US 4,509,998 AGrant
Emulsion Blasting Agent With Amine-Based Emulsifier
Issue Date:1985-04-09
•12 Claims
Abstract
An explosive oil-in-water emulsion and a method of manufacture is disclosed. The process comprises combining a liquid carbonaceous fuel and an aqueous solution of at least one inorganic oxidizing salt, with agitation, in the presence of ingredients A and B, ingredient A being selected from the group consisting of oleic acid, linoleic acid and mixtures thereof, and ingredient B being selected from the group consisting of C.sub.1 -C.sub.6 alkylamines, C.sub.1 -C.sub.6 alkyldiamines, hydrazine, C.sub.2 -C.sub.6 alkanolamines, urea and mixtures thereof, incorporating dispersed gas bubbles into the resulting water-in-oil emulsion, one of said ingredients A and B being added before or during agitation and the remaining ingredient of ingredients A or B being added during agitation.
Metadata
Assignee
- Du Pont Canada Inc.
Inventor
- Ernest A. Hajto
Application Information
Application Number:US 565775&
Filing Date:1983-12-27
Priority Date:1983-12-27
Art Unit:223
Classifications
IPC:
C06B 4500
Field of Search:
1492;21;43;44;46;71;89;92;93;105;109.6
Patent Drawings
This patent does not have any drawings.
Description
The present invention relates to water-in-oil emulsion type explosive compositions which contain an aqueous solution of inorganic oxidizing salt as a dispersed phase within a continuous carbonaceous fuel phase.
Water-in-oil emulsion type explosive compositions are known.
H. F. Bluhm, in U.S. Pat. No. 3,447,987 which issued June 3, 1969, discloses water-in-oil emulsion blasting agents. The blasting agents have an aqueous solution component forming a discontinuous emulsion phase, a carbonaceous fuel component forming a continuous emulsion phase and an occluded gas component dispersed within the emulsion and forming a discontinuous emulsion phase. A water-in-oil type emulsifying agent is used to form the emulsion. A large number of emulsifying agents are indicated as being suitable e.g. sorbitan fatty acid esters, polyoxyethylene sorbital esters and isopropyl ester of lanolin fatty acids. The emulsion blasting agent of Bluhm is made by mixing the aqueous solution and the carbonaceous fuel components with the emulsifying agent. The gas may be occluded during such mixing, or in a separate step after formation of the emulsion. The emulsifying agents disclosed are well known for forming water-in-oil emulsions.
E. A. Tomic, in U.S. Pat. No. 3,770,522 which issued Nov. 6, 1973, discloses a water-in-oil emulsion blasting agent which contains an ammonium or alkali metal stearate salt emulsifying agent. According to Tomic, a surprising feature of the blasting agent, in view of the fact that the value of the hydrophilic-lipophilic balance (HLB) of stearate salts is about 18, is that the stearate emulsifying agent forms a water-in-oil emulsion. In general, emulsifying agents having HLB values of 11-20, and particularly those having HLB values closer to 20 tend to form oil-in water emulsions rather than water-in-oil emulsions. The emulsion blasting agent of Tomic is made by mixing an aqueous solution of an oxidizing salt, a carbonaceous fuel component and the emulsifying agent.
The hydrophilic-lipophilic balance system is the subject of numerous publications, for example "Classification of surface active agents by HLB", W. C. Griffen, J. Soc. Cosmetics Chemists 1311 (1949); "Calculation of HLB values of non-ionic surfactants" ibid 5249 (1954); "The Atlas HLB system" Atlas Chemical Industries, Inc., Wilmington, Del., 4th printing, May 1971; and Proceedings Second Int. Congr. Sur. Act. 1426 (1957) Academic Press, New York, N.Y. HLB values reflect the hydrophilic content of the molecule to the compound under consideration.
W. B. Sudweeks and H. A. Jessop, in U.S. Pat. No. 4,141,767 which issued Feb. 27, 1979, disclose an emulsion blasting composition having, as an emulsifier, from about 0.5 to 5% by weight of the total composition, of a fatty acid amine or ammonium salt having a chain length from 14 to 22 carbon atoms. The method of preparing the emulsion comprises predissolving the emulsifier in a liquid hydrocarbon fuel and then adding the emulsifier/fuel mixture to a solution of oxidizing salts. Other ingredients may be added. Examples of suitable emulsifiers disclosed are Armac* HT saturated C.sub.16 -C.sub.18 alkylammonium acetate, Armac C C.sub.16 -C.sub.18 alkyl-ammonium acetate and Armac T unsaturated C.sub.16 -C.sub.18 alkyl-ammonium acetate.
J. H. Owen II, in U.S. Pat. No. 4,287,010 which issued Sept. 1, 1981, discloses an emulsion blasting agent comprising a carbonaceous fuel forming a continuous emulsion phase, an aqueous solution of an inorganic oxidizing salt forming a discontinuous emulsion phase dispersed in the continuous phase, dispersed gas bubbles and an ammonium or alkali metal salt of a fatty acid. The fatty acid salt is formed in situ from the fatty acid and the ammonium or alkali metal hydroxide at the time when the aqueous solution and carbonaceous fuel are brought together, or just before or after they are brought together. J. H. Owen II indicates that organic derivatives of ammonium hydroxide e.g. tetramethylammonium hydroxide may be used in lieu of ammonium hydroxide.
The emulsion blasting agents of Owen are believed to have better water resistance than those of, for example, Bluhm. However the ingredients used in the manufacture of the emulsifying agent used for making the blasting agents of Owen tend to be difficult to handle e.g. are corrosive and also tend to be expensive. Ingredients which overcome these disadvantages and which provide emulsion blasting agents which tend to be stable at low temperatures have now been found.
Accordingly the present invention provides a method for producing a water-in-oil emulsion-type explosive composition comprising combining a liquid carbonaceous fuel and an aqueous solution of at least one inorganic oxidizing salt, with agitation, in the presence of ingredients A and B, ingredient A being selected from the group consisting of oleic acid, linoleic acid and mixtures thereof, and ingredient B being selected from the group consisting of C.sub.1 -C.sub.6 alkylamines, C.sub.1 -C.sub.6 alkyldiamines, hydrazine, C.sub.2 -C.sub.6 alkanolamines, urea and mixtures thereof, incorporating dispersed gas bubbles into the resulting water-in-oil emulsion, one of said ingredients A and B being added before or during agitation and the remaining ingredient of ingredients A or B being added during agitation.
A preferred process comprises:
(a) adding a carbonaceous fuel, which is liquid at a temperature of at least 65.degree. C., or an aqueous solution of at least one inorganic oxidizing salt, to a blender;
(b) agitating said aqueous solution or carbonaceous fuel;
(c) adding an emulsifier precursor ingredient to the aqueous solution or carbonaceous fuel, said precursor ingredient being selected from ingredients A and B, said ingredient A being selected from the group consisting of oleic acid, linoleic acid and mixtures thereof, said ingredient B being selected from the group consisting of C.sub.1 -C.sub.6 alkylamines, C.sub.1 -C.sub.6 alkyldiamines, hydrazine, C.sub.2 -C.sub.6 alkanolamines, urea, and mixtures thereof;
(d) adding the carbonaceous fuel or aqueous solution whichever was not added during step (a);
(e) adding ingredient A or ingredient B, whichever was not added during step (c);
(f) increasing the rate of agitation of the mixture of ingredients added during steps (a), (c), (d), and (e) to form a water-in-oil emulsion.
In a preferred embodiment further ingredients may be added during any of steps (a) to (f), said further ingredients being selected from fuels, explosives, gas entraining agents and solid inorganic oxidizing salts.
The present invention also provides an explosive water-in-oil emulsion comprising from 5 to 22 parts by weight water, from 60 to 80 parts by weight of at least one oxidizing salt, from 2 to 10 parts by weight of a liquid carbonaceous fuel, and an emulsifier made from ingredients A and B, ingredient A being selected from the group consisting of oleic acid, linoleic acid and mixtures thereof, ingredient B being selected from the group consisting of C.sub.1 -C.sub.6 alkylamines, C.sub.1 -C.sub.6 alkyldiamines, hydrazine, C.sub.2 -C.sub.6 alkanoalamines, urea and mixtures thereof, said emulsion having a density between 1.00 and 1.35 g/cm.sup.3.
Examples of solid inorganic oxidizing salts include grained or prilled ammonium nitrate (AN), sodium nitrate (SN) and calcium nitrate. Examples of fuels include liquid carbonaceous fuels e.g. formamide, fuel oil or ethylene glycol, solid carbonaceous fuels e.g. coal, gilsonite or sugar, and non-carbonaceous fuels e.g. sulphur or aluminium. Examples of explosives are prilled or flaked trinitrotoluene (TNT), monomethylamine nitrate (MMAN), pentaerythritoltetranitrate (PETN) and Composition B. Examples of gas entraining agents are those agents which encapsulate the gas e.g. glass microballoons and agents which carry the gas in close association therewith e.g. expanded perlite, flake aluminium.
The amount of oxidizing salt employed in the present invention is generally between about 60 to 80 weight percent of the emulsion, and is preferably between about 70 and 78 weight percent. Preferably at least three quarters of the oxidizing salt is dissolved in aqueous solution. More preferably all of the oxidizing salt is dissolved in aqueous solution. Water is generally present between about 5 and 25 weight percent of the emulsion, preferably between 12 and 18 weight percent.
The liquid carbonaceous fuel which forms the continuous phase of the emulsion is generally present in amounts between about 2 and about 10 weight percent, preferably between about 3 and about 6 weight percent, of the emulsion. The amount selected may depend on the presence of other fuels in the emulsion and whether such other fuels are soluble or insoluble in the continuous phase. Examples of the liquid carbonaceous fuel are aliphatic, alicyclic and aromatic liquid hydrocarbons e.g. xylenes, kerosene, fuel oils, paraffin oils and other organic carbonaceous fuels. Other examples are Rando* HD-22 mineral oil, corvus oil and #2 diesel fuel.
Additional ingredients e.g. fuels, explosives and gas entraining agents may be added, in an amount generally up to about 12 weight percent of the emulsion.
If solid inorganic oxidizing salt e.g. grained or prilled AN, is added, it may be added alone or in combination with a fuel e.g. as ammonium nitrate/#2 diesel fuel (ANFO) or ammonium nitrate/nitropropane.
The density and sensitivity of the emulsion is affected by the presence or absence of dispersed gas bubbles in the emulsion. Such gas bubbles may be dispersed in the emulsion through incorporation of air occluded in the emulsion merely as a consequence of the agitation of the ingredients during mixing. The gas may be injected or otherwise deliberately introduced by sparging or by adding chemical agents e.g. N, N'dinitrosopentamethylenetetramine. Alternatively the gas bubbles may be encapsulated in glass or other known materials e.g. fly ash floaters. Encapsulated gas, sometimes referred to herein as microballoons, is advantageous where it is desired to detonate the emulsion under high hydrostatic pressures or in boreholes separated by low scaled distances e.g. between about 0.6 and 1.0. Generally, only about 0.5 to 2 weight percent of the microballoons in the emulsion are required. The required dimensions of the gas bubbles for obtaining pressure resistance and for sensitivity are well known in the art.
The emulsions made using the present process may be made by first dissolving most or all of the inorganic oxidizing salt or salts in water and heating the resulting aqueous solution to a temperature of between about 65 and about 150.degree. C. The solution may be added to a blender e.g. a ribbon blender or turbine blender, prior to adding one of the emulsifier precursor ingredients. It is preferred to add the emulsifier precursor ingredient to the aqueous solution while agitating the solution, in order to disperse the precursor ingredient.
Although it is not necessary to do so the fatty acid precursor ingredient e.g. oleic acid is usually added to the aqueous solution. It is preferable that the temperature of the solution at this stage be between about 40.degree. and 75.degree. C. At the lower end of the temperature range, an emulsion will form when the temperature of the mixture is at or above the solubility point of the salts in solution. Addition of certain salts e.g. monomethylamine nitrate, depresses the temperature at which the emulsion may form. At the upper end of the temperature range, less agitation is required in the subsequent step in order to form an emulsion. However, at temperatures above about 75.degree. C. it may be very difficult or impossible to form an emulsion. The most preferred temperature range of the solution at this stage is from about 50.degree. to 70.degree. C.
The carbonaceous fuel e.g. fuel oil, is then added, while continuing agitation in the blender. Subsequently the second emulsifier precursor ingredient is added. The rate of agitation necessary to form the emulsion is easily determined through routine experimentation. The rate of agitation required to form the emulsion is higher than that required to merely blend the ingredients. To exemplify, a 5 cm diameter laboratory mixer may require at least about 1200 revolutions per minute of the mixer blades, while a 30 cm diameter laboratory mixer may only require at least about 240 revolutions per minute of its mixer blades. As the emulsion forms, the emulsion becomes thicker and the power requirement for the blender increases sharply. The emulsion forms more easily at higher temperatures, less agitation being required than at lower temperatures. Ingredient B of the emulsifier may be added in solid i.e. powdered, form. It is not necessary that the solid be dissolved prior to addition.
Other liquid ingredients e.g. ethylene glycol, may be added at any time prior to formation of the emulsion. Other solid ingredients may be added at any time prior to the time where the sharp increase in power requirement occurs but it is preferable that such solid ingredients be added before addition of the first emulsifier precursor ingredient.
Commercially available oleic or linoleic acids tend to be mixtures of fatty acids. Such mixtures are also useful in the present invention and fall within the scope of the terms "oleic acid" and "linoleic acid".
The present process may be practised in relatively small blenders e.g. holding up to about 1000 kg, intended for preparing a sufficient quantity of emulsion for packaging into 25-150 mm diameter packages. The process may also be practised in large blenders e.g. holding up to about 2300 kg or more, in preparation for pumping the emulsion directly into boreholes.
It has been found that the temperature of the emulsion, when in the borehole, has little effect on sensitivity, to detonation, of the explosive. Temperature of the emulsion does have a marked effect on emulsion stability, however. At low temperatures e.g. below about 4.degree. C., crystallization of the salts in the emulsion may lead to emulsion breakdown. Presence, in the emulsion, of monomethylamine nitrate or other salts, tends to depress the lowest temperature at which emulsion breakdown becomes apparent. Presence of monomethylamine nitrate may depress this temperature to about -18.degree. C. At high temperatures, e.g. above 40.degree. C., evaporation may also cause instability.
Particularly preferred of ingredients B are the alkylamines and alkanolamines because the emulsions formed therewith tend to have better stability at low temperatures e.g. there is less of a tendency for the salts in the emulsion to crystallize at low temperatures. Of particular interest because of its cost and availability is ethanolamine. Other useful ingredients B include, but are not limited to, monomethylamine, ethylamine, dimethylamine, and guanidine. If ingredient B is gaseous at ambient temperature, e.g. monomethylamine, then it should first be dissolved in water prior to adding to the mixture.
The present invention is illustrated by reference to the following Examples.
Example 1
4.21 kg of an 80 wt % ammonium nitrate solution were added, at 88.degree. C., to a ribbon blender of 45.4 kg nominal capacity. 454 g of Q-Cell* 300 microballoons were added to the solution and the ribbon blades were rotated at 50 rpm for about one minute. A blend of 1589 g Rando HD-22 mineral oil and 795 g of oleic acid was added to the blender, and agitation of the ribbon blades at 50 rpm was continued for one minute. 454 g of ethanolamine were added to the blender and after 60 seconds the rotation of the ribbon blade was increased to 250 rpm for about 10 minutes. An emulsion was formed, the final temperature being about 59.degree. C. and the density, at 20.degree. C., being 1.26 g/cm.sup.3. The viscosity of the emulsion, after cooling to 50.degree. C., was 250 Pa.s. Over a period of 20 days at 20.degree. C., the viscosity increased to 355 Pa.s. Viscosity was measured using a Brookfield* VFN viscometer.
The emulsion explosive detonated at 6098 m/s, unconfined at 4.degree. C., in 150 mm diameter when primed with a No. 12 blasting cap plus a 450 g TNT primer.
Example 2
Example 1 was repeated except that 908 g of expanded fly ash was used instead of Q-Cell 300 microballons. The initial viscosity was 255 Pa.s, measured at 55.degree. C. The velocity of detonation was 5671 m.s.sup.-1 at 4.degree. C., in 150 mm diameter steel pipe, when primed with a No. 12 blasting cap plus a 450 g TNT primer.
Claims
I claim:
1. A method for producing a water-in-oil emulsion type explosive composition comprising combining a liquid carbonaceous fuel and an aqueous solution of at least one inorganic oxidizing salt, with agitation, in the presence of ingredients A and B, ingredient A being selected from the group consisting of oleic acid, linoleic acid and mixtures thereof, and ingredient B being selected from the group consisting of C.sub.1 -C.sub.6 alkylamines, C.sub.1 -C.sub.6 alkyldiamines, hydrazine, C.sub.2 -C.sub.6 alkanolamines, urea and mixtures thereof, incorporating dispersed gas bubbles into the resulting water-in-oil emulsion, one of said ingredients A and B being added before or during agitation and the remaining ingredient or ingredients A or B being added during agitation.
2. A process for producing a water-in-oil emulsion type explosive composition comprising: (a) adding a carbonaceous fuel, which is liquid at a temperature of at least 65.degree. C. or an aqueous solution of at least one inorganic oxidizing salt, to a blender; (b) agitating said aqueous solution or carbonaceous fuel; (c) adding an emulsifier precursor ingredient to the aqueous solution or carbonaceous fuel, said precursor ingredient being selected from ingredients A and B, said ingredient A being selected from the group consisting of oleic acid, linoleic acid and mixtures thereof, said ingredient B being selected from the group consisting of C.sub.1 -C.sub.6 alkylamines, C.sub.1 -C.sub.6 alkyldiamines, hydrazine, C.sub.2 -C.sub.6 alkanolamines and urea, and mixtures thereof; (d) adding the carbonaceous fuel or aqueous solution whichever was not added during step (a); (e) adding ingredient A or ingredient B, whichever was not added during step (c); (f) increasing the rate of agitation of the mixture of ingredients added during steps (a), (c), (d), and (e) to form a water-in-oil emulsion.
3. A method according to claim 2 wherein further ingredients selected from fuels, explosives, gas entraining agents and solid inorganic oxidizing salts are added during any one or more of steps (a) to (f).
4. A method according to claim 1 wherein ingredient A is oleic acid.
5. A method according to claim 2 wherein ingredient A is oleic acid.
6. A method according to claim 1 wherein ingredient B is selected from the group consisting of monomethylamine and ethanolamine.
7. A method according to claim 2 wherein ingredient B is selected from the group consisting of monomethylamine and ethanolamine.
8. An explosive water-in-oil emulsion comprising from 5 to 22 parts by weight water, from 60 to 80 parts by weight of at least one oxidizing salt, from 2 to 10 parts by weight of a liquid carbonaceous fuel, and an emulsifier made from ingredients A and B, ingredient A being selected from the group consisting of oleic acid, linoleic acid and mixtures thereof, ingredient B being selected from the group consisting of C.sub.1 -C.sub.6 alkylamines, C.sub.1 -C.sub.6 alkyldiamines, hydrazine, C.sub.2 -C.sub.6 alkanolamines, urea and mixtures thereof, said emulsion having a density between 1.00 and 1.35 g/cm.sup.3.
9. An emulsion according to claim 8 wherein ingredient A is oleic acid and ingredient B is selected from the group consisting of monomethylamine or ethanolamine.
10. An emulsion according to claim 9 wherein the emulsion contains between about 60 to 80 wt. % of the oxidizing salt.
11. An emulsion according to claim 9 wherein the emulsion contains between about 2 and about 10 wt. % of liquid carbonaceous fuel.
12. An emulsion according to claim 10 wherein the emulsion contains between about 2 and about 10 wt. % of liquid carbonaceous fuel.