JP2001080985A - Granular hydrous explosive composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a granular explosive which has the ease handling of the granular characteristic of ANFO explosive and the goodness of the reactivity of an emulsion explosive, has excellent water resistance as well and is free from stickiness by specifying a composition consisting of an oxidizing agent, water, desensitizing agent, foaming agent, emulsifying agent and wax. SOLUTION: The composition consisting of 60 to 90 wt.% oxidizing agent, 3 to 8% water, 0 to 20% desensitizing agent, 0 to 10% foaming agent, 1 to 10% emulsifying agent, 3 to 25% wax and 4 to 21% emulsifying agent + wax and has the total of their oxygen balances of -3 to -50 is molded, by which the granular hydrous explosive in a powder, granular or pellet form, of which about >=50% has a major axis of 1 to 5 mm is obtained. The oxidizing agent, of which about 80 to 100% is ammonium nitrate is more preferable. The emulsifying agent, of which about 50 to 100% is a sorbitan fatty acid ester and of which H.L.B. is about 2.5 to 6, is more preferable. Also, the wax is preferably a paraffin having a melting point of 70 to 120 deg.C, or the like, and the desensitizing agent is preferably monomethyl amine nitrate, or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a granular water-containing explosive composition for industrial use and a method for producing the same, and more particularly, to mining industries such as civil engineering construction, crushed stone, mining, coal mining, tunnel excavation, etc .; The present invention relates to a particulate hydrous explosive composition used for cutting, blasting, excavation, and the like in the fields of agriculture and forestry, such as clearing, root removal, and logging; and in the marine field, such as removal of undersea weeds and mud, and a method for producing the same.

[0002]

2. Description of the Related Art ANF is a major granular (solid) explosive.
O explosives are known. ANFO explosives are inexpensive because the raw material is composed of two components, prilled nitrate and light oil. Also, due to the insensitivity of booster detonation, loading into blast holes at the blasting site requires mechanical loading such as an unloader. It is possible.
For this reason, consumption has been attempted not only at quarry sites and limestone sites where there is little problem with gas after blasting, but also at tunnel sites. In recent years, attempts have been made to solidify emulsion explosives and the like in order to improve the drawbacks of ANFO explosives. For example, as disclosed in JP-A-7-223888, a method of forming a granular explosive in which a part of a discontinuous phase containing an oxidant salt is solid-crystallized is disclosed in JP-A-3-122.
No. 085 is known in which a mixture of an explosive mixture or an oxidizing agent such as prill nitrate and a water-in-oil emulsion explosive is molded into a pressurized explosive. Further, a method for producing an emulsion explosive is disclosed in JP-A-59-7899.
As disclosed in Japanese Patent Publication No. 4 (1999) -2004, a high-temperature aqueous solution of an oxidizing agent prepared by heating ammonium nitrate, sodium nitrate and water to about 100 ° C. is mixed with an emulsifier and a wax by about 100%.
About 1000 to 1000 ° C. while gradually adding to the molten mixture.
A method of making a W / O emulsion explosive by high-speed stirring at 2000 rpm is known.

[0003]

SUMMARY OF THE INVENTION However, ANF
O explosives have low reactivity and have poor gas after blasting. For example, if consumed at a site with poor ventilation such as a tunnel, the gas generated after the blasting may impair the health of workers at the blasting site. Occurs. For this reason, when consuming the ANFO explosives at the tunnel site, a large ventilation device that can provide sufficient ventilation is required, which raises the energy cost at the consuming site and the lack of water resistance of the ANFO explosives. In addition to being unusable at the water site, there is a problem to be solved such that it reacts with the blasted concrete on the inner wall of the humid tunnel and generates a large amount of ammonia gas to deteriorate the site environment.

[0004] For this reason, while maintaining the ease of use in granular form like an ANFO explosive, the water resistance and gas after blasting, which are the drawbacks of the ANFO explosive, are improved, and the shape can be loaded with a simple machine such as an unloader. Solid (granular) explosives are being tried but have not been put to practical use. For example,
As disclosed in JP-A-7-223888, a granular explosive partially crystallized in a discontinuous phase containing an oxidizer salt is used for storing the oxidizer salt crystals in the component for about one month after production. Not only does it grow into a large crystal mass gradually, but also the destruction of the emulsion structure itself progresses, and the water resistance gradually deteriorates, making it difficult to maintain practical water resistance. However, there still remains a problem to be solved, such as separation of components and remarkable reduction in explosion performance.
Pressure-formed explosives obtained by press-forming an explosive mixture or a mixture of an oxidizing agent such as prill nitrate and a water-in-oil emulsion explosive as described in Japanese Patent Application Laid-Open No. 3-120285 also provide practical water resistance. Requires a coating on the surface of the explosive, and without coating, there remains an issue to be improved such that practical water resistance cannot be maintained for a long time.

On the other hand, as a fluid explosive that is not solid (granular) but can be loaded into a machine equipped with a mono pump or the like, there is a non-priming detonating emulsion explosive, but it has a high tackiness and is sticky. In addition, there is a problem that it cannot be easily removed by adhering to the loading device or the packaging bag, and a viscous explosive adheres to the clothes and body of the worker, giving off a sticky smell and significantly impeding the working environment. The problem to be improved was left. Regarding the production method of emulsion explosives, since no explosive uses a sensitizer such as nitroglycerin contained in dynamite, if the components are commercialized in a non-uniform state, the performance quality is significantly reduced. For this reason, a great deal of labor has been spent on improving the stirring method and apparatus for uniformly mixing the components. Particularly, high-concentration aqueous solution of oxidizing agent, fuel such as paraffin, and emulsifier are emulsified by high-speed stirring at a high temperature of about 100 ° C. without containing a reaction accelerator (a sharp sensitivity agent) of an oxidizing agent such as monomethylamine nitrate. The performance quality of emulsion explosives manufactured by the method described above significantly varies depending on the stirring method such as the temperature of the medicine during emulsification and mixing, the stirring speed and the quality of the emulsifier. For this reason, there has been a problem that the production cost is high because the production conditions such as the stirring method, the quality of the emulsifier, and the like must be strictly controlled so as not to deviate from an appropriate region.

[0006] Under such circumstances, the present invention provides an ANFO
It is an object of the present invention to provide a granular explosive that is both granular and easy to handle like an explosive and has excellent reactivity of an emulsion explosive, and that is excellent in water resistance and has no stickiness.

[0007]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have made intensive studies and can form particles having a hardness such as ANFO explosive particles, and the granularity is comparable to the reactivity of emulsion explosives. We have completed the hydrous explosive. That is, the present invention is as follows.

(1) Oxidizing agent 60 to 90% by weight, water 3 to 8
% By weight, 0 to 20% by weight of sensitizer, 0 to 10% by weight of foaming agent, 1 to 6% by weight of emulsifier (A), 3 to 1 of wax (B)
5% by weight, and (A) + (B) 4-21% by weight
A particulate hydrous explosive composition comprising:

(2) H. of the emulsifier L. B. is about 2.5
The granular water-containing explosive composition according to the above (1), wherein

(3) The emulsifier is about 50 to 100% by weight of a sorbitan fatty acid ester, and L.
B. Is about 2.5 to 6 (1).
Or the granular water-containing explosive composition according to (2).

(4) The above (1), (2) or (3), wherein the wax has a melting point of 70 to 120 ° C.
The particulate hydrous explosive composition according to the above.

(5) The particulate hydrous explosive composition according to (1), (2), (3) or (4), wherein about 80 to 100% by weight or more of the oxidizing agent is ammonium nitrate.

(6) The above-mentioned (1), (2) or (2), wherein about 50% by weight or more of the water-containing granular explosive composition is a powdery, granular or pellet-like solid having a major axis of 1 to 5 mm.
(3) The granular water-containing explosive composition according to (4) or (5).

(7) The particulate hydrous explosive composition according to the above (1), (2), (3), (4), (5) or (6), wherein the sensitizer is monomethylamine nitrate.

(8) The above (1), (2), wherein the total oxygen balance of the oxidizing agent, the sharpening agent, the water, the wax, the emulsifier, the foaming agent and the like is -3 to -50. (3),
(4) The granular hydrous explosive composition according to (5), (6) or (7).

(9) 60 to 90% by weight of oxidizing agent, 3 to 8 water
% Of high-concentration dissolved salt solution of 0 to 20% by weight of sensitizer, 1 to 6% by weight of emulsifier (A), 3 to 15% by weight of wax (B), 4 to 21% by weight of (A) + (B) A water-containing granular explosive characterized by being added to a liquid mixture of the above, mixed and emulsified, added with a foaming agent in an amount of 0 to 10% by weight, reduced in temperature, and molded into a solid such as a flake, a granular or a powder. A method for producing the composition.

(10) The water-containing granular explosive according to the above (9), wherein one or two kinds selected from a static mixer, ultrasonic irradiation, and a dry fog nozzle are used for mixing and emulsifying the high-concentration dissolved salt solution and the liquid mixing section. A method for producing the composition.

It should be noted that in the present invention, the oxidizing agents 60 to 90 are used.
% Of water, 3 to 8% by weight of water, 0 to 20% by weight of a sensitizer, 0 to 10% by weight of a foaming agent, 1 to 6% by weight of an emulsifier (A), and 3 to 15% by weight of a wax (B) (A) + (B) When the content is 4 to 21% by weight, an emulsified composition (emulsion explosive) showing fluidity immediately after mixing the components is obtained. When the temperature of the drug is lowered, an oxidizing agent such as ammonium nitrate, an emulsifier, a wax, etc., which are main reaction components, are reduced. Not only are solids having properties similar to solid soap excellent in water resistance maintained in a very homogeneously dispersed state, but also the growth of microcrystals of salts contained in the solids is suppressed. Therefore, the performance such as explosiveness is to be preserved for a long time. In particular, if it is less than the above (A) + (B) 4, it is possible to obtain a solid granular hydrous explosive, but crystals such as ammonium nitrate which precipitates with a decrease in the temperature of the chemical after production are enlarged,
Due to loss of homogenization of the components, practical explosion resistance and water resistance cannot be maintained. On the other hand, if (A) + (B) exceeds 21, a practical explosion speed cannot be obtained. Further, H.I. L. B. (Atlas Powder Company method)
Sorbitan fatty acid ester of 5-6 and melting point of 70-1
When the wax at 20 ° C. is used, the quality of the emulsion composition obtained after the production is more stable. Due to the above, the emulsified composition solidifies with a decrease in drug temperature and shows no stickiness similar to a solid soap, and even if crystals are formed in a solid, the precipitated crystals are only refined and preserved. In addition, since fine voids effective for detonation performance are formed in the solid material, an explosive density region that maintains practical explosiveness without necessarily requiring a foaming agent is preserved. Further, in the case of general explosives, if the oxygen balance of the components is set to a large negative value of about minus 40, the explosion velocity is reduced and practical performance is lost. However, the granular water-containing explosive composition of the present invention has an oxygen balance of -3 to- Maintain practical performance in the range of 40%. In order to maintain the explosive property, particularly the explosive property, of the particulate hydrous explosive composition of the present invention, the above-mentioned H.I. L. B. An emulsifier in the range is required, and the H.E. L. B. Is set to about 4 to 5, effective bubbles are kept inside the explosive so that a foaming agent is unnecessary, and extremely stable explosiveness is obtained.

For the production of the particulate hydrous explosive composition of the present invention,
An ultrasonic wave, a static mixer, and a dry fog nozzle are selectively used in addition to the mixer used in the conventional emulsion production. If an ultrasonic wave, a static mixer, or a dry fog nozzle is used when mixing a high-concentration oxidizing agent aqueous solution, wax such as paraffin, and an emulsifier, a granular hydrous explosive composition having better quality and stable performance can be obtained. In particular, in the region where the amount of wax and emulsifier added is large, if ultrasonic waves, static mixers and dry fog nozzles are selected and used, the mechanical stirring by a conventional stirring blade or the like is substantially unnecessary, and the raw materials are not required. Emulsification and mixing can be performed very simply and easily. Further, in the production method of the present invention, the components can be made uniform without rotating the explosive at a high speed with the stirring blade as in the related art, and there is no need to worry about the unexpected situation that the stirring blade or the like comes off during the production, Irradiation of ultrasonic waves to a small amount of liquid contained in an aqueous solution of an oxidizing agent or a liquid fuel dissolves the aqueous solution of the oxidizing agent or the liquid fuel while increasing the temperature, and in a few minutes, Since an explosive exhibiting practical performance can be produced by emulsification, advanced technology and equipment such as a dissolving tank for an oxidizing agent aqueous solution and a fuel, which are indispensable for the conventional production of an emulsion explosive, are reduced or eliminated. Furthermore, by combining a small ultrasonic device, a static mixer, and a dry fog nozzle, it is easy to convert from the batch method used for the conventional hydrous explosive to the small-quantity continuous production method. Furthermore, production at the blasting site is possible because of the simple device.

As the oxidizing agent used in the present invention, those known in the technical field of explosives can be used. For example, ammonium, alkali metal, inorganic acid such as nitric acid, chloric acid, perchloric acid, etc.
It is a salt of an alkaline earth metal or the like, and can be selected alone or in combination. Among them, ammonium nitrate is a good oxidizing agent that is inexpensive and highly reactive.Even though ammonium nitrate alone can provide a practical explosive property, when sodium nitrate or calcium nitrate is used in combination, a stable good primer detonating property is obtained, and potassium nitrate is used. When potassium sulfate or potassium sulfate is used in combination, remarkably improved detonation can be obtained.

The oxidizing agent of the present invention is used in an amount of 60 to 90% by weight based on the total composition. If the content is other than 60 to 90% by weight, the explosive power is reduced, resulting in insufficient rock breakage.

As the sensitizer used in the present invention, those known in the technical field of explosives can be used. For example, water-soluble hydrazine nitrate, aliphatic hydrocarbon amine nitrate having 1 to 3 carbon atoms, ethanolamine nitrate, nitromethane,
One or more kinds selected from finely powdered metal aluminum and the like are used. Preferred are monomethylamine nitrate and hydrazine nitrate. The addition amount of the sensitizer of the present invention is from 0 to 2
0% by weight, a sharpening agent is not necessarily required, but 20% by weight is required to further increase the explosive power and efficiently break rock.
The following are used: If the content is 20% by weight or more, the cost is increased.

The water used in the present invention may be general industrial water. It is more preferable to remove impurities. The amount of water used in the present invention is 3 to 8% by weight based on the total composition. If the content is less than 3% by weight, the production temperature will be high, which will hinder safe production. If the content is more than 8% by weight, it takes a long time to solidify the explosive, which is not practical. Crystals such as ammonium nitrate are enlarged during the curing process, and the homogeneity of the components is lost, and the quality such as explosive property is remarkably deteriorated. Preferably, it is 4 to 6% by weight.

As the wax used in the present invention, those known in the technical field of explosives are used. For example, paraffin, liquid paraffin, petroleum wax containing 30% by weight or more of non-urea-added components, vegetable oil, light oil, coal powder, asphalt,
There are silicone oil, 12-hydroxyl stearic acid and the like, and these can be used alone or in combination. Preferred waxes for the production of explosives of the present invention have a melting point of 70 ° C. to 120 ° C. and do not deteriorate even in a high temperature range. The addition amount of the wax of the present invention is 3 to 15% by weight.
Is used. If the content is less than 3% by weight, the water resistance decreases and unexploited residue increases at the consuming site. If it is 15% by weight or more, the detonation property is reduced. Preferably, it is 7 to 12% by weight.

The emulsifier of the present invention is not particularly limited, and includes all conventionally known emulsifiers for forming a W / O emulsion. For example, sorbitan fatty acid esters, glycerin fatty acid esters, polyoxyalkylene fatty acid esters, oxazoline derivatives, imidazoline derivatives, phosphate esters, alkali or alkaline earth metal salts of fatty acids, primary, secondary and tertiary amines or , Primary, secondary and tertiary amine nitrates or acetates. These emulsifiers are used as one kind or as a mixture of two or more kinds. Preference is given to glycerin fatty acid ester series. L. B. Is 2.5 to 6. The above H. L. Outside the range B, it is difficult to obtain a stable explosive property. More preferably, a glycerin fatty acid ester is used. L. B. Is about 3 to 5.

The addition amount of the emulsifier of the present invention is 1 to 6% by weight. When the content is less than 1% by weight, the shape of the precipitated crystal becomes largely unstable, and when it is more than 6% by weight, the detonation property is reduced.
Preferably it is 2 to 4% by weight.

As the foaming agent of the present invention, known inorganic and organic fine hollow bodies used in conventional slurry explosives and emulsion explosives are used. For example, inorganic micro hollow bodies include pearlite, shirasu balloon, glass micro balloon, and the like. Organic micro hollow bodies include thermoplastic vinylidene chloride-acrylonitrile copolymer, methyl methacrylate-acrylonitrile copolymer, and the like. Fine particles containing low-boiling hydrocarbons are foamed. The shape and particle size of the foaming agent used in the present invention are not particularly limited. However, if the surface of the sphere becomes rough or the diameter increases, the crystal growth of the high-concentration oxidizing agent aqueous solution is promoted, and the performance with time is hindered. Preferably, the surface is easily wetted by water or smooth. The preferred particle size is 1000 microns or less, and more preferably 100 microns or less is 50% by weight or more.

The amount of the foaming agent of the present invention is 0 to 10% by weight.
Is used. The effective air bubbles necessary for detonation are formed in the micro-voids and the voids between the explosive particles formed inside the granular hydro-explosive explosive of the present invention, so that the foaming agent is not necessarily required, but in order to further stabilize the performance, 10% by weight or less is required. If it exceeds 10% by weight, the explosive power decreases.

As other components, as required, gilsonite, tire powder, sulfur, aluminum powder, flour, sucrose, molasses, glucose, fructose, lactic acid, sodium lactate, gluconic acid, glycine, citric acid, stearic acid, saccharin sodium Thiourea, urea, resin fine particles and the like may be used.

Examples of the preparation of the water-containing explosive composition of the present invention include: 76% by weight of ammonium nitrate, 10% by weight of sodium nitrate and 5% by weight of water.
A container for storing a transparent high-concentration oxidant aqueous solution is prepared by heating a container for storing the weight%. Next, while adding the above-mentioned high-concentration oxidizing agent aqueous solution into a storage container of wax or the like which is heated and adjusted to 7% by weight of wax and 3% by weight of emulsifier, ultrasonic waves of about 20 KHZ are applied to the mixed solution of both. Upon irradiation, the emulsion floats in about 2 to 3 minutes and forms emulsion seeds. After the seeds of the emulsion are formed, it may be subjected to ultrasonic irradiation as it is to form the emulsion composition and then granulated, but after low-speed stirring with a simple three-one mixer or the like, the emulsion composition is obtained. Granular molding may be used. In addition, the above-mentioned emulsified composition may optionally contain a foaming agent 2-3.
% By weight and then molded into a sheet or pellet to obtain a granular hydrous explosive composition, 66% by weight of ammonium nitrate, 12% by weight of sodium nitrate and 73% by weight
A container containing a 10% by weight aqueous monomethylamine nitrate solution is heated to prepare a container containing a transparent high-concentration oxidizing agent aqueous solution. Next, while adding the above-mentioned high-concentration oxidizing agent aqueous solution into a container of wax or the like which is heated and adjusted to 9% by weight of the wax and 3% by weight of the emulsifier, ultrasonic waves of about 20 KHZ are applied to the mixed solution of both. Upon irradiation, the emulsion floats in about 2 to 3 minutes and forms emulsion seeds. After the seeds of the emulsion are formed, the emulsion may be continuously irradiated with ultrasonic waves to form an emulsified composition, or may be stirred at a low speed with a simple three-one mixer or the like to form an emulsified composition.
A method in which the above-mentioned emulsified composition is formed into a sheet, allowed to cool, solidified, and then molded to obtain a particulate hydrous explosive composition, 75% by weight of ammonium nitrate, 10% by weight of sodium nitrate and 5% by weight of water
A container for storing a transparent high-concentration oxidant aqueous solution is prepared by heating a container for storing the weight%. Then, while adding 7% by weight of the wax and 3% by weight of the emulsifier to a storage container of a wax or the like which is made into a liquid by heating and adjusting, the mixed solution of both is mixed by a static mixer while adding the high-concentration oxidizing agent aqueous solution. After emulsifying to obtain an emulsified composition, a method for obtaining a granulated water-containing explosive composition by granulation in the process of standing and cooling to solidify, 73% by weight of ammonium nitrate, 10% by weight of sodium nitrate and 5% by weight of water
A container containing a transparent high-concentration oxidizing agent aqueous solution is prepared by heating a container containing a weight% of wax, and a container containing liquid wax and the like is prepared by heating 9% by weight of a wax and 3% by weight of an emulsifier. . Then, the high-concentration oxidizing agent aqueous solution is sprayed from one nozzle of a dry fog nozzle (manufactured by Mizokeike Co., Ltd.), and the liquid wax is sprayed from the other nozzle to form an emulsified composition. And a method in which the emulsified composition is formed into a sheet or a granule during the cooling and solidification process to obtain a granulated hydrous explosive composition.

The particulate hydrous explosive composition obtained by any of the methods exhibits liquid flow when the temperature of the drug is high immediately after production, but becomes non-fluid as the temperature of the drug decreases, and gradually solidifies. Therefore, it can be molded into a desired shape after curing at the stage of curing as the drug temperature decreases or after curing and solidification. A more efficient and stable molding method is to form a thin plate while hardening while leaving it to cool, leaving it thinly on a belt conveyor at the time of maintaining the plasticity that has not completely solidified and the curing is progressing. This is a method of molding into powder, granule, pellet, or the like.

[0032]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to examples. In addition, the measurement of water resistance, explosion velocity, stickiness, etc. was performed by the following method.

(Measurement of Water Resistance) A container (JI) having about 100 g of a sample provided with 18 openings (opening diameter 3 mm) on the outer periphery thereof was provided.
(SG3452 steel pipe 32A, pipe length 150 mm), and after closing the openings at both ends of the container, the container is allowed to stand still at the bottom of the bucket. Next, tap water is continuously injected into the bucket at a flow rate of 2 liters / minute, and the container with the sample is collected 7 hours after the start of the injection. The collection container was detonated with a No. 6 detonator to which 10 g of a booster 2 was attached.

(Measurement of explosion velocity) About 300 to 400 g of a sample was weighed using a JIS G3452 steel pipe (inner diameter 35.7 mm, pipe length 350
mm) and detonated with a No. 6 detonator to which 30 g of Booster 2 Enoki Dynamite was bound, and was set up by the Pharmacopoeia Standard ES-41.
The explosion velocity at room temperature was measured by the method of (2) and displayed as an explosion velocity value.

(Measurement of Stickiness) Five measurers measured the stickiness while taking the sample with their hands and extending them with their fingers. The results were recorded as を for no stickiness, Δ for small stickiness, and x for large stickiness. In addition, the stickiness was defined as a practical lower limit.

Example 1 Wax (trade name, manufactured by Nippon Seiwa; Hi-Hic2095)
7% by weight, emulsifier (trade name, manufactured by Kao; Reodol AO-1)
0, HLB; about 4.5) Transparent 3% by weight of a fuel component obtained by dissolving and mixing 3% by weight of 75% by weight of nitric acid (manufactured by Mitsubishi Chemical), 10% by weight of sodium nitrate (manufactured by Mitsubishi Chemical), and 5% by weight of water (industrial water). An ultrasonic homogenizer (ULTRASONIC GENERA) was placed below the liquid surface of the mixed solution to which the aqueous oxidizing agent solution was added.
TOR MODEL-US; manufactured by Nippon Seiki Seisakusho), and the homogenizer was operated at about 400 μA for about 3 minutes to produce an emulsified composition having a specific gravity of 1.28 at a production temperature of about 120 ° C., followed by Teflon. It was spread thinly on a sheet and molded to obtain a particulate hydrous explosive composition of the present invention in which particles of about 2 mm occupy the majority. Three days and one year later, the water resistance, explosion velocity, and stickiness were measured.
And Table 2.

Example 2 Wax (trade name, manufactured by Nippon Seiwa; Hi-Hic2095)
9% by weight, emulsifier (trade name, manufactured by Kao; Reodol AO-1)
0, HLB; about 4.5) 83% by weight of nitric acid (Mitsubishi Chemical), water (industrial water) 5
An ultrasonic homogenizer (ULTRASONIC GE) was placed under the liquid surface of a mixed solution to which a transparent aqueous solution of oxidizing agent of weight% was added.
Insert the tip end of NERATOR MODEL-US (manufactured by Nippon Seiki Seisaku-sho) into the
After operating at about 400 μA for about 1 minute to produce an emulsified composition having a specific gravity of 1.23 at a production temperature of about 120 ° C., it is spread thinly on a Teflon sheet and molded to form a particulate hydrous composition of the present invention in which particles of about 2 mm occupy the majority. An explosive composition was obtained. Three days and one year later, the water resistance, explosion velocity and stickiness were measured, and the results are shown in Tables 1 and 2.

Example 3 Wax (trade name, manufactured by Nippon Seiwa; Hi-Hic1045)
8% by weight, emulsifier (trade name, manufactured by Kao; Exel 300, H
LB: Approximately 2.8) 4% by weight of a fuel component mixed with 65% by weight of nitric acid (Mitsubishi Chemical), 8% by weight of sodium nitrate (Mitsubishi Chemical), 73% monomethylamine nitrate aqueous solution 1
While adding a transparent mixed aqueous solution of 5% by weight, an ultrasonic homogenizer (ULTRASONIC GENERATO) was used.
R MODEDEL-US; manufactured by Nippon Seiki Seisakusho) is inserted under the liquid surface of the mixed solution, and the homogenizer is operated at about 400 μA for about 5 minutes, and the production temperature is about 11 μm.
The emulsified composition having a specific gravity of 1.25 at 0 ° C. was thinly spread on a Teflon sheet, and then allowed to cool, followed by molding to obtain a particulate hydrous explosive composition of the present invention having a particle diameter of about 2 mm. . Three days and one year later, the water resistance, explosion velocity, and stickiness were measured, and the results are shown in Tables 1 and 2.

Example 4 Wax (trade name, manufactured by Nippon Seisaku; Hi-Hic2095)
9% by weight, emulsifier (trade name, manufactured by Kao; Reodol AO-1)
0, HLB; about 4.5) 3% by weight of a fuel component dissolved and mixed, 83% by weight of nitric acid (manufactured by Mitsubishi Kasei), 5% of water (industrial water)
% By weight and mixed and emulsified with a static mixer (manufactured by Noritake: Box blender) to obtain an emulsified composition having a specific gravity of 1.25 at a production temperature of about 120 ° C., and then thinly spread on a Teflon sheet. To obtain a particulate hydrous explosive composition of the present invention in which particles of about 2 mm occupy the majority. 3 days later and 1 year later,
The stickiness was measured, and the results are shown in Tables 1 and 2.

Example 5 Wax (trade name, manufactured by Nippon Seisaku; Hi-Hic2095)
9% by weight, emulsifier (trade name, manufactured by Kao; Reodol AO-1)
0, HLB; about 4.5) 3% by weight of a fuel component dissolved and mixed, 83% by weight of nitric acid (manufactured by Mitsubishi Kasei), 5% of water (industrial water)
% By weight of a transparent mixed aqueous solution was prepared in a separate container, and was passed through a dry fog nozzle (manufactured by Ikeuchi of Mist).
Each of the high-temperature liquids is spray-particled, spray-mixed and emulsified to produce an emulsified composition having a specific gravity of 1.15 at a production temperature of about 120 ° C., and then molded to form a particulate hydrous explosive of the present invention in which particles of about 2 mm occupy the majority. A composition was obtained. Three days and one year later, the water resistance, explosion velocity, and stickiness were measured, and the results were shown in Tables 1 and 2.
It was shown to.

Example 6 Wax (trade name, manufactured by Nippon Seisaku; Hi-Hic2095)
11% by weight, emulsifier (trade name, manufactured by Kao; Reodol AS-
10, HLB; about 4.7) Prepare a fuel container in which 4% by weight is dissolved and mixed. Next, an ultrasonic homogenizer (ULTRASONIC GENER) was placed on the liquid surface of the container.
After setting the tip of ATOR MODEL-US (manufactured by Nippon Seiki Seisakusho), the homogenizer was started to operate at about 400 μA, and 70% by weight of separately prepared nitrate ammonium (manufactured by Mitsubishi Chemical) and sodium nitrate (Mitsubishi Chemical) A transparent oxidizing agent solution of 10% by weight and 5% by weight of water (industrial water) is gradually added to the above-mentioned fuel container, and the tip of the tip is adjusted to maintain about 10 mm below the liquid level in the container. While operating for about 5 minutes, the production temperature is about 120 ° C
To obtain an emulsified composition having a specific gravity of 1.20. Then, it was thinly spread on a Teflon sheet and molded to obtain a granular hydro-explosive composition of the present invention in which particles of about 2 mm occupy the majority. Part 3
The water resistance, explosion velocity and stickiness after one day and one year were measured, and the results are shown in Tables 1 and 2.

Example 7 Wax (trade name, manufactured by Nippon Seiwa; Hi-Hic1045)
14% by weight, emulsifier (trade name, manufactured by Kao; Exel 300,
HLB; about 2.8) 4% by weight of a fuel component mixed and dissolved in 4% by weight of a transparent component of 60% by weight of nitrate (manufactured by Mitsubishi Kasei), 5% by weight of sodium nitrate (manufactured by Mitsubishi Kasei), and 15% by weight of a 73% aqueous solution of monomethylamine nitrate. While adding the mixed aqueous solution, use an ultrasonic homogenizer (ULTRASONIC GENERAT).
OR MODEL-US (manufactured by Nippon Seiki Seisakusho)) was inserted under the liquid surface of the mixed solution, and the homogenizer was operated at about 400 μA for about 5 minutes to obtain a production temperature of about 1 μm.
At 30 ° C., an emulsified composition having a specific gravity of 1.38 was prepared. A foaming agent (manufactured by Ichi Kasei; SMB4011) (2% by weight) was mixed with the emulsified composition, spread thinly on a Teflon sheet, allowed to cool, and then molded. A particulate hydrous explosive composition of the present invention having a particle size of about 2 mm was obtained. Three days and one year later, the water resistance, explosion velocity, and stickiness were measured, and the results are shown in Tables 1 and 2.

Comparative Example 1 Wax (trade name, manufactured by Nippon Seiwa; Hi-Hic1045)
12% by weight, emulsifier (trade name, manufactured by Kao; Exel 300,
HLB; about 2.8) An ultrasonic homogenizer (ULTRASONIC GEN) is added to a fuel component in which 8% by weight is dissolved and mixed.
ERATORMODEL-US; Nippon Seiki Seisakusho)
Of the fuel component, 62% by weight of nitric acid (manufactured by Mitsubishi Kasei), 10% by weight of sodium nitrate (manufactured by Mitsubishi Kasei), and 8% by weight of water while the homogenizer is operated at about 400 μA. % By weight of a transparent oxidizing agent aqueous solution was added little by little, and the homogenizer was operated for about 5 minutes to obtain an emulsion composition having a specific gravity of 1.40 at a production temperature of about 115 ° C., and then allowed to cool to obtain a particle size of about 2 mm. A particulate hydro-explosive composition comprising mostly particles was obtained. 3 days later and 1
After one year, the water resistance, explosion velocity and stickiness were measured, and the results are shown in Tables 1 and 2.

Comparative Example 2 Wax (trade name, manufactured by Nippon Seiwa; Hi-Hic2095)
9% by weight, emulsifier (trade name, manufactured by Kao; Reodol AO-1)
0, HLB; about 4.5) Transparent 3% by weight of a fuel component in which 3% by weight is dissolved and mixed, and 69% by weight of ammonium nitrate (manufactured by Mitsubishi Chemical), 10% by weight of sodium nitrate (manufactured by Mitsubishi Chemical), and 9% by weight of water (industrial water) An ultrasonic homogenizer (ULTRASONIC GENERA) was placed below the liquid surface of the mixed solution to which the aqueous oxidizing agent solution was added.
TOR MODEL-US; manufactured by Nippon Seiki Seisakusho), and the homogenizer was operated at about 400 μA for about 3 minutes to produce an emulsified composition having a specific gravity of 1.38 at a production temperature of about 110 ° C., followed by Teflon. It was thinly spread on a sheet and molded to obtain a granular hydrous explosive composition in which particles of about 2 mm occupy the majority. Three days and one year later, the water resistance, explosion velocity, and stickiness were measured, and the results were shown in Tables 1 and 2.
It was shown to.

Comparative Example 3 Solid paraffin (trade name, manufactured by Wako Pure Chemical Industries; paraffin) 4.
5% by weight, 0.5% by weight of liquid paraffin (trade name, manufactured by Ishizu Pharmaceutical Co., Ltd., liquid paraffin reagent grade 1), and 2% by weight of an emulsifier (trade name, manufactured by Kao; Exel 300, HLB; about 2.8) Under the liquid level of the components, a homogenizer (BI
O Mixera BM type (manufactured by Nippon Seiki Seisakusho), while operating at about 500 to 1000 rpm by inserting the tip of a gourin cell, 65% by weight of nitric acid (manufactured by Mitsubishi Kasei), 10% by weight of sodium nitrate (manufactured by Mitsubishi Chemical), water (industrial water) ) 15
% By weight of a transparent oxidizing agent aqueous solution was added little by little, and after stirring for about 10 minutes, 3% by weight of a foaming agent (manufactured by 3M; glass microballoon) was mixed to form an emulsified composition, and then a polyethylene bag And stored as an emulsion explosive composition. Three days and one year later, the water resistance, explosion velocity and stickiness were measured, and the results are shown in Tables 1 and 2.

Comparative Example 4 Wax (trade name, manufactured by Nippon Seiwa; Hi-Hic2095)
7% by weight, emulsifier (trade name, manufactured by Kao; Emulgen 404,
HLB; about 8) A homogenizer (BIO MIXERABM type;
Nippon Seiki Seisakusho Co., Ltd.) with the tip of the gourin cell set and operated at about 500-1000 rpm, 70% by weight of nitric acid (Mitsubishi Kasei), sodium nitrate (Mitsubishi Kasei) 1
A transparent oxidizing agent aqueous solution of 2% by weight and 5% by weight of water (industrial water) was added little by little, and the mixture was stirred for about 10 minutes from the completion of the addition, and then a foaming agent (manufactured by 3M; glass microballoon) 3
After mixing by weight, the mixture was stored in a polyethylene bag to obtain a water-containing explosive composition. Three days and one year later, the water resistance, explosion velocity and stickiness were measured, and the results are shown in Tables 1 and 2.

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[Table 1]

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[Table 2]

[0049]

EFFECTS OF THE INVENTION The granular water-containing explosive composition of the present invention and the method for producing the same improve the water-resistant and explosive properties, which are disadvantages of the conventional granular explosives, and improve the stickiness of emulsion explosives, and can be easily loaded into a machine. By making it possible to mold into a shape, safety at the time of blasting at the consumption site, handleability of explosives, and charging efficiency have been greatly improved. The use of ultrasonic, static mixers and dry fog nozzles in the manufacturing process has enabled the safety and efficiency of dangerous explosive manufacturing operations.

Claims (10)

[Claims] 1. An oxidizing agent of 60 to 90% by weight, water of 3 to 8% by weight, a sensitizing agent of 0 to 20% by weight, a foaming agent of 0 to 10% by weight, an emulsifier (A) of 1 to 6% by weight, a wax (B) 3.) A particulate hydrous explosive composition comprising 3 to 15% by weight and (A) + (B) 4 to 21% by weight. 2. The emulsifier of Hydrophile-Li
popile-Balance (hereinafter referred to as HLB
Is about 2.5-6. 3. The method according to claim 1, wherein the emulsifier is about 50 to 100% by weight of a sorbitan fatty acid ester. L. B. Is about 2.5-6.
The particulate hydrous explosive composition according to the above. 4. The granular water-containing explosive composition according to claim 1, wherein the wax has a melting point of 70 to 120 ° C. 5. The method of claim 1, wherein at least about 80-100% by weight of said oxidizing agent is ammonium nitrate.
5. The granular water-containing explosive composition according to 2, 3 or 4. 6. The powdery, granular, or pellet-like solid having a major axis of 1 to 5 mm in a proportion of about 50% by weight or more of the water-containing granular explosive composition. 5
The particulate hydrous explosive composition according to the above. 7. The granular water-containing explosive composition according to claim 1, wherein the sensitizer is monomethylamine nitrate. 8. The total oxygen balance of the oxidizing agent, the sensitizing agent, the water, the wax, the emulsifier, the foaming agent and the like is-
The granular hydrous explosive composition according to claim 1, 2, 3, 4, 5, 6, or 7, which has a molecular weight of 3 to -50. 9. A high concentration dissolved salt solution containing 60 to 90% by weight of an oxidizing agent, 3 to 8% by weight of water, and 0 to 20% by weight of a sensitizing agent, 1 to 6% by weight of an emulsifier (A), and a wax (B) 3 ~ 18% by weight,
(A) + (B) Add to a liquid mixture of 4 to 21% by weight, mix and emulsify, add 0 to 10% by weight of a foaming agent, lower the temperature of the medicine, and reduce the temperature of the solid to form flakes, granules or powder. A method for producing a granular hydrous explosive composition, characterized in that the composition is molded into a powder. 10. The water-containing granular explosive composition according to claim 10, wherein the emulsification of the high-concentration dissolved salt solution and the liquid mixing section is performed by using one or two selected from a static mixer, ultrasonic irradiation, and a dry fog nozzle. Manufacturing method.