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EP0044664A2 - Agent de sautage du type émulsion contenant du mononitrate d'hydrazine - Google Patents

Agent de sautage du type émulsion contenant du mononitrate d'hydrazine Download PDF

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Publication number
EP0044664A2
EP0044664A2 EP81303112A EP81303112A EP0044664A2 EP 0044664 A2 EP0044664 A2 EP 0044664A2 EP 81303112 A EP81303112 A EP 81303112A EP 81303112 A EP81303112 A EP 81303112A EP 0044664 A2 EP0044664 A2 EP 0044664A2
Authority
EP
European Patent Office
Prior art keywords
agent
discontinuous phase
gas
emulsion
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP81303112A
Other languages
German (de)
English (en)
Other versions
EP0044664A3 (fr
Inventor
John Cooper
Vladimir Sujansky
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.)
Imperial Chemical Industries Ltd
Original Assignee
Imperial Chemical Industries Ltd
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 Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
Publication of EP0044664A2 publication Critical patent/EP0044664A2/fr
Publication of EP0044664A3 publication Critical patent/EP0044664A3/fr
Withdrawn legal-status Critical Current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
    • 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
    • C06B47/02—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 the components comprising a binary propellant
    • C06B47/08—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 the components comprising a binary propellant a component containing hydrazine or a hydrazine derivative
    • 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
    • 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

Definitions

  • This invention relates to emulsion type blasting agents having a discontinuous phase and a carbonaceous fuel component forming a continuous phase.
  • Emulsion type blasting agents are well known commercial explosive compositions, but they are generally detonable only with difficulty and it is usual, therefore, to incorporate in them a sensitizing agent in the form of a gas, for example air, either in the form of bubbles or in microspheres of glass or plastic.
  • a sensitizing agent in the form of a gas, for example air, either in the form of bubbles or in microspheres of glass or plastic.
  • conventional EBA's commonly comprise a discontinous aqueous phase comprising a solution of oxidiser salts, often also containing oxidiser salt suspended as microscopically fine particles,in a continuous oil phase and containing also a third, gaseous, phase dispersed in the emulsion as fine gas cells.
  • the emulsion is stabilised against liquid separation by a lipophilic emulsifying agent.
  • Such emulsions can also serve as detonable matrices to carry solid fuels such as aluminium or inorganic oxidising agents of low solubility.
  • EBA's typically can be made in a variety of forms from stiff plastic creams to almost fluid pumpable compositions. A stiff cream consistency is usually preferred.
  • EBA's commonly have an intrinsic density in the region of 1.45 gm/cc, the occluded gas reducing this to 1.2 gm/cc or less, and the sensitivity of the gas sensitised EBA is inversely related to its density for a given chemical composition.
  • gas bubbles are included in the emulsion they tend to coalesce, reducing the detonability of the composition,and this is sometimes overcome by incorporating the gas in the form of micro spheres of glass or other material.
  • the use of such additional components increases the cost of the composition significantly.
  • the present invention therefore, provides an emulsion type blasting agent comprising a discontinuous phase and a carbonaceous fuel component forming a continuous phase, in which the discontinuous phase comprises hydrazine mononitrate.
  • the discontinuous phase is usually an aqueous phase, present as a solution of hydrazine mononitrate (and optionally solid hydrazine mononitrate) in water and also optionally may comprise other compatible watersoluble materials', particularly inorganic oxidising materials, for example ammonium salts, alkali metal and alkaline earth metal salts, in particular the nitrate, chlorate and perchlorate salts, such as are mentioned for example in US Patent No 3447978.
  • inorganic oxidising materials for example ammonium salts, alkali metal and alkaline earth metal salts, in particular the nitrate, chlorate and perchlorate salts, such as are mentioned for example in US Patent No 3447978.
  • the discontinuous phase usually forms from 20 to 97%, preferably 40% to 97%, more preferably 60% to 97% and particularly 70 to 97% by weight of the composition, though the precise composition will, of course, be influenced by the proportion of other components. present to the total of 100%.
  • the aqueous component of the emulsion is usually formed by heating the water and dissolving in it the desired water soluble components, the mixture usually being heated to about 80°C until complete solution occurs. Heating may be effected prior to or during formation of the emulsion. It is preferred that the proportions of solvent and solute are chosen so that in the final emulsion, after it has been cooled to ambient temperature, the aqueous component is supersaturated, although some crystallisation, resulting in the presence of crystals in the aqueous component, might not adversely affect the properties of the EBA unduly.
  • the aqueous phase may comprise also water soluble fuel-components to serve as supplemental fuels.
  • soluble carbohydrate materials e.g. glucose, sucrose, fructose, maltose, molasses, etc.
  • Other possible components include for example, lower glycols, formamide, urea, methyl/amine nitrate, hexamethylene tetramine, hexamethylene tetramine nitrate, other organic nitrates, etc.
  • the hydrazine nitrate conveniently is present in the discontinuous phase of the EBA of the invention in an amount forming at least 10%, preferably at least 30% and more preferably at least 50%, although usually it will exceed 70% and more usually exceed 80% or even 90% by weight. Broadly, therefore, it will form 10% to 100% of the discontinuous phase. Where the hydrazine mononitrate forms a very high proportion of the phase it will usually be in the presence of little or no water, for example such as may occur when molten hydrazine mononitrate is emulsified into the continuous phase.
  • the discontinuous phase may comprise, alternatively, a mixture of oxidising materials, including hydrazine mononitrate, emulsified in the continuous phase for example as a eutectic mixture.
  • hydrazine mononitrate is the only oxidising material in the discontinuous phase it will preferably form at least 60% and more preferably at least 70% of the phase by weight.
  • the second component of the EBA of the invention is a carbonaceous fuel component forming a continuous phase.
  • a component must be non-water soluble and must be capable of forming a water-in-oil emulsion with the discontinuous component when an appropriate emulsifying agent is present in suitable quantity.
  • the fuel component must be capable of being rendered fluid to permit formation of the emulsion. Although for some purposes it may be desirable for the emulsion as finally prepared to have a solid or near solid continuous phase it will usually be necessary for it to be capable of being rendered sufficiently liquid by raising its temperature to an appropriate level to enable emulsification to occur.
  • the carbonaceous fuel component preferably includes a wax and an oil component e.g. as an intimate wax/oil mixture, or a wax polymeric modified oil component.
  • the fuel component may thus include hydrocarbons, whether paraffinic or olefinic, naphthenic, aromatic, saturated or unsaturated.
  • Waxes which may form part of the carbonaceous fuel component include waxes derived from petroleum, mineral waxes, animal waxes, and insect waxes.
  • the preferred waxes are those which have melting points of at least 30°C and which are readily compatible with the formed emulsion.
  • the waxes Preferably have a melting point in the range 40 0 C to 75 0 C.
  • a petroleum of a suitable viscosity may be used as a component of the carbonaceous fuel and typical oils for this purpose may have Brookfield viscosities at 30°C in the range 2 to 5000, preferably 10 to 1000 centipoises.
  • Non-volatile, water insoluble polymeric or elastomeric materials such as natural rubber, synthetic rubber and polyisobutylene may be included in the fuel component, as may also be copolymers, for example of butadiene-styrene, of isopren-isobutylene, or of isobutylene-ethylene.
  • the carbonaceous fuel component is generally present in an amount from 2 to 8% by weight of the EB A , although higher proportions for example up to 10, 15 or even 20% may be acceptable.
  • Supplementary fuels which may be included in the carbonaceous fuel component include fatty acids, higher alcohols, vegetable oils; nitro-organic components both aliphatic and aromatic e.g. dinitrotoluene, nitrate esters; and solid particulate materials for example coal, graphite, carbon, sulphur, aluminium, magnesium, etc.
  • EBA's of the invention containing at - least 40%, and particularly containing 50% w /w of hydrazine mononitrate in the discontinuous phase are usually detonable without the inclusion of an occluded gas component we do not exclude the possibility that it may be preferred, particularly where the proportion of hydrazine mononitrate is less than the above, to include gas in some form, either a gas micro bubble or as gas in microspheres, in which case it will be convenient to include the gas, usually air, by any suitable known means.
  • At least 50% of such gas will be in the form of microbubbles or spheres of diameter between 20 and 90 ⁇ m, preferably 40 to 70 ⁇ m.
  • the gas component is usually added during cooling such that the prepared emulsion comprises from about 0.05 to 50% by volume of gas at ambient temperature and pressure.
  • the air will form less than 10%, preferably less than 7%, more preferably less than 5% and particularly less than 3% by volume.
  • the detonation velocities of the EBA of the invention as superior to those of more conventional voidage, which typically are of the order of 30% and rarely less than 15%, gas.
  • gas is included in the composition in the free state, as distinct from enclosed within microspheres it will usually be introduced simply by mixing the emulsion in an open vessel, although it may also be included by bubbling the gas through the emulsion or by chemical generation of the gas in situ.
  • the EBA of the invention also comprises means for effecting stable emulsification of the components.
  • a water-in-oil type surfactant or emulsifying agent is used in a proportion appropriate to the requirement to produce a sufficiently permanent emulsion.
  • the surfactant is used in an amount of 0.5 part to 5 parts by weight per 100 parts by weight of the EBA though the proportion for any particular composition can easily be determined by experiment.
  • surfactants include for example those derived from sorbitol by esterification, the glycerides of fat-forming fatty acids, the polyoxyethylene sorbitol esters, the isopropyl esters of lanolin fatty acids, mixtures of higher molecular weight fatty alcohols and wax esters, polyoxyethylene(4) lauryl ether, polyoxyethylene(2) oleyl ether, polyoxyethylene(2) stearyl ether, polyoxyalkylene oleyl laurate, oleyl acid phosphate, substituted oxazolines and phosphate esters etc. Mixtures of such surfactants may also be used.
  • the pH of the emulsion is usually between 2 and 8.
  • the EBA of the invention may be prepared typically by mixing water with the hydrazine nitrate and, where present, other oxidising agents to form a solution. Dissolution and preparation of a saturated solution may be facilitated by heating the water, though we do not exclude the possibility that all or most of the ingredient of the emulsions may be mixed together and heated together. The emulsifier and fuel are then added at an appropriate temperature and the resulting mixture agitated to produce the required emulsion. Other ingredients, particularly solids, are conveniently, though not essentially, added and further agitation applied.
  • the EBA's of the invention can be used as such, or they may be packaged into charges of convenient dimensions.
  • the invention is illustrated by the following examples, in which the emulsions were prepared by conventional techniques. Examples 3 and 25 to 30 provide controls to demonstrate the advantage of the presence of hydrazine mononitrate.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Cosmetics (AREA)
  • Medicinal Preparation (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Colloid Chemistry (AREA)
EP81303112A 1980-07-21 1981-07-08 Agent de sautage du type émulsion contenant du mononitrate d'hydrazine Withdrawn EP0044664A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8023813 1980-07-21
GB8023813 1980-07-21

Publications (2)

Publication Number Publication Date
EP0044664A2 true EP0044664A2 (fr) 1982-01-27
EP0044664A3 EP0044664A3 (fr) 1982-03-17

Family

ID=10514919

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81303112A Withdrawn EP0044664A3 (fr) 1980-07-21 1981-07-08 Agent de sautage du type émulsion contenant du mononitrate d'hydrazine

Country Status (8)

Country Link
EP (1) EP0044664A3 (fr)
JP (1) JPS5742594A (fr)
AU (1) AU556339B2 (fr)
GB (1) GB2080279B (fr)
NO (1) NO812481L (fr)
NZ (1) NZ197738A (fr)
ZA (1) ZA814926B (fr)
ZW (1) ZW16881A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0142271A1 (fr) * 1983-10-21 1985-05-22 Nippon Oil And Fats Company, Limited Composition explosive du type émulsion eau-dans-l'huile
US10087117B2 (en) 2014-12-15 2018-10-02 Dyno Nobel Inc. Explosive compositions and related methods

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NZ206983A (en) * 1983-02-15 1988-02-29 Ici Australia Ltd Dynamite explosive composition
JPS59156991A (ja) * 1983-02-24 1984-09-06 日本化薬株式会社 油中水滴型エマルジヨン爆薬
JPS59162194A (ja) * 1983-03-08 1984-09-13 日本油脂株式会社 油中水型エマルシヨン爆薬組成物
CA1188898A (fr) * 1983-04-21 1985-06-18 Howard A. Bampfield Emulsions de sautage a l'eau et la cire
JP2669836B2 (ja) * 1987-12-03 1997-10-29 日本工機株式会社 油中水型エマルジョン爆薬組成物
JP2669835B2 (ja) * 1987-12-03 1997-10-29 日本工機株式会社 油中水滴型エマルジョン爆薬の製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3431155A (en) * 1967-06-02 1969-03-04 Du Pont Water-bearing explosive containing nitrogen-base salt and method of preparing same
US3447978A (en) * 1967-08-03 1969-06-03 Atlas Chem Ind Ammonium nitrate emulsion blasting agent and method of preparing same
US3471346A (en) * 1968-01-25 1969-10-07 Du Pont Fatty alcohol sulfate modified water-bearing explosives containing nitrogen-base salt
FR1583223A (fr) * 1967-06-02 1969-10-24
US3523047A (en) * 1968-12-30 1970-08-04 Explosives Corp America Hydrazine and aluminum containing explosive compositions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3431155A (en) * 1967-06-02 1969-03-04 Du Pont Water-bearing explosive containing nitrogen-base salt and method of preparing same
FR1583223A (fr) * 1967-06-02 1969-10-24
US3447978A (en) * 1967-08-03 1969-06-03 Atlas Chem Ind Ammonium nitrate emulsion blasting agent and method of preparing same
US3471346A (en) * 1968-01-25 1969-10-07 Du Pont Fatty alcohol sulfate modified water-bearing explosives containing nitrogen-base salt
US3523047A (en) * 1968-12-30 1970-08-04 Explosives Corp America Hydrazine and aluminum containing explosive compositions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0142271A1 (fr) * 1983-10-21 1985-05-22 Nippon Oil And Fats Company, Limited Composition explosive du type émulsion eau-dans-l'huile
US10087117B2 (en) 2014-12-15 2018-10-02 Dyno Nobel Inc. Explosive compositions and related methods

Also Published As

Publication number Publication date
JPS5742594A (en) 1982-03-10
AU556339B2 (en) 1986-10-30
ZW16881A1 (en) 1983-02-23
EP0044664A3 (fr) 1982-03-17
GB2080279B (en) 1984-02-15
ZA814926B (en) 1982-07-28
AU7310081A (en) 1982-01-28
GB2080279A (en) 1982-02-03
NO812481L (no) 1982-01-22
NZ197738A (en) 1983-11-30

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Inventor name: COOPER, JOHN

Inventor name: SUJANSKY, VLADIMIR