WO2004009516A1

WO2004009516A1 - Waterproof granular explosive composition

Info

Publication number: WO2004009516A1
Application number: PCT/JP2003/009331
Authority: WO
Inventors: Hideaki Sugihara
Original assignee: Nippon Kayaku Kabushiki Kaisha
Priority date: 2002-07-24
Filing date: 2003-07-23
Publication date: 2004-01-29
Also published as: CN1671634A; CN100334043C; CA2493557A1

Abstract

A waterproof granular explosive composition which like conventional ANFO explosive, is excellent in handleability, for example, being usable in bulk form and having fluidity and can be produced by an easy process, and which exhibits satisfactory water resistance in an immersion time envisioned in practical use and further exhibits explosion performance. In particular, an explosive composition comprising porous prill ammonium nitrate and a nitro compound optionally together with an antiblocking agent characterized in that a waterproof resin coating film is formed from a thermosetting resin and the above components are covered with the waterproof resin coating film.

Description

Specification

Technical field of water-resistant granular explosive composition

TECHNICAL FIELD The present invention relates to an explosive composition widely used for industrial blasting operations such as crushed stone, mining, coal mining, and digging on steep roads. More specifically, the present invention relates to a water-resistant granular explosive composition that can be used by being directly loaded into a perforation or the like. Technology background

Well-known explosives used in industrial blasting operations include dynamite, hydrous explosives, nitrate explosives, and nitrate oil explosives (hereinafter referred to as AN FO explosives). Of these explosives, ANFO explosives are relatively easy to manufacture and are well known as cheaper and more secure explosives than other industrial explosives. Also, ANFO explosives consist of fluid particulate matter and can be poured directly into the perforations or loaded by a loader or other loading machine. For these reasons, AN F 0 explosives are very widely used.

The main component of ANFO explosives is porous granular (hereinafter referred to as porous prill) ammonium nitrate (hereinafter referred to as ammonium nitrate), which often accounts for more than 90% by weight of the entire explosive. The ANFO explosive is an explosive in which liquid fuel components such as light oil are mixed with ammonium nitrate. On the other hand, ammonium nitrate dissolves in about 120 g at 0: 100 g in water and about 9550 g at 100 ° C, and is very easily dissolved in water.

Therefore, ANFO explosives can easily dissolve nitric acid in the perforation hole if water is present in the perforation for blasting, if groundwater seeps into the perforation, or if water penetrates into the perforation in rainy weather. May lose explosive properties due to separation. Therefore, under these conditions, packaging explosives such as water-resistant dynamite and water-containing explosives are used, or (packaged) ANFO explosives are pre-loaded in a waterproof packaging material such as a polytube pharmaceutical cylinder. Is used. But, In the former case, the explosive used is more expensive than the ANFO explosive, which increases the blasting cost. The latter case not only loses the advantage that it can be easily loaded in bulk, but also creates a gap between the packaged explosive and the perforated wall, and puts ANF〇 explosive in the perforated hole. It does not provide a sufficient blasting effect compared to direct loading. Also, the ANF 0 explosive packaged in such a polytube is damaged by the sharp stones on the perforated wall when charging into the perforation, and as a result, water penetrates into the inside of the package, which causes the ANFO explosive to be charged. Explosion may be lost due to moisture absorption. Also, if there is a large amount of water in the perforation, it is necessary to drain the water to prevent the explosive from floating.

In an attempt to solve the above problems, several methods have been proposed to use explosives without loading them into polytubes. For example, ANF 爆 explosives with a water-absorbing agent added to explosives have been developed and put into practical use (Japanese Patent Application Laid-Open No. 2000-16991), but the water-absorbing performance is not sufficient, and when explosives are used, wastewater is discharged. It is necessary to once remove water from the perforation by the pump, which increases the number of steps in the charging operation. Also, JP-A-2001-31490, JP-A-2001-48698, JP-A-2001-892485, and In Japanese Patent Application Laid-Open Publication No. 2002-47078, various attempts have been made to improve the water resistance of polar sprill nitrate, but all of these methods involve melting high-melting-point wax, heating during film formation, and the like. Control of cooling temperature and time, spray coating of coating agent, production of emulsion explosive for coating, pre-coating process with powdered nitric acid, etc. Is expected. Disclosure of the invention

The present inventors have made the best use of the ANF explosives' excellent handling properties, such as being able to be used in bulk and having fluidity, as well as removing the water present in the perforations and the intruding water. Develop granular explosives that have water resistance properties that can be used and that can be easily manufactured with simple equipment. As a result of intensive studies, the present invention has been completed.

That is, the present invention

(1) an explosive composition comprising porous prill ammonium nitrate, a nitro compound and a thermosetting resin,

(2) an explosive composition comprising a porous prill ammonium nitrate, a nitro compound and a cured product of a thermosetting resin,

(3) The explosive composition according to the above (1) or (2), which contains an anti-blocking agent,

(4) The explosive composition according to any one of the above (1) to (3), wherein the content of the nitro compound with respect to the entire explosive composition is 2.5 to 25% by weight.

(5) The explosive composition according to any one of the above (1) to (4), wherein the nitro compound is an aromatic nitro compound,

(6) The explosive composition according to any one of (1) to (5), wherein the nitro compound has a melting point of 80 or less,

(7) A method for producing an explosive composition, comprising mixing a porous prill ammonium nitrate and a nitro compound with at least one selected from the group consisting of a thermosetting resin, a polymerizable monomer and a polymerizable oligomer,

(8) The method for producing an explosive composition according to the above (Ί), further comprising mixing a curing agent,

(9) The method for producing an explosive composition according to the above (7) or (8), further comprising mixing an antiblocking agent,

(10) The method for producing an explosive composition according to any one of the above (7) to (9), wherein the components are mixed and then the mixture is heated.

About. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

In the explosive composition of the present invention, usable porous prill nitrate is not particularly limited as long as it is generally used in explosives as porous ammonium nitrate, but its oil absorption rate is 5.0 to 24. 0%, average particle size 0. It is preferably from 5 to 2.5 mm. Such porous prill nitrate can be easily obtained from commercial products such as PK manufactured by Mitsubishi Chemical Corporation, CHP manufactured by Sumitomo Chemical Co., Ltd., and Tropical manufactured by Norsk Hydro Co., Ltd.

The oil absorption rate of porous prill nitrate is measured by immersing a certain amount of sample porous prill nitrate in light oil for a certain period of time, performing suction filtration, and calculating the adsorption amount of light oil from the weight difference before and after the test. . Specifically, 50 μm of sample porous prill nitrate is placed in a glass filter (11 G-1) having a diameter of 40 mm and a depth of 50 mm, weighed with a precision plate, and set in a vacuum device. Then, 40 ml of light oil is poured into the glass fill during the evening, and the mixture is thoroughly stirred with a thin rod to achieve mixed contact between porous prill nitrate and light oil. After leaving for 5 minutes, open the external cock attached to the glass filter and let light oil flow naturally for 2 minutes. Then, after aspirating with a vacuum pump for 5 minutes (flow rate: about 311 / min), weigh the glass filter containing the gas oil-adsorbed sample with the porous prill nitrate still in it using a precision plate. Here, the increased amount is the absorbed amount of light oil. After the above measurement, the ratio (%) of the light oil adsorption (g) to 50 g of the original sample porous prill nitrate is indicated as the oil absorption (%). The calculation formula is as shown in the following formula (1).

Oil absorption rate (% by weight) = Gas oil adsorption (g) Sample 50 (g) X 100 (1) The average particle size of porous prill nitrate is as follows. It is measured from the weight distribution of each sieve. The calculation formula is as the following formula (2).

D = ∑ (XX R / 100) (2)

Where D = average particle size (mm)

X = average mesh size of sieve mesh (mm)

R = Residual weight on sieve net (%)

As the porous prill nitrate used in the explosive composition of the present invention, one having a hardness of 0.5 to 25.0% is preferably used.

The hardness of porous prill nitrate is based on a certain amount of porous prill nitrate sample. It is measured by mechanically pulverizing under a certain condition with a hardness measuring device and measuring the amount of pulverization.

The instrument used for the measurement was a sample injection funnel, a flow pipe (inside diameter 16 mm, length 1 75 mm) connected to the compressed air inlet (inside diameter 4 mm, length 55 mm), and those It consists of a sample injection tube (inner diameter 12 mm, length 52 mm) that connects the upper part of the connection part and the funnel vertically, and a sample grinding tube (inner diameter 50 mm, length 3 15 mm) that is connected vertically to the flow tube. ing.

35 100 g of sample nitrate from which powder has been removed with a 5 mesh sieve is dropped from the funnel through the sample injection tube into the flow tube, and the sample is flowed by the compressed air (4 kg / cm ² ) flowing from the inlet hole. The sample nitrate is pulverized by colliding with the inner wall of the milling tube through the tube. The porous prill nitrate sample after the flow is sieved with 35 mesh, the amount (N) of +35 mesh is weighed, and the ratio is expressed as the ratio (%) of the powdered amount to 100 g of the original sample nitrate. . The calculation formula is as the following formula (3).

Hardness (%) = 100 (g) -N (g) (3)

As the nitro compound contained in the explosive composition of the present invention, it acts as a fuel and a sensitizer for the explosive, and can be rapidly adsorbed to porous prill nitrate in liquid form at the time of mixing and can penetrate into the interior of nitrate. Any organic compound having a sensitizing effect can be used. Specific examples of usable nitrogen compounds include aliphatic nitro compounds such as nitromethane and nitropropane, nitrone toluene and dinitrotoluene such as toluene; nitrobenzene such as nitrobenzene and dinitrobenzene, and nitroxylene And nitroxyxenes such as dinitroxylene; and aromatic dinitro compounds such as ditrophenols such as nitrophenol and dinitrophenol. In the present invention, among them, aromatic nitro compounds such as nitrotoluene are preferred. Aromatic nitro compounds include, for example, isomers such as o--, m--, and so on. In the present invention, no matter what kind of compound is used, or two or more kinds are mixed at an arbitrary ratio. Although nitro compounds may be used during the production of explosives, It is preferable that the melting point is usually 80 ° C. or less.

In the present invention, the amount of the nitrile compound is usually in the range of 2.5 to 25.0% by weight, preferably 4.0 to 10.0% by weight of the whole explosive composition. As the thermosetting resin used in the present invention, any substance can be used as long as it can form a water-resistant film on the surface of porous prilled nitrate, and these can be used alone or as a mixture of two or more kinds. . In addition, a polymerizable monomer or a polymerizable oligomer may be added to the raw materials when the explosive composition of the present invention is produced, and polymerized to form a film. The polymerizable monomer or the polymerizable oligomer preferably has a viscosity of 10 to 100 mPa · s (25 V). Further, a resin that forms a crosslinked structure by reacting with a curing agent, such as an epoxy resin, may be used alone in the present invention. However, it is preferable to use a curing agent in combination because a film having high water resistance is generated. When a polymerizable monomer or oligomer is used, or when a thermosetting resin and its curing agent are used in combination, a film is formed when mixed or heated after mixing, except for those that polymerize at room temperature. Let it. In the present invention, it is preferable that the thermosetting resin or its raw material (polymerizable monomer or polymerizable oligomer) and the curing agent in the coating step are liquid and solidify after coating. Further, when a curing agent is used, it is preferable to select a combination that undergoes a curing reaction at room temperature.

Specific examples of the thermosetting resin that can be used include epoxy resins, xylene resins, and vinyl resins described in “Chemical Products of 2014, pp. 101-104, Chemical Daily”. Examples include ester resins, phenol resins, unsaturated polyester resins, polyureas, and amino resins.

In the present invention, among the above, epoxy resins and polyureas are preferred.

Here, as the curing agent, in the case of an epoxy resin or polyurea, polyether, polyester, alcohols, amines, polyhydric phenols, acid anhydride, dalicol, or a mixture thereof is preferably used. Specific examples of preferred epoxy resins include bisphenol-type epoxy resins such as bisphenol A-type epoxy resin and bisphenol F-type epoxy resin, and diglycidylamine type epoxy resins. Preferred examples of the polymerizable monomer or polymerizable oligomer include polyisocyanates. In this case, the curing agent includes amines and diols.

The explosive composition of the present invention is prepared by adding a predetermined amount of a two-mouthed compound and a thermosetting resin or a raw material thereof to porous prill nitrate (if the thermosetting resin is a solid, add it after diluting the solvent). It can be obtained by mixing. At this time, a curing agent may be added or heating may be performed as described above.The thermosetting resin or its raw material is added to a mixture of the nitro compound and porous prill nitrate in advance to form a coating. It is also possible to let them. In the mixing step and the subsequent heating step, other components mainly composed of porous prill nitrate are coated with a thermosetting resin or a cured product thereof.

The amount of the thermosetting resin (including a polymerizable monomer and a polymerizable oligomer) or the cured product of the thermosetting resin in the explosive composition of the present invention is usually 3 to 30% by weight based on the entire explosive composition, Preferably, it is in the range of 5 to 15% by weight. The amount of the thermosetting resin used is approximately determined by the total weight of the thermosetting resin and the curing agent. When a curing agent is used, the amount of the curing agent is usually 1 equivalent or more, preferably 1.1 to 2 equivalents to the thermosetting resin.

An anti-blocking agent may be added to the explosive composition of the present invention. The anti-blocking agent is not particularly limited as long as it is a powder and can prevent the nitro compound and the porous prill nitrate coated with the thermosetting resin from adhering to each other and maintain the fluidity of the explosive composition.

Specific examples of anti-blocking agents that can be used include starches such as wheat starch and corn starch; carbon powders such as carbon black and graphite; metal powders such as aluminum powder and magnesium powder; Fine air particles such as balloons, resin microballoons, and shirasu microballoons; and talc. In the present invention, among the above, carbon powder, aluminum powder and fine hollow particles are preferred. When an anti-blocking agent is used, its amount is usually in the range of 0.05 to 3.00% by weight, preferably 0.1 to 2.0% by weight, based on the whole explosive composition. The addition can be made either at the time of coating the curable resin or before or after the coating.

The explosive composition of the present invention may contain a combustible fuel oil which is liquid at the time of mixing as an auxiliary fuel. For example, mineral oils such as light oil and kerosene, vegetable oils such as soybean oil, rapeseed oil and castor oil, animal oils such as tallow, squalene, alcohols such as methyl alcohol and ethyl alcohol, waxes such as paraffin wax and microcrystalline wax Can be used alone or in combination. Fuel oils with a high melting point can be used by mixing them with porous prill nitrate above the temperature at which it becomes liquid.

The explosive composition of the present invention, _c for example water-soluble can be subjected to measures static prevention and oil-soluble antistatic agent (JP 5 5 5 1 7 94 No., Hei 1 1- 1 47 No. 784, Japanese Patent Application Laid-Open No. 11-287788), and additives such as starches (Japanese Patent Application Laid-Open No. 10-28983) and fatty acid amides. Can be added.

The explosive composition of the present invention is generally prepared by mixing a porous prill ammonium nitrate and a nitro compound, a thermosetting resin or a raw material thereof, and, if necessary, a curing agent for a thermosetting resin in a mixer such as a kneader or a concrete mixer. It is manufactured by stirring and mixing auxiliary fuel and additives.

A preferred composition of the explosive composition of the present invention is as follows: 100 to 100 parts by weight of porous prill nitrate, 1 to 15 parts by weight of a dinitro compound, preferably 3 to 10 parts by weight, a thermosetting resin (polymerizable Monomer or polymerizable oligomer) or its cured product is 5 to 20 parts by weight, preferably 8 to 15 parts by weight. When the anti-blocking agent is used, the preferred amount is 0.1 to 2 parts by weight of the anti-blocking agent per 100 parts by weight of polar sprrill nitrate. Parts.

The explosive composition of the present invention can be used in bulk like a conventional ANFO explosive, has excellent fluidity, and has excellent handleability, and does not remove water present in the perforations and water that enters. Has the characteristic that it can be used. Example

The present invention will be described in more detail with reference to examples, but the present invention is not limited to only these examples. In the examples, “parts” indicates “parts by weight”.

Example 1

A high-speed mixer prepared by heating 82.8 parts of porous prill ammonium nitrate having an oil absorption of about 12.5% by weight, a hardness of 12.0%, and an average particle size of 1.2 mm at 80. O-Nitrotoluene (reagent grade: manufactured by Wako Pure Chemical Industries, Ltd., with a melting point of -9) heated to 80 while stirring at a rate of 300 revolutions per minute in a container. 2 parts, liquid epoxy resin (GAN: diglycidylaniline manufactured by Nippon Kayaku Co., Ltd.) 7.5 parts, and acid anhydride-based curing agent (KAHAARD MCD: Nippon Kayaku Co., Ltd.) 2.5 parts Was added to obtain 100 parts of the explosive composition of the present invention.

Example 2

87.1 parts of the same porous prill nitrate as in Example 1 was placed in a horizontal kneader equipped with a sigma wing heated to 9 O and stirred at a speed of 100 revolutions per minute. : Heated mixture of dinitrotoluene and dinitroxylene (DNT-SC: Nippon Kayaku Co., Ltd., melting point 0 ° C or less) 3. Add 4 parts and add polyisocyanate compound (Millionate MR-400: Nippon Polyurethane Industry Co., Ltd.) 6.0 parts, and modified polyamine (React CA-101: Sanyo Chemical Industry Co., Ltd.) 2.2 parts, and flake aluminum powder (P-0) 100: manufactured by Toyo Aluminum Co., Ltd.) 1. 3 parts were added to obtain 100 parts of the explosive composition of the present invention.

Example 3 Place 79.4 parts of porous prill nitrate having an oil absorption of about 11.4% by weight, a hardness of 4.Ί%, and an average particle size of 2.0 mm in a high-speed mixer container heated to 90, Dinitroxylene (DNX: Nippon Kayaku Co., Ltd., melting point 4-7) heated to 90 with stirring at a speed of 300 revolutions per minute 6. Add 9 parts of polyisocyanate Compound (Millionate MR-200: manufactured by Nippon Polyurethane Industry Co., Ltd.) 8.0 parts, modified polyamine (React CA-101: manufactured by Sanyo Chemical Industries, Ltd.) 2.5 parts, n-hexanol (reagent Grade 1: Hayashi Junyaku Kogyo Co., Ltd.) 3.0 parts and silica microballoon (Filarite 200Z7: Nippon Philite Co., Ltd.) 0.2 parts were added, and the explosive composition of the present invention was added. 100 parts were obtained. The particles of the obtained explosive composition were cleaved, and the cross section thereof was observed with a digital microscope VH-6300 (manufactured by KEYENCE). As a result, it was confirmed that the porous prill ammonium nitrate was coated with polyurea.

Comparative Example 1

Put 94.0 parts of porous prill nitrate having an oil absorption of about 12.0% by weight, a hardness of 5.5%, and an average particle size of 1.2mm in a high-speed mixer container. While stirring at a high speed, 6.0 parts of No. 2 light oil at room temperature was added to obtain 100 parts of a comparative explosive composition. (Explosives described in Japanese Unexamined Patent Publication No. Hei 8-2 559 365)

Evaluation test

(1) Fluidity and water resistance test

300 g of each explosive composition obtained in Examples 1 to 3 and Comparative Example 1 was poured into a transparent acryl tube having a diameter of 50 mm containing water, and the evaluation of fluidity and the evaluation of flooding and floating conditions were performed. The water resistance was evaluated by observation. The results of the water resistance test indicated the weight percentage of the suspended explosive composition in 300 g of the explosive composition.

(2) Bomb speed test 1

Each of the explosive compositions obtained in Examples 1 to 3 and Comparative Example 1 was filled into a steel pipe having an inner diameter of 53 mm in a quantity of 300 g, and 50 g of a water-containing explosive (Altex: Nippon Kayaku) Was detonated in the evening of the booth, and the detonation speed was measured.

(3) Bomb speed test 2

300 g of each explosive composition obtained in Examples 1 to 3 and Comparative Example 1 was poured into a steel pipe having an inner diameter of 53 mm and immersed in water for 1 hour and 4 hours. A 0 g wet explosive (described above) was detonated in the booth at night, and the explosion velocity was measured.

Table 1 shows the results. table 1

From Table 1, the explosive composition of the present invention can be manufactured by the same simple manufacturing process as the explosive of Comparative Example 1, which is a conventional ANF A explosive, has good fluidity, and can be directly poured and charged. It is clear that this is possible. In addition, since the explosive composition of Comparative Example 1 does not have water resistance, porous prill nitrate dissolves instantaneously in water, and No. 2 light oil floats on the water surface. On the other hand, the explosive composition of the present invention obtained in Examples 1 to 3 does not dissolve the porous prill nitrate in a short time even if it is poured into water. It is clear that more than 95% by weight of the entire product does not dissolve or float, and has superior water resistance compared to conventional ANFO explosives. In addition, the explosive performance in a dry state is equal to or higher than that of the conventional ANFO explosive. In contrast, the explosive composition of the present invention maintains sufficient explosive performance even when immersed in water for 4 hours. It is clear that you are. Industrial applicability

The explosive composition of the present invention can be handled in the same manner as conventional ANFO explosives, and can be manufactured in a simple process, and has excellent explosive performance, water resistance, and sufficient explosive performance in water. Things.

Claims

The scope of the claims

1. An explosive composition comprising porous prill ammonium nitrate, a nitro compound and a thermosetting resin.

2. An explosive composition comprising a cured product of porous prill ammonium nitrate, a nitro compound and a thermosetting resin.

3. The explosive composition according to claim 1 or 2, comprising an antiblocking agent.

4. The explosive composition according to any one of claims 1 to 3, wherein the content of the nitro compound with respect to the entire explosive composition is 2.5 to 25% by weight.

5. The explosive composition according to any one of claims 1 to 4, wherein the nitro compound is an aromatic nitro compound.

6. The melting point of the nitro compound is below 80 ° C. The explosive composition according to any one of claims 1 to 5, which is C.

7. A method for producing an explosive composition, comprising mixing porous prill ammonium nitrate and a two-necked compound with at least one selected from the group consisting of a thermosetting resin, a polymerizable monomer, and a polymerizable oligomer.

8. The method for producing an explosive composition according to claim 7, further comprising mixing a curing agent.

9. The method for producing an explosive composition according to claim 7 or 8, further comprising mixing an antiblocking agent.

10. The method for producing an explosive composition according to any one of claims 7 to 9, wherein the mixture is heated after each component is mixed.