KR890003676B1 - Storage-stable emulsion blend explosive and method of making the explosive - Google Patents

Abstract

A storage-stable blend explosive comprises a sensitized blend of an inorganic oxidizing salt particle (A) and a water-in-oil emulsion (B) . The particle contains at least 15 wt.% of fine particles (under 297 micron). The wt. ratio of (B):(A) is 20:80-70:30. The emulsion comprises a carbonaceous fuel having components which form a continuous emulsion phase, an aq. inorganic oxidzing salt soln. forming a discontinuous phase dispersed as discrete droplets within the continuous phase, and an emulsifying agent.

Description

Storage stability emulsion mixture explosives and preparation method thereof

The present invention relates to an explosive composition consisting of a sensitized blend of a water-in-oil emulsion and a solid particulate inorganic oxidizing salt, preferably ammonium nitrate (AN).

Explosives made up of a mixture of water-in-oil emulsions and solid particulate ANs, such as ANFO (fuel-coated AN prills) offer the advantages of high bulk density and blasting energy properties of emulsion explosives at an affordable price of AN. Due to the fact that the price is lowered, it is becoming more and more popular with blasters, but in some cases these mixed explosive products, referred to in the present invention as "emulsion mixture explosives" have a short shelf life, so “Short shelf life” refers to the lack of stability in explosive products, which entails detrimental change (s) in structure and / or composition to the extent that it is unbelievable to explode at the desired rate at the desired time. If the shelf life of the product is too short, the product is almost certainly Not suitable for use as a sheet form, especially when moved to the place of use, or if the turn in politics in sachu attack speed for a predetermined time after loading, is not suitable for use as a mass (bulk) type.

L.A. Serial number 696, 200 (filed date: 1985.1.29), co-pending with Sescon and N.J.Millette Junior, describes the preparation of an emulsion mixture explosive with improved low stability. In this application, in these explosives, preferably an anionic emulsification system consisting of fatty acid salts and free fatty acids, which are dissolved in the oil as a continuous emulsion phase, preferably by a continuous emulsion phase itself. Thanks to the water-carrying resistant barrier or medium formed by being present in the mixture, the mixture-stabilization action can be minimized, in which water is transported or lost from the aqueous dispersion phase of the emulsion to the mixed nitrate particles via the continuous oil phase. It is described. The application also describes that a water-carrying resistant barrier can be provided, for example, by low-diffusion coating (on water) on nitrate particles.

One of the substances commonly used as slime solids in emulsion mixture explosives is ANF

O. ANFO is a popular blasting product due to its economy and convenience, but it is well known that the drawbacks of this product are its water resistance length and low product density. Mixing ANFO with water-in-oil emulsions results in higher density products, and some water resistance can be achieved in the mixed products, especially when the weight ratio of emulsions / solids is high. Thus some unpackaged emulsion mixture products can be used in damp boreholes. Nevertheless, even storage stable emulsion mixture products can be used in a more economical way, i.e. in the form of a large mass of solids content, if the water resistance is improved.

The present invention relates to an inorganic oxidizing salt particles, a carbonaceous fuel having components forming a continuous emulsion phase, an inorganic forming a discrete emulsion phase dispersed in discrete droplet form in continuous inheritance. The present invention provides an improvement in an emulsion mixture explosive consisting of a sensitizing mixture with an oil-in-water emulsion containing an aqueous solution of an oxidizing salt and an emulsifier. Even more specifically, the improvement provided by the present invention applies to a storage-stable mixture of the above-described type, the characteristic of which is that in the inorganic oxidizing salt particles in the mixture, particles smaller than 297 micrometers, namely 50 At least about 15% by weight, preferably at least about 20%, by weight of the components consisting of particles passing through the sieve (US series) and the weight ratio of emulsion to total inorganic oxidizing salt particles are from about 20/80 to 70/30.

The particulate oxidizing salt component, consisting of particles smaller than 297 micrometers, is now referred to as "particulate" or "particulate component". This powder component may occupy the entirety of the oxidizing salt portion of the emulsion mixture explosive. That is, 100% by weight of the oxidizing salt particles may be composed of powder. However, in alternative embodiments, and in many preferred embodiments, the granulation component, together with the coarser particles, preferably contains a body larger than 420 micrometers, i.e., a sieve hole of 0.420 mm. Particles retained on the US series) are present with the coarse component contained therein. Preferably, the AN or ANFO prill is contained in the coarse component.

One of the beneficial effects exerted by the powder component in the particulate oxidizing salt portion of the emulsion mixture explosive is increased water resistance (i.e., explosive resistance against external water attack). The explosives are suitable for use in unpacked form in damp boreholes. Such increased water resistance results from the use of mixture explosives which feature a shelf life long enough to be stored, for example the product described in co-pending U.S. Patent Application Serial Numbers 696, 200.

Solid oxidizing salts in such a storage product are less susceptible to attack by internal or external water, thanks to a water-carrying resistant medium or barrier, which may itself be a continuous phase of the emulsion. By providing that the stability of the mixed product is protected by such a barrier or medium, the powder may be used in place of some or all of the solid inorganic oxidizing salt without essentially reducing the shelf life of the mixture. In a typical situation, it is believed that larger surface area separation attracts more water into the discontinuous phase of the emulsion, causing the mixture to destabilize. As will be explained below, the discovery that powder can be added into a storage stable emulsion mixture without adversely affecting the shelf life of the emulsion mixture is important in several respects, including an increase in the water resistance of the mixture as described above.

With respect to products containing "all-coarse" (i.e., greater than 420 micrometers) particulate inorganic oxidizing salts which may maintain their stability when some or all of the coarse particles are replaced by powder As used herein, the term "storage stable emulsion mixture explosive" refers to a mixture made from such "coarse" particulate salts and "storage stable emulsions".

As used herein, the term "storage stable emulsion", when mixed with AN blasting frills at a 50/50 weight ratio under a viscosity of 3000-3500 poise, stores the mixture for 7 days and then uses 40 g of initiator. It refers to an emulsion whose lead compression is at least 3.8 centimeters at the time of initiation (where lead compression is measured according to the lead compression test described herein). Any emulsion that results in this result in the 50/50 mixture described above is called "storage stability," and this emulsion is a coarse particulate inorganic oxidizing salt having an emulsion / salt ratio of 20/80 to 70 /. When used at 30, it provides a mixture that can be called "storage stability".

Another method for identifying storage stability emulsions and storage stability mixtures in the sense used herein is to make an emulsion and AN blasting frill 50/50 mixture under a viscosity of 3000-3500 poise to give this mixture The salt extraction test described in the above is carried out. This test measures the amount of inorganic oxidizing salt extracted from making a mixture by water, which is expressed as a percentage of total solids and dissolved salts in the mixture. The percentage of salt extraction may be thought to increase as the emulsion content of the emulsion mixture decreases, but from the standpoint of the behavior of the mixture when the powder is added, the expression "storage stability" is less than or equal to Up to about 70%) of emulsions and any coarse inorganic inorganic oxidizing salts. However, salt extraction tests performed on a 50/50 mixture of the same emulsion and AN prill resulted in a salt extract of no greater than about 7%.

The emulsion mixture product of the present invention is sensitized in order to be able to explode by means commonly used to initiate explosives, ie it contains sufficient sensitizer, for example dispersed gas bubbles or voids. This sensitization can be carried out in any conventional manner. For example, the pre-mixed emulsion can itself be fully sensitized-that is, if desired, in the form of an air-transfer solid material such as phenol-formaldehyde microspheres, glass microspheres, fly ash, etc. Explosive emulsion by incorporating air dispersed therein. Alternatively, amine nitrates such as chemical sensitizers, such as monomethylaminenitrate, trinitrotoluene, perchlorate, and the like may be incorporated into the emulsion. In addition, air-delivered solids can be added to the emulsion during mixing, and in fact, the porous inorganic nitrate frill can itself sensitize the mixture if it is present in a sufficient amount, typically about 30% or more of the weight of the mixture. Can function as an air transfer agent. Even more, the granulation itself may be combined with one or more additional sensitizers or serve as the sensitizing component of the mixture as a sole sensitizer (see Examples 20-22).

Oils and aqueous inorganic oxidizing salt solutions known in the art of explosive emulsions may be used in the emulsion portion of the blended product, for example oil and salt solutions disclosed in US Pat. No. 4, 287, 010. The contents of this patent are hereby incorporated by reference. Most frequently, the inorganic oxidizing salts present in the aqueous phase of the emulsion are ammonium, alkali or alkaline earth metal nitrates or perchlorates, preferably ammonium nitrate alone or for example up to about 50% of sodium nitrate (inorganic oxidizing salts in the aqueous phase). In combination with the total weight). The emulsifier used is a combination of fatty acid salts and fatty acids and salts with monovalent cations are preferred, which are described in the above mentioned US Pat. No. 4, 287, 010. Oils suitable for use in carbonaceous fuels include fuel oils and naphthenic or paraffinic materials, heavy aromatic lubricants, mineral oils, dewaxed oils and the like.

The oil content of the emulsion may be substantially sufficient to provide an oxygen-balance emulsion, or may contain excess oil if mixed with fuel, deficient or lead-free solid particulate inorganic oxidizing salts (and converting agents). -May be deficient). The advantages derived from using such "high oil" emulsions are described in the above-mentioned U.S. Patent Specification Serial Nos. 696, 200, which are incorporated herein by reference.

One or more catalytic catalysts, such as aluminum dichromate, copper chloride, etc., in addition to being able to contain a chemically sensitizer in an emulsion, for example, as a solution in its discontinuous aqueous phase or as a dispersion of finely divided solids. It may be present and as an emulsion or mixture of fine solid parts.

Various types of emulsifiers are known for emulsions used as explosives or in emulsion mixed explosives. Whether a given emulsifier is suitable for use in an emulsion incorporated into the mixture product of the invention depends on the storage stability of the resulting mixture. This can be determined by the above mentioned lead compression test performed on a coarse 50/50 mixture (ie a mixture of 50% emulsion and 50% AN valpapril). The salt extraction test mentioned above can also be used. A preferred emulsifying system is a combination of fatty acid salts and fatty acids, which provides good storage stability as described in US Pat. No. 696, 200 above. In these systems, the free fatty acids are in solution in oil, and the oil solution forms a continuous emulsion phase. Fatty acids and fatty acids together with oils form carbonaceous fuels.

In the preparation of the preferred emulsion, the fatty acid of choice is added to the oil and the fatty acid salt is introduced in a linearized state, or it is combined with oil and an aqueous salt solution as disclosed in US Pat. No. 4, 287, 010. It can be produced in-house from fatty acids and bases in forming emulsions. Fatty acids are preferably saturated or mono, di- or tri-unsaturated monocarboxylic acids having about 12-22 carbon atoms and the salts are preferably alkali metal, ammonium, and / or alkylammonium salts of fatty acids.

In the mixed product of the present invention, the emulsion is present in the mixture in a weight ratio of particulate inorganic oxidizing salt and emulsion to particulate oxidizing salt of about 20 / 80-70 / 30. At least about 15, preferably at least about 20% by weight of the particulate oxidizing salt is composed of particles of 297 micrometers or less, ie at least about 15, preferably at least about 20% of "particulate". The emulsion may be mixed with the particulate oxidizing salt, which consists substantially of the whole, i.e., to produce a mixture containing about 30-80% of the powder based on the total weight of the mixture. It is often desirable to use powder in combination with particles larger than a meter. Most preferably, the coarse component is present in some of the particles therein (typically at least about 15% or less of the particulate inorganic oxidizing salt weight) greater than 420 micrometers, such as AN or ANFO prills.

For a mixture of emulsions of about 20 / 80-40 / 60% by weight to oxidizing salt particles, it is preferred that the particulate salts contain about 20-70% by weight of particulate (based on the total mixture weight, about 12-56). Powder content of%). If the fine salts in these mixtures contain 30-60% of the granules by weight (which is about 18-48% of the granular content based on the total mixture weight), an optimum result (mainly considered to be improved water resistance) is obtained. Lose.

The main advantage of powder / coarse particle combinations in mixtures containing large amounts of emulsions (i.e. 40% by weight or more) is the good distribution of solid particles in the mixture, with further improvements in water resistance Along with the load, a particle / coarse weight ratio of about 34/66 or more is also selected based on other desirable properties such as sensitivity to initiation, explosion rate, and the like.

It is an unexpected finding that the addition of solids to certain emulsion mixtures does not lead to mixture destabilization due to the large surface area of the granules and in fact leads to an increase in water resistance in these mixtures. The following discussion is provided in order to provide a more detailed understanding of the advantages associated with the emulsion content of the mixture, which can be obtained with a powder addition. It is to be understood that the discussion is not intended to limit the invention to any theoretical basis found there.

Particulate inorganic oxidizing salts in the emulsion mixture explosives (such as those described in US Pat. No. 696, 200, for example) usually consist of porous AN prills. It has been found to replace some of these prills with powder in the above-described storage stability emulsion blend explosives, and if the emulsion content of the mixture is about 20%, the powder content of the fine salt portion of the mixture is about 15%. Significant improvements in the water resistance of OH become apparent. At this emulsion level and at levels below the 30-40% range, the mixture appears to behave as if it is "emulsion-deficient", that is, contains an emulsion that is insufficient to wrap particulate inorganic oxidizing salts. In this case, the "all-separated" particulate solids are more desirable than no segregation at all, but in the case of emulsion-deficient mixtures the improvement in water resistance is in the range of about 30-60% (the weight of the total particulate solids). Optimal in segregation, and other properties such as mixture density and fluidity follow the same trend.

If large amounts of emulsion are present in the mixture (eg 40% or more), the mixture appears to behave as if it is "emulsion-sufficient", ie it contains enough emulsion to cover the particulate inorganic oxide salts. . In this case, the water resistance continues to increase with increasing the powder content, but is relieved markedly when the powder / coarse particle weight ratio exceeds about 34/66. The mixture density is also even. However, it is very useful to provide a product having high sensitivity as well as improved water resistance in the emulsion-fill mixture of about 34-100% by weight of particulate solids. With large amounts of particulate addition in these products, improved susceptibility and explosion rate can be obtained without the additional undesirable undesirable density reduction that results from the use of conventional physical sensitizers such as micro hollow tools.

Inorganic acid salts forming the particulate solid portion of the inventive mixtures are ammonium nitrate (AN), ammonium perchlorate, alkali metal nitrates such as sodium nitrate (SN), alkali metal perchlorates, alkaline earth metal nitrates such as calcium nitrate (CN ), Or an alkaline earth metal perchlorate or any combination of two or more of these nitrates, lightly coagulated with granules or prills or fuel oils (e.g., known " ANFO " usually having an AN / FO ratio of about 94/6). And / or prills coated according to the method described in US Pat. No. 669, 200, supra. AN prills may be valpapril or agricultural or chemical fertilizer prills that are commonly used in explosives. Valpapril is usually less dense and more porous than chemical fertilizers. If only fertilizer prills are used, a mixture containing at least about 25% emulsion and a high level of separation (eg, at least about 25%), based on the total solid particulate weight, is required to achieve the desired sensitivity.

The granular component may be a ground AN prill or an inorganic perchlorate such as ammonium or an alkali metal perchlorate or a combination of AN and perchlorate. Regardless of the particular salt (s) used, sufficient fuel, preferably oil, is mixed therein or incorporated into the emulsion to essentially produce an oxygen-balancing mixture. The use of less porous granules, such as SN granules, is advantageous in that it provides a more easily pumpable mixture, because (a) less absorption of the oil required for oxygen-balancing purposes (porous AN granules). Relative to the amount of oil absorbed) and (b) greater fluidity due to the large amount of oil required to oxygen-group the SN-containing mixture.

Useful powders of the present invention may be prepared from any of a variety of standard mills. For example, it may be advantageous to use a hammer mill that is found in ANFO plants and used to grind ammonium nitrate to ANFO-HD dimensions. In crushing the prills, care must be taken to prevent contamination for both safety and performance reasons. When grinding ammonium nitrate, water is known to cause prill degeneration, so care should be taken to minimize exposure to all forms of water. The degree of grinding depends on the intended end use, ie the level of granulation desired for the final product. This, of course, means that about 15% of the particulate inorganic oxide salts can be ground on a hammer mill so that they have a dimension of 297 micrometers or less. Alternatively, the prills can be ground to a total of no more than 297 micrometers. As previously described, the material, which can be used directly in the mixture, or in the latter case, which is essentially whole, can be mixed with ammonium nitrate to provide the desired level of granularity in the mixture of coarse and granulated particles. Characteristics of the grinding conditions are known to those skilled in the art.

The granulation itself and the mixture with the coarse particles can be easily characterized by standard sieving techniques and the determined particle size distribution.

Emulsion mixture explosives described in the following examples were prepared as follows:

a. Emulsion

US Patent Nos. 4, 287, 0, except for missing glass micro hollow tools and fly ash

An emulsion of the following formulation was prepared according to the method described in Example 1 of No. 10.

Emulsion (a) Emulsion (b)

%%

--

Ammonium Nitrate (Dissolved) 70.9 75.8

Water 15.6 16.6

Oil 7.6 4.3

Oleic acid 3.8 2.1

Sodium hydroxide (50% aqueous solution) 2.1 1.2

The percentages given for oleic acid and sodium hydroxide solutions represent the ratios of oleate used to prepare emulsifiers in-house.

b. Emulsion mixture

A mixture of utaga solution (a) and (b) and solid particulate AN was prepared by two methods. One method (here referred to as the "laboratory method") Example: Emulsion is added to the bowl of the Hobart Model C-100 Mixer (9.61 volume), a selected amount of crushed and intact AN prill is added, and the emulsion is And solid were mixed at about 60 rpm for 4 minutes. If addition of oil is required to oxygen-balance the mixture, oil is added before AN and the emulsion and oil are mixed for 2 minutes. In the second method, the cement-mixing method, prills (pulverized and intact if necessary) are added to a 45 kg capacity cement mixer and adjusted to their lowest angle. After the emulsion was added, the solids and emulsion were mixed at the lowest rate adjusted for good disruption. If necessary, oil was added and mixed with AN before the emulsion was added.

c. Fine AN

Four different powder / coarse particle combinations were used. AN valpapril was triturated to give AN product I, AN product II-IV, which is a mixture of crushed and intact AN prills (obtained from two different sources) typical of those obtained in ANFO-HD preparation, No oil was added at all. Screen analysis of the 4 products was as follows.

product

I II III IV

Jam on% 50 ^* (> 297μ) 14.0 85.5 66.2 62.5

= Rough

% Pass / stuck 50/100 ^* 27.9 7.6 32.5 19.5

(<297μ,> 149μ)

% Pass / Through 100/140 ^* 14.4 2.4 0.65 7.35

(<149μ,> 105μ

% Pass / stuck 140/200 ^* 3.5 0.2 0.05 5.8

(<105μ,> 74μ)

% Pass / stuck 200/325 ^* 27.6 3.2 0 3.7

(<74μ,> 44μ)

% Pass 325 ^* 12.6 1.1 1.05 1.15

(<44 μ)

* U.S. Sieve devise

[Example 1-12]

Product I Pulverized The mixture is prepared by the above-described wrap method using AN prill alone or with all AN valpaprils (greater than 420 microns) in various proportions. Evaluate the water resistance and shelf life of the mixture. Water resistance is evaluated by the following salt extraction test.

중량으로 이것은 사용된 물의

만 무게를 달았기 때문이다. 추출된 염의 백분율은 다음과 같이 계산된다.100 g of water and 100 g of the mixture are weighed and placed in a 237 ml-wide inlet glass bottle (10.8 cm high by 5.1 cm in diameter). The closed bottle is placed in a ball mill with a roller speed of 260 rpm for 15 minutes. Weigh 50 ml of aqueous layer. The increase in water weight is based on the amount of ammonium nitrate (aqueous phase of particles and emulsion) that can be extracted from the mixture and indicates a large amount of poor mixture water resistance. In this test, the difference in the 50 ml weight of water before and after the rotation described above was determined by the total amount of salt extracted.

By weight this is the amount of water used

Because only weighed. The percentage of salt extracted is calculated as follows.

×100Extracted salt% =

× 100

(The total weight of salt in 100 g of the mixture is the weight of the ammonium nitrate in the aqueous phase dispersed in the emulsion plus the weight of AN particles in the mixture.)

Salt extraction tests are designed to provide a meaningful assessment of the resistance of mixed emulsions to degradation by water under conditions commonly encountered in this field practice. In this field, it is possible to pour or put the mixture into a water-containing hole. In some cases, stagnation as well as operation may be in the wetting cavity. This test with rotational action on water and mixed emulsions stimulates the following conditions that occur in the borehole upon loading.

After several days of storage the storage period is assessed based on the lead block compression of the mixture. The explosive product is placed in a cylindrical 0.95-1 paper cup (16.5 cm high x 8.73 cm internal diameter) and packaged to its maximum bulk density by tapering the cup on a support surface. The cup is placed on a plain steel sheet 1.9 cm by 10.8 cm thick and placed again on a lead cylinder 10.2 cm high by 6.2 cm in diameter. Place the lead cylinder on a steel sheet similar to the above. The product starts from the open top of the cup and the size of the initiator used varies with the sensitivity of the mixture. The height reduction of the resulting lead cylinders is measured.

The results are shown in Table I below.

TABLE 1

Emulsions in Examples 1-12 and Controls A, D, G, J, M, and N (a).

The mixtures in Control B, C, E, F, H, I, K, and L were emulsions prepared according to US Pat. No. 3,447, 978, using 0.5% mono-oleic acid sorbitan as an emulsifier. Made with. The emulsion does not increase or decrease on its own.

** The mixture comprising the granules is prepared from the total AN blasting frill + AN product I sufficient to provide% of indicated particles (coarse) larger than 297μ particles (particulate) of less than 297μ. Whole prills are used to produce compounds with coarse particle / granulation ratios greater than 14/86.

*** WG = 20 g "Detaprime" (a mixture of 75% PETN extruded tubular in elastomeric binder)

1/2 WG = 1/2 20g "Detaprime"

UA = 6g "Detaprime"

Flex = 3.8 cm diameter cylinder with 75% PERN in elastomeric bond.

Table I shows mixed emulsions with all coarse ANs, which are storage-stable as defined herein (mixtures made in Controls A, D, G, and J) and containing 25-50% emulsion, have a bad effect on storage period. It can be seen that the water resistance can be improved by adding AN granules to the mixture without giving the result. (Comparative experiment A of Examples 1, 2 and 3; A comparative experiment of Examples 4, 5 and 6; D; Comparative experiments of Examples 7, 8 and 9; G; Comparative experiments of Examples 10, 11 and 12) The table also generally shows that no significant improvement in water resistance was observed with the addition of the granules, as judged by the lead compression test, for a mixture containing no storage-stability and 15% emulsion (see Controls B vs. C vs E). F, H vs I, K vs L, M vs N).

[Examples 13 and 14]

50/50 mixtures of solid AN particles and emulsion (a) are prepared by the cement mixer method, and the storage period is regularly tested by attempting to bombard the non-contained ones in a polyethylene keg. Solid AN particles are the AN product in the amount of 32.8% of the mixture, coarse AN (greater than 297μ) and in the amount of providing granules in an amount of 17.2% of the mixture (65.6% coarse AN and 34.4% coarse based on the particle component) and I am composed of AN valpapril. The keg is unsealed with 0.45 kg cast primer known as HDP-1 primer.

* 6.8 kg gun barrel with a diameter of 10.16 cm.

** 13.6 kg powder canister with a diameter of 12.7 cm.

Example 15-18

A 50/50 mixture of AN products I, II, III and IV with emulsion (a) is prepared by the lab method. I do not add AN prill. The product has the following properties.

* Based on the total weight of AN particles

** See Table I

The results show the effect of AN separation (compared to Comparative Experiment A in Table I) to improve the water resistance of the mixed emulsion over a wide range of powder content. The result is better water resistance with a solid ammonium nitrate product having a dispersion with more dispersed particle sizes, essentially with the same powder content (Examples 17 and 18) (Product IV vs. Product III).

Example 19

A 50/50 mixed emulsion is prepared by the cement mixer method using emulsion (a), AN product I and whole AN valpapril. Emulsion (a) contains no sufficient increase or decrease in the amount of gas bubbles or voids dispersed in itself and balances the AN oxygen dissolved therein as well as the solid AN in the mixture. The rough AN content is 32.8% based on the total weight of the mixture and the AN granular content is 17.2%.

When placed in polyethylene keg and unsealed with 0.45 kg cast primer, the mixture explodes at speeds of 3713, 3432 and 2822 m / sec at 12.7, 19.2 and 7.6 cm diameters, respectively.

Conversely, mixtures containing no segregation and made in the same manner from the same emulsion have an explosion rate of 3810, 3350 and 2108 m / sec at diameters of 12.7, 10.2 and 7.6 cm, respectively, only when 5.7% by weight of ash is included in the formulation. Therefore, the use of oxidative inorganic salts in discrete form in this given mixture makes it possible to avoid the need for relatively inexpensive physical sensitizers in the product.

Example 20-22

According to the present invention, a series of experiments were performed with a 50/50 emulsion / AN mixture containing AN fractions to show that AN agricultural prills could replace valpapril. Emulsion (b) is mixed with AN product made by grinding AN agricultural prills (wrap method) to a size distribution similar to AN product I. If necessary, the milled product is used with a full AN agricultural prill having a particle density of 1.59 g / cc. The following table shows the results of the lead compression test performed on a 7 day-tied mixture.

* All agricultural ruffles

** Rough part of the milled product + ruffle

*** See Table I

Example 23

A 50/50 mixture is prepared in a cement mixer from the solid AN component and emulsion (a) used in Example 22. The mixture is placed in a 12.7 cm diameter polyethylene powder container and weighed 13.6 kg. The explosion rate is measured in steel pipes after 7 and 29 days. HDP-1 initiator is used. The packaged mixture explodes at 3504 and 4198 m / sec after 7 and 29 days, respectively.

The same mixture, containing only whole agricultural prills (no granulation), explodes at 2102 and 3894 m / sec after 7 and 29 days, respectively.

Claims (27)

Water-in-oil emulsion consisting of inorganic oxidizing salt particles, carbonaceous fuel having components forming a continuous emulsion phase, an aqueous solution and an emulsifier of an inorganic oxidizing salt forming a discrete phase dispersed in discrete droplet form in the continuous inheritance A storage stable emulsion mixture explosive comprising a sensitizing mixture with a liquid, wherein the inorganic oxidizing salt particles contain at least about 15% by weight of a particulate component consisting of inorganic oxidizing salt particles smaller than 297 micrometers. (Iii) explosives, characterized in that the weight ratio of all inorganic oxidizing salt particles is about 20/80 to 70/30. The explosive charge according to claim 1, wherein the powder component comprises one or more salts selected from the group consisting of nitrates and perchlorates. 2. The emulsion according to claim 1, wherein the emulsion contains salts of fatty acids and fatty acids dissolved in oil in its emulsification system, the oil solution forms the continuous emulsion phase and the fatty acids, fatty acid salts and oils Explosives that together form the carbonaceous fuel. The explosive of claim 1, wherein the powder component comprises substantially all of the amount of the inorganic oxidizing salt particles. The explosive of claim 4, wherein the percent emulsion in the mixture is at least 40. 6. The explosive according to claim 5, wherein said powder component is composed of one or more salts selected from the group consisting of nitrates and perchlorates. The explosive of claim 1, wherein the inorganic oxidizing salt particles contain a coarse component consisting of particles larger than 297 micrometers. 8. The explosive according to claim 7, wherein said granular component is composed of one or more salts selected from the group consisting of nitrates and perchlorates. The explosive charge of Claim 8 in which the said granulation component contains sodium nitrate. 10. The explosive according to claim 8, wherein the coarse component and the granular component are composed of an ammonium nitrate ripple, an ammonium nitrate-fuel oil prill or a combination of ammonium nitrate and an ammonium nitrate-fuel oil prill in an intact and pulverized state. The explosive according to claim 10, wherein the percent emulsion in said mixture is about 20-40, and the powdered content of intact prills and ground prills is about 30-60%. The explosive according to claim 10, wherein the percent emulsion in said mixture is at least 40, and the granular content of intact prills and ground prills is at least about 34%. 8. The explosive according to claim 7, wherein said coarse component contains particles larger than 420 micrometers. The explosive of claim 13, wherein the particles larger than 420 micrometers comprise at least about 15% by weight of the inorganic oxidizing salt particles. 15. The explosive of claim 14, wherein said coarse ingredient contains intact ammonium nitrate, ammonium nitrate-fuel oil prill, or a combination thereof. The explosive of claim 7 wherein the percent emulsion in said mixture is about 20-40%. 17. The explosive of claim 16, wherein said powder component is contained in about 20-70% of said inorganic oxidizing salt particles. 8. The explosive of claim 7, wherein the percentage of emulsion in said mixture is at least 40. 19. The explosive of claim 18, wherein said inorganic powder particles are contained in at least about 20% of said particulate component. The explosive agent according to claim 10, wherein the mixture is made of an emulsion containing, as a raw material, an amount of increase or decrease of dispersed gas bubbles or voids. The explosive according to claim 10, wherein the mixture is made from an emulsion having no dispersed gas bubbles or voids by the amount of increase or decrease, and the mixture is increased or decreased by air carried therein by a prill. The explosive according to claim 10, wherein the mixture is made from an emulsion having no gas bubbles or voids dispersed as much as the amount of increase and decrease, and the mixture is increased or decreased by the powder component. The explosive according to claim 1, wherein the explosive is made from an emulsion containing oil in an amount sufficient to balance oxygen of both the mixture and the fine inorganic oxidizing salt. The emulsion according to claim 1, wherein the mixture comprises (a) an emulsion containing an amount of oil sufficient to balance the oxygen of the inorganic oxidizing salt of the discontinuous emulsion inheritance, and (b) a portion or all of the particulate inorganic oxidizing salt. Explosives made from oil added as needed to balance oxygen. 25. The explosive according to claim 24, wherein the mixture is made from a mixture of oil-treated intact AN prills and pulverized AN prills and the emulsion. About 30-80% by weight of inorganic oxidizing salt particles larger than 420 micrometers and a carbonaceous fuel having components that form a continuous emulsion phase, which form a discrete emulsion phase dispersed in discrete droplet form in its succession. Water-in-oil emulsion consisting of an aqueous solution of an inorganic oxidizing salt and an emulsifier is in a mixture with about 70-20% by weight, and when mixed with AN valpapril at a weight ratio of 50/50 under a viscosity of 3000-3500 poise, it is stored for 10 days. A process for preparing an emulsion mixture explosive with increased water resistance, using a storage stable emulsion mixture that results in lead compression of 3.8 centimeters or more when initiated with a 40 g initiator, wherein at least about 15% by weight of the particles Characterized by replacing with inorganic oxidizing salt particles smaller than 297 micrometers. 27. The method of claim 26, wherein the emulsion contains salts of fatty acids and fatty acids dissolved in oil in its emulsification system.