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WO1996026911A1 - Explosifs utilisant des residus de la distillation d'ethylene glycol - Google Patents

Explosifs utilisant des residus de la distillation d'ethylene glycol Download PDF

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Publication number
WO1996026911A1
WO1996026911A1 PCT/US1995/002726 US9502726W WO9626911A1 WO 1996026911 A1 WO1996026911 A1 WO 1996026911A1 US 9502726 W US9502726 W US 9502726W WO 9626911 A1 WO9626911 A1 WO 9626911A1
Authority
WO
WIPO (PCT)
Prior art keywords
glycol
bottoms
ethylene glycol
composition according
still bottoms
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.)
Ceased
Application number
PCT/US1995/002726
Other languages
English (en)
Inventor
Donald M. Strmquist
Boyd J. Wathen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AN/GEL INTERNATIONAL
Original Assignee
AN/GEL INTERNATIONAL
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 AN/GEL INTERNATIONAL filed Critical AN/GEL INTERNATIONAL
Priority to PCT/US1995/002726 priority Critical patent/WO1996026911A1/fr
Priority to AU20947/95A priority patent/AU2094795A/en
Priority to CA002216921A priority patent/CA2216921C/fr
Priority to BR9510275A priority patent/BR9510275A/pt
Priority claimed from CA002216921A external-priority patent/CA2216921C/fr
Priority to ZA952068A priority patent/ZA952068B/xx
Publication of WO1996026911A1 publication Critical patent/WO1996026911A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
    • C06B31/02—Compositions containing an inorganic nitrogen-oxygen salt the salt being an alkali metal or an alkaline earth metal nitrate
    • 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

Definitions

  • the invention is in the field of explosives, especially those using nitrate salt oxidizers, and specifically ammonium nitrate-fuel oil explosives (ANFO) .
  • ANFO ammonium nitrate-fuel oil explosives
  • Explosives and blasting agents are an important part of the mining industry. It is estimated that over three billion pounds of explosives are used each year in the mining industry in the United States alone. The most commonly used explosive is a mixture of about 94% ammonium nitrate (AN) and about 6% fuel oil (FO) , commonly referred to as ANFO. It is sold in the form of dry, loose particles called “prills", generally marketed in bags or in bulk.
  • ANFO fuel oil
  • Explosive power is measured in terms of weight strength and bulk strength.
  • the term "weight strength”, usually expressed in kilocalories per gram, is used to compare explosives which employ nitrate salt oxidizers with ANFO explosives, the standard for the industry. The value of the weight strength for ANFO is frequently assumed to be 1.0 kcal/gm.
  • Bulk strength a function of the density of the explosive, is used to compare the explosive power of two products on a bulk or volume basis. The higher the volume density, the higher the bulk strength. Its unit of measure is kilocalories per cubic centimeter, abbreviated kcal/cc.
  • ANFO is relatively inexpensive and widely used, however, its low volume density (about 0.8 gm/cc) limits the amount of useful energy that can be obtained per charge. Efforts to increase the density and therefore the bulk strength of ANFO have included methods using finely ground ammonium nitrate as opposed to nitrate prill particles and the use of high density metallic fuel additives such as aluminum or ferrosilicon.
  • ANFO is desensitized by water, precluding its use in water-filled boreholes.
  • many water-in-oil and oil-in-water emulsion products have been described in numerous patents.
  • Attempts have also been made to waterproof ANFO by using thickeners and cross-linkers; for example, Sheeran, U.S. Patent No. 4,933,029 and Stromquist and Wathen, U.S. Patent No. 4,693,763.
  • the invention encompasses explosive compositions comprising a mixture of at least one nitrate salt oxidizer and glycol still bottoms used alone or diluted with water.
  • the glycol still bottoms can be mixed with other additives such as thickeners, cross-linkers and pH adjusters to form a matrix composition, herein termed "bottoms matrix”.
  • This matrix composition can then be mixed with at least one nitrate salt oxidizer to form an explosive composition.
  • Glycol still bottoms abbreviated to “still bottoms” or “bottoms” herein, have been found to be a suitable replacement for the commonly used fuel oils in ANFO explosives. Therefore, still bottoms plus water or a bottoms matrix are also herein referred to as “FOR” for "fuel oil replacement”.
  • the explosives which use a combination of ammonium nitrate (AN) and FOR are herein called “FOR-AN” explosives.
  • Glycol still bottoms are the waste-product remaining in distillation units during the process for making marketable glycol products.
  • Primary glycol producers extract ethylene glycol, diethylene glycol, triethylene glycol, and other lower glycols from a mixed glycol starting material.
  • the remaining by-product in the distillation unit after extraction of the lower glycols is used by secondary producers to extract additional lower glycols.
  • the material remaining in distillation units after extraction of the additional lower glycols is a still more concentrated form of a waste product termed glycol still bottoms.
  • Still bottoms comprise a mixture of lower and higher glycols, polyglycols, glycol-ethers as well as various derivatives.
  • glycol still bottoms have a high pH value and cannot be used as taken directly from distillation units due to the inherent hazards encountered when handling materials of high pH value. Neutralization of the still bottoms with HC1 lends the bottoms non-hazardous and non-flammable.
  • glycol still bottoms The principal use of glycol still bottoms has been in the coal industry for de-icing.
  • the glycol-rich bottoms prevent individual coal lumps from freezing together during inclement weather, thus avoiding handling problems. This use is limited, however, and at times the disposal of still bottoms has become problematic, often forcing producers to pay for removal.
  • glycol still bottoms cannot be used as taken directly from distillation units due to the inherent hazards encountered when handling materials of high pH value. Neutralization of the still bottoms with HC1 lends the bottoms non-hazardous and non ⁇ flammable.
  • glycol still bottoms may be used in place of fuel oil to make a nitrate salt explosive.
  • the glycol still bottoms may be used as a replacement for the fuel oil normally mixed with ammonium nitrate to produce an ANFO explosive.
  • Glycol still bottoms as removed from distillation units, even after neutralization, may still be too viscous for efficient use in the present invention.
  • the advantageous properties of the bottoms in the manufacture of explosive compositions equal or exceed those of diesel fuel or mineral oil.
  • Still bottoms have a freeze point far below temperatures encountered in mining and quarrying in the United States and Canada and a flash point far above that of fuel oil or mineral oil.
  • the bottoms can easily be pumped and handled, have no known health hazard, and are not regulated in shipment or storage. Also, unlike fuel oil and mineral oil, there is no measurable evaporation of the still bottoms, even when mixed with up to 35% water, under normal storage conditions.
  • Typical water analysis equals about 10% after neutralization with HCl to bring pH values to about 6.5-7
  • Water can be added to the still bottoms to adjust viscosity before mixing the bottoms with nitrate salt oxidizers. Water can also be added after the bottoms and oxidizer have been mixed. Further, a matrix can be made of bottoms plus water plus other additives and the matrix can then be mixed with nitrate salt oxidizers. In some cases, water can be a solute for nitrate salt oxidizers to become a part of a bottoms matrix.
  • nitrate salt oxidizers of the invention are ammonium nitrate, sodium nitrate, calcium nitrate, magnesium nitrate, and combinations of these.
  • Ammonium nitrate is the preferred oxidizer and may be present in the explosive in amounts from about 50% to 98%, more preferably from about 85% to 96%, by explosive weight. Up to about 50% of the ammonium nitrate can be replaced with other nitrate salt oxidizers.
  • thickeners optionally cross-linking thickeners
  • thickeners and cross-linking agents can be separately added to the bottoms to accomplish the same purpose.
  • Commonly used thickeners of the invention are cold water swellable and able to produce high viscosities within a matter of hours, for example, guar gums, gum arabic, starched, xanthan gums, polyacrylamide, cellulose and cellulose derivatives. Guar gums are presently preferred.
  • cross-linking or non-cross-linking guar gums may be used in the amount of from about 0.2% o 1.5%, more preferably, from about 0.2% to 0.8%.
  • No. 2379 guar gum sold by Rhone-Poulenc, Louisville, Kentucky contains the cross-linker potassium pyroantimonate.
  • a non-cross-linking guar gum may be used and cross-linking can be accomplished with the addition to the bottoms matrix of about 1.0-1.5% based on guar gum concentration.
  • Preferable cross- linkers include antimonates, especially potassium antimony tartrate; dichromates; borates, especially sodium tetratobrate; tannic acids; and other selected organic acids, among other. The antimonates, especially the pyroantimonates are most preferable.
  • additives to the still bottoms to create a bottoms matrix may include weak acids for pH adjustment.
  • pH adjustment when using gum thickeners with or without cross-linkers, adjustment of the matrix mixture with glacial acetic acid to a final pH of 5.5-6.5 provides for successful completion of chemical reactions.
  • the first propagated above-ground unconfined test shootings of the FOR-AN explosives of the invention employed a formulation compounded from glycol still bottoms and ammonium nitrate prills.
  • the mixture for explosive Charge 1 of this example was hand- mixed using conventional bench-top techniques.
  • Glycol still bottoms purchased from KMCO, Inc., containing about 10%-12% H 2 0 at pH 6.5-7.5, were mixed with additional water to give the still bottoms a 19% water content.
  • the bottoms were then mixed with ammonium nitrate prills in the proportions given in Table Ill-
  • the term “detonation” means that the main charge, when primed and initiated, tripped or detonated a 25 grain detonating cord embedded in the charge at the cylinder end opposite the primer initiation end.
  • detonation was measured as a visually estimated disturbance or fragmentation in the earth or rock surrounding the charges.
  • detonation was measured with instruments.
  • ammonium nitrate prills in this and the following examples were obtained from either LaRoche Chemicals, Geneva, Utah or Wycon Chemicals, Cheyenne, Wyoming.
  • Other sources of ammonium nitrate prills which have been successfully used with glycol still bottoms to make the explosive compositions of the invention have been supplied by ICI Chemical Company, Calgary, Alberta, Canada; IRECO, Donora, Pennsylvania; ETI Chemicals, Seneca, Illinois; and Nitrochem, Ontario, Canada.
  • glycol bottoms used in the Examples were obtained from KMCO, Inc. , Houston, Texas.
  • Example 2 Materials and methods were essentially the same as described in Example 1.
  • the formulation of the explosives consisted of 8% still bottoms (19% H 2 0) and 92% of ammonium nitrate prills.
  • Example 3 One thousand grams of the explosive was packed into cardboard cylinders measuring 3 inches, 3.5 inches and 4 inches in diameter and 12 inches in length. One hundred twenty grams of pentolite equivalent primer was used. All charges detonated showing similar sensitivity and bulk strength as commonly exhibited by ANFO explosives.
  • Example 3 Other repetitive unconfined tests were performed using mixtures of still bottoms and ammonium nitrate prills in which the water content of the still bottoms was varied to account for up to 35% of the bottoms (up to about 3.5% of the explosive). Materials and methods for making the charges were essentially the same as in Charge 1 of Example 1. Formulations for high- water content charges are found in Table IV. These tests showed results similar to the results from the Examples 1 and 2 test detonations. Detonations occurred in each case.
  • Example 4 Further repetitive unconfined tests were completed using the explosive charges of the formulations illustrated in Table V. To make the bottoms matrix for Charges 1 and 2, a small amount of still bottoms (10% H20) was mixed with water and then with the gum. The remainder of the still bottoms and water were added to the mixture.
  • the charge mixtures not only exhibited a viscous consistency and appearance, water resistance was apparent, especially in charge mixture 2.
  • the No. 2379 gum contained a cross-linker, potassium pyroantimonate, which assisted in forming a more viscous bottoms matrix.
  • FOR-AN charges contained 20% less weight of explosive in each hole than did the HANFO charge, i.e., typically 320 lbs. of charge material were placed into the HANFO holes compared to 260 lbs. in the FOR-AN holes.
  • the density of the FOR-AN explosive was 0.95-0.97 g./cc.
  • the density of the HANFO explosive was about 1.2 gm/cc. All charges detonated. After shooting, fragmentation was visually compared. No apparent differences were observed between the results of the FOR-AN detonations and the results of the HANFO detonations.
  • ANFO and FOR-AN explosives were prepared using the methods of Example 5.
  • ANFO explosive mixtures consisting of 6% mineral oil and 94% ammonium nitrate prills were packed to give a density of 0.83 gm/cc.
  • FOR-AN explosive mixtures of the formulation in Table VI were packed to give a density of 0.96 gm/cc.
  • Holes were dug to be about 6 inches in diameter and 43 feet deep, arranged in a pattern of a 16 foot spacing by a 16 foot burden. Approximately one-half of the holes were filled with about 330 lbs. each of ANFO explosives and the other half with 311 lbs. each of FOR-AN explosives.
  • the FOR-AN explosive compositions of this invention show an increase in density when compared to ANFO explosive compositions. It follows that a corresponding increase in weight and bulk strength will be observed for FOR-AN explosives when compared to ANFO explosives of the same weight.
  • glycol still bottoms as a waste product in distillation units after extraction of lower glycols from a mixed glycol starting material.
  • the use of such waste material is presently preferred because of its status as a waste material, its availability and resulting low cost.
  • the still bottoms as defined herein could be specifically manufactured for use in the invention rather than merely collected as a waste product.
  • the still bottoms mixture can include, in addition to water up to about 35%, any one or more of the glycols listed in Table l.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention porte sur des compositions explosives comportant un oxydant à base de sel de nitrate et des résidus de la distillation d'éthylène glycol seuls ou associés à de l'eau. Ces résidus de distillation remplacent le fuel-oil (FOR) utilisé pour les explosifs nitrate-fuel (ANFO). On peut les mélanger à des épaississeurs, à des agents de réticulation et à d'autres additifs afin de constituer une matrice de produits de fond se combinant avec un oxydant à base de sel de nitrate pour produire des compositions explosives qui présentent des caractéristiques de fonctionnement améliorées ainsi qu'une meilleure résistance à l'eau si on les compare aux explosifs ANFO classiques.
PCT/US1995/002726 1995-03-01 1995-03-01 Explosifs utilisant des residus de la distillation d'ethylene glycol Ceased WO1996026911A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
PCT/US1995/002726 WO1996026911A1 (fr) 1995-03-01 1995-03-01 Explosifs utilisant des residus de la distillation d'ethylene glycol
AU20947/95A AU2094795A (en) 1995-03-01 1995-03-01 Explosives using glycol still bottoms
CA002216921A CA2216921C (fr) 1995-03-01 1995-03-01 Explosifs utilisant des residus de la distillation d'ethylene glycol
BR9510275A BR9510275A (pt) 1995-03-01 1995-03-01 Composição explosiva
ZA952068A ZA952068B (en) 1995-03-01 1995-03-13 Explosives using glycol still bottoms

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
PCT/US1995/002726 WO1996026911A1 (fr) 1995-03-01 1995-03-01 Explosifs utilisant des residus de la distillation d'ethylene glycol
CA002216921A CA2216921C (fr) 1995-03-01 1995-03-01 Explosifs utilisant des residus de la distillation d'ethylene glycol
ZA952068A ZA952068B (en) 1995-03-01 1995-03-13 Explosives using glycol still bottoms

Publications (1)

Publication Number Publication Date
WO1996026911A1 true WO1996026911A1 (fr) 1996-09-06

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PCT/US1995/002726 Ceased WO1996026911A1 (fr) 1995-03-01 1995-03-01 Explosifs utilisant des residus de la distillation d'ethylene glycol

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3886008A (en) * 1969-11-13 1975-05-27 Ireco Chemicals Blasting composition for use under high temperature conditions
US4294633A (en) * 1979-06-07 1981-10-13 Clay Robert B Blasting composition
US4614146A (en) * 1984-05-14 1986-09-30 Les Explosifs Nordex Ltee/Nordex Explosives Ltd. Mix-delivery system for explosives
US4685375A (en) * 1984-05-14 1987-08-11 Les Explosifs Nordex Ltee/Nordex Explosives Ltd. Mix-delivery system for explosives
US4736683A (en) * 1986-08-05 1988-04-12 Exxon Chemical Patents Inc. Dry ammonium nitrate blasting agents
US4746380A (en) * 1986-06-11 1988-05-24 Imperial Chemical Industries Plc Explosive compound comprising ammonium nitrate and glycine
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
US4889570A (en) * 1989-03-23 1989-12-26 Eti Explosives Technologies International (Canada), Ltd. Blasting explosive with improved water resistance
US5099763A (en) * 1990-05-16 1992-03-31 Eti Explosive Technologies International Method of blasting

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3886008A (en) * 1969-11-13 1975-05-27 Ireco Chemicals Blasting composition for use under high temperature conditions
US4294633A (en) * 1979-06-07 1981-10-13 Clay Robert B Blasting composition
US4614146A (en) * 1984-05-14 1986-09-30 Les Explosifs Nordex Ltee/Nordex Explosives Ltd. Mix-delivery system for explosives
US4685375A (en) * 1984-05-14 1987-08-11 Les Explosifs Nordex Ltee/Nordex Explosives Ltd. Mix-delivery system for explosives
US4746380A (en) * 1986-06-11 1988-05-24 Imperial Chemical Industries Plc Explosive compound comprising ammonium nitrate and glycine
US4736683A (en) * 1986-08-05 1988-04-12 Exxon Chemical Patents Inc. Dry 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
US4889570A (en) * 1989-03-23 1989-12-26 Eti Explosives Technologies International (Canada), Ltd. Blasting explosive with improved water resistance
US5099763A (en) * 1990-05-16 1992-03-31 Eti Explosive Technologies International Method of blasting

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