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WO1997042141A1 - Explosifs constitues d'un melange sel/emulsion oxydant et resistants a l'eau - Google Patents

Explosifs constitues d'un melange sel/emulsion oxydant et resistants a l'eau Download PDF

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Publication number
WO1997042141A1
WO1997042141A1 PCT/IB1997/000504 IB9700504W WO9742141A1 WO 1997042141 A1 WO1997042141 A1 WO 1997042141A1 IB 9700504 W IB9700504 W IB 9700504W WO 9742141 A1 WO9742141 A1 WO 9742141A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
weight
percent
composition according
polygalactomannan
Prior art date
Application number
PCT/IB1997/000504
Other languages
English (en)
Inventor
Gerald L. Schrock
Mark Rainbird
Original Assignee
Rhone-Poulenc Inc.
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 Rhone-Poulenc Inc. filed Critical Rhone-Poulenc Inc.
Priority to AU23997/97A priority Critical patent/AU2399797A/en
Publication of WO1997042141A1 publication Critical patent/WO1997042141A1/fr

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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
    • 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

Definitions

  • water soluble inorganic oxygen supplying salts such as nitrates, chlorates and perchlorates
  • Ammonium nitrate and sodium nitrate find extensive use in commercial high explosives and blasting agents
  • explosives often are stored under conditions of high relative humidity and are used under wet conditions
  • the hygroscopicity and water solubility of the inorganic oxygen supplying salts are undesirable characteristics which may lead to deterioration of the explosive composition and to failures in use
  • the present invention provides waterproof explosive compositions which can tolerate extended exposure to moisture
  • a novel explosive blend composition comprising
  • the total weight of the composition being 100 weight percent
  • component (1) additionally includes one or more fuel oils, the amount of polygalactomannan plus crosslinker is present in amount ranging from about 0 1 to about 10 percent by weight of the inorganic oxidizing salt and fuel oil and the amount of emulsion is less than 30 percent by weight of the composition
  • An object of the present invention is to provide a novel explosive which demonstrates excellent water resistance
  • Another object of the present invention is to provide a novel heavy ANFO explosive which uses a minimal amount of emulsion
  • the first component of the novel explosive compnses a mixture of one or more inorganic oxidizing salts, optionally, fuel oil, and a polygalactomannan plus crosslinker
  • the inorganic oxidizing salts useful in this invention include ammonium, alkali metal and alkaline earth metal nitrates, perchlorates, sulfates and the like Specific examples of commonly employed salts are ammonium nitrate, ammonium perchlorate sodium nitrate sodium perchlorate potassium nitrate, potassium perchlorate, magnesium nitrate, magnesium perchlorate calcium nitrate and the like Mixtures of these salts can be used The preferred salt is ammonium nitrate and it is used in prill form
  • the fuel oils useful in this invention are petroleum based oils such as kerosene fuel oils lubricating oils and other relatively high flash point crude oil fractions including crude oil itself
  • the preferred fuel is No 2 fuel oil
  • Additional fuels which can be used in combination with the fuel oil include aluminum powder, sawdust coal dust flour wood pulp, dextrin starch sulfur and the like Up to about 50 weight percent of fuel oil can be substituted with the additional fuel
  • Such emulsions are manufactured "fuel nch” and can oxygen balance the oxidizing salt such as ammonium nitrate even if the ammonium nitrate has no added fuel oil
  • the polygalactomannans useful in this invention are guar gum and locust bean gum and derivatives of these gums
  • Guar gum is the milled endosperm of the seeds of the leguminous plant
  • Cyamop ⁇ s tetragonolobus Locust bean gum is the milled endosperm of the seeds of the plant Ceratonia siliqua Derivatized polygalactomannans include one or more non-ionic anionic or cationic groups
  • Examples of the types of functional groups involved in producing the de ⁇ vatives include hydroxyalkyl groups, carboxyalkyl groups, quaternary ammonium groups sulfonate groups, cyanoalkyl groups, phosphate groups siloxane groups and the like having varying degrees of substitution and molecular substitution
  • the resulting polygalactomannans may be multiple derivatives, such as double and triple derivatives having various degrees of substitution and molar substitution
  • preferred derivatized polygalactomannans include hydroxypropyl guar gum, hydroxyethyl guar gum, 2-hydroxypropyl-tr ⁇ methylammon ⁇ um halide guar gum (quaternary ammonium cationic guar) 2-hydroxypropyl-d ⁇ methylalkylammon ⁇ um halide guar gum (quaternary ammonium cationic guar, alkyl represents a long chain moiety having between 6 and 24 carbon atoms), 2-hydroxyethyl-d ⁇ methylalkylarnmo ⁇ um halide guar gum (quaternary ammonium cationic guar, alkyl represents a long chain moiety having between 6 and 24 carbon atoms), carboxyethyl guar gum carboxymethyl guar gum carboxymethylhydroxypropyl guar gum carboxymethylhydroxyethyl guar gum and the like
  • the preferred polygalactomannan for use in this invention is non-de ⁇ vatized guar gum
  • Crosslinking agents which are used in combination with the polygalactomannans are any of the well-known polyfunctional reagents which react with the ⁇ s-hydroxyls of the polygalactomannans Suitable crosslinking agents are disclosed in U S Pat No 3 301 723 which is hereby incorporated by reference Disclosed crosslinkers are the ions of scandium titanium vanadium chromium manganese, iron, yttrium, zirconium, niobium, lanthanum, hafnium and tantalum These metal ions are used to crosslink polygalactomannans at pH s of about 6-13
  • crosslinking agents are disclosed in U S Pat No 4,033 415 which is hereby inco ⁇ orated by reference
  • Such disclosed crosslinkers contain the ions lead (II), arsenic (III) tin (II) antimony (III), antimony (V).t ⁇ tan ⁇ um (IV), manganese (VII), chromium (VI) tantalum (V) and niobium (V)
  • Specific crosslinking agents include antimony oxide which cross-links the polygalactomannans at a pH above 7, lead chromate, pH above 8, potassium antimony tartrate and potassium dichromate, pH 2 5-7, potassium pyroantimonate, pH of 5 or lower and potassium permanganate pH above 5
  • crosslinking agent for polygalactomannans is the borate ion which crosslinks at alkaline pH
  • a preferred crosslinking agent for use in this invention is potassium pyroantimonate
  • cross-linking agent Generally, about 0 005 to about 5 millimoles of cross-linking agent are used per one gram of polygalactomannan
  • the amount of polygalactomannan and crosslinking agent ranges from about 0 1 to about 10 parts by weight per 100 parts by weight oxidizing salt and, if present fuel oil, with preferred amounts ranging from about 1 0 to about 7 5 parts by weight per 100 parts by weight oxidizing salt and fuel oil with most preferred amounts ranging from about 2 0 to about 6 0 parts by weight per 100 parts by weight oxidizing salt and fuel oil
  • buffers i e acids or bases
  • buffers include fumaric acid sulfamic acid, ⁇ t ⁇ c acid, oxalic acid, sodium acid fumarate, disodium acid citrate, hexamme salts tnsodium citrate, sodium hydroxide, sodium bicarbonate, sodium carbonate and the like
  • the first component of the explosive composition of the present invention is produced by simply combining the various components to yield a suitably homogeneous mixture
  • oxidizing salt e.g., a mixture of the components as described above (e.g., a mixture of the components as described above (e.g., a mixture of the components as described above (e.g., a mixture of the components as described above (e.g., a mixture of the components as described above (e
  • the second component of the explosive composition comprises an emulsion
  • emulsion comprises principally a water-m-oil emulsion
  • the emulsion may optionally include a crosslinkable and/or polymerizable component in the external continuous phase, which typically includes fuel oil as one of its primary components It also has an internal discontinuous oxidizing phase
  • the emulsion comprises an emulsion phase and a sensitizer, and may also contain additional fuels, additional solid oxidizers, and any other necessary or desirable components to control energy and/or density of the final explosive product
  • the preferred emulsion for use comprises a sensitized water-m-oil bulk emulsion
  • emulsions are commercially available and typically have a bulk density ranging from about 1 0 g/cc to about 1 5 g/cc, with a bulk density of between about 1 2 g/cc to about 1 3 g/cc being particularly preferred
  • the two components are simply mixed together
  • a composition containing between about 40 and about 99 parts by weight of the first component are mixed with about 1 to about 60 parts by weight of the second component in amounts to yield a composition of 100 parts by weight
  • a composition containing between about 90 and about 99 percent by weight of the first component and between about 1 to about 10 percent by weight of the emulsion The use of minimal amounts of the emulsion when producing the resulting explosive composition can result in significant cost savings as the emulsion is much more costly than the oxidizing salt/optional fuel oil/polygalactomannan and crosslinker component
  • the waterproof explosive of the invention is placed in a dewatered bore hole, by use of means known in the art such as a discharge auger, which contains a blasting cap and booster which contains high explosives connected to a blasting cord
  • a discharge auger which contains a blasting cap and booster which contains high explosives connected to a blasting cord
  • the explosive composition can be delivered to the explosion site either in bulk form as described above or in packaged form (e g polymeric bags, bags made of naturally occurring fabrics, drums, etc )
  • packaged form e g polymeric bags, bags made of naturally occurring fabrics, drums, etc
  • the most preferred level of polygalactomannan admixed with the oxidizing salt/optional fuel oil may vary with the method of delivery of the explosive to the formation
  • the explosives are covered with sand, rocks and the like
  • the blasting agent is activated, which causes the composition of the present invention to ignite, resulting in an explosion which fractures or otherwise alters the integrity of the formation
  • inventive composition will resist desensitization resulting from water leaching into the bore hole unlike matenals without the galactomannan and crosslinker Therefore, this invention may be used in many areas in which conventional ammonium nitrate fuel oil/emulsions fail due to water desensitization
  • ammonium nitrate/fuel oil/ emulsion (Heavy ANFO blends) contains 94 percent ammonium nitrate prills and 6 percent #2 diesel fuel resulting in a material with a bulk density of 0 85 g/cc
  • the emulsion used is a water-m- oil bulk emulsion (sensitized) having a bulk density of about 1 25 g/cc
  • guar flour is blended with potassium pyroantimonate, fumaric acid and monosodium phosphate This is known as the premix
  • the composition of the premix is as follows
  • Example 7 In the 70/30 blends (Examples 7-9) it is difficult to visually detect water penetration except in the case of Example 7, 24 hours soak time Increased density can be an indicator of water abso ⁇ tion The abso ⁇ tion of water results in a significant increase in density This apparently occurs in Example 7 (no gum) but not in Examples 8-9
  • compositions of the present invention may be capable of demonstrating improved explosive performance properties as compared to prior art compositions

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Composition formée de: (a) 40 à 99 pour cent en poids d'un mélange comprenant: (1) un sel oxydant inorganique; et (2) un agent de réticulation ajouté à du polygalactomannane, et (b) 1 à 60 pour cent en poids d'une émulsion; le pourcentage en poids total étant donné. Cette composition est particulièrement utile en tant qu'explosif.
PCT/IB1997/000504 1996-05-08 1997-05-06 Explosifs constitues d'un melange sel/emulsion oxydant et resistants a l'eau WO1997042141A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU23997/97A AU2399797A (en) 1996-05-08 1997-05-06 Waterproof oxidizing salt/emulsion blend explosives

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US64656696A 1996-05-08 1996-05-08
US08/646,566 1996-05-08

Publications (1)

Publication Number Publication Date
WO1997042141A1 true WO1997042141A1 (fr) 1997-11-13

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB1997/000504 WO1997042141A1 (fr) 1996-05-08 1997-05-06 Explosifs constitues d'un melange sel/emulsion oxydant et resistants a l'eau

Country Status (2)

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AU (1) AU2399797A (fr)
WO (1) WO1997042141A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1359135A2 (fr) * 2002-04-29 2003-11-05 Dyno Nobel Inc. Explosif à haute énergie contenant des particules moulées
EP3020694A4 (fr) * 2014-07-31 2017-08-23 Exsa S.A. Procédés d'élaboration de compositions explosives d'anfo et d'anfo lourd

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4104092A (en) * 1977-07-18 1978-08-01 Atlas Powder Company Emulsion sensitized gelled explosive composition
US4637849A (en) * 1985-09-03 1987-01-20 Celanese Corporation Waterproof ammonium nitrate fuel oil explosives
US4693765A (en) * 1986-05-22 1987-09-15 Stromquist Donald M Gel type slurry explosive and matrix and method for making same
US4718954A (en) * 1986-03-26 1988-01-12 Thermex Energy Corporation Explosive compositions
US4756779A (en) * 1986-10-08 1988-07-12 C-I-L Inc. Inc. Process for the production of particulate, water resistant explosives based on ammonium nitrate
EP0276934A2 (fr) * 1987-01-30 1988-08-03 Ici Australia Operations Proprietary Limited Composition explosive
US4780156A (en) * 1986-10-06 1988-10-25 Sheeran Harold W Water resistant sensitizing additive for ammonium nitrate blasting agents
AU598162B2 (en) * 1987-11-18 1990-06-14 Dyno Nobel Asia Pacific Limited Binding additive for explosive compositions
USRE33788E (en) * 1977-09-19 1992-01-07 Hanex Products, Inc. Water-in-oil blasting composition
US5409556A (en) * 1993-04-02 1995-04-25 Mining Services International Method of lowering the density of ammonium nitrate-based mining explosives with expanded agricultural grain so that a density of 0.3g/cc to 1.0g/cc is achieved

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4104092A (en) * 1977-07-18 1978-08-01 Atlas Powder Company Emulsion sensitized gelled explosive composition
USRE33788E (en) * 1977-09-19 1992-01-07 Hanex Products, Inc. Water-in-oil blasting composition
US4637849A (en) * 1985-09-03 1987-01-20 Celanese Corporation Waterproof ammonium nitrate fuel oil explosives
US4718954A (en) * 1986-03-26 1988-01-12 Thermex Energy Corporation Explosive compositions
US4693765A (en) * 1986-05-22 1987-09-15 Stromquist Donald M Gel type slurry explosive and matrix and method for making same
US4780156A (en) * 1986-10-06 1988-10-25 Sheeran Harold W Water resistant sensitizing additive for ammonium nitrate blasting agents
US4756779A (en) * 1986-10-08 1988-07-12 C-I-L Inc. Inc. Process for the production of particulate, water resistant explosives based on ammonium nitrate
EP0276934A2 (fr) * 1987-01-30 1988-08-03 Ici Australia Operations Proprietary Limited Composition explosive
AU598162B2 (en) * 1987-11-18 1990-06-14 Dyno Nobel Asia Pacific Limited Binding additive for explosive compositions
US5409556A (en) * 1993-04-02 1995-04-25 Mining Services International Method of lowering the density of ammonium nitrate-based mining explosives with expanded agricultural grain so that a density of 0.3g/cc to 1.0g/cc is achieved

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1359135A2 (fr) * 2002-04-29 2003-11-05 Dyno Nobel Inc. Explosif à haute énergie contenant des particules moulées
EP1359135A3 (fr) * 2002-04-29 2005-06-01 Dyno Nobel Inc. Explosif à haute énergie contenant des particules moulées
EP3020694A4 (fr) * 2014-07-31 2017-08-23 Exsa S.A. Procédés d'élaboration de compositions explosives d'anfo et d'anfo lourd

Also Published As

Publication number Publication date
AU2399797A (en) 1997-11-26

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