CS269987B2 - Emulsion explosive mixture - Google Patents

Abstract

In emulsion blend explosives, the replacement of coarse salt particles, e.g., prills, by fines, i.e., particles which pass a No. 50 U.S. sieve, increases the water resistance of the explosive without deleteriously affecting its shelf life provided that the explosive, prior to such replacement, is storage-stable as determined by the Salt Extraction and lead compression tests described herein. Products containing a combination of whole and crushed ammonium nitrate prills, and emulsions made with an anionic emulsifying agent such as a fatty acid salt, are preferred. Depending on the fines content and chemical composition, other properties such as sensitivity to initiation and detonation velocity also may be improved.

Description

The invention relates to an explosive composition comprising a sensitized mixture of a water-in-oil emulsion and a particulate solid inorganic oxidation salt, preferably the salt is ammonium nitrate.

Explosive mixtures that contain a mixture of a water-in-oil emulsion and solid particulate ammonium nitrate (AN), such as ANFO, which is lumpy AN coated with fuel oil, have recently become increasingly used, This results from the benefits of emulsion explosives, which include high bulk density and characteristic explosive energy, while making these explosive mixtures less expensive than other materials due to the lower cost of ammonium nitrate. However, in some cases it has been found that these explosive mixtures, commonly referred to as emulsion explosive mixtures **, have a short shelf life, which implies the need to use these products immediately after they have been prepared. This short shelf life means that these explosive substances are losing stability, are subject to undesirable changes in structure and / or composition to such an extent that they cannot be relied upon to cause them to explode at the required time and reaches the desired detonation velocity. In addition, if the shelf life of this product is very short, it is almost certain that the product is unsuitable for use in packaged form and it is also often inappropriate to use it in free form, especially when it is necessary transport the product to the place of use or leave it for a period of time in the holes drilled to store the explosive raw material.

SUMMARY OF THE INVENTION The present invention provides a storage-stable emulsion explosive composition consisting of a sensitized mixture of particles of an inorganic oxidation salt, in particular particulate or coarse ammonium nitrate coated with fuel oil and a water-in-oil emulsion comprising a continuous liquid carbonaceous fuel and an aqueous solution. inorganic oxidation salts as a discontinuous phase, which consists of: (a) 20 to 70% of a water-in-oil emulsion in which the continuous phase consists of fuel oil, heavy, aromatic naphthenic or paraffinic lubricating oil, mineral oil nobo paraffinic oil and discontinuous phase form an aqueous solution of inorganic oxidation salts of ammonium nitrate, alkali metal and alkaline earth metal nitrate, ammonium perchlorate, alkali metal and alkaline earth metal perchlorate, the emulsion further comprises an emulsifying agent and consists of 50 to 95 µh % of inorganic oxidation salts, 1 to 21% by weight of carbonaceous fuel and 5 to 25% by weight of water; and

(b) 30 to 80 4 particles of inorganic oxidation salts selected from the group consisting of ammonium nitrate, ammonium perchlorate, alkaline earth alkali nitrates and mixtures thereof, 10 to 100 4 of which are replaced by fine particles of less than 297 µm in diameter.

U.S. Pat. No. 4,714,503 (L.A. Cescon and N.J.Millet Jr.) discloses the manufacture of an emulsion explosive composition having improved shelf life. It is stated in this patent application that the transport of water or the loss of water from the aqueous dispersed phase of this emulsion by the continuous oil phase to the admixed nitrate particles, which causes the emulsion I to be isolated, can be minimized by forming a barrier or media. water, wherein the barrier or medium is preferably formed. For example, a continuous emulsion phase can be utilized as the continuous emulsion phase in the presence of an anionic emulsion system consisting of a fatty acid salt and a free fatty acid. The aforementioned patent application further states that the barrier to the water transport can also be formed, for example, by coating the nitrate particles with a low water-diffusibility coating.

One of the materials commonly used in particulate emulsion explosive compositions is ANFO, which are lumpy ammonium nitrate particles coated with fuel oil. This material is very popular as an explosive and time used material, and because of its suitability and also for economic reasons, this popularity is justified, but are also well known disadvantages of this product, which include insufficient protection, respectively. water-resistant, low density product. By mixing this ANFO with a water-in-oil emulsion, a higher density product can be obtained and a certain degree of semi-toxic water resistance can be obtained with the mixed product, especially when the weight ratio of emulsion to solids is high. In view of the above, some unpackaged emulsion mixtures can also be used in cases where they fill the wet holes drilled to store the explosive. However, it should be noted that only those emulsion explosive mixtures that are storage-stable, i. such use, wherein the compositions are in free, unpackaged, high solids form, and where their water resistance is better than hitherto.

The present invention relates to improved emulsion explosive compositions comprising a sensitized mixture of particles of an inorganic oxidation salt and a water-in-oil emulsion comprising a hydrocarbon fuel whose components form a continuous emulsion phase, an aqueous solution of an inorganic oxidation salt which they form a discontinuous emulsion phase, dispersed in the form of discrete droplets in a continuous phase, and an emulsifying agent. In particular, the present invention, which relates to an emulsion explosive composition of the above-mentioned type, which is stable in storage, consists in that the composition comprises particles of inorganic oxidation salt, at least about 15% of which, and preferably An embodiment of the invention of at least 20% of this component (intended as a percentage by weight) consists of particles that are less than 297 microns, i.e. that the particles pass through a No. 50 sieve a series of sieves wherein the sieve mesh diameter is 0.297 millimeters, wherein the weight ratio of the emulsion to the total inorganic oxidation salt particle content ranges from about 20/80 to 70/30.

The particulate oxidizing inorganic salt component, which is in the form of particles smaller than 297 microns, is referred to herein as particulate matter or as a dust component. This dust component may comprise the entire proportion of the oxidizing salt in particulate form that is present in the emulsion explosive composition, i.e. 100 percent by weight of the oxidizing salt particles are the dust component. However, in many preferred embodiments, in an alternative embodiment of the invention, the dust component is used together with the coarser particles, and in a preferred embodiment of the invention a coarser component is used which consists of particles larger than 420 microns, i.e. these particles are trapped on a No. 40 / US sieve A series of sieves in which the mesh size is 0.420 millimeters. Preferably, the coarser particle component is lumpy ammonium nitrate or ANFO (i.e. ammonium nitrate coated with fuel oil.

One of the main advantageous features of the use of the particulate oxidizing salt component * used as part of the emulsion explosive composition is that the use of this particulate component increases the protection against the action of water (i.e. by increasing the ability to protect said product from the effects of external water, thereby achieving that the explosive mixture can be suitably used both in the unpackaged form and in the wet drilled holes for storing the cartridge in the form of an explosive mixture. This increased water-resistance is comparable to that of explosive mixtures characterized by a long shelf life, such as those described in the above-mentioned U.S. Patent Application No. 696,200. of the aforementioned well-storable products, the solid oxidation salt is less sensitive to the action of internal water or external water due to the use of a medium or barrier that prevents water transport within the emulsion composition, which barrier or medium may be the continuous phase of the emulsion composition. Provided that the stability of the emulsion mixture is thus protected by this barrier or medium, a portion of the solid inorganic oxidation salt can be substituted for this portion of the inorganic oxidation salt. present? in the granular composition, the dust component without substantially reducing the shelf life of the explosive mixture. In this context, it would normally be expected that a greater surface area of said dust component would mean a greater ability to bind water in the discontinuous phase of said emulsion, rendering the mixture unstable. As will be discussed below, it has been found unexpectedly that it is possible to add a dust fraction to the emulsion compositions of the above type without compromising their original good stability and shelf life, which is important for several reasons, including the above. said increase in water resistance.

The term emulsion explosive composition storage stable ^'1, which was used in the above text relating to a product that contains only coarse particulate inorganic oxidizing salt / i.e., particles greater than 420 micrometers / and which is able to maintain its stability in when some or all of the coarse grains are replaced by a dust component, it denotes a mixture which is prepared from this particulate inorganic oxidizing salt containing only the coarse grains and from the storage-stable emulsion. By the term storage-stable emulsion as used hereinabove is meant a composition which, when it has a viscosity in the range from 300 to 350 Pa.s., and is mixed with lumpy tear particles of 50/50 ammonium nitrate after initiation with an initiator weighing 40 grams, and after being stored for 7 days in a lead roller bristle test, which will be described in more detail in the examples, compressing the lead roller by at least 3.8 centimeters. Any emulsion that can achieve the same results as the above composition containing the emulsion and the 50/50 ammonium nitrate breakable lump particles is said to be stable in storage, and with this emulsion a mixture can be prepared which it is referred to as storage-stable, which mixture is prepared by mixing with any particulate inorganic oxidation salt containing only coarse-grained particles in the emulsion / salt ratio ranging from 20/80 to 7030.

Another method for analyzing and determining a storage-stable emulsion and a storage-stable emulsion composition in the above sense is to prepare an emulsion composition having a viscosity ranging from 300 to 350 Pa · s with tear-shaped lumpy AN particles in a ratio of 50/50, and then this mixture is subjected to an extraction test for salt, which will be described in detail in the examples. In carrying out this test, the amount of inorganic oxidizing salt extracted from the mixture with water is determined as a percentage of the total amount of solid salt and dissolved salt present in the mixture. Since the percentage of salt extracted from the above mixture can be expected to be greater if the emulsion content of the above mixture decreases, this storage-stable term regarding the behavior of the dust-containing compositions applies to the less-containing compositions. more than 50 percent by weight of the emulsion (up to about 20% by weight of the emulsion), as well as mixtures containing a greater proportion of the emulsion (up to about 70 percent by weight) and mixtures prepared using any particulate inorganic oxidizing salt with coarse particles. in a salt extraction test conducted with a 50/50 mixture of the same emulsion and lumpy ammonium nitrate particles, a salt extraction value of at most about 7 percent is achieved. '

The emulsion explosive composition of the present invention is in a sensitized state, i.e. it contains a sufficient amount of a sensitizer, such as dispersed gas bubbles or voids, to allow the emulsion explosive mixture to explode using known means to initiate the explosive. mixtures. The sensitization of said emulsion explosive composition can be accomplished by any conventional method known in the art. For example, the premixed emulsion can be completely sensitized per se, i.e. converting it into an explosive emulsion, for example by mixing it with air dispersion, if necessary by admixing a solid air-containing material such as phenol-formaldehyde. microspheres, glass microspheres, fly ash, etc. In an alternative embodiment of the present invention, chemical sensitizing agents such as aminonitrates such as monomethyleneamine nitrate, trinitrotoluene, perchlorates, etc. may also be incorporated into the emulsion. prepared by mixing, adding air-containing solids, in which in fact the porous inorganic nitrate lumpy particles may also serve as such as substances which they introduce into the air / air carrier emulsion and lim fun

CS 269987 82, whereby the improved water-inhibiting property becomes apparent when the dust content of the salt particles in the composition is about 15 percent by weight, provided that the emulsion content of the composition is about 20 percent. At this emulsion content up to an emulsion content in the range of about 30 to 40 percent, these compositions behave as if they have an insufficient emulsion content, i. emulsion-deficient, wherein the amount of emulsion is insufficient to coat the inorganic oxidizing salt particles. In this case, solid particles which are entirely dust-containing are more suitable than solid particles which do not contain dust, but the improvement of the water-proofing properties of the emulsion-insufficient emulsion / t compositions. The composition of the composition defined by the emulsion (can be achieved at an optimum dust content of from about 30 weight percent to about 60 weight percent (based on the weight of the total solids content)) and other properties such as density and flowability of the composition. show the same trend as above.

When a larger amount of emulsion is included in the composition, such as 40 percent or more, the behavior of the compositions corresponds to compositions with a sufficient emulsion content, i.e., the compositions contain a sufficient amount of emulsion to cover the inorganic oxidation salt particles. In this case, the water retention capacity gradually increases as the dust content increases, but this increase moderates considerably when the weight ratio of the fine dust to the coarse grains exceeds about 34/66. Also, the emulsion density is uniform. However, a dust content in the range of from about 34 weight percent to about 100 weight percent based on the weight of the solids particles may be very useful in such compositions with sufficient emulsion content when it is desired to obtain a product that not only has improved exposure to water, but also a higher degree of sensitivity. The addition of large amounts of dust to these products allows for increased sensitivity and detonation velocity without at the same time undesirably reducing the density that occurs with conventional physical sensitizers such as microspheres.

The inorganic oxidizing salt forming the solids particles in the final mixture according to the invention may be, for example, ammonium nitrate AN, ammonium perchlorate, alkali metal nitrate such as sodium nitrate SN, alkali metal perchlorate, alkaline earth nitrate such as is, for example, calcium nitrate CN, or alkaline earth metal perchlorate, or any combination of two or more of said nitrates which are in the form of granules or lumpy particles, or in the form of lumpy particles which are provided with a weak layer of fuel oil, such as ANFO (ammonium nitrate coated with fuel oil), which usually has an AN / FO ratio, i.e. of ammonium nitrate to fuel oil, about 94/6, or coated according to the method described in United States Patent Application No. 696,200. For the coarse component, lumpy ammonium nitrate and nitrate particles are preferably used. with a layer of fuel oil. The lumpy ammonium nitrate particles may be, for example, explosive lumpy particles generally used in explosives, or may be lumpy ammonium nitrate particles commonly used for agricultural purposes and for fertilization. Fissile lump ammonium nitrate particles usually have a lower density and are more porous than the lump particles used for fertilization. When using only lumpy particles used as fertilizer, it is desirable to prepare a composition containing at least about 25 percent emulsion and a higher dust content, such as at least 25 percent dust based on the total weight of the particles, to achieve the desired sensitivity. solid material.

As regards the dust fraction, the component may be ammonium nitrate in the form of crushed lumpy particles, or an inorganic perchlorate such as ammonium perchlorate or an alkali metal perchlorate or a combination of ammonium nitrate and perchlorate. With respect to the salt particles or salts used in the composition of the invention, a sufficient amount of fuel may be mixed with this component, preferably the fuel is an oil,

CS 269987 82 or it can be added to the emulsion as described above to prepare a mixture with a substantially equilibrium oxygen content. The use of a less porous dust fraction, such as sodium nitrate dust, may be advantageous in that more pumpable mixture due to greater fluidity resulting from / less oil absorption required to achieve an equilibrium oxygen content (relative to the amount of oil absorbed by the porous ammonium nitrate dust), and / b) the greater amount of oil required to achieve equilibrium the oxygen content of the mixture containing sodium nitrate.

The solids dust used in the present invention can be produced in any of the conventional milling equipment. For example, an existing hammer mill used in ANFO nitrate nitrate plants can be advantageously used. with a fuel oil coating), and by means of this grinding apparatus, ground the lumpy ammonium nitrate particles to ANFO-HD dimensions. Care should be taken when grinding these lumpy particles and taking precautions to avoid contamination of the material, both for safe operation and for achieving the desired purpose. In the case where the lumpy ammonium nitrate particles are ground, sufficient precautions should be taken to minimize contact of this material with water in any form, as water is known to cause degradation of the lumpy particles. The degree of grinding of the material depends on the intended end use of the product, i.e. the level of dust required in the final product. This means, of course, that the inorganic oxidation salt particles can be milled directly on a hammer mill so that the material has a size of less than 297 microns. Alternatively, the lumpy particles may be ground in such a manner that substantially all particles are less than 297 microns. As mentioned above, the material can be used directly to prepare an explosive mixture, or in the latter case, the material consisting essentially of a dust portion can be mixed with lumpy ammonium nitrate particles to achieve a desired dust level concentration. in a mixture of coarse-grained particles and dust particles. The specificity of the grinding process and the conditions of the grinding process are well known to those skilled in the art.

The dust component itself and mixtures containing the dust fraction and coarse grain particles can be easily characterized by standard screening methods and from particle size distribution determination.

The emulsion explosive mixtures described in the following examples were prepared as follows:

a / Emulsion

In the same manner as in Example 1 of U.S. Pat. No. 4,287,010, emulsions having the following composition were prepared except that no glass microspheres and fly ash were used:

Emulsion (s) Emulsion / b / ammonium nitrate (dissolved) 70,9 \ 75,0 \ water 15,6 4 16.6% oil 7,6 \ 4.3% oleic acid 3.8 4 2.1% sodium hydroxide (50% aqueous solution) 2> 1 4 1.2%

The percentage content of oleic acid and sodium hydroxide is that used to prepare the oleic acid salt as an emulsifier in situ.

CS 269987 82 will act as a sensitizer to the emulsion composition when present in a sufficient amount, which is generally about 30 percent by weight of the composition or more. In addition, the dust component itself may also act as a sensitizing component of the emulsion composition, wherein the dust component may be used in combination with one or more sensitizing agents or the dust component may be used as a single sensitizer of the composition. which will be illustrated further in Examples 20-22].

With respect to the emulsion fraction of the total blend product of the present invention, oils and aqueous solutions of inorganic oxidation salts well known in the art of explosive emulsion blends, such as oils and saline, may be used to prepare the fraction. the solutions disclosed in U.S. Patent 4,287,010, which is given by way of example only in the prior art. Most often, the inorganic oxidation salt contained in the aqueous phase of the emulsions of the above type is ammonium nitrate or perchlorate, and further alkali metal or alkaline earth nitrate or perchlorate, preferably ammonium nitrate which may be used. alone or in combination with other substances, for example sodium nitrate, present in an amount of up to about 50 weight percent based on the total weight of the inorganic oxidizing salt in the aqueous phase. Where a combination of fatty acid and fatty acid salts is used as emulsifying agents, preferably monovalent cation salts are used as inorganic oxidation salts, as explained in U.S. Pat. 287 010. Preferably, hydrocarbon oils, including fuel oils and lubricating oils derived from heavy aromatic hydrocarbons, naphthenic hydrocarbons or paraffinic raw materials, mineral oils, dewaxed oils, etc. are used as oils for the purposes of the present invention.

The oil content of the emulsion must be sufficient to achieve a substantially equilibrium oxygen content of the emulsion since the emulsion may contain an excess of oil (and thus contain an insufficient amount of oxidizing agent), which emulsion is prepared by mixing with a solid inorganic oxidizing salt Particles that contain insufficient fuel or this particulate inorganic oxidation salt do not contain the fuel at all. The advantages that result from the use of high oil emulsions are disclosed in the above-cited United States Patent Application No. 696,200, which is cited herein by way of example only.

In addition to the optional content of chemical sensitizers (mentioned above) in an emulsion of the above type, for example in a solution in the discontinuous aqueous phase of the emulsion or in the form of a dispersion of finely divided solid particles therein, they may be present either in the emulsion or the above mixtures of one or more detonation catalysts such as ammonium dichromate, copper chloride, etc.

Many different types of emulsifiers are known with respect to emulsifiers that are used in emulsions that are used as explosives or as emulsion explosive mixtures. Whether or not such emulsifying agents are suitable for use in an emulsion that is part of the final product of the present invention or not is determined by the storage stability of the resulting compositions. This can be ascertained by conducting a lead roller check test carried out with a 50/50 mixture which contains only coarse particulate material (i.e., a mixture of 50% emulsion and 50% tear-lined ammonium nitrate particles). A salt extraction test can also be used for the above assay. Preferably, the combination of a fatty acid salt and a fatty acid is used as the emulsifier system, and the combination provides good shelf life and stability as disclosed in the above-mentioned U.S. Patent Application No. 696 200. With respect to the above system, said free fatty acid is present in solution in an oil and this oil solution forms a continuous emulsion phase. Said fatty acid and fatty acid salt together with the oil form a carbonaceous fuel.

In preparing the preferred emulsions of the present invention, the selected fatty acid is added to the oil and the fatty acid salt is added in a preformed state or may be prepared in situ, such as the method described in U.S. Patent 4,287,010, starting with a fatty acid and a base, and emulsion is prepared by mixing oil 8 with an aqueous salt solution. The fatty acid is preferably a saturated monocarboxylic acid having about 12 to 22 carbon atoms, or a mono-unsaturated, di-unsaturated or tri-unsaturated acid, and the salt is preferably an alkali metal salt, a salt an ammonium and / or alkylammonium salt derived from the aforementioned fatty acid.

In the final composition of the present invention, the emulsion is present in a mixture with the particulate inorganic oxidation salt in a weight ratio ranging from 20/80 to 70/30, intended as the ratio of the emulsion to the particulate oxidation salt, at least about 15% by weight, and preferably at least about 20 percent by weight of the particulate oxidizing salt comprises particles that are less than 297 microns, that is, about 15 percent by weight, and preferably at least about 20 percent by weight is a "dust component". Although the emulsion may be prepared by mixing with a particulate oxidizing salt, and substantially all of the material may be a dusty material, such as in the preparation of a blend containing about 30 to 80 percent of the blend, use dust material in combination with coarser particles, i.e. particles larger than 297 microns. Most preferably, a coarse-grained component is used in which there is a proportion of particles, typically at least about 15 percent by weight of particulate inorganic oxidizing material in the form of salt greater than 420 microns, for example ammonium nitrate or ammonium nitrate coated with fuel oil. in the form of lumpy particles, i. ANFO.

In the case of compositions having a percentage of emulsion to oxidizing salt particles in the range of about 20/80 to about 40/60, by weight, it is preferred that the salt particles contain from about 20 weight percent to about 70 weight percent dusts (thereby achieving a dust component content in the range of about 12 to about 56 percent by weight based on the total weight of the composition) optimal results, when taking into account mainly improved water resistance, are achieved when the salt particles used For the preparation of said compositions, they comprise 30 to about 60 percent by weight of the dust component (thereby achieving a dust component content in the range of from about 18 to about 48 percent by weight based on the total weight of the composition).

The main advantage of mixtures using a combination of dust and coarse particles, which contain a greater percentage of emulsion, such as 40 percent by weight or more, is that the solid particles are better distributed in the mixture, For mixtures, the weight ratio of dust to coarse grains greater than about 34/66 is used mainly to achieve other desired properties, such as the sensitivity of the mixture to initiation, detonation rate, etc., although some further improvement of the water resistance of these mixtures also reaches.

Unexpectedly, it has been found that the addition of a solid dust portion to certain emulsion compositions does not cause destabilization of these compositions due to the greater surface area of the dust portion, but in fact an increase in the water resistance is achieved. The following discussion is given in order to more specifically elucidate the advantages obtainable according to the invention by the addition of a dusting component in relation, for example, to the emulsion content of the final mixture. However, this analysis is not intended to limit the scope of the invention nor to limit the scope of the invention as set forth below.

The particulate inorganic oxidizing salt contained in the emulsion explosive composition, such as the composition disclosed in the above-cited U.S. Patent No. 696,200, is usually composed of porous, lumpy ammonium nitrate particles. According to the present invention, it has been found that if a certain proportion of these lumpy particles contained in the above-mentioned storage-stable emulsion explosive mixture is replaced by a dust fraction, a significant improvement in the water resistance of these

CS 269987 82 b / Emulsion mixture

Mixtures of emulsions (α / α / Ь) and ammonium nitrate solid particles were prepared using the following two methods. According to a first method (referred to as a laboratory method), the emulsion was placed in a 9.6 liter Hobart Model C-100 mixer, after which a selected amount of crushed lumpy ammonium nitrate particles was introduced and If necessary also the whole of these particles and the mixture of emulsion and solid particles were stirred for 4 minutes at a rotation speed of about 60 rpm. Where it was necessary to add oil to achieve oxygen balance in the mixture, the oil was added prior to the addition of ammonium nitrate and emulsion and the oil was mixed for two minutes. When performing the second method, i. using a cement mixer, the lump particles (crushed and, if necessary, whole) were placed in a 45 kilogram cement mixer set at the lowest possible angle. After addition of the emulsion, the solids and emulsions were mixed at the lowest rate to obtain a good roll-over effect. If necessary, an oil was also added, which was added and mixed with the ammonium nitrate portion before the emulsion was added.

с / Ammonium nitrate particles

Four different combinations of dust particles and coarse-grained particles were used in the examples. The ammonium nitrate product I was obtained by grinding the explosive lumpy ammonium nitrate particles and the ammonium nitrate II-IV products were mixtures of crushed lumpy ammonium nitrate particles and whole particles (obtained from two different suppliers), usually used in the production of ANFO-HO ammonium coated with fuel oil) and no oil has been added to these products. The network analysis of these four products was as follows:

Product based on ammonium nitrate I II III IV

the retentate in the sieve No. 50 * in% /> 297 microns / = coarse grain fraction 14.0 85.5 66.2 62.5 Expired / Retained Net 50/100 *% / <297 μ> 149 _? u / 27.9 7.6 32.5 19.5 * expired / retention on 100/140 * in% / <149 p> 105 p / 14.4 2.4 0.65 7.35 expired share / seized share in networks 140/200 * in% / 4105 of у 74 / 3.5 0.2 0.05 5.8 r dust expired / retention share on networks 200/325 * v \ / <74 / U> 44 _{/ U} / 27.6 3.2 0 3.7 sieve share 324 * / <44 12.6 1.1 1.05 ^1,15 >

U.S. Pat. network designation

CS 269987 82

Examples 1-12

In these examples, emulsion mixtures were prepared using the laboratory method using Product I, which was ground ammonium nitrate particles which were used alone or together with whole explosive lumpy nitrate particles (particles greater than 420 microns / v). different ratios. Thereafter, these mixtures were evaluated for their water resistance and shelf life. The ability to withstand the effects of water was estimated by a salt extraction test conducted as follows:

First, 100 grams of water was weighed, and then 100 grams of the mixture was placed in a 237 ml wide-necked glass bottle (10.8 centimeters high and 5.1 centimeters in diameter). The vessel was sealed and placed in a ball mill for 15 minutes at a rotational speed of 260 rpm. 50 ml of an aqueous solution were then weighed. The increase in the weight of water is due to the amount of ammonium nitrate (from the particles or from the aqueous phase of the emulsion) that has been extracted from the mixture, with the greater the amount being extracted, the worse the ability to prevent water. In this test, a weight difference of 50 milliliters of water before and after the rotating action is one half of the total amount of salt extracted, except that only one half of the water used is weighed. The percentage of extracted salt was calculated according to the following equation:

% Extracted salt = weight 50 ml Н po 0 after extraction - weight 50 ml Η ^ 0 half the total weight of the salt in 100 g of the mixture / total weight of salt in 100 g of the mixture is the weight of the ammonium nitrate dispersed in the emulsion plus the weight of the ammonium nitrate particles in mixture.

The salt extraction test has been developed for the purpose of good determination of the water-resistant ability of the emulsion mixture, these adverse effects commonly occurring under field conditions. Under these terrain conditions, the mixture can be pumped or introduced into drilled holes containing water. In some cases, it is possible to encounter running water or standing water that occurs in these drill holes for explosive charges. The above test, in which the emulsion mixture is subjected to the rotational effect of water, simulates the conditions under which the flowing water acts on the emulsion mixture in the drilled holes for storing the explosive mixture during charge deposition.

The shelf life was determined by conducting a lead roller test after storing the mixture for several days. The explosive product was placed in a 0.95 liter cylindrical paper cavity (16.5 centimeters high and 8.73 centimeters internal diameter), filled to the maximum bulk density by shaking the cavity on the support surface. . The paper cavity was then placed on a 1.9 cm thick steel plate that was square in length

10.8 centimeters. This steel plate was placed on a lead cylinder of 10.2 centimeters and a diameter of 6.2 centimeters. The lead roller was then placed on a steel plate that was similar to the one above the steel roller. The explosive mixture was then initiated from the free end of the cavity, the initiator used varying according to the sensitivity of the mixture. The reduction in the height of the lead roller used was measured.

The results obtained are shown in Table 1 below

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The mixtures containing the dust fraction were prepared from an ammonium nitrate-based product I and whole AN particles in an amount sufficient to form an ammonium nitrate (AN).

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CS 269987 82

From the results shown in Table 1 it is evident that emulsion mixtures containing only coarse-grained ammonium nitrate particles in which the emulsion content is in the range of 25 to 50 percent and which are stable in storage / as can be seen from the above, see mixtures prepared according to control experiments A, D, Б and 3), they have an increased resistance to water, which is achieved by adding the ammonium nitrate powder to these mixtures while at the same time having no adverse effect on the shelf life of these mixtures (see Examples 1, 2). and 3 compared to control experiment A; examples 4, 5, and 6 as compared to control experiment D γ further examples 7, 8 and 9 as compared to control experiment G; and Examples 10, 11 and 12 as compared to Comparative Example J /. It is also apparent from the results in this table that mixtures containing 15 percent emulsion and which are not storage stable, as determined by the lead roller bristle test, do not show any significant improvement in water resistance, and generally state that their quality deteriorates by the addition of a dust fraction / see control experiment V versus control C; control experiment E versus control experiment F; control experiment H vs. control I, control experiment К vs. control L, and control M vs. control N /.

Examples 13 and 14 ‘

The emulsion and / or solid particulate ammonium nitrate (50/50) blends were prepared using a cement mixer blend method, and the blends were embedded in polyethylene cartridges and successively tested for shelf life by that they were allowed to detonate freely. The solid particulate ammonium nitrate consisted of an ammonium nitrate based product I and whole lumpy ammonium nitrate particles used for explosives in an amount to achieve a coarse-grained ammonium nitrate / i. particles of greater than 297 microns / in the blend of 32.8 percent, and a dust content of the blend of 17.2 percent / t. The content of coarse ammonium nitrate was 65.6 percent and the dust content was 34.4 percent, based on the particulate component. known as the GDP-1 primer. The results obtained are shown in Table 2. &lt; tb &gt;

Table 2

Example Checklist Coarse - grained proportion Dust fraction Shelf life / WATER Shelf life / WATER C. Experiment no. AN (%) AN (4) (days / m / s) (months / m / s) 13 ⁺ 32.8 17.2 5/3463 1.75 / 3228 0 ⁺ 50 0 5/3000 1.5 / 2959 14 ^ 32.8 17.2 5/3552 2.5 / 3419 P ⁺⁺ 50 0 5/3300 2.5 / 3019

⁺ hub weighing 6.8 kg and a diameter of 10.16 cm hub weighing 13.6 kg and a diameter of 12.7 cm

Examples 15. - 18

Ammonium nitrate emulsion mixtures and / or products I, II, III and IV were prepared according to these examples using a laboratory method. In these processes, no lumpy ammonium nitrate particles were added. The products had the following properties, which are listed in Table 3

CS 269987 82

Table 3

Example # Product based on ammonium nitrate Dust fraction (4) Extracted salt (%) Initiator ** pressed to reach 3.8 cm after 7 days storage in the lead roller test 15 Dec AND 86 0.1 l / UA 16 II 14.5 0.9 UA 17 III 33.8 2.1 1/2 UA 18 IV 37.5 1.0 1 1/2 UA

based on the total weight of the ammonium nitrate particles see Table δ. 1.

The above results show the efficacy of the ammonium nitrate dust fraction in improving the water retention capability of emulsions with a wide dust content range (as compared to control experiment A in Table 1). It is also apparent from the above results that with substantially the same dust content (see Examples 17 and 18), the better water-resistance is achieved with solid ammonium nitrate with a more dispersed particle size distribution (see product XV versus product III).

Example 19

A 50/50 emulsion mixture was prepared using a cement mixer method and the starting materials used were an ammonium nitrate emulsion and / or product I and whole explosive lumpy ammonium nitrate particles. as such, it was devoid of sensitizing amounts of dispersed gas in the form of bubbles or voids, and the emulsion contained sufficient oil to achieve an equilibrium content of oxygen, ammonium nitrate dissolved in the emulsion, as well as solid ammonium nitrate. With respect to the total weight of the mixture, the proportion of coarse-grained ammonium nitrate was 32.8 percent and the dust content of ammonium nitrate was

17.2 percent.

After filling this mixture into polyethylene cartridges and after free initiation by a cast igniter of 0.45 kg, the mixture was detonated at a speed of 3713 m / s, 3432 m / s and 2822 m / s in spaces of diameter 12.7 cm,

10.2 cm and 7.6 cm.

In contrast to the above experiments, detonation velocities of 3810 m / s, 3350 m / s and 2108 m / s in spaces of 12.7 cm, 10.2 cm and 7.6 mm diameter were achieved with mixtures of the same composition but containing no dust fraction. cm, but only if 5.7 percent by weight of fly ash was added to the mixtures. From the foregoing, it can be seen that relatively expensive physical sensitizers can be avoided in the compositions in which the inorganic oxidizing salt in the form of dust is used.

Examples 20-22

A series of 50/50 emulsion / ammonium nitrate blend trials containing the ammonium nitrate powder fraction of the present invention were conducted to confirm that the lumpy lump particles could be replaced by lumpy nitrate particles ammonium, used in agriculture. Emulsion b) was mixed with ammonium nitrate (laboratory metoca), which was obtained by grinding the lumpy particles of ammonium nitrate used. agriculture, for particle size distribution similar to that of product I based on ammonium nitrate. If necessary, the milled product was used together with the whole lumpy ammonium nitrate particles used in agriculture, and the density of these particles was 1.59 g / cm &lt; -1 &gt;. mixtures stored for 7 days.

Table 4

Example C. Control experiment no. Coarse ammonium nitrate (4) Ammonium nitrate (4) High Roller Compression (cm) lead test Initiator 20 May 7.0 43.0 5,56 40g Flex Q 50,0 * 0 0 40g Flex 21 24,2 ⁺⁺ 25.8 4.60 60g Flex 22nd 32.8 ⁺⁺ 17.2 4.14 BOg Flex

contained only lumpy particles used in agriculture lumpy particles plus coarse grain fraction of crushed product see Table 1

Example 23

In this example, a cement mixer method was used to prepare a mixture of emulsion and / or solid ammonium nitrate used in Example 22, 50/50 diameter. The mixture was then filled into polyethylene cartridges with a diameter of 12.7 cm and a weight of 13.6 kg, and the detonation rate was measured in a steel tube after 7 and 29 days of storage of the mixture. GDP-1 was used as an initiator. This packaged mixture detonated with a speed of 3504 m / s and 4198 m / s after 7 days of storage respectively. after 29 days. With the same mixture, which contained only whole lumpy particles used for agricultural purposes (without dust), detonation velocities of 2102 m / s and 3894 m / s were achieved after 7 days of storage of the mixture, respectively. after 29 days of storage.

Claims (7)

A storage-stable emulsion explosive mixture consisting of a sensitized mixture of particles of an inorganic oxidation salt, in particular particulate or coarser ammonium nitrate, coated with fuel oil and a water-in-oil emulsion comprising a continuous liquid carbonaceous fuel and an aqueous inorganic solution oxidizing salts as a discontinuous phase, characterized in that it consists of a) 20 to 70 4 water-in-oil emulsions in which the continuous phase consists of fuel oil, lubricating oil of heavy, aromatic, naphthenic or paraffinic fractions, mineral oil or paraffinic oil and the discontinuous phase consists of an aqueous solution of inorganic ammonium nitrate oxidizing salts , an alkali metal and alkaline earth metal nitrate, ammonium perchlorate, alkali metal and alkaline earth metal perchlorate, the emulsion further comprises an emulsifying agent and consists of 50 to 95% by weight of inorganic oxidation salt, 1 to 21% by weight of carbonaceous fuel and 5 to 22% by weight water and (b) 30 to 80 4 particles of inorganic oxidation salts of ammonium nitrate, ammonium perchlorate, alkali metal nitrate, alkali metal perchlorate and alkaline earth metal perchlorate and mixtures thereof, Wherein 10 to 100% of these particles are replaced by fine particles with a diameter of less than 297 pm. 2. An emulsion explosive composition according to claim 1, characterized in that it comprises as an emulsifying agent (a) an alkali metal salt of a saturated monocarboxylic acid or monocarboxylic acid having one, two or three unsaturated bonds of 12 to 22 carbon atoms, its ammonium salt or an alkylammonium salt; and b) a free fatty acid in solution in an oil which forms a continuous phase, wherein the fatty acid, its salt and oil together form a carbonaceous fuel. 3. The explosive emulsion mixture of claim 1, wherein the fine particles comprise the entire proportion of the inorganic oxidation salt particles present and the mixture comprises 40% emulsion. 4. The emulsion explosive mixture of claim 1, wherein the particles of the inorganic oxidizing mixture comprise a coarse-grained component with particles larger than 297 µm and the fine particles comprise sodium nitrate. . ’ 5. The emulsion explosive composition of claim 4, wherein the coarse-grained component comprises particles that are larger than 420 microns. 6. The emulsion explosive composition of claim 5, wherein the particles larger than 420 µm make up at least 15% by weight of the particles of the inorganic oxidation salt. 7. The emulsion explosive composition of claim 6, wherein the coarse-grained component comprises whole lumpy ammonium nitrate particles, lumpy ammonium nitrate particles with fuel oil, or a combination thereof.