WO1998013318A1 - Water resistant explosive composition - Google Patents

Water resistant explosive composition Download PDF

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Publication number
WO1998013318A1
WO1998013318A1 PCT/NO1997/000262 NO9700262W WO9813318A1 WO 1998013318 A1 WO1998013318 A1 WO 1998013318A1 NO 9700262 W NO9700262 W NO 9700262W WO 9813318 A1 WO9813318 A1 WO 9813318A1
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WO
WIPO (PCT)
Prior art keywords
water
anfo
water resistant
explosive
filled
Prior art date
Application number
PCT/NO1997/000262
Other languages
French (fr)
Inventor
Jan Hans Vestre
Original Assignee
Dyno Industrier Asa
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dyno Industrier Asa filed Critical Dyno Industrier Asa
Priority to GB9905420A priority Critical patent/GB2331515B/en
Priority to CA002265905A priority patent/CA2265905A1/en
Priority to NZ334819A priority patent/NZ334819A/en
Priority to US09/147,954 priority patent/US6261393B1/en
Priority to JP51553398A priority patent/JP2001505520A/en
Priority to AU44753/97A priority patent/AU720922B2/en
Priority to MXPA99002740A priority patent/MXPA99002740A/en
Priority to BRPI9712149-5A priority patent/BR9712149B1/en
Publication of WO1998013318A1 publication Critical patent/WO1998013318A1/en
Priority to SE9901113A priority patent/SE521310C2/en
Priority to HK99102598A priority patent/HK1017339A1/en

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Classifications

    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S149/00—Explosive and thermic compositions or charges
    • Y10S149/11—Particle size of a component
    • Y10S149/112—Inorganic nitrogen-oxygen salt

Definitions

  • ANFO Ammonium nitrate fuel oil explosives
  • ANFO ammonium nitrate fuel oil explosives
  • FO fuel oil
  • ANFO has this dominant position as the world's most used explosive, is mainiy because the explosive consists of two rather cheap raw materials, besides being very easy to produce.
  • ANFO can either be produced in a factory, or be produced directly at the user's site. When produced at a factory, ANFO is usually filled in bags containing 25 or 1000 Gs.
  • ANFO prills have good flow properties, that is, they flow easily in pipelines, and they are specially well suited for bulk loading with pneumatic loading equipment. ANFO is then filled in a pressure vessel, usually called a "pressure pot", and compressed air with a pressure of 3-6 bar is applied. By means of a valve at the outlet of the pressure pot, which opens and closes, the ANFO is blown down to or into the bore holes.
  • One of the methods recommends adding a certain percentage of an emulsion explosive to the ANFO. This is described in US-patents No. 4.1 1 1.727 and 4.181.546.
  • the explosive resulting from this is called Heavy ANFO, and is usually classified as a special type of explosive.
  • Heavy ANFO can not be loaded by means of pneumatic loading equipment. Normally, Heavy ANFO will not be considered as a water resistant ANFO.
  • US-patent No. 4.933.029 describes a water resistant ANFO-explosive where the water resistance is achieved by using a water thickening agent like guar gum.
  • a water thickening agent like guar gum.
  • water repellent agents like fatty acids, wax, etc.
  • fillers like talc, glass, expanded perlite, sulphur, etc., may be used for preventing water to penetrate into the ANFO.
  • US-patent No. 5.480.500 describes such a water resistant ANFO-explosive.
  • the water resistance is achieved by both applying a water thickening agent as guar gum, and simultaneously adding a particulate filling agent, for instance pulverised ammonium nitrate in order to stop penetration of water into the ANFO.
  • the characteristic feature by applying above mentioned product in accordance with the technique already known, is the fact that one will allow some water to penetrate into the explosive, resulting in a reaction with the ANFO. This again will form a barrier against further water penetration. At areas where the water has "reacted" with ANFO in order to form a barrier against further water penetration, the ANFO in this area is damaged. The degree of water penetration into the ANFO is often used as a measure of how good the water resistant ANFO in question really is.
  • the present invention provides a water resistant ANFO-product which will detonate even when poured into a bore hole partly filled with water. Therefore, this concept is not based on the previously known principle that the water "reacts" with
  • the invention with this current water resistant ANFO patent is that it utilises water in the bore hole so that the dry ANFO and water in the borehole form a slurry.
  • This water resistant ANFO may thus be described as an "instant slurry" of the watergel type.
  • a watergel-slurry is characterised by consisting of dissolved salts of nitrates and/or perchlorate, and the water content may vary from approx. 10 to 30 %.
  • the slurry is thickened with various types of gums and will also often contain some undissolved salt, usually ammonium nitrate.
  • a watergel slurry is usually sensitised either by chemical gassing or by addition of porous particles such as hollow micro balloons or expanded perlite.
  • the water resistant ANFO in accordance with the current invention (“instant slurry * ') may therefore consist of the same components (except for water, which is present in the bore hole) known from the patent literature related to a watergel slurry.
  • gassing reagents responding to water in the bore hole, which will develop gas bubbles sensitising the explosive.
  • gassing reagents which may be used are: Sodium bicarbonate, aluminium, nitrite (particularly sodium nitrite) and calcium carbide.
  • the water In order to get the first three previous mentioned substances to respond to water developing a gas, the water has to have a low pH-level. Consequently, the bore hole water has to be made acidic by ensuring that the water resistant ANFO also contains an acid, lowering the pH-level sufficiently for a reaction and development of gas. It is preferred to use one or more of organic acids chosen amongst citric acid, tartaric acid, ascorbic acid or acetic acid. It may also be used an inorganic acid which lowers the water ' s pH in an adequate way.
  • the two last-mentioned gassing reagents will easily decompose or react, when stored for a longer period together with AN and small amounts of humidity always being present in the ANFO. These should therefore be given a protecting water soluble layer, for instance through a micro encapsulation process.
  • Sodium bicarbonate NaHCO 3
  • Sodium bicarbonate can be used in volumes from 0,1 to 10 % by weight of the total mixture. The preferred volume is from 0,5 % by weight to 5 % by weight.
  • citric acid it is preferred to use citric acid as a pH lowering agent, in amounts of 0,5 to 10 % by weight of the total mixture.
  • the preferred amount of citric acid used together with sodium bicarbonate is 2 to 7 % by weight.
  • solid density reducing agents may be added. These agents are well known from the slurry literature and include hollow micro balloons, perlite, foamed glass, volcanic ash or other porous particles with open or closed pores which have an adequate low volume density.
  • thickening agent for water in accordance with the invention may be used several different types and combinations. These are also known from the patent literature, both concerning water resistant ANFO and watergel slurry. Some examples of such thickening agents are: Guar gum, xanthan gum, CMC (carboxymethyl cellulose), various types of alginates and "super-absorbents" used in modern napkins and sanitary towels. These water thickening agents must tolerate salts in the water, and must have an ability to thicken the water with a suitable speed (that is during 1-10 minutes).
  • cross-linking agent may for example potassium pyroantimonat or sodium dichromate be used.
  • the thickening agent(s) should be present in an amount of 0,1 % to 10 %. based on the weight of the explosive mixture. The preferred amount will be from 2 % by weight to 7 % by weight.
  • a water resistant ANFO When a water resistant ANFO, according to the invention, with added sodium bicarbonate and an organic acid is poured into a bore hole where water is present, for instance with water some meters from the bottom of the bore hole and up, the ANFO will sink to the bottom and expel the water upwards, at the same time as parts of the ANFO will start dissolving.
  • the added acid will also dissolve in the water, and lower the pH so that sodium bicarbonate will start to decompose and develop C0 2 -gas.
  • the developed gas will force the water which is in the process of being thickened further up in the dry ANFO-column. This lowers the concentration of water in the bottom of the bore hole, and makes it more easy to detonate.
  • the thickening agent should not thicken the water too fast, but gradually as the gassing develops and starts pushing the water further upwards into the dry ANFO-column.
  • Table 1 shows results with some test mixtures compared to two of Scandinavia's commercially available water resistant types of ANFO, namely Aqanol and Solamon.
  • Citric acid 4 0 % 4,0 % - 3,0 %

Abstract

Water resistant ANFO-explosive, containing one or more organic fuels, one or more inorganic salts, one or more thickening agents, together with a gassing reagent which is developing gas by contact by water.

Description

Water Resistant Explosive Composition
Ammonium nitrate fuel oil explosives, hereafter called ANFO, have today a dominant position in the world's total use of commercial explosives. ANFO is basically made of two components, namely ammonium nitrate (AN) as oxidiser, and fuel oil (FO) as fuel.
The reason why ANFO has this dominant position as the world's most used explosive, is mainiy because the explosive consists of two rather cheap raw materials, besides being very easy to produce. ANFO can either be produced in a factory, or be produced directly at the user's site. When produced at a factory, ANFO is usually filled in bags containing 25 or 1000 Gs.
ANFO prills have good flow properties, that is, they flow easily in pipelines, and they are specially well suited for bulk loading with pneumatic loading equipment. ANFO is then filled in a pressure vessel, usually called a "pressure pot", and compressed air with a pressure of 3-6 bar is applied. By means of a valve at the outlet of the pressure pot, which opens and closes, the ANFO is blown down to or into the bore holes.
The greatest disadvantage with the ANFO-explosives is their lack of water resistance. Usually this problem is solved by blowing the bore holes free for water by means of compressed air immediately before charging, and then carry out the blasting as soon as possible after loading. In many cases this method works well in order to charge ANFO in water filled bore holes, except for cases when cracks in the rock will lead the water into the bore hole after having loaded the ANFO.
Lots of work has been done in order to make the ANFO more water resistant. However, new additives that will make ANFO more water resistant, will at the same time result in both a more expensive and complicated product to manufacture. Consequently, the main advantage with ANFO, namely low price, will be reduced, and other water resistant explosive alternatives will become more competitive.
From the patent literature there are two known principles for making ANFO water resistant:
One of the methods recommends adding a certain percentage of an emulsion explosive to the ANFO. This is described in US-patents No. 4.1 1 1.727 and 4.181.546. The explosive resulting from this is called Heavy ANFO, and is usually classified as a special type of explosive. Besides, Heavy ANFO can not be loaded by means of pneumatic loading equipment. Normally, Heavy ANFO will not be considered as a water resistant ANFO.
The other method described is adding so called water thickening agents to the ANFO. These agents will then "react" with the water, making this highly viscous and thereby stopping further penetration of water into the product.
US-patent No. 4.933.029 describes a water resistant ANFO-explosive where the water resistance is achieved by using a water thickening agent like guar gum. In addition to this, it is known to use water repellent agents, like fatty acids, wax, etc. Also fillers like talc, glass, expanded perlite, sulphur, etc., may be used for preventing water to penetrate into the ANFO.
US-patent No. 5.480.500 describes such a water resistant ANFO-explosive. In this patent the water resistance is achieved by both applying a water thickening agent as guar gum, and simultaneously adding a particulate filling agent, for instance pulverised ammonium nitrate in order to stop penetration of water into the ANFO.
The characteristic feature by applying above mentioned product in accordance with the technique already known, is the fact that one will allow some water to penetrate into the explosive, resulting in a reaction with the ANFO. This again will form a barrier against further water penetration. At areas where the water has "reacted" with ANFO in order to form a barrier against further water penetration, the ANFO in this area is damaged. The degree of water penetration into the ANFO is often used as a measure of how good the water resistant ANFO in question really is.
In US-patent No. 5.480.500 the water penetration in the ANFO is measured by pouring 100 ml cold water in the middle of an ANFO column which is filled in a 1000 ml graduated cylinder. During 15 seconds the water is carefully poured at top of the explosive column. The water resistant ANFO and the water is left for one hour, for thereafter to measure how deep the water has penetrated into the ANFO. The best result in the above mentioned patent was a water penetration of 5,5 cm. In bore holes with flowing water this means that the explosive will have a layer of 5.5 cm where the ANFO is damaged by water and cannot contribute to detonation. Furthermore, if one should put today's water resistant ANFO in a bore hole partly filled with water, the explosive would be mixing with the water, and one would have a mixture unable to detonate. The present invention provides a water resistant ANFO-product which will detonate even when poured into a bore hole partly filled with water. Therefore, this concept is not based on the previously known principle that the water "reacts" with
ANFO and forming a barrier for preventing further water penetration into the ANFO- explosive.
The invention with this current water resistant ANFO patent, is that it utilises water in the bore hole so that the dry ANFO and water in the borehole form a slurry. This water resistant ANFO may thus be described as an "instant slurry" of the watergel type.
A watergel-slurry is characterised by consisting of dissolved salts of nitrates and/or perchlorate, and the water content may vary from approx. 10 to 30 %. The slurry is thickened with various types of gums and will also often contain some undissolved salt, usually ammonium nitrate. A watergel slurry is usually sensitised either by chemical gassing or by addition of porous particles such as hollow micro balloons or expanded perlite. The water resistant ANFO in accordance with the current invention ("instant slurry*') may therefore consist of the same components (except for water, which is present in the bore hole) known from the patent literature related to a watergel slurry.
In accordance to the current invention, it is possible to apply any chemical gassing reagent responding to water in the bore hole, which will develop gas bubbles sensitising the explosive. Some examples of gassing reagents which may be used are: Sodium bicarbonate, aluminium, nitrite (particularly sodium nitrite) and calcium carbide.
In order to get the first three previous mentioned substances to respond to water developing a gas, the water has to have a low pH-level. Consequently, the bore hole water has to be made acidic by ensuring that the water resistant ANFO also contains an acid, lowering the pH-level sufficiently for a reaction and development of gas. It is preferred to use one or more of organic acids chosen amongst citric acid, tartaric acid, ascorbic acid or acetic acid. It may also be used an inorganic acid which lowers the water's pH in an adequate way.
The two last-mentioned gassing reagents will easily decompose or react, when stored for a longer period together with AN and small amounts of humidity always being present in the ANFO. These should therefore be given a protecting water soluble layer, for instance through a micro encapsulation process. Sodium bicarbonate (NaHCO3) is the preferred gassing reagent because it is cheap, easy to use, and has storage stability together with ANFO. Sodium bicarbonate can be used in volumes from 0,1 to 10 % by weight of the total mixture. The preferred volume is from 0,5 % by weight to 5 % by weight. Together with sodium bicarbonate it is preferred to use citric acid as a pH lowering agent, in amounts of 0,5 to 10 % by weight of the total mixture. The preferred amount of citric acid used together with sodium bicarbonate is 2 to 7 % by weight.
In combination with a gassing reagent, solid density reducing agents may be added. These agents are well known from the slurry literature and include hollow micro balloons, perlite, foamed glass, volcanic ash or other porous particles with open or closed pores which have an adequate low volume density.
As thickening agent for water in accordance with the invention, it may be used several different types and combinations. These are also known from the patent literature, both concerning water resistant ANFO and watergel slurry. Some examples of such thickening agents are: Guar gum, xanthan gum, CMC (carboxymethyl cellulose), various types of alginates and "super-absorbents" used in modern napkins and sanitary towels. These water thickening agents must tolerate salts in the water, and must have an ability to thicken the water with a suitable speed (that is during 1-10 minutes).
It is possible also to cross-link the thickened gum. As cross-linking agent may for example potassium pyroantimonat or sodium dichromate be used. Generally, the thickening agent(s) should be present in an amount of 0,1 % to 10 %. based on the weight of the explosive mixture. The preferred amount will be from 2 % by weight to 7 % by weight.
When a water resistant ANFO, according to the invention, with added sodium bicarbonate and an organic acid is poured into a bore hole where water is present, for instance with water some meters from the bottom of the bore hole and up, the ANFO will sink to the bottom and expel the water upwards, at the same time as parts of the ANFO will start dissolving. The added acid will also dissolve in the water, and lower the pH so that sodium bicarbonate will start to decompose and develop C02 -gas. The developed gas will force the water which is in the process of being thickened further up in the dry ANFO-column. This lowers the concentration of water in the bottom of the bore hole, and makes it more easy to detonate. In order to avoid too high water concentration in the bottom of the bore hole, the thickening agent should not thicken the water too fast, but gradually as the gassing develops and starts pushing the water further upwards into the dry ANFO-column. To avoid a too high water concentration in the bottom charge, it may also be beneficial to use an ANFO-mixture with partly crushed prills, because this will also expel the water more effectively.
Examples
To simulate a partly filled bore hole, we used a steel tube with a diameter of 64 mm and a length of 400 mm. The tube was filled with water up to a level of 65 mm above the bottom, that means approx. 16 % of the tube length (or volume) was filled with water. The various test explosives were poured directly into the water until this was expelled and then further until the tube was completely filled. The bottom of the tube was closed by means of a strong tape, and immediately after the tubes had been filled with ANFO, the top of the steel tube was closed with a second strong tape, which however, was perforated with small holes to let out the excess gas. The steel tubes were test shot using a 150 gram primer attached to the bottom of the tubes, and the velocity of detonation (VOD) was measured at the uppermost 100 mm of the steel tube.
Table 1 shows results with some test mixtures compared to two of Scandinavia's commercially available water resistant types of ANFO, namely Aqanol and Solamon.
In the examples various water resistant ANFO mixtures were filled in 64 mm steel tubes which in advance had 16 % of the total tube volume filled with water. The velocity detonating (VOD) was compared with the before mentioned commercial water resistant ANFO explosives, and with ANFO-mixtures without gassing reagent. TABLE 1
The components are given in % by weight of the total mixture
Example No. 1 2 3" 4 5'> 6'>
AN-prill 83,5 % 85,5 % 84,0 % 86,0 %
Fuel oil 4,0 % 4,0 % - 5,0 %
Glycol - - 9,0 % -
Urea 2,0 % 2,0 % - -
Guar gum F-21 4,0 % 4,0 % 4,0 % 4,0 %
Citric acid 4,0 % 4,0 % - 3,0 %
Tartaric acid - - 1,5% -
Sodium 2,0 % - 1,5% 2,0 % bicarbonate
Borresperse 2) 0,5 % 0,5 % - -
Aqanol 100%
Soiamon 100%
VOD (m/s) F 3> F 3) 2400 F 3> 3100 2900
" = Examples according to the invention
2> = Sodium lignosulphonate from Orkla ASA
3) _ = Fail (no detonation)

Claims

Patent claims
1. A water resistant ANFO-explosive, containing one or more organic fuels, one or more inorganic salts, and one or more waterthickening agents. c harac teri s ed by that the ANFO-explosive also contains a gas generating substance which develops a gas when it comes in contact with water.
2. Water resistant ANFO-explosive according to claim 1 , c harac teri sed by that the gas generating substance is sodium bicarbonate (NaHCO -
3. Water resistant ANFO-explosive according to claim 2, characterised by that it also contains an organic acid as pH-reducing agent.
PCT/NO1997/000262 1996-09-27 1997-09-25 Water resistant explosive composition WO1998013318A1 (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
GB9905420A GB2331515B (en) 1996-09-27 1997-09-25 Water resistant explosive composition
CA002265905A CA2265905A1 (en) 1996-09-27 1997-09-25 Water resistant explosive composition
NZ334819A NZ334819A (en) 1996-09-27 1997-09-25 Water resistant ANFO (Ammonium Nitrate Fuel Oil) explosive composition combined with sodium bicarbonate
US09/147,954 US6261393B1 (en) 1996-09-27 1997-09-25 Water resistant explosive composition
JP51553398A JP2001505520A (en) 1996-09-27 1997-09-25 Water resistant explosive composition
AU44753/97A AU720922B2 (en) 1996-09-27 1997-09-25 Water resistant explosive composition
MXPA99002740A MXPA99002740A (en) 1996-09-27 1997-09-25 Water resistant explosive composition.
BRPI9712149-5A BR9712149B1 (en) 1996-09-27 1997-09-25 Water resistant amphibian explosive composition.
SE9901113A SE521310C2 (en) 1996-09-27 1999-03-26 Water resistant explosive composition
HK99102598A HK1017339A1 (en) 1996-09-27 1999-06-17 Water resistant explosive composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NO964107A NO300318B1 (en) 1996-09-27 1996-09-27 Waterproof explosive mixture
NO964107 1996-09-27

Publications (1)

Publication Number Publication Date
WO1998013318A1 true WO1998013318A1 (en) 1998-04-02

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PCT/NO1997/000262 WO1998013318A1 (en) 1996-09-27 1997-09-25 Water resistant explosive composition

Country Status (13)

Country Link
US (1) US6261393B1 (en)
JP (1) JP2001505520A (en)
AU (1) AU720922B2 (en)
BR (1) BR9712149B1 (en)
CA (1) CA2265905A1 (en)
GB (1) GB2331515B (en)
HK (1) HK1017339A1 (en)
ID (1) ID22041A (en)
MX (1) MXPA99002740A (en)
NO (1) NO300318B1 (en)
NZ (1) NZ334819A (en)
SE (1) SE521310C2 (en)
WO (1) WO1998013318A1 (en)

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RU2564812C1 (en) * 2014-05-20 2015-10-10 Закрытое акционерное общество "Петровский научный центр "Фугас" Method of producing water-resistant ammonium nitrate granules (versions)

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US7740069B2 (en) * 2007-01-04 2010-06-22 Michael Roy Young Process for two-step fracturing of subsurface formations
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PE20201366A1 (en) 2018-01-29 2020-11-30 Dyno Nobel Inc MECHANICALLY GASIFIED EMULSION EXPLOSIVES AND METHODS RELATED TO THEM

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NO964107A (en) 1997-05-12
GB2331515B (en) 2000-08-16
MXPA99002740A (en) 2002-07-22
JP2001505520A (en) 2001-04-24
SE9901113L (en) 1999-05-05
BR9712149B1 (en) 2008-11-18
GB2331515A (en) 1999-05-26
GB9905420D0 (en) 1999-05-05
ID22041A (en) 1999-08-26
SE521310C2 (en) 2003-10-21
CA2265905A1 (en) 1998-04-02
NZ334819A (en) 2000-05-26
NO300318B1 (en) 1997-05-12
SE9901113D0 (en) 1999-03-26
HK1017339A1 (en) 1999-11-19
US6261393B1 (en) 2001-07-17
AU4475397A (en) 1998-04-17
AU720922B2 (en) 2000-06-15
BR9712149A (en) 2000-01-18
NO964107D0 (en) 1996-09-27

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