attempts to emulsify the above was conducted, 2 attempts without any solid adsorbent and 2 attempts with addition of approximately 0.8% by weight of a finely divided solid adsorbent in the form of powdery wheat starch (wheat flour) with an estimated particle size of 10-40 microns.
  • Phase separation (ps) and pH was monitored over a 5-day period.
  • the samples were stored in room temperature (21° C). Oxygen balance was calculated to -4%. If phase separation was detected, no further test where done. Density of the samples day 1 was approximately 1.15 g/cm 3 .
  • Table 3 Phase separation and pH change during 5 days using compositions with and without solid adsorbent.
  • Table 4 Density change in gassed HP emulsion Sample Un sensitized density Gassed density Day 1 Day 2 Day 3 Day 4 Day 5 1 1.15 0.98 0.97 0.94 0.94 0.93 0.93 2 1.15 1.03 1.01 1.00 0.98 0.97 0.97 3 1.15 1.05 1.05 1.03 1.03 1.02 1.00
  • Detonation testing of the above compositions comprising a solid adsorbent were performed where the compositions where chemically gassed and pumped into drilled holes in boulders. The holes were drilled to a diameter of 48 mm and charges of about 1 kg where used. Initiation was done with an 8d electric detonator in combination with a 20 gram PETN primer. VOD was measured using the MREL microtrap copper probes. The charges were left to sleep in the holes for 48 hours at a temperature of 12-14°C. Detonation speeds from 4100 to 4300 m/s where measured and performance where deemed acceptable for mining applications.

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Claims (14)

  1. Composition pour former un explosif en émulsion à base de peroxyde d'hydrogène, laquelle composition comprend :
    - une phase oxydante comprenant au moins 15 % en poids de peroxyde d'hydrogène et au moins 15 % en poids d'eau,
    - une phase combustible comprenant au moins un combustible de type huile,
    - un émulsifiant,
    - au moins un adsorbant solide finement divisé inclus et dispersé dans la phase combustible continue, dans laquelle
    la phase oxydante est dispersée de manière discontinue dans toute la phase combustible continue.
  2. Composition selon la revendication 1, comprenant en outre un sensibilisateur, de sorte que la composition forme un explosif en émulsion sensibilisé.
  3. Composition selon la revendication 2, dans laquelle le sensibilisateur comprend des bulles de gaz ou des vides enfermés qui sont générés à l'intérieur de la composition explosive par une réaction chimique.
  4. Composition selon la revendication 2 dans laquelle le sensibilisateur comprend des bulles de gaz ou des vides enfermés qui sont ajoutés mécaniquement dans la composition explosive.
  5. Composition selon l'une quelconque des revendications 1 à 4 dans laquelle au moins une partie de l'adsorbant solide finement divisé peut être mouillée à la fois par l'oxydant et par la phase combustible.
  6. Composition selon l'une quelconque des revendications 1 à 5 dans laquelle les particules de l'adsorbant solide finement divisé ont une taille moyenne inférieure à 10 micromètres.
  7. Composition selon l'une quelconque des revendications 1 à 6 dans laquelle l'adsorbant solide finement divisé comprend au moins un solide choisi dans le groupe constitué par les poudres de polymère acrylique, les poudres d'amidon de blé, de pomme de terre, de riz ou de maïs, les poudres de gomme organique, les poudres de réticulation d'alginate, la poudre de silice fumée, la silice colloïdale, la poudre de silice, la poudre de zéine polymère, la poudre de gluten et les particules d'argile.
  8. Composition selon l'une quelconque des revendications 1 à 7 dans laquelle le carburant de type huile comprend au moins une huile choisie dans le groupe constitué par les huiles minérales, les huiles aromatiques, les bio-huiles, les huiles combustibles synthétiques, les huiles diesel, les huiles de lubrification, les huiles de kérosène, les huiles de naphta, les huiles de paraffine, les huiles de paraffine chlorées, le benzène, le toluène, les huiles polymères, les huiles de colza, les huiles de coco et les huiles de poisson.
  9. Composition selon l'une quelconque des revendications 1 à 8 comprenant en outre un carburant additif modifiant la densité comprenant au moins l'un parmi la poudre d'aluminium, la poudre de silice, les sucres, le glycérol, la cellulose ou les alcools.
  10. Composition selon l'une quelconque des revendications 1 à 9, dans laquelle l'émulsifiant comprend au moins l'un parmi l'anhydride succinique de polyisobutylène (PIBSA), les dérivés aminés de PIBSA, la PIB-lactone ou ses dérivés aminés, le monooléate de sorbitane (SMO), le sesquioléate de sorbitane, la lécithine, les alcoxylates, des combinaisons d'esters, les amines grasses, les alkyloxazolines, les alcényloxazolines, les imidazolines, les sulfonates d'alkyle, les sulfonates d'alkylaryle, les sulfosuccinates d'alkyle, les phosphates d'alkyle, les phosphates d'alcényle ou les esters de phosphate.
  11. Composition selon l'une quelconque des revendications 1 à 10, dans laquelle la composition contient moins de 1,5 % en poids de nitrates.
  12. Composition selon l'une quelconque des revendications 1 à 11 dans laquelle la viscosité apparente de la composition non sensibilisée est supérieure à 35 000 centipoises [cP] à 25 °C.
  13. Composition selon l'une quelconque des revendications 2 à 12 dans laquelle la masse volumique de la composition explosive sensibilisée est comprise entre 0,4 et 1,25 g/cm3.
  14. Procédé de préparation d'une composition explosive de type émulsion, lequel procédé comprend :
    - la fourniture d'une phase oxydante comprenant au moins 15 % en poids de peroxyde d'hydrogène et au moins 15 % en poids d'eau,
    - la fourniture d'une phase combustible comprenant au moins un type d'huile,
    - la fourniture d'au moins un émulsifiant,
    - la fourniture d'au moins un adsorbant solide finement divisé inclus et dispersé dans la phase combustible continue,
    - la formation d'une émulsion comprenant la phase oxydante, la phase combustible, l'émulsifiant et l'absorbant solide, et
    - la sensibilisation de l'émulsion en ajoutant des micro-ballons solides compressibles remplis de gaz, et/ou en générant des bulles de gaz au moyen d'un agent de gazage et/ou en ajoutant des bulles de gaz à l'émulsion.
EP21172313.5A 2021-05-05 2021-05-05 Composition de formation d'un explosif en émulsion à base de peroxyde d'hydrogène Active EP4086237B1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
EP21172313.5A EP4086237B1 (fr) 2021-05-05 2021-05-05 Composition de formation d'un explosif en émulsion à base de peroxyde d'hydrogène
US18/289,140 US20240217892A1 (en) 2021-05-05 2022-05-04 Composition for forming a hydrogen peroxide based emulsion explosive
EP22727840.5A EP4334269A1 (fr) 2021-05-05 2022-05-04 Composition de formation d'un explosif à émulsion à base de peroxyde d'hydrogène
PE2023003005A PE20242121A1 (es) 2021-05-05 2022-05-04 Composicion para formar una emulsion explosiva a base de peroxido de hidrogeno
PCT/EP2022/062007 WO2022233948A1 (fr) 2021-05-05 2022-05-04 Composition de formation d'un explosif à émulsion à base de peroxyde d'hydrogène
AU2022268594A AU2022268594A1 (en) 2021-05-05 2022-05-04 Composition for forming a hydrogen peroxide based emulsion explosive
CA3217755A CA3217755A1 (fr) 2021-05-05 2022-05-04 Composition de formation d'un explosif a emulsion a base de peroxyde d'hydrogene
CL2023003266A CL2023003266A1 (es) 2021-05-05 2023-11-03 Composición para formar una emulsión explosiva a base de peróxido de hidrógeno
ZA2023/11166A ZA202311166B (en) 2021-05-05 2023-12-04 Composition for forming a hydrogen peroxide based emulsion explosive

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP21172313.5A EP4086237B1 (fr) 2021-05-05 2021-05-05 Composition de formation d'un explosif en émulsion à base de peroxyde d'hydrogène

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AU (1) AU2022268594A1 (fr)
CA (1) CA3217755A1 (fr)
CL (1) CL2023003266A1 (fr)
PE (1) PE20242121A1 (fr)
WO (1) WO2022233948A1 (fr)
ZA (1) ZA202311166B (fr)

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WO2026069214A1 (fr) * 2024-09-27 2026-04-02 Aeci Mining Limited Explosifs en émulsion avec nanoparticules

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013013272A1 (fr) 2011-07-27 2013-01-31 Cmte Development Limited Composition explosive améliorée
WO2018107213A1 (fr) 2016-12-12 2018-06-21 Cmte Development Limited Composition explosive améliorée

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4475965A (en) * 1983-10-24 1984-10-09 Standard Oil Company (Indiana) Shale oil explosives
FR2599487B1 (fr) 1986-05-30 1988-08-12 Interox Procede pour la fabrication de cartouches explosives et cartouches explosives obtenues par ledit procede
US7491279B1 (en) 2004-12-09 2009-02-17 The United States Of America As Represented By The Secretary Of The Navy Emulsion explosive
ES2399477T3 (es) 2007-12-13 2013-04-01 Akzo Nobel N.V. Disoluciones de peróxido de hidrógeno estabilizadas
EP3530745A4 (fr) 2016-10-21 2020-07-22 Pepsico, Inc. Procédé de préparation de rébaudioside n à l'aide d'un procédé enzymatique
CA3065235A1 (fr) * 2017-05-30 2018-12-06 Orica International Pte Ltd Composition d'explosifs
MA51772B1 (fr) * 2018-01-29 2024-08-30 Dyno Nobel Inc. Explosifs à émulsion gazée mécaniquement et procédés associés
AU2020287072A1 (en) 2019-06-07 2021-12-23 Cmte Development Limited Explosives based on hydrogen peroxide with improved sleep time

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013013272A1 (fr) 2011-07-27 2013-01-31 Cmte Development Limited Composition explosive améliorée
WO2018107213A1 (fr) 2016-12-12 2018-06-21 Cmte Development Limited Composition explosive améliorée

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TSHILUMBU NSENDA NGENDA, MASALOVA IRINA: "Stabilization of highly concentrated emulsions with oversaturated dispersed phase: Effect of surfactant/particle ratio", CHEMICAL ENGINEERING RESEARCH AND DESIGN, ELSEVIER, AMSTERDAM, NL, vol. 102, 1 October 2015 (2015-10-01), AMSTERDAM, NL, pages 216 - 233, XP093395295, ISSN: 0263-8762, DOI: 10.1016/j.cherd.2015.06.025

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EP4086237A1 (fr) 2022-11-09
CL2023003266A1 (es) 2024-04-12
ZA202311166B (en) 2024-03-27
US20240217892A1 (en) 2024-07-04
CA3217755A1 (fr) 2022-11-10
EP4334269A1 (fr) 2024-03-13
AU2022268594A1 (en) 2023-12-21
WO2022233948A1 (fr) 2022-11-10
EP4086237C0 (fr) 2025-08-06
PE20242121A1 (es) 2024-10-28

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