KR102674075B1 - Emulsion explosive composition comprising Porous Prilled Ammonium Nitrate - Google Patents
Emulsion explosive composition comprising Porous Prilled Ammonium Nitrate Download PDFInfo
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- 239000000839 emulsion Substances 0.000 title claims abstract description 79
- 239000002360 explosive Substances 0.000 title claims abstract description 63
- 239000000203 mixture Substances 0.000 title claims abstract description 55
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000004014 plasticizer Substances 0.000 claims abstract description 20
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007800 oxidant agent Substances 0.000 claims abstract description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims abstract description 8
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 8
- 101000700835 Homo sapiens Suppressor of SWI4 1 homolog Proteins 0.000 claims abstract 7
- 102100029338 Suppressor of SWI4 1 homolog Human genes 0.000 claims abstract 7
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- -1 amine salt Chemical class 0.000 claims description 8
- 229920005652 polyisobutylene succinic anhydride Polymers 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 3
- CJFLBOQMPJCWLR-UHFFFAOYSA-N bis(6-methylheptyl) hexanedioate Chemical compound CC(C)CCCCCOC(=O)CCCCC(=O)OCCCCCC(C)C CJFLBOQMPJCWLR-UHFFFAOYSA-N 0.000 claims description 2
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 claims 2
- 230000000052 comparative effect Effects 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000002480 mineral oil Substances 0.000 description 7
- 235000010446 mineral oil Nutrition 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 6
- 229910052683 pyrite Inorganic materials 0.000 description 6
- 239000011028 pyrite Substances 0.000 description 5
- 238000004880 explosion Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 150000002823 nitrates Chemical class 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YKGYQYOQRGPFTO-UHFFFAOYSA-N bis(8-methylnonyl) hexanedioate Chemical compound CC(C)CCCCCCCOC(=O)CCCCC(=O)OCCCCCCCC(C)C YKGYQYOQRGPFTO-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003721 gunpowder Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052960 marcasite Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000011787 zinc oxide Substances 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
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
- C06B31/28—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
- C06B31/28—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
- C06B31/285—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with fuel oil, e.g. ANFO-compositions
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Colloid Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Cosmetics (AREA)
- Medicinal Preparation (AREA)
Abstract
본 발명은 에멀젼 폭약 조성물 40 내지 80 중량% 및 외삽 산화제로서 다공성 질산암모늄(PPAN) 20 내지 60 중량%;를 포함하는 폭약 조성물으로서,
상기 에멀젼 폭약 조성물은 (a) 질산암모늄, 질산칼슘, 우레아를 포함하는 산화제 수용액 70~95 중량%, (b) 유화제 0.1~10 중량%, (c) 유류 0.1~10 중량%, 및 (e) 내열성 가소제인 지방족 아디페이트류 가소제 0.1~10 중량%;를 포함하는 것을 특징으로 하는 PPAN 포함 에멀젼 조성물을 제공한다.The present invention is an explosive composition comprising 40 to 80% by weight of an emulsion explosive composition and 20 to 60% by weight of porous ammonium nitrate (PPAN) as an extrapolated oxidizing agent,
The emulsion explosive composition includes (a) 70 to 95% by weight of an oxidizing agent aqueous solution containing ammonium nitrate, calcium nitrate, and urea, (b) 0.1 to 10% by weight of emulsifier, (c) 0.1 to 10% by weight of oil, and (e) It provides an emulsion composition containing PPAN, characterized in that it contains 0.1 to 10% by weight of an aliphatic adipate plasticizer, which is a heat-resistant plasticizer.
Description
본 발명은 PPAN 포함 에멀전 폭약 조성물에 관한 것이다. The present invention relates to an emulsion explosive composition comprising PPAN.
반응성 지반이란 일반적으로 Sulfide와 같은 pyrite를 포함하는 지역을 말하며, 질산염 성분과 반응할 수 있는 화학종을 포함하고 있다. 상업적으로 사용되는 질산염 기반의 폭발물은 반응성 지반에서 사용되거나, 지반의 온도가 상승할 경우 안정성과 발파효과가 저하될 수 있다. 질산염 기반의 폭약이 반응성 지반의 hole에 충전되면, 질산성분이 황화 금속 및 산과 반응해 열을 발생시켜 조기에 폭발할 수 있다. 이러한 조기폭발은 인접한 bore hole에 있는 폭발물을 연속으로 폭발시키고, 작업자의 부상 또는 사망을 유발할 수 있다. Reactive ground generally refers to an area containing pyrite such as sulfide, and contains chemical species that can react with nitrate components. Commercially used nitrate-based explosives may have reduced stability and blasting effectiveness when used in reactive ground or when ground temperature rises. When a nitrate-based explosive is charged into a hole in reactive ground, the nitric acid component may react with metal sulfide and acid to generate heat, causing an early explosion. This premature explosion can cause explosives in adjacent bore holes to explode continuously and cause injury or death to workers.
반응성 지반내에 화산활동이 있거나, 태양복사에 의한 지열의 온도 상승, 지구 내부의 깊이 증가에 따른 온도 상승(geothermal gradient), 석탄 추출로 인한 온도 상승 등 반응성 지반의 온도가 높으면 이러한 반응이 더욱 빠르게 발생할 수 있다.This reaction will occur more rapidly if the temperature of the reactive ground is high, such as when there is volcanic activity in the ground, an increase in geothermal temperature due to solar radiation, a temperature increase due to an increase in depth inside the Earth (geothermal gradient), or a temperature increase due to coal extraction. You can.
질산염과 황화금속, 산과의 반응을 억제하기 위해서 inhibitor을 사용(Phosphates, borates, zinc oxide, urea)하거나, Liner을 도입할 수 있다. 그러나 Liner의 경우 가격이 비싸며 다루기가 어렵다. 또한 장전 중 Leak가 발생할 수 있다. 이러한 단점들로 인하여 Inhibitor가 포함된 제품을 사용하는 것이 더 안정적이며 효과적이다. Z.-X. Xu et al은 Thermal stability and mechanism of decomposition of emulsion explosives in the presence of pyrite(2015)에서 Pyrite와 질산암모늄 기반의 에멀전이 만나서 반응할 때의 열적 거동에 대한 연구를 실시하였다. DSC, DTA/TG 분석 결과 inhibitor 중 Urea를 함유한 에멀전 화약이 가장 좋은 열적 안정성을 가지는 것을 확인하였다. To inhibit the reaction between nitrates, metal sulfides, and acids, inhibitors (Phosphates, borates, zinc oxide, urea) can be used or liners can be introduced. However, liners are expensive and difficult to handle. Additionally, leaks may occur during loading. Due to these shortcomings, it is more stable and effective to use products containing inhibitors. Z.-X. Xu et al conducted a study on the thermal behavior when pyrite and ammonium nitrate-based emulsion meet and react in Thermal stability and mechanism of decomposition of emulsion explosives in the presence of pyrite (2015). As a result of DSC and DTA/TG analysis, it was confirmed that emulsion gunpowder containing urea had the best thermal stability among inhibitors.
일반적으로 에멀전 폭약은 위력을 높이고 예감을 위해 PPAN(다공성 질산암모늄)을 에멀전과 혼합하여 사용한다. 이때 단순히 Urea만 포함한 Inhibited 제품의 경우 고온(100℃)의 반응성 지반의 경우, PPAN(다공성 질산암모늄)이 포함된 에멀전 폭약 조성물을 사용할 수 없다는 단점이 있다. PPAN(다공성 질산암모늄)을 30%이상 에멀전 조성물에 혼합하여 사용할 경우, 고온(100℃)에서 PPAN이 1~2시간만에 모두 용해되며, 에멀전이 물층과 오일층으로 분리되는 현상이 발생한다. 에멀전의 특성상 완전히 밀폐된 계가 아니기 때문에 고온으로 온도가 상승되며 에멀전이 미세하게 깨지기 시작하고, 그 틈으로 외부 고온에 노출된 수증기에 의해 PPAN이 용해되는 것으로 예상된다. In general, emulsion explosives are used by mixing PPAN (porous ammonium nitrate) with an emulsion to increase power and foreshadow. At this time, the inhibited product that simply contains urea has the disadvantage of not being able to use an emulsion explosive composition containing PPAN (porous ammonium nitrate) in the case of high temperature (100°C) reactive ground. When PPAN (porous ammonium nitrate) is used by mixing more than 30% of the emulsion composition, PPAN is completely dissolved in 1 to 2 hours at high temperature (100°C), and the emulsion is separated into a water layer and an oil layer. Due to the nature of the emulsion, it is not a completely sealed system, so as the temperature rises to a high temperature, the emulsion begins to break finely, and it is expected that PPAN will be dissolved by water vapor exposed to the external high temperature through the cracks.
그러므로, 이러한 문제를 해소할 수 있는 기술 개발이 요구되고 있다. Therefore, there is a need to develop technology that can solve these problems.
본 발명은 종래기술의 상기와 같은 문제를 해소하기 위하여 안출된 것으로서, The present invention was devised to solve the above problems of the prior art,
고온 안정성이 개선되어 고온 반응성 지반에서도 안정적으로 안전하게 사용할 수 있는 PPAN(다공성 질산암모늄) 포함 에멀전 폭약 조성물을 제공하는 것을 목적으로 한다. The purpose is to provide an emulsion explosive composition containing PPAN (porous ammonium nitrate) that has improved high-temperature stability and can be used stably and safely even in high-temperature reactive ground.
본 발명은 This invention
에멀젼 폭약 조성물 40 내지 80 중량% 및 외삽 산화제로서 다공성 질산암모늄(PPAN) 20 내지 60 중량%;를 포함하는 폭약 조성물으로서, An explosive composition comprising 40 to 80% by weight of an emulsion explosive composition and 20 to 60% by weight of porous ammonium nitrate (PPAN) as an extrapolated oxidizing agent,
상기 에멀젼 폭약 조성물은 The emulsion explosive composition is
(a) 질산암모늄, 질산칼슘, 우레아를 포함하는 산화제 수용액 70~95 중량%, (a) 70 to 95% by weight of an oxidizing agent aqueous solution containing ammonium nitrate, calcium nitrate, and urea,
(b) 유화제 0.1~10 중량%,(b) 0.1 to 10% by weight of emulsifier,
(c) 유류 0.1~10 중량%, 및(c) 0.1 to 10% by weight of oil, and
(d) 내열성 가소제인 지방족 아디페이트류 가소제 0.1~10 중량%;를 포함하는 것을 특징으로 하는 PPAN 포함 에멀젼 조성물을 제공한다.(d) 0.1 to 10% by weight of an aliphatic adipate plasticizer, which is a heat-resistant plasticizer. An emulsion composition containing PPAN is provided.
본 발명의 PPAN 포함 에멀전 폭약 조성물은 고온 안정성이 개선되어 고온 반응성 지반에서도 안정적으로 안전하게 사용할 수 있는 효과를 제공한다.The PPAN-containing emulsion explosive composition of the present invention has improved high-temperature stability and can be used stably and safely even in high-temperature reactive ground.
도 1은 시험예 1에서 PPAN 포함 에멀젼 폭약을 100℃의 오븐에서 8시간 동안 보관하면서 에멀젼의 안정성을 확인한 결과를 나타낸 그래프이다.
도 2는 시험예 3에서 PPAN 포함 에멀젼 폭약의 반응성 평가 결과를 나타낸 그래프이다.Figure 1 is a graph showing the results of confirming the stability of the emulsion in Test Example 1 while storing the PPAN-containing emulsion explosive in an oven at 100°C for 8 hours.
Figure 2 is a graph showing the reactivity evaluation results of the PPAN-containing emulsion explosive in Test Example 3.
이하에서 본 발명을 자세하게 설명한다. The present invention will be described in detail below.
본 발명의 PPAN 포함 에멀젼 조성물은 에멀젼 폭약 조성물 40 내지 80 중량% 및 외삽 산화제로서 다공성 질산암모늄(PPAN) 20 내지 60 중량%;를 포함한다. The PPAN-containing emulsion composition of the present invention includes 40 to 80% by weight of the emulsion explosive composition and 20 to 60% by weight of porous ammonium nitrate (PPAN) as an extrapolated oxidizing agent.
상기 에멀젼 폭약 조성물은 The emulsion explosive composition is
(a) 질산암모늄, 질산칼슘, 우레아를 포함하는 산화제 수용액 70~95 중량%, (a) 70 to 95% by weight of an oxidizing agent aqueous solution containing ammonium nitrate, calcium nitrate, and urea,
(b) 유화제 0.1~10 중량%,(b) 0.1 to 10% by weight of emulsifier,
(c) 유류 0.1~10 중량%, 및(c) 0.1 to 10% by weight of oil, and
(d) 내열성 가소제인 지방족 아디페이트류 가소제 0.1~10 중량%;를 포함하는 것을 특징으로 한다.(d) 0.1 to 10% by weight of an aliphatic adipate plasticizer, which is a heat-resistant plasticizer.
일반적으로 에멀전 폭약은 위력을 높이고 예감을 위해 PPAN(다공성 질산암모늄)을 에멀전과 혼합하여 사용한다. 이때 단순한 Inhibited 에멀전 폭약 조성물의 경우 고온(100℃ 이상)의 반응성 지반에서 사용하는 경우, PPAN(Porous Prilled Ammonium Nitrate, 다공성 질산암모늄)을 혼합하여 사용할 수 없다는 단점이 있다. 즉, PPAN(다공성 질산암모늄)을 에멀전 폭약 조성물에 혼합하여 사용할 경우, 고온에서 PPAN이 1~2시간만에 모두 용해되며, 에멀전이 물층과 오일층으로 분리되는 현상이 발생한다. 에멀전의 특성상 완전히 밀폐된 계가 아니기 때문에 고온으로 온도가 상승되면 에멀전이 미세하게 깨지기 시작하고, 그 틈으로 외부 고온에 노출된 수증기에 의해 PPAN이 용해되는 것으로 보인다. In general, emulsion explosives are used by mixing PPAN (porous ammonium nitrate) with an emulsion to increase power and foreshadow. At this time, in the case of a simple inhibited emulsion explosive composition, there is a disadvantage that it cannot be mixed with PPAN (Porous Prilled Ammonium Nitrate) when used in reactive ground at high temperature (over 100°C). That is, when PPAN (porous ammonium nitrate) is mixed and used in an emulsion explosive composition, PPAN is completely dissolved in 1 to 2 hours at high temperature, and the emulsion is separated into a water layer and an oil layer. Due to the nature of the emulsion, it is not a completely sealed system, so when the temperature rises to a high temperature, the emulsion begins to break finely, and PPAN appears to be dissolved by water vapor exposed to the external high temperature through the cracks.
그러므로, 본 발명은 종래 PPAN 포함 에멀젼 폭약 조성물의 문제점을 해소한 것을 특징으로 한다.Therefore, the present invention is characterized by solving the problems of the conventional emulsion explosive composition containing PPAN.
상기 산화제 수용액은 에멀젼 폭약 조성물 총중량에 대하여 70~95 중량%로 포함될 수 있다. 상기 산화제 수용액의 조성비가 상기 범위를 벗어나면 폭약의 위력이 높아 미진동의 특성을 상실할 수 있으며, 양이 적을 경우에는 불폭되는 문제가 발생할 수 있다.The oxidizing agent aqueous solution may be included in an amount of 70 to 95% by weight based on the total weight of the emulsion explosive composition. If the composition ratio of the oxidizing agent aqueous solution is outside the above range, the power of the explosive may be high and the characteristic of microvibration may be lost, and if the amount is small, a problem of non-explosion may occur.
본 발명의 일 실시형태에 있어서, 상기 산화제 수용액은 질산암모늄 30~60중량%, 질산칼슘 30~60중량%, 물 1~20중량%, 우레아(Urea) 1~20중량%을 포함할 수 있다.In one embodiment of the present invention, the aqueous oxidizing agent solution may include 30 to 60% by weight of ammonium nitrate, 30 to 60% by weight of calcium nitrate, 1 to 20% by weight of water, and 1 to 20% by weight of urea. .
본 발명의 일 실시형태에 있어서, 상기 유화제는 인화점이 100℃ 이상이며, 산가가 7~8이고, 아민가가 40~60인 것이 바람직하게 사용될 수 있다. In one embodiment of the present invention, the emulsifier may preferably have a flash point of 100°C or higher, an acid value of 7 to 8, and an amine value of 40 to 60.
상기 유화제는 PPAN 포함 에멀젼 폭약 조성물 총중량에 대하여 0.1~10 중량%로 포함된다. 상기 유화제의 함량이 상기 범위를 벗어나면 에멀젼이 형성되지 않거나 불폭되는 문제가 발생할 수 있다. The emulsifier is included in an amount of 0.1 to 10% by weight based on the total weight of the emulsion explosive composition containing PPAN. If the content of the emulsifier is outside the above range, the emulsion may not be formed or the emulsion may not detonate.
본 발명의 일 실시형태에 있어서, 상기 유화제로는 SMO(Sorbitan monoleate) 및 PIBSA 아민염(Amine salt of polyisobutylenesuccinicanhydride) 등으로 이루어진 군으로부터 선택되는 1종 이상이 사용될 수 있으나, 이들로 한정되는 것은 아니다. In one embodiment of the present invention, the emulsifier may be one or more selected from the group consisting of sorbitan monoleate (SMO) and amine salt of polyisobutylenesuccinicanhydride (PIBSA), etc., but is not limited thereto.
상기 유화제는 인화점이 100℃ 이상이며, 산가가 7~8이고, 아민가가 40~60인 PIBSA 아민염(Amine salt of polyisobutylenesuccinicanhydride)을 포함하는 것이 더욱 바람직하게 사용될 수 있다. 상기 유화제는 상기 PIBSA 아민염(Amine salt of polyisobutylenesuccinicanhydride)으로만 구성될 수도 있다.The emulsifier may more preferably contain PIBSA amine salt (Amine salt of polyisobutylenesuccinicanhydride) with a flash point of 100°C or higher, an acid value of 7 to 8, and an amine value of 40 to 60. The emulsifier may consist only of the PIBSA amine salt (Amine salt of polyisobutylenesuccinicanhydride).
상기 유류는 에멀젼 폭약 조성물 총중량에 대하여 0.1~10 중량%로 포함된다. 상기 유류는 연료유 및 오일을 포함할 수 있다. The oil is contained in an amount of 0.1 to 10% by weight based on the total weight of the emulsion explosive composition. The oil may include fuel oil and oil.
상기 연료유는 50~80℃에서 액체화되는 탄소질 연료유가 바람직하게 사용될 수 있으며, 예를 들어, 왁스, 광유 및 경유 등으로 이루어진 군으로부터 선택되는 1종 이상이 사용될 수 있다.The fuel oil may preferably be a carbonaceous fuel oil that liquefies at 50 to 80°C, and for example, one or more types selected from the group consisting of wax, mineral oil, and diesel oil may be used.
상기 오일로는 미네랄 오일, 윤활유 등에서 선택되는 1종 이상이 사용될 수 있다. As the oil, one or more types selected from mineral oil, lubricating oil, etc. may be used.
상기 내열성 가소제인 지방족 아디페이트류 가소제는 에멀젼 폭약 조성물 총 중량에 대하여 0.1~10 중량%로 포함될 수 있다. 상기 지방족 아디페이트류 가소제가 상술한 범위 미만으로 포함되는 경우, 고온 반응성 지반에서 PPAN 포함 에멀젼 폭약 조성물의 안정성이 부족할 수 있으며, 10 중량%를 초과하는 경우에는 위력이 낮아질 수 있다는 점에서 바람직하지 않을 수 있다.The heat-resistant plasticizer, an aliphatic adipate plasticizer, may be included in an amount of 0.1 to 10% by weight based on the total weight of the emulsion explosive composition. If the aliphatic adipate plasticizer is included in less than the above-mentioned range, the stability of the emulsion explosive composition containing PPAN may be insufficient in high temperature reactive ground, and if it exceeds 10% by weight, the power may be lowered, which is not desirable. You can.
상기 지방족 아디페이트류 가소제로는 다이옥틸아디페이트(dioctyl adipate, DOA), 다이아이소옥틸 아디페이트(di-iso-octyl adipate, DIOA), 및 다이아이소데실 아디페이트(di-isodecyl adipate, DIDA) 등으로 이루어진 군으로부터 선택되는 1종 이상이 사용될 수 있다. The aliphatic adipate plasticizers include dioctyl adipate (DOA), di-iso-octyl adipate (DIOA), and di-isodecyl adipate (DIDA). One or more types selected from the group consisting of may be used.
이하에서, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나, 하기의 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예에 의하여 한정되는 것은 아니다. 하기의 실시예는 본 발명의 범위 내에서 당업자에 의해 적절히 수정, 변경될 수 있다. Below, the present invention will be described in more detail through examples. However, the following examples are intended to illustrate the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.
실시예 1: PPAN 포함 에멀젼 폭약의 제조Example 1: Preparation of emulsion explosives containing PPAN
우레아 10 중량%를 포함하고 질산암모늄 40 중량%, 질산칼슘 40 중량% 및 물 10 중량%을 혼합하여 산화제 수용액을 제조하였다. An aqueous oxidizing agent solution was prepared by mixing 10% by weight of urea, 40% by weight of ammonium nitrate, 40% by weight of calcium nitrate, and 10% by weight of water.
다음으로, 상기에서 제조된 산화제 수용액 90 중량%를 혼화기에 넣고 가열하여 70℃를 유지시켰다. 다른 용기에 미네랄 오일 3 중량%, 내열성 가소제로서 다이옥틸아디페이트(dioctyl adipate, DOA) 6 중량%, 유화제 1 중량%를 50℃이상의 온도로 가열하여 균일하게 섞었다. 상기 제조된 혼합물들을 혼화기에서 섞고, 질산염이 모두 용해되면 2분동안 고속 교반하여 균일하게 섞어서 에멀젼 폭약 조성물을 제조하였다. Next, 90% by weight of the oxidizing agent aqueous solution prepared above was placed in a mixer and heated to maintain the temperature at 70°C. In another container, 3% by weight of mineral oil, 6% by weight of dioctyl adipate (DOA) as a heat-resistant plasticizer, and 1% by weight of emulsifier were heated to a temperature of 50°C or higher and mixed evenly. The prepared mixtures were mixed in a mixer, and when all nitrates were dissolved, they were stirred at high speed for 2 minutes and mixed uniformly to prepare an emulsion explosive composition.
다음으로, 상기 에멀젼 폭약 조성물 70 중량%와 PPAN(다공성 질산 암모늄) 30 중량%를 혼합하여 PPAN 포함 에멀젼 폭약 조성물을 제조하였다.Next, 70% by weight of the emulsion explosive composition and 30% by weight of PPAN (porous ammonium nitrate) were mixed to prepare an emulsion explosive composition containing PPAN.
실시예 2: PPAN 포함 에멀젼 폭약의 제조Example 2: Preparation of emulsion explosives containing PPAN
실시예 1에서 에멀젼 폭약 조성물 50 중량%와 PPAN(다공성 질산 암모늄) 50 중량%를 혼합한 것을 제외하고는 상기 실시예 1과 동일하게 PPAN 포함 에멀젼 폭약 조성물을 제조하였다.An emulsion explosive composition containing PPAN was prepared in the same manner as Example 1, except that 50% by weight of the emulsion explosive composition and 50% by weight of PPAN (porous ammonium nitrate) were mixed.
비교예 1: PPAN 포함 에멀젼 폭약의 제조Comparative Example 1: Preparation of emulsion explosives containing PPAN
실시예 1에서 내열성 가소제를 사용하지 않고 미넬랄 오일의 함량을 9 중량%로 늘려서 사용한 것을 제외하고는 상기 실시예 1과 동일하게 PPAN 포함 에멀젼 폭약 조성물(PPAN 30 중량% 혼합)을 제조하였다.An emulsion explosive composition containing PPAN (mixed with 30% by weight of PPAN) was prepared in the same manner as Example 1, except that the heat-resistant plasticizer was not used and the mineral oil content was increased to 9% by weight.
비교예 2: PPAN 포함 에멀젼 폭약의 제조Comparative Example 2: Preparation of emulsion explosives containing PPAN
실시예 2에서 내열성 가소제를 사용하지 않고 미네랄 오일의 함량을 9 중량%로 늘려서 사용한 것을 제외하고는 상기 실시예 2와 동일하게 PPAN 포함 에멀젼 폭약 조성물(PPAN 50 중량% 혼합)을 제조하였다.An emulsion explosive composition containing PPAN (50 wt% PPAN mixed) was prepared in the same manner as in Example 2, except that the heat-resistant plasticizer was not used and the mineral oil content was increased to 9 wt%.
비교예 3: 에멀젼 폭약 조성물 제조(PPAN 미포함)Comparative Example 3: Preparation of emulsion explosive composition (without PPAN)
우레아 10 중량%를 포함하고 질산암모늄 40 중량%, 질산칼슘 40 중량% 및 물 10 중량%을 혼합하여 산화제 수용액을 제조하였다. An aqueous oxidizing agent solution was prepared by mixing 10% by weight of urea, 40% by weight of ammonium nitrate, 40% by weight of calcium nitrate, and 10% by weight of water.
다음으로, 상기에서 제조된 산화제 수용액 90 중량%를 혼화기에 넣고 가열하여 70℃를 유지시켰다. 다른 용기에 미네랄 오일 3 중량%, 내열성 가소제로서 다이옥틸아디페이트(dioctyl adipate, DOA) 6 중량%, 유화제 1 중량%를 50℃이상의 온도로 가열하여 균일하게 섞는다. 상기 제조된 혼합물들을 혼화기에서 섞고, 질산염이 모두 용해되면 2분동안 고속 교반하여 균일하게 섞어서 에멀젼 폭약 조성물을 제조하였다Next, 90% by weight of the oxidizing agent aqueous solution prepared above was placed in a mixer and heated to maintain 70°C. In another container, heat 3% by weight of mineral oil, 6% by weight of dioctyl adipate (DOA) as a heat-resistant plasticizer, and 1% by weight of emulsifier to a temperature of 50°C or higher and mix evenly. The prepared mixtures were mixed in a mixer, and when all nitrates were dissolved, they were stirred at high speed for 2 minutes and mixed uniformly to prepare an emulsion explosive composition.
비교예 4: 에멀젼 폭약 조성물 제조(PPAN, 우레아 미포함)Comparative Example 4: Preparation of emulsion explosive composition (PPAN, without urea)
질산암모늄 40 중량%, 질산칼슘 40 중량% 및 물 20 중량%을 혼합하여 산화제 수용액을 제조하였다. An aqueous oxidizing agent solution was prepared by mixing 40% by weight of ammonium nitrate, 40% by weight of calcium nitrate, and 20% by weight of water.
다음으로, 상기에서 제조된 산화제 수용액 90 중량%를 혼화기에 넣고 가열하여 70℃를 유지시켰다. 다른 용기에 미네랄 오일 3 중량%, 내열성 가소제로서 다이옥틸아디페이트(dioctyl adipate, DOA) 6 중량%, 유화제 1 중량%를 50℃이상의 온도로 가열하여 균일하게 섞는다. 상기 제조된 혼합물들을 혼화기에서 섞고, 질산염이 모두 용해되면 2분동안 고속 교반하여 균일하게 섞어서 에멀젼 폭약 조성물을 제조하였다Next, 90% by weight of the oxidizing agent aqueous solution prepared above was placed in a mixer and heated to maintain 70°C. In another container, heat 3% by weight of mineral oil, 6% by weight of dioctyl adipate (DOA) as a heat-resistant plasticizer, and 1% by weight of emulsifier to a temperature of 50°C or higher and mix evenly. The prepared mixtures were mixed in a mixer, and when all nitrates were dissolved, they were stirred at high speed for 2 minutes and mixed uniformly to prepare an emulsion explosive composition.
시험예 1: PPAN 포함 에멀젼 폭약의 안정성 평가Test Example 1: Stability evaluation of emulsion explosives containing PPAN
상기 실시예 1 및 2과 비교예 1 및 2의 PPAN 포함 에멀젼 폭약을 100℃의 오븐에서 8시간 동안 보관하면서 에멀젼의 안정성을 확인하였다. 상기 안정성 확인 결과는 도 1에 나타내었다.The stability of the emulsion was confirmed by storing the PPAN-containing emulsion explosives of Examples 1 and 2 and Comparative Examples 1 and 2 in an oven at 100°C for 8 hours. The stability confirmation results are shown in Figure 1.
도 1에서 확인되는 바와 같이, 내열성 가소제가 포함되지 않은 비교예 1 및 비교예 2의 PPAN 포함 에멀젼 폭약의 경우, 8시간 경과 후 에멀젼의 물층과 연료층으로 분리되며 PPAN이 모두 용해되는 현상이 발생하였다. 반면, 내열성 가소제가 포함된 실시예 1 및 2의 PPAN 포함 에멀젼 폭약의 경우 PPAN의 입자크기가 약간 작아졌을 뿐 에멀젼의 분리현상이 발생하지 않았다. As can be seen in Figure 1, in the case of the PPAN-containing emulsion explosives of Comparative Examples 1 and 2 that did not contain a heat-resistant plasticizer, the emulsion was separated into a water layer and a fuel layer after 8 hours, and all of the PPAN was dissolved. did. On the other hand, in the case of the PPAN-containing emulsion explosives of Examples 1 and 2 containing a heat-resistant plasticizer, the particle size of PPAN was slightly reduced and no separation of the emulsion occurred.
이러한 결과는 본 발명의 PPAN 포함 에멀전 폭약 조성물은 고온환경에서의 안정성이 매우 우수함을 나타낸다.These results indicate that the PPAN-containing emulsion explosive composition of the present invention has excellent stability in a high temperature environment.
시험예 2: PPAN 포함 에멀젼 폭약의 장기 보관 후의 성능 평가Test Example 2: Performance evaluation of emulsion explosives containing PPAN after long-term storage
실시예 1에서 제조된 PPAN 포함 에멀젼 폭약을 100℃의 오븐에서 32시간 동안 보관하면서 폭발속도를 평가하고, 그 결과를 하기 표 1에 나타내었다.The PPAN-containing emulsion explosive prepared in Example 1 was stored in an oven at 100°C for 32 hours to evaluate the explosion speed, and the results are shown in Table 1 below.
상기 표 1의 결과로부터 본 발명의 PPAN 포함 에멀젼 폭약은 100℃에서 32시간 보관 후에도 초기 성능이 유지되는 것을 확인할 수 있다. 이러한 결과는 본 발명의 PPAN 포함 에멀전 폭약 조성물은 고온환경에서 장시간 보관 후에도 성능에 차이가 없음을 나타낸다.From the results in Table 1, it can be seen that the PPAN-containing emulsion explosive of the present invention maintains its initial performance even after storage at 100°C for 32 hours. These results indicate that the PPAN-containing emulsion explosive composition of the present invention shows no difference in performance even after being stored for a long time in a high temperature environment.
시험예 3: PPAN 포함 에멀젼 폭약의 장기 보관 후의 성능 평가Test Example 3: Performance evaluation of emulsion explosives containing PPAN after long-term storage
AEISG(Australian Explosive Industry And Safety Goup Inc.) Elevated temperature and reactive ground Edition 4에 기재된 반응성 평가법에 따라 실시예 1 및 2의 반응성 평가를 진행하였다. The reactivity evaluation of Examples 1 and 2 was conducted according to the reactivity evaluation method described in AEISG (Australian Explosive Industry And Safety Goup Inc.) Elevated temperature and reactive ground Edition 4.
PPAN이 30 중량% 혼합된 실시예 1; PPAN이 50 중량% 혼합된 실시예 2; PPAN이 혼합되지 않은 비교예 3; PPAN 및 우레아가 포함되지 않은 비교예 4;의 에멀젼 폭약 조성물을 평가하여 그 결과를 비교하였다. 해당 반응성 평가법을 준수하되, 실제 암석 샘플의 수급불가로 Pyrite(FeS2, 100%, 300mesh, Aldrich社)로 대체하여 평가를 진행하였으며, 결과는 도 2에 나타내었다. Example 1 where 30% by weight of PPAN was mixed; Example 2 where 50% by weight of PPAN was mixed; Comparative Example 3 without PPAN mixed; The emulsion explosive composition of Comparative Example 4, which did not contain PPAN and urea, was evaluated and the results were compared. The reactivity evaluation method was followed, but due to the unavailability of actual rock samples, Pyrite (FeS2, 100%, 300mesh, Aldrich) was substituted for evaluation. The results are shown in Figure 2.
도 2에서 확인되는 바와 같이, 본 발명의 에멀젼 폭약 조성물은 PPAN 함량에 상관없이 pyrite와 반응하지 않았으며, 육안상으로 가스발생이 관찰되지 않았다.As can be seen in Figure 2, the emulsion explosive composition of the present invention did not react with pyrite regardless of the PPAN content, and no gas generation was observed with the naked eye.
또한, Inhibitor인 우레아가 미포함된 비교예 4의 에멀젼 폭약 조성의 경우, 그래프와 같이 온도가 급격히 상승하는 현상을 보이나, 우레아를 포함한 실시예 1, 2 및 비교예 3의 경우는 온도 변화 없는 구간이 32시간 이상 유지되는 것을 확인하였다. 이는 본 발명의 실시예 1 및 2의 PPAN 포함 에멀젼 폭약 조성물은 반응성 지반에서 NOx 가스 발생 없이 안전하게 사용할 수 있음을 의미한다.In addition, in the case of the emulsion explosive composition of Comparative Example 4 that does not contain urea, which is an inhibitor, the temperature rises rapidly as shown in the graph, but in the case of Examples 1, 2 and Comparative Example 3 that include urea, there is a section without temperature change. It was confirmed that it was maintained for more than 32 hours. This means that the PPAN-containing emulsion explosive composition of Examples 1 and 2 of the present invention can be safely used in reactive ground without generating NOx gas.
Claims (4)
상기 에멀젼 폭약 조성물은
(a) 질산암모늄, 질산칼슘, 우레아를 포함하는 산화제 수용액 70~95 중량%,
(b) 유화제 0.1~10 중량%,
(c) 유류 0.1~10 중량%, 및
(d) 내열성 가소제인 지방족 아디페이트류 가소제 0.1~10 중량%;를 포함하는 것을 특징으로 하는 PPAN 포함 에멀젼 조성물.An explosive composition comprising 40 to 80% by weight of an emulsion explosive composition and 20 to 60% by weight of porous ammonium nitrate (PPAN) as an extrapolated oxidizing agent,
The emulsion explosive composition is
(a) 70 to 95% by weight of an oxidizing agent aqueous solution containing ammonium nitrate, calcium nitrate, and urea,
(b) 0.1 to 10% by weight of emulsifier,
(c) 0.1 to 10% by weight of oil, and
(d) 0.1 to 10% by weight of an aliphatic adipate plasticizer, which is a heat-resistant plasticizer. An emulsion composition containing PPAN.
상기 산화제 수용액은 질산암모늄 30~60중량%, 질산칼슘 30~60중량%, 물 1~20중량%, 및 우레아 1~20중량%을 포함하는 것을 특징으로 하는 PPAN 포함 에멀젼 조성물.According to paragraph 1,
The oxidizing agent aqueous solution is an emulsion composition containing PPAN, characterized in that it contains 30 to 60% by weight of ammonium nitrate, 30 to 60% by weight of calcium nitrate, 1 to 20% by weight of water, and 1 to 20% by weight of urea.
상기 유화제는 인화점이 100℃ 이상이며, 산가가 7~8이고, 아민가가 40~60인 PIBSA 아민염(Amine salt of polyisobutylenesuccinicanhydride)을 포함하는 것을 특징으로 하는 PPAN 포함 에멀젼 조성물.According to paragraph 1,
An emulsion composition containing PPAN, wherein the emulsifier includes PIBSA amine salt (Amine salt of polyisobutylenesuccinicanhydride) with a flash point of 100°C or higher, an acid value of 7 to 8, and an amine value of 40 to 60.
상기 지방족 아디페이트류 가소제는 다이옥틸아디페이트(dioctyl adipate, DOA), 다이아이소옥틸 아디페이트(di-iso-octyl adipate, DIOA), 및 다이아이소데실 아디페이트(di-isodecyl adipate, DIDA)로 이루어진 군으로부터 선택되는 1종 이상인 것을 특징으로 하는 PPAN 포함 에멀젼 조성물.According to paragraph 1,
The aliphatic adipate plasticizer consists of dioctyl adipate (DOA), di-iso-octyl adipate (DIOA), and diisodecyl adipate (DIDA). An emulsion composition containing PPAN, characterized in that it is one or more selected from the group.
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| US20040055677A1 (en) | 2000-01-24 | 2004-03-25 | Filippini Brian B. | Partially dehydrated reaction product, process for making same, and emulsion containing same |
| KR101272390B1 (en) | 2012-06-15 | 2013-06-07 | 주식회사 한화 | Composition of low vibration emulsion explosives |
| WO2019136515A1 (en) | 2018-01-09 | 2019-07-18 | Dyno Nobel Asia Pacific Pty Limited | Explosive compositions for use in reactive ground and related methods |
| CN111662145A (en) | 2020-06-12 | 2020-09-15 | 北矿亿博(沧州)科技有限责任公司 | Thickening type emulsion explosive and manufacturing method thereof |
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| KR20080083920A (en) | 2007-03-14 | 2008-09-19 | 주식회사 한화 | Water-in-oil emulsion explosive |
| KR101796724B1 (en) * | 2016-12-19 | 2017-11-10 | 주식회사 한화 | Composition of emulsion explosives and manufacturing method therefor |
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| US20040055677A1 (en) | 2000-01-24 | 2004-03-25 | Filippini Brian B. | Partially dehydrated reaction product, process for making same, and emulsion containing same |
| KR101272390B1 (en) | 2012-06-15 | 2013-06-07 | 주식회사 한화 | Composition of low vibration emulsion explosives |
| WO2019136515A1 (en) | 2018-01-09 | 2019-07-18 | Dyno Nobel Asia Pacific Pty Limited | Explosive compositions for use in reactive ground and related methods |
| CN111662145A (en) | 2020-06-12 | 2020-09-15 | 北矿亿博(沧州)科技有限责任公司 | Thickening type emulsion explosive and manufacturing method thereof |
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