EP4334269A1 - Zusammensetzung zur herstellung eines emulsionssprengstoffs auf wasserstoffperoxidbasis - Google Patents
Zusammensetzung zur herstellung eines emulsionssprengstoffs auf wasserstoffperoxidbasisInfo
- Publication number
- EP4334269A1 EP4334269A1 EP22727840.5A EP22727840A EP4334269A1 EP 4334269 A1 EP4334269 A1 EP 4334269A1 EP 22727840 A EP22727840 A EP 22727840A EP 4334269 A1 EP4334269 A1 EP 4334269A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phase
- composition
- oils
- fuel
- emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 239000000203 mixture Substances 0.000 title claims abstract description 107
- 239000000839 emulsion Substances 0.000 title claims abstract description 90
- 239000002360 explosive Substances 0.000 title claims abstract description 74
- 239000007787 solid Substances 0.000 claims abstract description 50
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000446 fuel Substances 0.000 claims abstract description 34
- 239000003463 adsorbent Substances 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 7
- 239000003921 oil Substances 0.000 claims description 60
- 235000019198 oils Nutrition 0.000 claims description 57
- 239000007789 gas Substances 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 30
- 239000007800 oxidant agent Substances 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 150000002823 nitrates Chemical class 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229920005652 polyisobutylene succinic anhydride Polymers 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 claims description 5
- 239000002250 absorbent Substances 0.000 claims description 5
- 230000002745 absorbent Effects 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 239000001593 sorbitan monooleate Substances 0.000 claims description 5
- 235000011069 sorbitan monooleate Nutrition 0.000 claims description 5
- 229940035049 sorbitan monooleate Drugs 0.000 claims description 5
- 239000000295 fuel oil Substances 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 241000209140 Triticum Species 0.000 claims description 3
- 235000021307 Triticum Nutrition 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- -1 alkoxylates Chemical class 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 235000000346 sugar Nutrition 0.000 claims description 3
- 150000008163 sugars Chemical class 0.000 claims description 3
- CUNWUEBNSZSNRX-RKGWDQTMSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;(z)-octadec-9-enoic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O CUNWUEBNSZSNRX-RKGWDQTMSA-N 0.000 claims description 2
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 claims description 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 2
- 229920002261 Corn starch Polymers 0.000 claims description 2
- 108010068370 Glutens Proteins 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 2
- 244000061456 Solanum tuberosum Species 0.000 claims description 2
- 235000002595 Solanum tuberosum Nutrition 0.000 claims description 2
- 229920002494 Zein Polymers 0.000 claims description 2
- 229940072056 alginate Drugs 0.000 claims description 2
- 235000010443 alginic acid Nutrition 0.000 claims description 2
- 229920000615 alginic acid Polymers 0.000 claims description 2
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 claims description 2
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 2
- 239000010692 aromatic oil Substances 0.000 claims description 2
- 239000012075 bio-oil Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 239000003240 coconut oil Substances 0.000 claims description 2
- 235000019864 coconut oil Nutrition 0.000 claims description 2
- 239000008119 colloidal silica Substances 0.000 claims description 2
- 239000008120 corn starch Substances 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 229940013317 fish oils Drugs 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- 235000021312 gluten Nutrition 0.000 claims description 2
- 150000002462 imidazolines Chemical class 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- 239000000787 lecithin Substances 0.000 claims description 2
- 235000010445 lecithin Nutrition 0.000 claims description 2
- 229940067606 lecithin Drugs 0.000 claims description 2
- 238000005461 lubrication Methods 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 229940100486 rice starch Drugs 0.000 claims description 2
- 229960005078 sorbitan sesquioleate Drugs 0.000 claims description 2
- 239000005019 zein Substances 0.000 claims description 2
- 229940093612 zein Drugs 0.000 claims description 2
- 239000012071 phase Substances 0.000 description 61
- 239000000243 solution Substances 0.000 description 23
- 230000008569 process Effects 0.000 description 20
- 238000005474 detonation Methods 0.000 description 15
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 238000004945 emulsification Methods 0.000 description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 9
- 206010070834 Sensitisation Diseases 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910002651 NO3 Inorganic materials 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 8
- 239000000499 gel Substances 0.000 description 8
- 238000005065 mining Methods 0.000 description 8
- 238000005422 blasting Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000008313 sensitization Effects 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000010408 film Substances 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 238000010276 construction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- 239000011435 rock Substances 0.000 description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000006399 behavior Effects 0.000 description 3
- 238000004581 coalescence Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004622 sleep time Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical class [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
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 liquid emulsifiers. The two phases are combined in a continuous or batch mixing process which normally implements pressurized high shear mixing.
- AN Ammonium nitrate
- NOx 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.
- 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. 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.
- 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.
- 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.
- Adsorption - Shall mean the ability and tendency of a solid particle to cling to the dissimilar particles or surfaces formed by the liquids in the peroxide-based composition.
- Coalescence - Shall mean the process by which the droplets of the two immiscible liquids in an emulsion pulls together to form larger droplets which destabilizes the emulsion and eventually separates the two liquids.
- Colloidal - Shall mean a characteristic of a solid particle which may be used to form a colloidal dispersion in a liquid.
- Emulsion - Shall mean a liquid dispersed and suspended in another liquid in the form of finely divided droplets and is a mixture between two immiscible liquids.
- An emulsion has higher viscosity than any of the immiscible liquids.
- Emulsifier - Shall mean a chemical molecule in liquid form with at least one lipophilic moiety and at least one hydrophilic moiety which may form a multi molecular film around the dispersed particles and may stabilize the two immiscible liquids by increasing the kinetic stability of the composition.
- Wetting - Shall mean the ability of a liquid to establish and maintain contact with a solid surface as a result of an intermolecular interaction between the solid and liquid through Adsorption.
- Solid adsorbent - Shall mean solid particles, or mixture of solid particles which cannot be solved into HP, water or oil. The particles may however be dispersed or suspended in a liquid medium.
- Finely divided - shall mean a material in a powder or pellets form, including particles suspended or dispersed in a liquid medium.
- Surfactant - Shall mean compounds that lower the surface tension between two liquids. Surfactant shall in this context have the same meaning as Emulsifier.
- 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 liquid emulsifier and at least one finely divided solid colloidal non-sensitizing adsorbent.
- 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 is commercially offered in liquid form and due to high viscosity in cold teperatures 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.
- emulsifiers may be supplied in liquid for with a reasonable solubility in oil. This is to allow for incorporation into the liquid oil-based fuel phase.
- oils and emulsifiers affects the ability to form a stable emulsion at cold temperatures and often, inconsistent stability overtime 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.
- the emulsifier molecule ’s lipophilic moiety bonds to the surface of an oil droplet and the hydrophilic moiety bonds to the surface of a proximate aqueous droplet forming a film between the droplets and bonding them through a polar/non-polar bonding force.
- 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 liquid 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 providing an oxidizer-phase comprising at least 15% by weight of hydrogen peroxide and at least 15% by weight of water, providing a fuel-phase comprising at least one oil type, providing at least one liquid emulsifier, providing at least one finely divided solid colloidal adsorbent, forming an emulsion comprising the oxidiser phase, the fuel-phase, the liquid emulsifier and the solid colloidal absorbent, and sensitizing the emulsion by adding gas filled compressible solid micro-balloons, and/or by generating gas bubbles by means of a gassing agent and/or by adding gas bubbles to the emulsion.
- the liquid emulsifier and/or the solid colloidal 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 collodial 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 colloidal 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 (CH3COOH) 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.
- 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 Such compositions may have the properties listed in Table 2: Table 2: Properties of the exemplifying compositions
- 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.
- 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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PCT/EP2022/062007 WO2022233948A1 (en) | 2021-05-05 | 2022-05-04 | Composition for forming a hydrogen peroxide based emulsion explosive |
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US7491279B1 (en) | 2004-12-09 | 2009-02-17 | The United States Of America As Represented By The Secretary Of The Navy | Emulsion explosive |
EP2225175B1 (de) | 2007-12-13 | 2012-12-12 | Akzo Nobel N.V. | Stabilisierte wasserstoffperoxidlösungen |
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