EP4086238B1 - Zusammensetzung zur bildung eines sprengstoffs mit einer emulsion aus wasserstoffperoxid und einem ölartigen brennstoff - Google Patents

Zusammensetzung zur bildung eines sprengstoffs mit einer emulsion aus wasserstoffperoxid und einem ölartigen brennstoff Download PDF

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EP4086238B1
EP4086238B1 EP21172315.0A EP21172315A EP4086238B1 EP 4086238 B1 EP4086238 B1 EP 4086238B1 EP 21172315 A EP21172315 A EP 21172315A EP 4086238 B1 EP4086238 B1 EP 4086238B1
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Prior art keywords
oils
phase
fuel
composition
emulsion
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English (en)
French (fr)
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EP4086238A1 (de
EP4086238C0 (de
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Thomas GUSTAVSSON
Robert HÅKLAND
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 ES21172315T priority Critical patent/ES2976313T3/es
Application filed by Hypex Bio Explosives Technology AB filed Critical Hypex Bio Explosives Technology AB
Priority to EP21172315.0A priority patent/EP4086238B1/de
Priority to PE2023003006A priority patent/PE20242122A1/es
Priority to AU2022269827A priority patent/AU2022269827A1/en
Priority to PCT/EP2022/062011 priority patent/WO2022233952A1/en
Priority to CA3217779A priority patent/CA3217779A1/en
Priority to US18/289,145 priority patent/US20240239722A1/en
Publication of EP4086238A1 publication Critical patent/EP4086238A1/de
Priority to CL2023003267A priority patent/CL2023003267A1/es
Priority to ZA2023/11168A priority patent/ZA202311168B/en
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
    • C06B47/14—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase comprising a solid component and an aqueous phase
    • C06B47/145—Water in oil emulsion type explosives in which a carbonaceous fuel forms the continuous phase
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/002—Sensitisers or density reducing agents, foam stabilisers, crystal habit modifiers
    • C06B23/003—Porous or hollow inert particles

Definitions

  • the present invention relates to a composition for forming an emulsion type hydrogen peroxide-based explosive which can reach steady detonation in small diameters.
  • the invention also relates to a method of preparing such an emulsion type explosive.
  • 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
  • NO x toxic nitrogen oxide
  • nitrate residues in the blasted rock or un-detonated explosives forms nitrogen leaching which pollutes water based ecological systems and ground water.
  • nitrated used in areas where concrete or cement products are used may cause an ammonia generating reaction.
  • shotcrete spray concrete is used for wall stabilization.
  • Nitrate residues from blasting reacts with the shotcrete to form ammonia gas which is toxic and creates very hazardous working environments.
  • These problems are well known in the mining and construction industry and are directly related to the use of ammonium nitrate. It is therefore desirable to investigate the use of alternative oxidizers which preferably should be nitrogen free. Ideally these oxidizers should exhibit good detonation performance comparable to status quo and improve on the environmental and health aspects of the explosive.
  • the toxic NO x gas is predominantly an issue for underground blasting operations which are common in mining and tunnelling applications.
  • the amount of explosive used per cubic meter rock is normally higher for these applications compared to surface blasting operations due to the confined nature of the rock. It is also commonplace that a significant amount of the explosives follows non-ideal detonation behaviour where some amounts of the explosive does not detonate.
  • the undetonated explosive combined with the nitrate polluted rock mass leads to the leaching issue as discussed above.
  • HP Hydrogen peroxide
  • HP Hydrogen peroxide
  • 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 ( US7491279B1 ) for an HP based explosive composition and another patent ( US4942800 ) was granted to Bouillet et. al in 1990.
  • 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.
  • WO 2013/013272 (Araos ) and WO 2020/243788 A1 (Kettle ) represents some of the most recent research in the field and proposes various types of water gel and a few emulsion type explosives bases on hydrogen peroxide.
  • Araos and Kettle focuses on water gel technology and argues that HP based compositions could be a relevant alternative to AN based mining explosives.
  • Kettle builds on Araos work and argues that compositions proposed by Araos suffer from too short sleep time making them difficult to use practically.
  • Kettle proposes the addition of density stabilizers which in the context are described as HP stabilizers (i.e., various types of phosphonate based compounds). These have shown to have a stabilizing effect on the density of the HP based explosive compositions.
  • HP The properties of HP are well known. Among the known risks is the peroxide's highly reactive behaviour in combination with many catalytic or reactive 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. Risk of aggressive reactivity which may lead to explosive events increases with higher concentration HP solutions (over 60%) and in particular if the HP solution is combined with organic fuels such as sugars, alcohols or similar which is the case for water gel type explosives.
  • a high water content will lower the detonation heat capacity leading to inability to reach steady state detonation and/or lower detonation velocity and performance. More particularly, it might counteract reliable and stable detonation in smaller diameters, at lower densities and/or when using smaller primer initiation charges.
  • HP solutions at these pH levels are normally very stable if pure, i.e. void of contaminants, 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.
  • an increasing temperature could be a 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 previously known in the art, in particular water gel type compositions, challenging to handle, use safely, and store. It has been shown that water gels with high HP concentrations can react aggressively with alkaline, sulfuric or mineral rock types commonly found in blast holes. These reactions of fuelled water gels may reach temperatures over 150 °C at which point conventional detonators initiates. The reactive behaviour of the HP itself and such compositions is the main reason why HP based explosives have been discarded as an unsafe alternative and not used in the industry.
  • 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 lowers or eliminates the generation of toxic NO x gas in the post detonation fumes and does not leach any nitrates.
  • a further object is to offer an emulsion type explosive composition which allows for good detonation, rock blasting performance and stability in smaller diameter holes commonly used in tunnelling and underground blasting operations.
  • 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 35% by weight of hydrogen peroxide and at least 25% by weight of water, a fuel-phase comprising at least one primary oil type fuel with a flash point below 100 °C, and at least one secondary oil type fuel with a flash point over 150° C and at least one emulsifier, wherein the oxidizer-phase is discontinuously dispersed throughout the continuous fuel-phase.
  • emulsion type HP explosives exhibits a greater resistance to HP decomposition catalysts and should be considered to be less reactive compared to water gel compositions. This is due to a range of factors such as separation of fuel and oxidizer (fuel oil is immiscible in the HP solution), the oil and emulsifier coating of the HP droplets disallowing for mass transfer of HP molecules and the significantly higher viscosities possible with emulsions compared to water gels which physically hinders impurities to migrate through the explosive column.
  • fuel and oxidizer fuel oil is immiscible in the HP solution
  • the oil and emulsifier coating of the HP droplets disallowing for mass transfer of HP molecules and the significantly higher viscosities possible with emulsions compared to water gels which physically hinders impurities to migrate through the explosive column.
  • Emulsions should further be considered significantly more stable compared to water gels from a reactivity perspective due to the encapsulation of droplets and restriction of HP mass movement. This assumes stable consistency of the composition which must stay in an emulsified state to ensure the bond between the HP and the fuel oil droplets over the storage and use period.
  • HP emulsion explosives have been proven to deliver blast results comparable to AN based emulsion and could offer an attractive, nitrate-free and more environmentally friendly alternative.
  • Ventilation must be in place to eliminate this risk. This is particularly important in underground operations where ventilation of the gases must occur after each blast. Normally, fresh air is fed from the surface down into the tunnel structures to eject the fumes. Such ventilation takes long periods of time and lead to significant energy and production loss and is commonplace in the underground industry as all explosives are principally based on nitrate bearing compounds. It is therefore of significant interest and importance to develop explosives which minimize or eliminate the toxic nitrate footprint but simultaneously also performs equally or better in the smaller diameter holes used in underground tunnel development. HP emulsions offers a solution to this problem.
  • blast holes are predominantly (but not exclusively) used.
  • the blast hole diameters range from 34-54 mm which should be contrasted to vertical surface production blast holes which normally ranges from diameters 64 mm and upwards.
  • Surface blast holes are normally stemmed (i.e confined) using drill chippings, rock aggregate, plastic plugs or other confiners. This is usually not done in underground due to time aspects and challenges in charging horizontal holes.
  • the flash point of the oil type fuels selected plays a significant role in the detonation behaviour of the HP based emulsions consisting of more than 40% water.
  • Emulsions made only from oil fuels with flash points over approximately 100° C have been found to be significantly harder to reliably detonate in smaller diameters (less than 40 mm) where emulsions made with at least one oil having a flashpoint below 100 ° C shows excellent detonation performance behaviour in diameters under 40 mm.
  • the fuel-phase further comprises at least one secondary one oil type fuel with a flash point over 150° C, preferably over 200° C.
  • the secondary oil type fuel has a molecular structure comprising 20 to 40 carbon atoms.
  • Such high flash point oil type fuels have been shown to supress exothermic reactions of the HP to some extent and to increase viscosity of the emulsion.
  • the composition may further comprise a sensitizer, whereby the composition forms a sensitized emulsion explosive.
  • a sensitizer such as a detonator of conventional strength with or without an amplification charge (booster or primer) such as normally used in blasting.
  • 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 and/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 the point of insertion into the drill hole.
  • the agent generates bubbles of gas as a result of a chemical reaction.
  • the bubbles may e.g. be generated by hydrogen peroxide decomposition.
  • the generation of gas bubbles may further be delayed such that the gas bubbles are generated in-situ of the drill hole.
  • the sensitizer may comprise gas bubbles or voids which are formed inside the explosive composition as a result of 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 may comprise enclosed gas bubbles or voids which are mechanically added into the composition.
  • voids may be formed of hollow microspheres or-balloons of e.g. glass, plastic or cellulose. These balloons/bubbles are preferably made to resist high pressures and does not allow for coalescence and prohibit bubble collapse. Advantages of using pre-made microspheres are found in situations where an exact density must be maintained over longer periods of time or when handling, transport or other operational aspects may cause gas bubbles to migrate in the explosive or when high pressures are exercised on the explosive, for example, at the bottom of deep drill holes.
  • the size of the gas bubbles may preferably be between 5-200 micrometres (microns) and preferably larger than the dispersed droplets of the oxidizer phase. Bubbles larger than that may otherwise join, thereby forming instabilities in the emulsion matrix.
  • the at least one fuel with flash points under 100° C may comprise at least one oil selected from the group consisting of mineral oils, kerosene oils, synthetic kerosene oils, naphtha oils, synthetic oils, bio oils, gasoline oils, diesel oils, synthetic diesel oils, line seed oils and neatsfoot oils.
  • the first oil type fuel with flash point under 100 °C may constitute between 0.1 and 10% by weight of the total composition.
  • the amount should be balanced depending on the water content of the composition.
  • the low flash point oil component constitutes 0.8-4.5% by weight of the total composition.
  • the composition may further comprise at least one oil type fuel with a viscosity of at least 50 cP at 15 °C to increase the emulsion composition viscosity. It has been discovered that incorporating oils with a high viscosity at low temperatures (15 °C) significantly improves emulsion stability, both pre and post sensitization. Further, it has been found that such compositions as proposed herein readily detonates after 3 days in a small diameter hole (48 mm) when sensitized chemically and initiated with a 25 gram PETN booster in combination with a standard detonator resulting in acceptable blast performance.
  • the secondary oil type fuel may be selected from the group of mineral oils, petroleum oils, aromatic oils, bio-oils, synthetic fuel oils, diesel oils, lubrication oils, kerosene oils, naphtha oils, paraffin oils, chlorinated paraffin oils, micro benzene oils, toluene oil, polymeric oils, rapeseed oils, coconut oils silicone oils, and fish oils or mixtures thereof.
  • Wax components may also be comprised in the fuel-phase, in order to increase viscosity and to improve texture of the composition which could be particularly important for packaged emulsions where significant manual handling is involved.
  • the fuel phase may further comprise at least one wax selected from the group consisting of microcrystalline wax, paraffin wax, animal wax, plant wax, montan wax, polyethylene wax and polyethylene derivative wax.
  • the composition may further comprise a grease lubricant in the form of a solid or semifluid dispersion of a thickener in oil. It has been found that small amounts (1-3%) of solid or semi-solid greases normally consisting of oils with thickeners can decrease the compositions tendency to react and improve stability over time.
  • the grease may also modify the compositions texture making it potentially stickier which could be beneficial in horizontal or upward facing holes.
  • the grease should preferably be added post emulsification to not significantly disrupt the HP droplet turnover/connection area to the droplets of the low flash point oils.
  • emulsifier or "emulgent” employed in the present invention should represent chemicals which stabilize the oxidiser phase and fuel phase dispersion by increasing the kinetic stability of the composition by bonding the droplets and which comprise at least one lipophilic moiety and at least one hydrophilic moiety.
  • the at least one emulsifiers may be selected from the group consisting of Polyisobutylene succinic anhydride (PIBSA), PIBSA amine derivatives, Polyisobutenyl succinic acid anhydride (PIBDIBA), PIBDIBA derivates, 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 and phosphate esters and mixtures thereof.
  • PIBSA Polyisobutylene succinic anhydride
  • PIBDIBA Polyisobutenyl succinic acid anhydride
  • SMO Sorbitan monoole
  • the at least one emulsifier may constitute of 5-30% by weight of the fuel phase and/or 0.5-5% by weight of the total composition.
  • the most preferred content of emulsifier used is in the range from Preferably, the at least one emulsifier constitutes 0.8-2.5% by weight of the total composition.
  • the viscosity of the HP emulsion composition will be discussed in terms of apparent viscosity.
  • apparent viscosity refers to a viscosity measure using a Brookfield RVT viscometer, #7 spindle at 20 r.p.m. It is preferred that the unsensitized composition has an apparent viscosity greater than 35 000 centipoise (cP).
  • the apparent viscosity of the composition may e.g. be between 35 000 and 120 000 centipoise (cP). Apparent viscosity is more preferably in the range 60 000 to 120 000 cP.
  • the explosive composition can be pumped.
  • a thickener may be added to the fuel phase prior to mixing.
  • Thickeners which may be crosslinked, may be selected from a large array of available compounds such as gums (Xhantan, guar or alginates) or fumes silica but preferably are selected from the group of polymeric materials such as carbopol (polyacrylic acid or polyacrylamide) with the formula (C 3 H 4 O 2 ) n .
  • the optional thickener component may constitute 0.1-5% of the total weight of the composition.
  • the thickener component may constitute 0.5-1.5% by weight of the total weight of the composition.
  • the density of the sensitized emulsion explosive may preferably be between 0.4 - 1.25 grams / cm 3 .
  • gas bubbles should be added until the sensitized emulsion explosive reaches a density between 0,4-1,25
  • 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.
  • the required amount of the chemical substance 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 oxidizer phase may exhibit a hydrogen peroxide concentration of 35-60% by weight, preferably between 40 and 49.5% by weight.
  • the oxidizer-phase may comprise a secondary oxidizer such as another peroxide oxidizers such as sodium or potassium peroxide or a perchlorate such as potassium perchlorate may be added to the oxidizer phase in combination with the hydrogen peroxide and water solution. Also at such embodiments, the concentration of hydrogen peroxide should be no less than 35%.
  • the fuel phase may comprise oil type fuels which are water immiscible in a concentration from 2.5 to 12% by weight, preferably 4.5-9% by weight comprising at least one oil with max 18 carbon atoms in the molecular structure, preferably 10 to 18 carbon atoms in the molecular structure with a flash point under 100°C, preferably a flash point between 50-85°C.
  • oil type fuels which are water immiscible in a concentration from 2.5 to 12% by weight, preferably 4.5-9% by weight comprising at least one oil with max 18 carbon atoms in the molecular structure, preferably 10 to 18 carbon atoms in the molecular structure with a flash point under 100°C, preferably a flash point between 50-85°C.
  • all components comprised in the composition are free from nitrogen or comprise very small amounts of nitrogen so that the total nitrogen content of the explosive composition is less than 1%.
  • a method of preparing an emulsion type explosive composition comprises;
  • a composition for forming a hydrogen peroxide based emulsion explosive as set out in appended claim 1.
  • the composition comprise a oxidizer phase comprising at least 35% by weight of hydrogen peroxide and at least 25% by weight of water, a fuel phase comprising at least one oil type fuel with a flash point below 100 °C, at least one secondary oil type fuel with a flash point over 150 °C, and an emulsifier, wherein the oxidizer-phase is discontinuously dispersed throughout the continuous fuel phase.
  • 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 should be added to the fuel phase prior to mixing.
  • the emulsifier 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.
  • 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 composition becomes detonation enabled and explosive though initiation with conventional means such as a detonator with or without an amplification charge (known as a primer or booster).
  • the sensitizer bubbles may be chemically generated though a chemical reaction caused by 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. When vinegar and bicarbonate is used, these two substances react with each other to form hot carbon dioxide bubbles acting as hot spots.
  • a sensitizer comprising enclosed gas bubbles in the form of hollow microspheres formed of e.g. glass, ceramic, plastic or cellulose are added mechanically and mixed into the composition making the composition sensitized and thereby detonation enabled immediately.
  • the composition of the invention can be used for many purposes, but in particular to break and move rock in mining operations.
  • composition it comprises the types of functional components listed in Table 1; wherein the amount of secondary oil fuels with a flash point over 150 °C is more than 0% by weight;
  • Table 1 Typical types of functional components and ratios exemplifying compositions Type of functional component Ratios in % by weight of the total composition HP (primary oxidizer) From 35 to 60 Water From 25 to 55 Primary oil fuels with flash point under 100°C From 0.1 to 10 Secondary oil fuels with flash point over 150°C From 0 to 5 Non-oil secondary fuels From 0 to 10 Secondary oxidizers From 0 to 30 Emulsifiers From 0.8 to 5 Additives From 0 to 5
  • 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 0.4 to 1.25 Viscosity From 35 000 to 120 000 cP Velocity of detonation 2200 - 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 Function Component Oxidizers(s) At least 35% Hydrogen peroxide by weight, optionally potassium peroxide/and, or sodium peroxide/ and, or perchlorate salts/and, or chlorate salts.
  • Function Component Oxidizers(s) At least 35% Hydrogen peroxide by weight, optionally potassium peroxide/and, or sodium peroxide/ and, or perchlorate salts/and, or chlorate salts.
  • Mineral oils mineral oils, petroleum oils, aromatic oils, bio-oils, synthetic fuel oils, diesel oils, lubrication oils, kerosene oils, naphtha oils, paraffin oils, lubrication oils, chlorinated paraffin oils, micro benzene oils, toluene oil, polymeric oils, rapeseed oils, coconut oils and fish oils, metal powders, sugars, glycerol or alcohols.
  • Emulsifiers Emulsifiers containing lipophilic and hydrophilic moieties (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) able to bond the HP solution.
  • PIBSA Polyisobutylene succinic anhydride
  • SMO Sorbitan monooleate
  • sorbitan sesquioleate sorbithin
  • alkoxylates esters combinations
  • fatty amines alkyloxazolines
  • the present invention can be used for a variety of forms of emulsion type explosive compositions provided of course that the principles of the invention as described herein are observed.
  • the invention is further illustrated with reference to the following examples.
  • Table 4 Composition rations used in example 1 Component Function Ratio (weight %) Comment Hydrogen peroxide (50%) Oxidizer Discontinuous phase 92.6 50% HP solution Synthetic paraffin oil Fuel Continuous phase 2.7% Flash point over 200° C Synthetic kerosene Fuel Continuous phase 2% Flash point 70° C PIBSA Emulsifier/Fuel Continuous phase 1.3% SMO Emulsifier/Surfactant Continuous phase 1.4%
  • a hydrogen peroxide explosive composition was prepared according to Table 4;
  • the continuous phase was prepared separately and heated to approximately 50° C before adding the discontinuous oxidizer phase.
  • Oxidizer phase was added slowly during high shear mixing ensuring emulsification.
  • the formulation resulted in a thick emulsion with an apparent viscosity of approx. 85 000 cP and a pH level of 3.9. Cup density was measured to 1.15 g/cm 3 .
  • a hydrogen peroxide explosive composition was prepared similar to the one illustrated in Table 4, however without the low flash point component (Synthetic Kerosene).
  • the composition is presented in Table 5 below; Table 5: Composition ratios used in example 2.
  • Component Function Ratio weight %) Comment
  • Oxidizer Discontinuous phase 92.6 50% HP solution Synthetic paraffin oil
  • Fuel Continuous phase 4.7% Flash point over 200° C PIBSA Emulsifier/Fuel Continuous phase 1.3%
  • SMO Surfactant Continuous phase 1.4%
  • the continuous phase was prepared separately and heated to approximately 50° C before adding the discontinuous oxidizer phase.
  • Oxidizer phase was added slowly during high shear mixing ensuring emulsification.
  • the formulation resulted in a thick emulsion with a higher apparent viscosity compared to example 1 of approx. 100 000 cP and a pH level of 4.1. Cup density was measured to 1.16 g/cm 3 .

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  • Chemical & Material Sciences (AREA)
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Claims (15)

  1. Zusammensetzung zum Bilden eines Emulsionsexplosivstoffs auf Wasserstoffperoxidbasis, welche Zusammensetzung umfasst:
    - eine Oxidationsmittelphase umfassend wenigstens 35 Gew.-% Wasserstoffperoxid und wenigstens 25 Gew.-% Wasser,
    - eine Brennstoffphase umfassend wenigstens einen primären Brennstoff vom Öltyp mit einem Flammpunkt von unter 100 °C und wenigstens einen sekundären Brennstoff vom Öltyp mit einem Flammpunkt von über 150 °C und
    - wenigstens einen Emulgator, wobei
    die Oxidationsmittelphase diskontinuierlich in der kontinuierlichen Brennstoffphase verteilt ist.
  2. Zusammensetzung gemäß Anspruch 1, ferner umfassend einen Sensibilisator, wodurch die Zusammensetzung einen sensibilisierten Emulsionsexplosivstoff bildet.
  3. Zusammensetzung gemäß Anspruch 2, ferner umfassend ein Gasierungsmittel, das dafür beschaffen ist, den Sensibilisator in der Form von Gasblasen durch eine chemische Reaktion zu bilden.
  4. Zusammensetzung gemäß Anspruch 2, wobei der Sensibilisator mechanisch zugegebene, eingeschlossene hohle Mikrokügelchen oder -ballons umfasst.
  5. Zusammensetzung gemäß einem der Ansprüche 1-4, wobei der wenigstens eine primäre Brennstoff vom Öltyp wenigstens ein Öl ausgewählt aus der Gruppe bestehend aus Mineralölen, Kerosinölen, synthetischen Kerosinölen, Naphthaölen, synthetischen Ölen, Bioölen, Benzinölen, Dieselölen, synthetischen Dieselölen, Leinsamenölen und Klauenölen umfasst.
  6. Zusammensetzung gemäß einem der Ansprüche 1-5, wobei der erste Brennstoff von Öltyp mit einem Flammpunkt von unter 100 °C zwischen 0,1 und 10 Gew.-% der Zusammensetzung bildet.
  7. Zusammensetzung gemäß einem der Ansprüche 1-6, wobei die Brennstoffphase ferner wenigstens einen Brennstoff von Öltyp mit einer Viskosität von wenigstens 50 cP bei 15 °C zum Erhöhen der Viskosität der Emulsionszusammensetzung umfasst.
  8. Zusammensetzung gemäß einem der Ansprüche 1-7, wobei der sekundäre Brennstoff vom Öltyp ausgewählt ist aus der Gruppe von Mineralölen, Petroleumölen, aromatischen Ölen, Bioölen, synthetischen Brennstoffölen, Dieselölen, Schmierölen, Kerosinölen, Napthaölen, Paraffinölen, Schmierölen, chlorierten Paraffinölen, Mikrobenzolölen, Toluolöl, polymeren Ölen, Rapssamenöl, Kokosnussölen, Siliconölen und Fischölen.
  9. Zusammensetzung gemäß einem der Ansprüche 1-8, wobei die Brennstoffphase ferner wenigstens ein Wachs ausgewählt aus der Gruppe bestehend aus mikrokristallinem Wachs, Paraffinwachs, Tierwachs, Pflanzenwachs, Montanwachs, Polyethylenwachs und Polyethylenderivatwachs umfasst.
  10. Zusammensetzung gemäß einem der Ansprüche 1-9, ferner umfassend ein Schmierfett in der Form einer festen oder halbfesten Dispersion eines Verdickungsmittels in Öl.
  11. Zusammensetzung gemäß einem der Ansprüche 1-10, wobei der wenigstens eine Emulgator ausgewählt ist aus der Gruppe bestehend aus: Polyisobutylenbernsteinsäureanhydrid (PIBSA), PIBSA-Aminderivaten, Polyisobutenylbernsteinsäureanhydrid (PIBDIBA), PIBDIBA-Derivaten, PIB-Lacton und seinen Aminoderivaten, Sorbitanmonooleat (SMO), Sorbitansesquioleat, Lecithin, Alkoxylaten, Esterkombinationen, Fettaminen, Alkyloxazolinen, Alkenyloxazolinen, Imidazolinen, Alkylsulfonaten, Alkylarylsulfonaten, Alkylsulfosuccinaten, Alkylphosphaten, Alkenylphosphaten, Phosphatestern und Gemischen davon.
  12. Zusammensetzung gemäß einem der Ansprüche 1-11, wobei die scheinbare Viskosität der Zusammensetzung zwischen 35 000 und 120 000 Centipoise (cP) beträgt.
  13. Zusammensetzung gemäß einem der Ansprüche 2-12, wobei die Dichte des sensibilisierten Emulsionsexplosivstoffs zwischen 0,4 und 1,25 Gramm pro cm3 beträgt.
  14. Zusammensetzung gemäß einem der Ansprüche 1-13, wobei die Brennstoffphase wenigstens ein Öl mit nicht mehr als 18 Kohlenstoffatomen in der Molekülstruktur, vorzugsweise 10 bis 18 Kohlenstoffatomen, aufweist.
  15. Verfahren zur Herstellung einer Explosivstoffzusammensetzung vom Emulsionstyp, welches Verfahren umfasst:
    - Bereitstellen einer Oxidationsmittelphase umfassend wenigstens 35 Gew.-% Wasserstoffperoxid und wenigstens 25 Gew.-% Wasser,
    - Bereitstellen einer Brennstoffphase umfassend wenigstens einen primären Brennstoff vom Öltyp mit einem Flammpunkt von unter 100 °C und wenigstens einen sekundären Brennstoff vom Öltyp mit einem Flammpunkt von über 150 °C,
    - Bereitstellen wenigstens eines Emulgators,
    - Bilden einer Emulsion, die die Oxidationsmittelphase, die Brennstoffphase und den Emulgator umfasst, wobei in der Emulsion die Oxidationsmittelphase diskontinuierlich in der kontinuierlichen Brennstoffphase verteilt ist, und
    - Sensibilisieren der Emulsion durch Zugeben von gasgefüllten komprimierbaren festen Mikroballons und/oder durch Erzeugen von Gasblasen mithilfe eines Gasierungsmittels und/oder durch Zugeben von Gasblasen zu der Emulsion.
EP21172315.0A 2021-05-05 2021-05-05 Zusammensetzung zur bildung eines sprengstoffs mit einer emulsion aus wasserstoffperoxid und einem ölartigen brennstoff Active EP4086238B1 (de)

Priority Applications (9)

Application Number Priority Date Filing Date Title
EP21172315.0A EP4086238B1 (de) 2021-05-05 2021-05-05 Zusammensetzung zur bildung eines sprengstoffs mit einer emulsion aus wasserstoffperoxid und einem ölartigen brennstoff
ES21172315T ES2976313T3 (es) 2021-05-05 2021-05-05 Composición para formar un explosivo que comprende una emulsión de peróxido de hidrógeno y un combustible de tipo aceite
AU2022269827A AU2022269827A1 (en) 2021-05-05 2022-05-04 Composition for forming an explosive comprising an emulsion of hydrogen peroxide and an oil type fuel
PCT/EP2022/062011 WO2022233952A1 (en) 2021-05-05 2022-05-04 Composition for forming an explosive comprising an emulsion of hydrogen peroxide and an oil type fuel
CA3217779A CA3217779A1 (en) 2021-05-05 2022-05-04 Composition for forming an explosive comprising an emulsion of hydrogen peroxide and an oil type fuel
US18/289,145 US20240239722A1 (en) 2021-05-05 2022-05-04 Composition for forming an explosive comprising an emulsion of hydrogen peroxide and an oil type fuel
PE2023003006A PE20242122A1 (es) 2021-05-05 2022-05-04 Composicion para formar un explosivo que comprende una emulsion de peroxido de hidrogeno y un combustible de tipo de aceite
CL2023003267A CL2023003267A1 (es) 2021-05-05 2023-11-03 Composición de explosivo que comprende emulsión de peróxido de hidrógeno y un combustible de aceite
ZA2023/11168A ZA202311168B (en) 2021-05-05 2023-12-04 Composition for forming an explosive comprising an emulsion of hydrogen peroxide and an oil type fuel

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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
DK2225175T3 (da) 2007-12-13 2013-03-18 Akzo Nobel Nv Stabiliserede hydrogenperoxidopløsninger
WO2013013272A1 (en) 2011-07-27 2013-01-31 Cmte Development Limited Ιμproved explosive composition
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PE20242122A1 (es) 2024-10-28
EP4086238A1 (de) 2022-11-09
WO2022233952A1 (en) 2022-11-10
CA3217779A1 (en) 2022-11-10
EP4086238C0 (de) 2024-01-03
AU2022269827A1 (en) 2023-12-21

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