EP2367776A1 - Amine reacted alpha, beta-unsaturated carbonyl compound thickened explosive emulsions - Google Patents
Amine reacted alpha, beta-unsaturated carbonyl compound thickened explosive emulsionsInfo
- Publication number
- EP2367776A1 EP2367776A1 EP09833946A EP09833946A EP2367776A1 EP 2367776 A1 EP2367776 A1 EP 2367776A1 EP 09833946 A EP09833946 A EP 09833946A EP 09833946 A EP09833946 A EP 09833946A EP 2367776 A1 EP2367776 A1 EP 2367776A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- emulsion
- emulsion explosive
- thickened
- unsaturated carbonyl
- amine
- 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.)
- Withdrawn
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 393
- 239000002360 explosive Substances 0.000 title claims abstract description 247
- 150000001728 carbonyl compounds Chemical class 0.000 title claims abstract description 93
- 150000001412 amines Chemical class 0.000 title description 46
- -1 amine compound Chemical class 0.000 claims abstract description 93
- 230000008719 thickening Effects 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 50
- 239000000446 fuel Substances 0.000 claims description 50
- 238000011068 loading method Methods 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 42
- 239000003995 emulsifying agent Substances 0.000 claims description 29
- 239000007800 oxidant agent Substances 0.000 claims description 29
- 238000004806 packaging method and process Methods 0.000 claims description 20
- 238000005422 blasting Methods 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000002562 thickening agent Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 description 70
- 239000012071 phase Substances 0.000 description 62
- 239000000376 reactant Substances 0.000 description 52
- 239000000047 product Substances 0.000 description 47
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 35
- DSROZUMNVRXZNO-UHFFFAOYSA-K tris[(1-naphthalen-1-yl-3-phenylnaphthalen-2-yl)oxy]alumane Chemical compound C=1C=CC=CC=1C=1C=C2C=CC=CC2=C(C=2C3=CC=CC=C3C=CC=2)C=1O[Al](OC=1C(=C2C=CC=CC2=CC=1C=1C=CC=CC=1)C=1C2=CC=CC=C2C=CC=1)OC(C(=C1C=CC=CC1=C1)C=2C3=CC=CC=C3C=CC=2)=C1C1=CC=CC=C1 DSROZUMNVRXZNO-UHFFFAOYSA-K 0.000 description 32
- 230000000295 complement effect Effects 0.000 description 31
- 239000003921 oil Substances 0.000 description 29
- 239000002243 precursor Substances 0.000 description 28
- 235000019198 oils Nutrition 0.000 description 26
- 238000004519 manufacturing process Methods 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 23
- 230000000694 effects Effects 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 19
- 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 14
- 150000003839 salts Chemical class 0.000 description 14
- 238000003860 storage Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000011159 matrix material Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 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
- 230000008569 process Effects 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- 241000196324 Embryophyta Species 0.000 description 10
- 235000010469 Glycine max Nutrition 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- 238000009472 formulation Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 10
- 230000008859 change Effects 0.000 description 9
- 238000012669 compression test Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000001993 wax Substances 0.000 description 9
- 230000003068 static effect Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000002285 corn oil Substances 0.000 description 7
- 235000005687 corn oil Nutrition 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 229920000459 Nitrile rubber Polymers 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 6
- 239000002283 diesel fuel Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000000518 rheometry Methods 0.000 description 5
- 235000010344 sodium nitrate Nutrition 0.000 description 5
- 239000004317 sodium nitrate Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- 150000003141 primary amines Chemical group 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000007762 w/o emulsion Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000007764 o/w emulsion Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920005372 Plexiglas® Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 235000012054 meals Nutrition 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229920005652 polyisobutylene succinic anhydride Polymers 0.000 description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 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 description 1
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920013646 Hycar Polymers 0.000 description 1
- 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 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- KHPLPBHMTCTCHA-UHFFFAOYSA-N ammonium chlorate Chemical compound N.OCl(=O)=O KHPLPBHMTCTCHA-UHFFFAOYSA-N 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 229940092738 beeswax Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000828 canola oil Substances 0.000 description 1
- 235000019519 canola oil Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000008121 dextrose Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010685 fatty oil Substances 0.000 description 1
- 229940013317 fish oils Drugs 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052806 inorganic carbonate Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 125000004971 nitroalkyl group Chemical group 0.000 description 1
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 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
- C06B23/001—Fillers, gelling and thickening agents (e.g. fibres), absorbents for nitroglycerine
Definitions
- the present invention relates to emulsion explosives and, in particular, to emulsion explosives with desirable rheology characteristics.
- the present invention also relates to methods for producing such emulsion explosives, to their use and to methods of blasting that utilise them.
- Emulsion explosives are widely used in the explosives industry. They include an aqueous oxidizer phase dispersed in a fuel phase, or vice versa.
- a desirable property of emulsion explosives is that they are of low viscosity during processing and handling but of high viscosity in packaged cartridges or as a bulk product following loading into a borehole. This combination of viscosity properties facilitates efficient processing and provides excellent properties in the field. During processing low viscosities ease pumping, improve the flow of emulsion in pipes and hoses, and minimise adhesion to the walls of tanks and conduits of manufacturing systems. Higher viscosities in packaged products permit good tamping and allow cartridges to be cut cleanly.
- the present invention seeks to provide an alternative to the presently available emulsion explosives thickened using waxes and resins that does not suffer the practical drawbacks discussed above or, at least, a useful alternative thereto.
- a method of producing a thickened emulsion explosive comprises reacting in an emulsion explosive an amine compound and an ⁇ , ⁇ -unsaturated carbonyl compound such that thickening of the emulsion explosive occurs.
- the invention further provides a thickened emulsion explosive produced in accordance with this method.
- a thickened emulsion explosive produced by the method of the present invention, i.e. containing a thickening agent comprising the reaction product of an amine compound and an ⁇ , ⁇ - unsaturated carbonyl compound.
- Also provided is a method of loading a borehole with a thickened emulsion explosive which comprises introducing an emulsion explosive into the borehole and reacting (in the borehole) an amine compound and an ⁇ , ⁇ -unsaturated carbonyl compound in the emulsion explosive such that thickening of the emulsion explosive occurs.
- a method of producing a packaged emulsion explosive which method comprising reacting in an emulsion explosive an amine compound and an ⁇ , ⁇ -unsaturated carbonyl compound such that thickening of the emulsion explosive occurs, and packaging the emulsion explosive.
- a method of producing a thickened emulsion explosive comprises forming an emulsion explosive by mixing an aqueous oxidizer phase, a fuel phase and an amine compound and reacting in the emulsion explosive the amine compound and an ⁇ , ⁇ -unsaturated carbonyl compound such that thickening of the emulsion explosive occurs.
- the amine compound and the ⁇ , ⁇ - unsaturated carbonyl compound are contacted and reacted whilst the emulsion explosive is being mixed in order to form a thickened emulsion explosive.
- Also provided is a method of loading a borehole with a thickened emulsion explosive which comprises forming an emulsion explosive by mixing an aqueous oxidizer phase, a fuel phase and an amine compound, introducing the emulsion explosive into the borehole and reacting (in the borehole) the amine compound and an ⁇ , ⁇ -unsaturated carbonyl compound emulsion such that thickening of the emulsion explosive occurs.
- Another related aspect provides is a method of producing a packaged emulsion explosive, which method comprises forming an emulsion explosive by mixing an aqueous oxidizer phase, a fuel phase and an amine compound, reacting the amine compound and an ⁇ , ⁇ - unsaturated carbonyl compound in the emulsion explosive such that thickening of the emulsion explosive occurs, and packaging the resultant emulsion explosive.
- Figure 1 is a schematic illustrating implementation of an embodiment of the present invention
- Figure 2 is a schematic of a process for producing a packaged thickened emulsion explosive
- Figure 3 is a process flow diagram of a plant for producing a packaged thickened emulsion explosive
- Figure 4 is a graph of the compression test results for Example 4.
- Figure 5 is a graph of the compression test results for Example 4.
- Figure 6 is a graph of the compression test results for Example 4.
- Figure 7 is a graph of the compression test results for Example 12.
- Figure 8 is a graph of the compression test results for Example 12.
- Figure 9 is a graph of the compression test results for Example 12. DETAILED DESCRIPTION OF THE INVENTION
- the first aspect of the present invention is based on the selection of suitable amine and ⁇ , ⁇ -unsaturated carbonyl compounds that will react with each other in an emulsion explosive to provide a desirable rheological effect, namely thickening of the emulsion explosive.
- the first aspect requires incorporation of appropriate amine and ⁇ , ⁇ - unsaturated carbonyl compounds into the emulsion explosive in a suitable manner and in sufficient amounts to achieve a desired thickening of the emulsion explosive.
- the degree of thickening that is achieved will depend upon a variety of factors including the selection of the ⁇ , ⁇ -unsaturated carbonyl compound and the amine compound, the relative proportions of the ⁇ , ⁇ -unsaturated carbonyl compound and the amine compound to each other and to the other components of the emulsion explosive, and the extent to which the amine and ⁇ , ⁇ -unsaturated carbonyl compounds are dispersed in the emulsion explosive. These parameters may be varied in order to control the degree of rheological change that takes place in accordance with this aspect of the present invention.
- the amine compound and the ⁇ , ⁇ -unsaturated carbonyl compound react within the body of the emulsion explosive by a Michael-type addition reaction resulting in the formation of a crosslinked polymeric network within the emulsion explosive. It is this crosslinked network that is believed to result in thickening of the (base) emulsion explosive. This may be because the network in some way binds or interacts with molecules of the fuel phase within the emulsion explosive thereby limiting mobility of such molecules. The extent to which this network forms will influence the extent to which the emulsion explosive is thickened. At one extreme the formation of the crosslinked network may be extensive enough to result in a continuous network extending through the emulsion explosive. In all aspects of the present invention, thickening includes polymerization.
- the amine and ⁇ , ⁇ -unsaturated carbonyl compounds, and the amounts thereof, are selected on the basis of suitably reactive combinations.
- the amine and ⁇ , ⁇ -unsaturated carbonyl compounds should react with each other at an appropriate rate at the prevailing processing temperature.
- the reaction between the ⁇ , ⁇ -unsaturated carbonyl compound and the amine compound should not destabilise or have a detrimental effect upon the properties of the emulsion explosive.
- the reaction of the amine and ⁇ , ⁇ - unsaturated carbonyl compounds should not devalue the detonability or basic explosive energy of the emulsion explosive.
- suitable amine and ⁇ , ⁇ -unsaturated carbonyl compounds and the optimum amounts to be used may be determined experimentally.
- any amine compound and ⁇ , ⁇ -unsaturated carbonyl compound that undergo a Michael-type addition reaction and that cause thickening of an emulsion explosive may be used in the present invention.
- any amine compound and ⁇ , ⁇ -unsaturated carbonyl compound that undergo a Michael-type addition reaction and that cause thickening of an emulsion explosive may be used in the present invention.
- each compound should have suitably available and reactive sites.
- each compound should have multiple reactive sites so that an extensive crosslinked network can be formed.
- a reactive site of the amine or ⁇ , ⁇ - unsaturated carbonyl compound may also be preferred for a reactive site of the amine or ⁇ , ⁇ - unsaturated carbonyl compound to be capable of reacting with more than one molecule of the complementary reactant. In that case the number of reactive sites per molecule of the respective compound may be reduced whilst retaining high crosslinking ability.
- a lower degree of substitution may be required in an amine compound substituted with primary amine reactive sites when compared to a compound having secondary amine reactive sites due to the increased capacity of a primary amine to bond with an ⁇ , ⁇ -unsaturated carbonyl compound.
- the amine compound will be a polyamine having at least two primary amine functionalities that are suitably reactive towards the ⁇ , ⁇ -unsaturated carbonyl compound.
- the latter may also include more than one reactive site viz-a-viz the amine.
- amine-terminated polymer may be selected as a suitable amine compound.
- the amine compound include at least two primary amine groups that are reactive toward the ⁇ , ⁇ - unsaturated carbonyl. Secondary amine functionalities may be present provided they give the requisite reactivity.
- the amine compound may also include one or more functionalities that render the amine moieties more nucleophilic and thus reactive with respect to the ⁇ , ⁇ -unsaturated carbonyl compound.
- One skilled in the art would be familiar with such functionalities.
- Examples of compounds that have been found to be useful in practice of the first aspect of the present invention include amine-terminated butadiene-acrylonitrile copolymers of formula:
- m is about 10 - 170 and n is about 2 — 60 and such that the proportion of acrylonitrile in the copolymer can range from about 10-30%.
- the amine-terminated butadiene-acrylonitrile copolymers found to be useful have molecular weights of approximately 4000. Accordingly, in those embodiments m is around 50-70 and n is around 5-25.
- Such compounds are commercially available, for example Hycar Reactive Liquid Polymer ATBN 1300X21.
- the ⁇ , ⁇ -unsaturated carbonyl compound may be an ⁇ , ⁇ -unsaturated aldehyde or ketone, or any other Michael-type acceptor.
- the general structure of an ⁇ , ⁇ -unsaturated carbonyl compound is shown below.
- Examples of readily available compounds that have been found to be useful in practice of the first aspect of the invention include ⁇ , ⁇ -unsaturated acrylates, such as epoxidized vegetable oils. Examples of such include epoxidized soya oil, expoxidised castor oil, expoxidised rape-seed oil and epoxidized linseed oil. The use of epoxidized soy oil acrylate may be preferred. An example of the structure of a typical epoxidized soy oil acrylate is shown below.
- the ⁇ , ⁇ -unsaturated acrylates may be derived from mineral oils, for example, the ⁇ , ⁇ -unsaturated acrylates may be an ethoxylated trimethylopropane triacrylate in which the number of epoxylated groups may be at least three and may be in excess of 20.
- a polymeric ⁇ , ⁇ -unsaturated acrylate may be desirable to use.
- Suitable polymeric ⁇ , ⁇ -unsaturated acrylates may be selected from the group consisting of polyisoprene diacrylate, polybutadiene diacrylate, copolymers thereof and mixtures thereof. It is possible to use one or more amine compounds and one or more ⁇ , ⁇ -unsaturated carbonyl compounds in order to achieve the desired effect in accordance with the first aspect of the present invention.
- the amine compound is an amine-terminated butadiene-acrylonitrile copolymer of the formula shown below and the ⁇ , ⁇ -unsaturated carbonyl compound is epoxidized soy oil acrylate of the formula shown below.
- the value of m is approximately 67 and the value of n is approximately 8.
- the formula shown below only illustrates a single reactive site of the epoxidized soy oil acrylate.
- the epoxidized soy oil acrylate may have at least two reactive sites and will typically be derived from epoxidized soy oil with an average of 4.1 - 4.6 epoxy rings per triglyceride molecule.
- Reaction of these compounds is believed to give a product in which the amine compound is bonded to at least two, preferably three or four, molecules of the acrylate. This is illustrated in the following reaction scheme in which the reaction product includes three moieties derived from the acrylate bound to an amine molecule.
- the first aspect of the present invention is implemented by formulating a modified emulsion composition comprising the amine compound or ⁇ , ⁇ -unsaturated carbonyl compound, and by introducing into the modified emulsion the complementary reactant when thickening is required.
- the amine or ⁇ , ⁇ -unsaturated carbonyl compound is blended with the fuel component prior to formation of the emulsion, or it may be added externally after the base emulsion explosive has been formed. In the latter case it is likely that the reactant compound will migrate to the fuel phase.
- the base emulsion may be of conventional type and may be formulated in conventional manner.
- the emulsion may be an oil-in-water emulsion but the first aspect may have greater applicability in relation to water-in-oil emulsions.
- the ⁇ , ⁇ -unsaturated carbonyl compound will be the reactant that is added to the fuel phase of the emulsion or externally to the emulsion.
- the base emulsion or the modified emulsion may be sensitized using conventional methods such as, for example, through the addition of glass or plastic microspheres. It is also possible to add substances or mixtures of substances which are oxygen releasing salts or which are themselves suitable as explosive materials.
- the thickened emulsion explosive may be a gassed product and/or the density of the product may be varied as appropriate using known techniques. However, the application of these techniques, such as gassing the emulsion explosive, may need to be modified to ensure that adequate modification is performed prior to the completion of the thickening reaction.
- the relevant reactant is thoroughly dispersed in the emulsion explosive composition prior to addition of the complementary reactant.
- amine and ⁇ , ⁇ - unsaturated carbonyl compounds may constitute a relatively small proportions of the emulsion explosive composition, effective mixing may be very important to ensure that the reaction takes place throughout the composition.
- the appropriate degree of mixing may be achieved through the use of in-line static mixers.
- the emulsion explosive composition containing the relevant reactant may be prepared and stored, and possibly transported, as necessary prior to use. If stored it may be desirable to agitate the emulsion explosive composition thoroughly prior to use.
- Addition of the amine or ⁇ , ⁇ -unsaturated carbonyl compound to the base emulsion explosive (and thorough blending therewith) preferably does not cause any significant viscosity increase in itself. Some viscosity change can be tolerated provided it does not make subsequent handling and processing unduly difficult.
- the complementary reactant is added to the formulated modified emulsion when the thickening effect is required to take place. At that time it is believed to be important that the complementary reactant is mixed thoroughly into the modified emulsion so that reaction between the amine and ⁇ , ⁇ -unsaturated compounds takes place throughout the emulsion explosive composition. In this way localised thickening can be avoided.
- the complementary reactant is dispersed in the modified emulsion it is possible to first dissolve or disperse the reactant into a solvent comprising the fuel as the fuel component, or materials compatible with the fuel component, for example corn oil.
- the complementary reactant may be combined with the solvent in a 50/50 ratio determined by weight.
- the ratio by weight of the amine compound to ⁇ , ⁇ -unsaturated carbonyl compound will be between 10:1 and 1:3, preferably the ratio is around 1:2.
- the total weight of amine and ⁇ , ⁇ -unsaturated carbonyl compounds included or to be included in the emulsion explosive composition will be 0.4-2.5% based on the total weight of the emulsion explosive composition.
- the thickened emulsion explosives in accordance with the first aspect of the present invention may be utilised in packaged or bulk explosives suitable for surface or underground applications.
- the thickened emulsion explosive may be prepared by a number of different methods, depending upon the ultimate use of the product. When preparing packaged product a relatively slow thickening effect may be tolerated with the full extent of the rheological change taking place prior to cutting and packaging. Alternatively, components may be mixed thoroughly just prior to packaging with the thickening effect developing within the packaging.
- the thickening reaction will occur at the prevailing temperature used in the production of conventional emulsion explosives.
- the thickening reaction may be occur across a range of temperatures from about 15 0 C to about 100 0 C.
- the rate of thickening increases with temperature and at the upper end of the temperature range the reaction may be instantaneous.
- the rate of thickening may also be varied through the addition of a polyvalent inorganic salt or polyvalent organic salt.
- the addition of calcium nitrate to the emulsion explosive can increase the rate of thickening.
- the degree to which the resulting emulsion explosive is thickened can vary. Thickening includes an increase in viscosity and a degree of rheological change up to, and including, the formation of a thickened emulsion explosive with a non-fluid, deformable rheology such as a stiff gel.
- the thickened emulsion explosive composition has a viscosity of 40,000 - 1,000,000+ cps, as measured a Brookfield Viscometer using T bar E or F.
- it takes the form of a stiff gel. This property in particular makes the composition of great utility in bulk applications where up-hole retention is required.
- Embodiments of the thickened emulsion explosive may be thickened to such a degree that it may be possible to cut the stiff gel formed and have the cut product retain its shape. Accordingly, it may be possible to further process the composition to form a granulated product. It is of course possible to manipulate the final viscosity as might be required in the field.
- the resulting degree of rheological change can be maintained across a range of temperatures.
- the ease with which the thickened emulsion explosive may be cut is not usually significantly affected over such temperature ranges. Accordingly, the properties of a thickened emulsion explosive in accordance with the invention may not be sensitive to temperature fluctuations.
- the thickened emulsion explosive When used as a bulk product it is important that the thickening effect takes place within a borehole that is being loaded rather than in the equipment used for formulation and pumping of the bulk product. If thickening takes place within this equipment, loading difficulties and fouling may occur.
- the thickened emulsion explosive when using the thickened emulsion explosive as a bulk product it may be desirable for the thickening effect to take place very rapidly and preferably instantaneously when the respective reactants come into contact with each other within the emulsion explosive. Rapid thickening is especially important when loading up-holes or upwardly included boreholes where product retention is vital. In such cases, if the thickening effect associated with this aspect of the invention is too slow, the bulk product will not be retained in place as required.
- one loading hose may be used to deliver emulsion explosive composition containing one of the reactants into the borehole with a separate loading hose delivering the complementary reactant. Mixing of these individual components as they exit the respective loading hoses may be achieved using a suitable mixing nozzle.
- the loading hoses may be arranged in parallel along a common axis. In a preferred arrangement one component may be delivered down a loading hose provided as a centre-line within another larger diameter hose, i.e. as a concentric arrangement. In both cases a nozzle mixer may be used to thoroughly blend the components as they exit respective loading hoses.
- FIG. 1 A schematic of a preferred loading hose (10) for the production of a thickened bulk product is shown in Figure 1.
- a modified emulsion which comprises a preferred ⁇ , ⁇ -unsaturated carbonyl compound, epoxidized soy oil acrylate, is pumped from bulk emulsion storage tank (11) using a pump (12) and into the loading hose (10).
- the complementary reactant, the amine compound is centre line injected using pump (13) through the complementary reactant line (14) into the loading hose.
- a static mixer (17) is positioned at the nozzle (15) and mixes the modified emulsion and complementary reactant together to form the thickened emulsion explosive.
- a packaged thickened emulsion explosive by producing the modified emulsion at a bulk emulsion plant and then transporting the first component to a packaging facility.
- the emulsion may be transported to a packaging facility (regional packaged plant) where it may be stored in silos.
- the product may then be pumped into the blender where it is sensitized.
- the sensitized emulsion may also be stored in a silo prior to use.
- the modified emulsion and complementary reactant are combined to form the thickened product.
- the base emulsion may be produced at a bulk emulsion plant, then modified through the addition of a reactant at the packaging plant and stored prior to being combined with the complementary reactant.
- the thickened emulsion explosive may be packaged to the desired diameter after the emulsion has thickened.
- the emulsion explosive composition may be packaged as the emulsion thickens. If a significant proportion of any reaction between the amine compound and the ⁇ , ⁇ -unsaturated carbonyl compound takes place during packaging, infrastructure costs may be reduced by removing the need to use the cooling bath that is often required for the production of explosive compositions thickened using waxes. However, in embodiments it may be desirable for the majority of the thickening to occur after packaging.
- FIG. 2 is a schematic of the process used to package the thickened emulsion explosive in accordance with the method previously described.
- a modified emulsion which comprises a preferred ⁇ , ⁇ -unsaturated carbonyl compound, epoxidized soy oil aery late, is pumped from a bulk emulsion storage tank (18) using a pump (not shown) and into the emulsion line (20).
- the complementary reactant, the amine compound is centre line injected using pump (21) through the complementary reactant line (22) into the emulsion line (20).
- As the components are pumped through the emulsion line (20) into the cartridge production unit (19) they are combined using a static mixer (23) to produce the thickened emulsion explosive.
- the cartridges of the thickened emulsion explosive are transported by a conveyor belt (24) to the packaging unit (25).
- Figure 3 illustrates a process flow diagram of a packaging plant suitable for use in accordance with the method previously described.
- a modified emulsion comprising an ⁇ , ⁇ -unsaturated carbonyl compound, for example a epoxidized soy oil acrylate, is pumped from a production plant transport truck (26) into a bulk emulsion storage tank (28) using a pump (27).
- Bulk sensitizing agents, including microballoons, other components, such as ammonium nitrate prills and granulated aluminium powder are transferred into respective feed hoppers (29), (30) and (31). These additives agents are then fed into a primary hopper (32) via their respective transport lines (34), (35) and (36).
- the first component is also pumped through line (38) into the primary hopper (32) using a feed pump (37).
- the modified emulsion and the sensitizing agents are combined using a ribbon blender (39) to produce a sensitized emulsion, which is transported from the ribbon blender (39) via a line (40) using an unloading pump (41).
- the sensitized emulsion is pumped through a line (42) into the sensitized emulsion storage tank (44). Samples of the sensitized emulsion may be collected using a sample port (43).
- the complementary reactant, the amine compound is unloaded and weighed using scales (45) before being loaded into the complementary reactant storage tank (46).
- the sensitized emulsion is pumped into the flow line (51) using a feed pump (50).
- the complementary reactant is pumped through line (47) using feed pump (48) before being centre line injected into the flow line (51) using an injector (49).
- the modified emulsion and complementary reactant in the flow line (51) are then combined using static mixers (52) to produce the thickened emulsion explosive.
- the thickened emulsion explosive is transported via a line (53) into the packaging machine (54).
- the packaged thickened emulsion explosive is then transported using conveyor belts (55) and (56) to the boxing station (57) where it is prepared for transportation.
- the second aspect of the present invention and related embodiments are based on the selection of suitable amine compounds that will form an emulsion explosive when mixed with the aqueous oxidizer phase and a fuel phase. That is, in certain embodiments the amine compound functions as an emulsifier, thereby removing the need to use a separate (conventional) emulsifier to form an emulsion of the aqueous and fuel phases.
- suitable amine compounds are ones that will react with suitable ⁇ , ⁇ - unsaturated carbonyl compounds to give a desirable rheological effect thereby producing a thickened emulsion explosive comprising the aqueous oxidizer phase and the fuel phase components.
- Embodiments in accordance with the second aspect of the invention require the addition of appropriate amine compounds to the aqueous oxidizer phase and a fuel phase in a suitable manner and in sufficient amounts to achieve the desired emulsifying effect to form an emulsion explosive. Furthermore, these embodiments then require the addition of an appropriate ⁇ , ⁇ -unsaturated carbonyl compounds to the emulsion explosive in a suitable manner and in sufficient amounts to achieve a desired thickening effect by reaction in the emulsion of the amine compound and ⁇ , ⁇ -unsaturated carbonyl compound.
- the second aspect of the present invention provides a method of forming an emulsion explosive followed by thickening of the emulsion explosive.
- the degree of thickening that is achieved will depend upon a variety of factors including the selection of the ⁇ , ⁇ -unsaturated carbonyl compound and the amine compound, the relative proportions of the ⁇ , ⁇ -unsaturated carbonyl compound and the amine compound to each other and to the other components of the emulsion explosive, and the extent to which the amine and ⁇ , ⁇ -unsaturated carbonyl compounds are dispersed in the aqueous oxidizer phase and the fuel phase. These parameters may be varied in order to control the degree of rheological change that takes place in accordance with the second aspect of the present invention. These parameters will also influence the degree of emulsification that occurs.
- the amine compound and the ⁇ , ⁇ - unsaturated carbonyl compound react by a Michael-type addition reaction, as discussed above in relation to the first aspect of the present invention, to form a crosslinked polymeric network in the finished emulsion explosive.
- the considerations relating selection of the reactants for the first aspect apply equally to embodiments in accordance with the second aspect.
- the same exemplary reactants as the first aspect may be useful in the second aspect of the invention.
- the formation of a crosslinked polymeric network which results in thickening of the emulsion explosive, also assists in achieving stable emulsification. This may be because the network in some way binds or interacts with molecules of the fuel phase thereby limiting mobility of such molecules.
- the limited mobility of the fuel phase molecules is believed to assist in maintaining the dispersion of the aqueous oxidizer phase and accordingly the formation of an emulsion.
- the amine compound may be used in conjunction with a conventional emulsifier for production of the emulsion explosive. However, emulsification will typically be performed without conventional emulsifiers.
- the emulsion explosive may be formed by (vigorous) mixing of known fuel phase and oxidiser phase combinations with one or more appropriate amine compounds.
- the emulsion is formed using the amine compound as emulsifier, with the complementary reactant, i.e. the ⁇ , ⁇ -unsaturated carbonyl compound, being mixed into the emulsion explosive when thickening is required.
- Addition of the ⁇ , ⁇ - unsaturated carbonyl compound may also refine the structure of the emulsion formed using the amine compound alone.
- the emulsion formed using the amine should be intact when the complementary reactant is added and mixed into the emulsion. The stability of the emulsion formed using the amine will therefore influence how the second aspect of the invention is implemented.
- the bulkiness, molecular weight, degree of branching, number of functional groups and/or concentration of the amine compound may influence the viscosity characteristics of the emulsion explosive that is formed and its stability.
- Amine compounds with two or more terminal functional groups have been found to be particularly useful as emulsifiers in practice of the invention.
- Useful multi-functional amine compounds are generally polymeric with polar, hydrophilic head groups connected to lipophilic hydrocarbon segments. These polymeric amine compounds have sufficient conformational freedom and flexibility for each amine terminal (head) group to interact with the aqueous phase of the emulsion and for the lipophilic segments to interact with the fuel phase.
- the viscosity of the emulsion explosive may increase significantly and blending in the ⁇ , ⁇ -unsaturated carbonyl and further processing may become difficult.
- the selection of an amine compound with relevant functionality and an appropriate molecular weight is particularly important when the amine compound is selected to act as an emulsifier.
- the amine compound may be blended with the fuel component prior to formation of the emulsion explosive, or it may be added externally after a precursor emulsion comprising the aqueous oxidiser and fuel phases has been formed. In the latter case it is likely that the amine compound will migrate to the fuel phase.
- the precursor emulsion may be an oil-in- water emulsion, but this aspect of the invention may have greater applicability in relation to water-in-oil emulsions.
- the thickened emulsion explosive may be sensitized or gassed using conventional methods. Substances or mixtures of substances which are oxygen releasing salts or which are themselves suitable as explosive materials may also be added.
- the thickened emulsion explosive may be a gassed product and/or the density of the product may be varied as appropriate using known techniques.
- the amine compound is thoroughly dispersed in the emulsion explosive prior to addition of the ⁇ , ⁇ -unsaturated carbonyl compound. Thorough dispersion of the amine compound will generally occur during formation of the emulsion explosive.
- the amine and ⁇ , ⁇ -unsaturated carbonyl compounds may constitute a relatively small proportion of the emulsion explosive and effective mixing may be very important to ensure that the reaction takes place throughout the explosive. The appropriate degree of mixing may be achieved through the use of in-line static mixers.
- the ⁇ , ⁇ -unsaturated carbonyl compound is added to the emulsion when the thickening effect is required to take place. At that time it is believed to be important that the ⁇ , ⁇ - unsaturated carbonyl compound is mixed thoroughly into the emulsion so that reaction between the amine and ⁇ , ⁇ -unsaturated compounds takes place throughout the emulsion. In this way localised thickening can be avoided.
- a suitable solvent which may comprise the fuel as the fuel component, or materials compatible with the fuel component, for example corn oil.
- the ⁇ , ⁇ -unsaturated carbonyl compound may be combined with the solvent in a 50/50 ratio determined by weight.
- the relative proportions of the amine or ⁇ , ⁇ -unsaturated carbonyl compounds are generally the same as those for the first aspect of the invention.
- the total weight of amine and ⁇ , ⁇ -unsaturated carbonyl compounds to be included in the emulsion explosive composition will be 0.4-2.5% based on the total weight of the emulsion explosive composition. Adding the amine compound at a proportion of around 1% based upon the total weight has been found useful when the amine compound acts as the emulsifying agent.
- the thickened emulsion explosives in accordance with the second aspect may be utilised for the same applications as those in accordance with the first aspect.
- the thickening reaction and the resulting thickened emulsion explosive tend to have similar characteristics across all aspects of the invention.
- a thickened emulsion explosive in accordance with the second aspect of the invention may be used as a bulk product.
- one loading hose may be used to deliver a emulsion explosive formed using the amine compound into the borehole with a separate loading hose delivering the ⁇ , ⁇ -unsaturated carbonyl compound.
- Mixing of the ⁇ , ⁇ -unsaturated carbonyl compound and the emulsion explosive as they exit the respective loading hoses may be achieved using a suitable mixing nozzle.
- the loading hoses may be arranged in parallel along a common axis.
- one component may be delivered down a loading hose provided as a centre-line within another larger diameter hose, i.e. as a concentric arrangement.
- a nozzle mixer may be used to thoroughly blend the components as they exit respective loading hoses.
- Figure 1 may also be useful in illustrating implementation of the second aspect of the invention.
- an emulsion explosive which comprises as emulsifier an amine compound, an amine-terminated butadiene-acrylonitrile copolymer, is pumped from bulk emulsion storage tank (11) using a pump (12) and into the loading hose (10). While in the storage tank (11) the emulsion explosive may be agitated to prevent the phases from separating.
- the complementary reactant, the ⁇ , ⁇ -unsaturated carbonyl compound e.g. epoxidized soy oil acrylate
- ⁇ , ⁇ -unsaturated carbonyl compound As the ⁇ , ⁇ -unsaturated carbonyl compound is pumped towards the nozzle (15) of the loading hose (10) it passes through a water ring injector (16).
- a static mixer (17) is positioned at the nozzle (15) and mixes the emulsion explosive and ⁇ , ⁇ -unsaturated carbonyl compound together to form the thickened emulsion explosive.
- the amine compound used to form the emulsion explosive should result in a stable (intact) emulsion. Otherwise, the phases of the emulsion may separate in the borehole. Once in the borehole the reactants will react thereby thickening the emulsion explosive. Thus, in accordance with this aspect of the invention it is possible to load the borehole with an emulsion explosive, which will continue to thicken once it is in the borehole.
- a packaged thickened emulsion explosive by producing an emulsion explosive using the amine as emulsifier, which may also be sensitized.
- the emulsion explosive and ⁇ , ⁇ -unsaturated carbonyl compound are combined to form a thickened product which is then packaged.
- the thickened emulsion explosive may be packaged to the desired diameter after the majority of the thickened has occurred.
- the emulsion explosive composition may be packaged as the emulsion thickens. If a significant proportion of any reaction between the amine compound and the ⁇ , ⁇ -unsaturated carbonyl compound takes place during packaging, infrastructure costs may be reduced by removing the need to use a cooling bath. However, depending upon the relative stability of the emulsion explosive, in some embodiments it may be desirable for the majority reaction between the reactants, and accordingly the thickening, to occur after packaging.
- an emulsion explosive which comprises a preferred amine compound, an amine-terminated butadiene-acrylonitrile copolymer, is pumped from a bulk emulsion storage tank (18) using a pump (not shown) and into the emulsion line (20) before proceeding as described above to product the packaged thickened emulsion explosive.
- Figure 3 illustrates a process flow diagram of a packaging plant which may be modified so it is suitable for use in accordance with the method previously described for the second aspect of the invention.
- the emulsion explosive may be produced onsite rather than at a separate production plant. Accordingly, the production plant transport truck (26) would be replaced by amine compound, fuel phase component and oxidizer phase component storage tanks and blenders suitable for producing the emulsion explosive.
- the emulsion explosive may be sensitized in the same manner as described above. However, the sensitized emulsion explosive may require agitation in the sensitized emulsion storage tank (44) to prevent phase separation. The remainder of the manufacturing process may be performed as described above in relation to the aspect related to the first aspect of the present invention.
- a precursor emulsion may be formed using a conventional emulsif ⁇ er or amine emulsifier as discussed herein. This precursor emulsion may be formed by (vigorous) mixing of known fuel phase and oxidiser phase combinations with the emulsifier(s). However, the precursor emulsion is not stable until the addition of and blending with the reactive amine and ⁇ , ⁇ -unsaturated carbonyl compounds to produce a thickened emulsion explosive.
- precursor emulsion may be formed so as to include either the amine compound or ⁇ , ⁇ -unsaturated carbonyl compound, with the complementary reactant, i.e. the ⁇ , ⁇ - unsaturated carbonyl compound or amine, being mixed into the precursor emulsion when thickening is required.
- the complementary reactant i.e. the ⁇ , ⁇ - unsaturated carbonyl compound or amine
- Formation of the precursor emulsion with the amine compound or ⁇ , ⁇ -unsaturated carbonyl compound may result in increased emulsion stability.
- the amine or ⁇ , ⁇ -unsaturated carbonyl compound may be blended with the fuel component prior to formation of the precursor emulsion, or it may be added externally after the precursor emulsion has been formed. In the latter case it is likely that the reactant compound will migrate to the fuel phase.
- the precursor emulsion may be an oil-in-water emulsion, but this aspect of the invention may have greater applicability in relation to water-in-oil emulsions.
- the ⁇ , ⁇ -unsaturated carbonyl compound will be the reactant that is added to the fuel phase or externally to the precursor emulsion, with the amine being blended into the precursor emulsion subsequently.
- the thickened emulsion explosive may be sensitized or gassed using conventional methods.
- the relevant reactant is thoroughly dispersed in the precursor emulsion prior to addition of the complementary reactant.
- the amine and ⁇ , ⁇ - unsaturated carbonyl compounds may constitute a relatively small proportion of the emulsion explosive and effective mixing may be very important to ensure that the reaction takes place throughout the explosive.
- the addition of the amine or ⁇ , ⁇ -unsaturated carbonyl compound to the relevant component of the precursor emulsion, or the precursor emulsion itself, (and thorough blending therewith) preferably does not cause any significant viscosity increase in itself. Any viscosity change should not make subsequent handling and processing unduly difficult.
- the complementary reactant is added to precursor emulsion the when the emulsifying and thickening effects are required to take place. At that time it is believed to be important that the complementary reactant is mixed thoroughly into the precursor emulsion so that reaction between the amine and ⁇ , ⁇ -unsaturated compounds takes place throughout the precursor emulsion. In this way localised thickening and/or emulsification can be avoided.
- the relative and gross proportions of the amine or ⁇ , ⁇ - unsaturated carbonyl compounds are generally the same as those for the first aspect of the invention.
- the thickened emulsion explosives in accordance with these alternative embodiments may be utilised for the same applications as those in accordance with the first and second aspects.
- the thickening reaction and the resulting thickened emulsion explosive tend to have similar characteristics across all aspects of the invention.
- a thickened emulsion explosive in accordance with these alternative embodiments may be used as a bulk product.
- one loading hose may be used to deliver a emulsion explosive containing the amine compound into the borehole with a separate loading hose delivering the ⁇ , ⁇ -unsaturated carbonyl compound.
- the fuel phase component and the relevant reactant may be delivered using one hose and the aqueous oxidizer phase and the complementary component may be delivered in the other. Mixing of these individual components as they exit the respective loading hoses may be achieved using a suitable mixing nozzle.
- the loading hoses may be arranged in parallel along a common axis or, preferably, a concentric arrangement.
- the precursor emulsion will be emulsified to form an emulsion explosive as the reactants react and as it is pumped into the borehole. Once in the borehole the reactants will continue to react thereby thickening the emulsion explosive.
- an emulsion explosive which will continue to thicken once it is in the borehole.
- a packaged thickened emulsion explosive by producing the precursor emulsion, which may also be sensitized.
- the precursor emulsion and complementary reactant are combined to form an emulsified and thickened product which is then packaged.
- the base emulsion or precursor emulsion used in accordance with all aspects of the present invention include the known fuel phase and oxidiser phase combinations for the production of conventional emulsion explosives.
- emulsion is taken to include a precursor emulsion.
- Suitable oxygen releasing salts for use in the oxidizer phase of the emulsion of the present invention include the alkali and alkaline earth metal nitrates, chlorates and perchlorates, ammonium nitrate, ammonium chlorate, ammonium perchlorate and mixtures thereof.
- the preferred oxygen releasing salts include ammonium nitrate, sodium nitrate and calcium nitrate. However, the effect of calcium nitrate upon the rate of thickening should be considered when selecting salts.
- the oxygen releasing salt typically comprises ammonium nitrate or a mixture of ammonium nitrate and sodium nitrate.
- the oxygen releasing salt component of the oxidizer phase of the compositions of the present invention generally comprises from 45 to 95 % w/w and preferably from 60 to 90 % w/w of the total thickened emulsion explosive.
- the oxidizer phase comprises a mixture of ammonium nitrate and sodium nitrate the preferred composition range for such a blend is from 5 to 80 parts of sodium nitrate for every 100 parts of ammonium nitrate.
- the oxygen releasing salt component of the oxidizer phase comprises from 45 to 95 % w/w (of the total thickened emulsion explosive) ammonium nitrate or mixtures of from 0 to 40 % w/w, sodium or calcium nitrates and from 50 to 95 % w/w ammonium nitrate.
- the amount of water employed in the oxidizer phase of the thickened emulsion explosives of the present invention is in the range of from 0 to 30 % w/w of the total emulsion composition.
- the amount employed is from 4 to 25 % w/w and more preferably from 6 to 20 % w/w.
- Suitable organic fuels for use in the fuel phase include aliphatic, alicyclic and aromatic compounds and mixtures thereof which are in the liquid state at the formulation temperature.
- Suitable organic fuels may be chosen from fuel oil, diesel oil, distillate, furnace oil, kerosene, naphtha, paraffin oils, benzene, toluene, xylenes, asphaltic materials, polymeric oils such as the low molecular weight polymers of olefines, animal oils, vegetable oils, fish oils and other mineral, hydrocarbon or fatty oils and mixtures thereof.
- Preferred organic fuels are liquid hydrocarbons generally referred to as petroleum distillates such as gasoline, kerosene, fuel oils and paraffin oils.
- the fuel phase of the emulsion comprises from 2 to 15 % w/w and preferably 3 to 10 % w/w of the total thickened emulsion explosive.
- the emulsifier may be chosen from the wide range of emulsifiers known in the art for the preparation of emulsion explosives.
- the emulsifier used may be one of the well known emulsifiers based on the reaction products of poly[alk(en)yl] succinic anhydrides and alkylamines, including the polyisobutylene succinic anhydride (PiBSA) derivatives of alkanolamines.
- Suitable emulsifiers for use in the thickened emulsion explosive of the present invention include alcohol alkoxylates phenol 5 alkoxylates, poly(olyalkylene)glycols, poly(oxyalkylene)fatty acid esters, amine alkoxylates, fatty acid esters of sorbitol and glycerol, fatty acid salts, sorbitan esters, poly(oxyalkylene) sorbitan esters, fatty amine alkoxylates, poly(oxyalkylene)glycol esters, fatty acid amines, fatty acid amide alkoxylates, fatty amines, quaternary amines, alkyloxazolines, alkenyloxazolines, imidazolines, alkylsulphonates, alkylarylsulphonates, alkylsulphosuccinates, alkylarylsulpnonates, alkylsulphosuccinates, alkylphosphates, alkenylphosphates
- the emulsifier of the emulsion comprises up to 5 % w/w of the thickened emulsion explosive.
- Stable emulsions can be formed using relatively low levels of emulsifier and for reasons of economy it is preferable to keep the amount of emulsifying agent used to the minimum required to form the emulsion.
- the preferred level of emulsifying agent used is in the range of from 0.1 to 3.0 % w/w of the thickened emulsion explosive.
- lower levels of emulsifier may be used in certain embodiments.
- the amine compound functions as an emulsifier.
- secondary fuels may be incorporated into the emulsion in addition to the fuel phase.
- secondary fuels include finely divided solids and water miscible organic liquids which can be used to partially replace water as a solvent for the oxygen releasing salts or to extend the aqueous solvent for the oxygen releasing salts in the oxidizer phase.
- finely divided materials include sulphur, aluminium, urea and carbonaceous materials such as gilsonite, comminuted coke or charcoal, carbon black, resin acids such as abietic acid, sugars such as glucose or dextrose and vegetable products such as starch, nut meal, grain meal and wood pulp.
- water miscible organic liquids include alcohols such as methanol, glycols such as ethylene glycol, amides such as formamide and urea and amines such as methylamine.
- the optional secondary fuel component of the composition of the present invention comprises up to 30 % w/w of the total composition. It lies within the invention that there may also be incorporated into the emulsion explosive (prior to thickening) other substances or mixtures of substances which are oxygen releasing salts or which are themselves suitable as explosive materials.
- nitrate prills include doping the emulsion with ammonium nitrate prills of low density or high density, sodium nitrate prills, calcium nitrate prills, sodium perchlorate prills and/or any known oxidizers in prill form, including those mixed with diesel oil and/or nitroalkane, for example, nitrotoluene etc; doping the emulsion with RDX, PETN, TNT, MAN, EAN, EDDN or HN as organic nitrate sensitizer; and doping the emulsion with granulated aluminum powder, atomized aluminum, paint grade aluminum, foamed aluminum, nanoparticle aluminum, foam nickel, foamed iron, foamed silicon, foamed aluminum silicon alloy metal etc.
- the base emulsion or the modified emulsion may be sensitized using foamed metal, foams of natural or synthetic liquids or solids, foams of ammonium nitrate or oxygen releasing salts, water based foams, or oil based foam etc. Additionally or alternatively, metal based nano-materials, natural or synthetic nano-materials, or inorganic or organic nano-materials based upon amine nitrate, etc. may be used. Furthermore, the base emulsion or modified emulsion may be sensitized by gassing. Gassing my by performed using a number of compounds including nitrite compounds, organic carbonates, inorganic carbonates, peroxides, and nitrogen gas generating from an inorganic or organic compound.
- the composition of the sample is shown in Table 1 and produced as follows.
- the amine compound, ATBN was mixed into the mineral oil in a Hobart bowl at mixing at speed 2.
- the ammonium nitrate solution was produced by dissolving the ammonium nitrate in the water.
- the ammonium nitrate solution was then slowly poured into the mixing bowl while the mixer is running.
- the mixture was then digested for 2 minutes and continuously mixed for another 3 minutes.
- the resulting precursor emulsion was very fluid, globular and unstable with a viscosity of 6000 cps at 75°C when measured using a Brookfield Viscometer using spindle 7 at 20rpm.
- the ⁇ , ⁇ -unsaturated carbonyl compound, ESOA was mixed into the emulsion at speed 2 for 11 minutes.
- the resulting emulsion was stable, thick and gelled with a Brookfield viscosity at 75°C as shown in Table 2.
- a further composition was synthesized by weighing the required DN60, SMO, HT-22 and ESOA (shown in Table 3) into the Hobart mixing bowl, applying steam to the mixing bowl and mixing the components at speed 2.
- the temperature of the oil mixtures reached 60 °C
- the AN/SN/Water solution was poured into the oil mixture. It took 2 minutes to digest the solution to form the water in oil emulsion. The solution was then mixed further at speed 2 for 3 minutes. Then the Brookfield viscosity was taken.
- Brookfield viscosity - Spindle 7 at 10 rpm at 82 °C 88400 cps
- the Hobart bowl was placed back to the mixer and mixed further at speed 3 for 3 minutes to refine the emulsion, before the Brookfield viscosity was measured again.
- Brookfield viscosity - Spindle 7 at 10 rpm at 76 °C 250000 cps
- Brookfield viscosity - Spindle 7 at 10 rpm at 76 °C 275000 cps
- the ATBN was mixed with corn oil and then mixed into the emulsion.
- the emulsion gelled and became thick.
- the Hobart bowl was placed back into the mixer and mixed further at speed 3 for 3 minutes to refine the emulsion. Then the Brookfield viscosity was taken.
- the temperature of the oil mixtures reached 50 0 C the AN/Water oxidizer solution was poured into the oil mixture.
- the mixture was digested for 1 minute and 15 seconds to form a water-in-oil emulsion.
- the emulsion was mixed further at speed 2 for 4 minutes. Then the Brookfield viscosity was taken.
- the Hobart bowl was placed back to the mixer and mixed further at speed 3 for 3 minutes to refine the emulsion. Then the Brookfield viscosity was taken.
- a 200Og sample of the emulsion was divided into two equal parts. The following materials were added into the emulsion and mixed at a temperature of between 70-75 °C.
- sample 1 and sample 2 dropped slightly due to the additional oil added into the emulsion.
- the following materials were also added to the samples.
- the ATBN was mixed into the emulsion resulting in the emulsion thickening and gelling in less than one minute.
- the samples were packaged into 25 mm diameter High Density Polyethylene (HDPE) film for compression tests.
- the samples had a length of 30mm and were stored at room temperature prior to performing the compression tests.
- the results of the compression tests following 2 days, 4 days and 1 week of storage are shown in Figures 4, 5 and 6, respectively.
- Emulsions were prepared using a standard operating procedure for manufacturing small- scale laboratory mixes. The required amount of an aqueous oxidizer solution at 9O 0 C was added slowly for five minutes to the fuel phase containing ESOA at speed 2 in a steam jacketed mixing bowl. Additional emulsion refinement was required for the packaged emulsion formulations and achieved by mixing at speed 3 for 5 minutes. Once the bulk or packaged emulsion was refined to the desired viscosity and droplet size, the product was sensitized with plastic microspheres to the desired density. After the addition of the microspheres ATBN was then added to the emulsion and thoroughly mixed for about two minutes and then cartridged in plastic or cardboard containers.
- the optimum level of ESOA and ATBN was found to be 0.2% and 0.375%, respectively. At 0.375% ATBN in the product, an acceptable rate of polymerization was achieved. Any level below 0.375% did not polymerize.
- oils were used experimentally to find the best solvent. In each test a mixture comprising 95.18% the contemplated oil, 2.41% ESOA and 2.41% ATBN was mixed and observed. The oils considered were: SGI lOO, SC1500 (biodegradable methyl esters derived from soybean oil), CEI lO (biodegradable methyl ester derived from canola oil), Varsol 110, HT-22, Corn Oil, and Diesel oil.
- the solubility of the mixture was determined visually in the laboratory.
- the SGl 100 was the best solvent for the ESOA and ATBN product, and may be used for cleaning plant equipment.
- HT-22, corn oil, and diesel oil did not completely dissolve the product.
- Emulsion Pilot Plant Trials was to determine the feasibility of manufacturing thickened emulsion explosives in a non-laboratory setting.
- an explosive emulsion composition containing a carbonaceous fuel continuous phase, an aqueous discontinuous phase containing dissolved oxidiser salt and an emulsifier was produced in the EMMA II pilot plant using pin mill mixer technology.
- ESOA was mixed into the matrix using a 125L Panocopter kitchen mixer.
- ATBN was delivered at the centre of the emulsion to obtain uniform mixing.
- a blue dye was added to the ATBN to help determine the dispersion within the matrix as it was mixed and to assist evaluating the amount of mixing.
- the experiments were carried out using a 5m loading hose. All the flows were calibrated and curves were established.
- the emulsion matrix containing ESOA was pumped at a rate of 30 kg/min with 2.0% water lubrication.
- the addition of ATBN was delivered at 2.0% using the F5 method, in the centre of the emulsion.
- Two Sulzer static mixers were installed at the end of the loading hose to obtain uniform mixing with ATBN additive.
- the emulsion pumping pressure at a flow rate of 30kg/min was measured as 11 bars and 14 bars of pressure at the ATBN pump.
- Two plexiglass tubes (3.5 and 4 inch in diameter) were filled with the thickened emulsion explosive to evaluate up-hole retention properties.
- the thickened emulsion explosive stayed within the clear plexiglass tubes without slumping for over three months. Accordingly, the thickened emulsion explosive demonstrated excellent up-hole retention properties.
- the gassing performance was also examined to determine if the thickened emulsion explosive could be chemically gassed.
- the thickened emulsion explosive was capable of being gassed to a cup density of 1.05 g/cc after 45 minutes at 25O 0 C. Results showed that the thickened emulsion explosive did not detrimentally affect the chemical gassing process.
- Zinc nitrate did not show the same polymerization effect as calcium nitrate, even though it also contains a di-cation (Ca +2 and Zn +2 ). This may be due to the pH difference of Ca +2 and Zn +2 ions or the chelating property of calcium.
Abstract
Description
Claims
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US14076908P | 2008-12-24 | 2008-12-24 | |
PCT/AU2009/001705 WO2010071946A1 (en) | 2008-12-24 | 2009-12-24 | Amine reacted alpha, beta-unsaturated carbonyl compound thickened explosive emulsions |
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EP2367776A1 true EP2367776A1 (en) | 2011-09-28 |
EP2367776A4 EP2367776A4 (en) | 2016-10-05 |
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EP09833946.8A Withdrawn EP2367776A4 (en) | 2008-12-24 | 2009-12-24 | Amine reacted alpha, beta-unsaturated carbonyl compound thickened explosive emulsions |
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EP (1) | EP2367776A4 (en) |
AU (1) | AU2009329835B2 (en) |
CA (1) | CA2748090C (en) |
CL (1) | CL2011001570A1 (en) |
PE (1) | PE20120566A1 (en) |
WO (1) | WO2010071946A1 (en) |
ZA (1) | ZA201104375B (en) |
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WO2013009372A1 (en) * | 2011-07-11 | 2013-01-17 | Huntsman Petrochemical Llc | Phosphorus-containing secondary amine compounds |
EP4056544A1 (en) * | 2021-03-08 | 2022-09-14 | Yara International ASA | Emulsion-type explosives of the water-in-oil type |
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SE457952B (en) * | 1982-09-15 | 1989-02-13 | Nitro Nobel Ab | SPRAENGAEMNE |
US5920031A (en) * | 1992-03-17 | 1999-07-06 | The Lubrizol Corporation | Water-in-oil emulsions |
DE19847868C2 (en) * | 1998-10-16 | 2003-09-25 | Clariant Gmbh | Explosives containing modified copolymers of polyisobutylene and maleic anhydride as emulsifiers |
JP2001011491A (en) * | 1999-06-30 | 2001-01-16 | Lion Corp | Composition with improved lathering |
JP2001130993A (en) * | 1999-08-26 | 2001-05-15 | Nippon Kayaku Co Ltd | Explosive composition |
US6514361B1 (en) * | 2000-02-02 | 2003-02-04 | Nelson Brothers, Inc. | Preparation of emulsions |
-
2009
- 2009-12-24 CA CA2748090A patent/CA2748090C/en not_active Expired - Fee Related
- 2009-12-24 EP EP09833946.8A patent/EP2367776A4/en not_active Withdrawn
- 2009-12-24 PE PE2011001243A patent/PE20120566A1/en not_active Application Discontinuation
- 2009-12-24 AU AU2009329835A patent/AU2009329835B2/en not_active Ceased
- 2009-12-24 WO PCT/AU2009/001705 patent/WO2010071946A1/en active Application Filing
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2011
- 2011-06-13 ZA ZA2011/04375A patent/ZA201104375B/en unknown
- 2011-06-23 CL CL2011001570A patent/CL2011001570A1/en unknown
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ZA201104375B (en) | 2012-11-28 |
CA2748090C (en) | 2017-08-01 |
AU2009329835A1 (en) | 2011-06-30 |
WO2010071946A1 (en) | 2010-07-01 |
PE20120566A1 (en) | 2012-05-21 |
AU2009329835B2 (en) | 2015-11-05 |
CA2748090A1 (en) | 2010-07-01 |
CL2011001570A1 (en) | 2011-09-23 |
EP2367776A4 (en) | 2016-10-05 |
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