AU2017382081A1 - Emulsion explosive composition and preparation method therefor - Google Patents

Emulsion explosive composition and preparation method therefor Download PDF

Info

Publication number
AU2017382081A1
AU2017382081A1 AU2017382081A AU2017382081A AU2017382081A1 AU 2017382081 A1 AU2017382081 A1 AU 2017382081A1 AU 2017382081 A AU2017382081 A AU 2017382081A AU 2017382081 A AU2017382081 A AU 2017382081A AU 2017382081 A1 AU2017382081 A1 AU 2017382081A1
Authority
AU
Australia
Prior art keywords
ammonium nitrate
emulsion
emulsifier
oxidizing agent
aqueous solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
AU2017382081A
Other versions
AU2017382081B2 (en
Inventor
Eung So Lee
Moon Young Lim
Jee Hee Park
Ha Na Woo
Duck Hwan Yun
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hanwha Corp
Original Assignee
Hanwha Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hanwha Corp filed Critical Hanwha Corp
Publication of AU2017382081A1 publication Critical patent/AU2017382081A1/en
Application granted granted Critical
Publication of AU2017382081B2 publication Critical patent/AU2017382081B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
    • C06B31/28—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
    • C06B31/32—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with a nitrated organic compound
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
    • C06B31/28—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
    • C06B31/30—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with vegetable matter; with resin; with rubber
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
    • C06B47/14—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase comprising a solid component and an aqueous phase
    • C06B47/145—Water in oil emulsion type explosives in which a carbonaceous fuel forms the continuous phase
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
    • C06B31/28—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
    • C06B31/285—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with fuel oil, e.g. ANFO-compositions

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Colloid Chemistry (AREA)

Abstract

The present invention provides an emulsion explosive composition and a preparation method therefor, the composition: having a precondition that at least one of an industrial ammonium nitrate, an agricultural ammonium nitrate, and a low-specific gravity ammonium nitrate for an ammonium nitrate fuel oil explosive are used, without separate impurity filtration or removal, as an oxidizing agent aqueous solution constituting the emulsion explosive composition; and comprising, on the basis of the total weight, 85 to 95 wt% of an oxidizing agent aqueous solution, 0.3 to 5 wt% of an emulsifier, and 3 to 10 wt% of oil, wherein the emulsifier comprises an amine salt of polyisobutylene succinic anhydride (PIBSA) salt having an acid value of 30 or less and an amine value of 45 to 65.

Description

EMULSION EXPLOSIVE COMPOSITION AND PREPARATION METHOD THEREFOR
Technical Field [0001] The present invention relates to an emulsion composition for an emulsion explosive, in which stability is ensured when granular ammonium nitrate including an organic or inorganic material is provided in the form of an oxidizing agent aqueous solution using water, without an additional filtration process, and to a method of preparing the same.
Background Art [0002] In bulk emulsion explosives, which are currently used as industrial explosives at mining sites for metals, coal, limestone and the like worldwide, including Korea, an ammonium-nitrate-based oxidizing agent has been utilized. Specifically, an emulsion explosive is produced by preparing a liquid oxidizing agent through the synthesis of nitric acid and ammonia in a plant for manufacturing a liquid oxidizing agent, which is separately constructed. When the liquid oxidizing agent thus synthesized is used, a pure ammonium nitrate oxidizing agent may be obtained, and the prepared emulsion is advantageous because the stability thereof may be ensured for about 3 months or more, as required by the consumer, but investment costs are undesirably increased due to the need to construct a separate plant for producing a liquid oxidizing agent. Therefore, in order to minimize the cost of constructing a plant for producing liquid ammonium nitrate, a method of purchasing and dissolving solid ammonium nitrate has been employed as an alternative, but is problematic because ammonium nitrate, having high purity, is solidified due to chemical properties that facilitate absorption of moisture during storage, and thus a crusher has to be additionally used.
[0003] In order to ensure handling convenience, moreover, granular ammonium nitrate including a solidification inhibitor is produced and sold in the form of, depending on the end use thereof, agricultural ammonium nitrate, porous ammonium nitrate for ammonium nitrate fuel oil explosives, high-specific-gravity ammonium nitrate, etc. However, in order to prepare an emulsion, in the case in which such ammonium nitrate is used in the form of an oxidizing agent aqueous solution by dissolving the same in water, the emulsion cannot be formed or the emulsion stability may deteriorate due to the solidification inhibitor and the additional organic or inorganic material. With the goal of solving these problems, the emulsion is typically prepared using an oxidizing agent aqueous solution resulting from filtering and removing impurities other than the ammonium nitrate, but problems such as the cost of disposal of the removed impurities, the increased risk due to handling of materials at high temperatures, and lowered productivity due to additional processing may occur.
[ 0004 ] Meanwhile, Korean Patent Application Publication No. 10-2005-0074279 discloses a waterproof granular explosive composition (Laid-open date: July 18, 2005), comprising porous ammonium nitrate, a nitro compound and the like, whereby the explosive composition is easy to handle, is easily manufactured, and has sufficient water resistance and explosion performance for a typical immersion time upon practical use, but is difficult to apply to an emulsion explosive composition.
Disclosure
Technical Problem [0005] Accordingly, the present invention has been made keeping in mind the problems encountered in the related art, and an objective of the present invention is to provide an emulsion composition for an emulsion explosive, having high storage stability, in which, in order to exhibit stability effects suitable for use in industrial emulsion explosives, ammonium nitrate including a solidification inhibitor and other organic or inorganic materials, such as agricultural ammonium nitrate, porous ammonium nitrate for an ammonium nitrate fuel oil explosive or high-specific-gravity ammonium nitrate, which is granular ammonium nitrate, is used, without an additional filtration or removal process, in the form of a disperse-phase aqueous solution in a water-in-oil emulsion, together with a polyisobutylene succinic anhydride (PIBSA) amine salt emulsifier having an acid value of 30 or less and an amine value of 45 to 65, and a method of preparing the same.
Technical Solution [0006] The present invention provides an emulsion composition for an explosive, comprising an oxidizing agent aqueous solution including ammonium nitrate; and a fuel solution including an emulsifier and fuel oil, in which the emulsifier includes a PIBSA (polyisobutylene succinic anhydride) amine salt having an acid value of 30 or less and an amine value of 45 to 65.
[0007] In addition, the present invention provides a method of preparing an emulsion composition for an explosive, the method comprising: preparing an oxidizing agent aqueous solution including ammonium nitrate at 50 to 95°C; and preparing an emulsion by emulsifying the oxidizing agent aqueous solution at 50°C to 95° C using a fuel solution including an emulsifier and fuel oil, without removal of impurities other than the ammonium nitrate through additional filtration, in which the emulsifier includes a PIBSA (polyisobutylene succinic anhydride) amine salt having an acid value of 30 or less and an amine value of 45 to 65.
Advantageous Effects [0008] According to the present invention, an emulsion composition for an emulsion explosive can be manufactured at low cost and can exhibit superior stability compared to conventional emulsions for emulsion explosives. In particular, the emulsion composition for an emulsion explosive according to the present invention can manifest superior long-term storage stability and mixing stability, and also, material costs can be desirably reduced by about 12% by virtue of the use of ammonium nitrate including a solidification inhibitor and other organic or inorganic materials, such as agricultural ammonium nitrate, porous ammonium nitrate for an ammonium nitrate fuel oil explosive or high-specific-gravity ammonium nitrate, which is granular ammonium nitrate having a price, on average, of about 80% compared to conventional liquid ammonium nitrate.
Mode for Invention [0009] Hereinafter, a detailed description will be given of the present invention.
[0010] A preferred embodiment of the present invention is specified below with reference to the appended drawings. Before the detailed description of the present invention, it must be noted that the terms and words used in the present specification and claims should not be interpreted as being limited to typical meanings or dictionary definitions. Therefore, the embodiments described in the present specification and the constructions shown in the drawings are merely preferred embodiments of the present invention, and do not represent all of the technical ideas of the present invention, and thus it is to be understood that a variety of equivalents and modifications able to substitute therefor may be provided at the point in time at which the present invention is filed.
[0011] The present invention pertains to an emulsion composition for an emulsion explosive, comprising an oxidizing agent aqueous solution including ammonium nitrate and a fuel solution including an emulsifier and fuel oil, and to a method of preparing the same, in which a significant improvement in stability has been experimentally confirmed when ammonium nitrate including a solidification inhibitor and other organic or inorganic materials, such as agricultural ammonium nitrate, porous ammonium nitrate for an ammonium nitrate fuel oil explosive or high-specific-gravity ammonium nitrate, which is granular ammonium nitrate, is used together with an emulsifier having a specific amine value and acid value, thus culminating in the present invention.
[0012] The ammonium nitrate may include, as granular ammonium nitrate, at least one of agricultural ammonium nitrate, porous ammonium nitrate for an ammonium nitrate fuel oil explosive and high-specific-gravity ammonium nitrate, and an organic or inorganic material.
[0013] The organic or inorganic material may include, for example, a phasetransition inhibitor, a solidification inhibitor, a coating agent, and the like, and is exemplified by at least one of a phase-transition inhibitor, a solidification inhibitor, and a coating agent.
[0014] More specifically, the organic or inorganic material may include at least one selected from among magnesium nitrate, silicate, clay, aluminum sulfate, diatomaceous earth, talc, and an amine salt.
[0015] [0016] Specifically, the emulsion composition for an emulsion explosive according to the present invention includes an oxidizing agent aqueous solution including ammonium nitrate and a fuel solution including an emulsifier and fuel oil, in which the emulsifier includes a PIBSA (polyisobutylene succinic anhydride) amine salt having an acid value of 30 or less and an amine value of 45 to 65.
[0017] [0018] The emulsion composition for an explosive according to the present invention is described in detail below.
[0019] Ammonium nitrate [ 0020 ] The ammonium nitrate used in the oxidizing agent aqueous solution of the emulsion composition for an explosive is ammonium nitrate including a solidification inhibitor and other organic or inorganic materials, such as agricultural ammonium nitrate, porous ammonium nitrate for an ammonium nitrate fuel oil explosive or high-specificgravity ammonium nitrate, which is granular ammonium nitrate.
[0021] The three kinds of ammonium nitrate above are classified based on the following characteristics.
[0022] Agricultural ammonium nitrate is UN No. 2067 Ammonium Nitrate
Fertilizer 5.1, and is configured such that ammonium nitrate contains an inorganic material or a chemical material. Here, 90% or more of ammonium nitrate and 0.2 wt% or less of a combustible material are included.
[0023] Porous ammonium nitrate for an ammonium nitrate fuel oil explosive and high-specific-gravity ammonium nitrate are classified as the same group of UN No. 1942. Specifically, porous ammonium nitrate is configured such that granular ammonium nitrate is formed with pores and thus has a bulk density of less than 0.9 g/cc, and high-specificgravity ammonium nitrate is granular ammonium nitrate having no pores and thus has a bulk density of 0.95 g/cc or more.
[0024] [0025] Oxidizing agent aqueous solution [0026] The oxidizing agent aqueous solution may be composed of an oxidizing agent and water, and the oxidizing agent essentially contains ammonium nitrate. In particular, the ammonium nitrate used in the oxidizing agent aqueous solution of the present invention is preferably ammonium nitrate including a solidification inhibitor and other organic or inorganic materials, such as agricultural ammonium nitrate, porous ammonium nitrate for an ammonium nitrate fuel oil explosive or high-specific-gravity ammonium nitrate, which is granular ammonium nitrate, and more preferably is used without an additional filtration or removal process.
[0027] [0028] The oxidizing agent may further include at least one selected from the group consisting of sodium nitrate and calcium nitrate.
[0029] [ 0030 ] The oxidizing agent aqueous solution preferably includes 75 to 85 wt% of the oxidizing agent and 15 to 25 wt% of water, in order to ensure booster explosiveness. If the amount of water is less than 15 wt%, the power of an explosive may increase, thus making it impossible to realize booster explosiveness, and also, the crystallization temperature of the oxidizing agent aqueous solution is elevated, thus deteriorating the stability of the emulsion. On the other hand, if the amount of water exceeds 25 wt%, the sensitivity of the explosive may decrease, thus lowering explosiveness. Hence, these amounts preferably fall in the above weight ranges in order to attain an explosive having bulk emulsion explosive properties.
[0031] [0032] Fuel solution [ 0033] The fuel solution may include an emulsifier and fuel oil.
[0034] The emulsifier of the present invention mainly includes a PIBSA (polyisobutylene succinic anhydride) amine salt. Here, SMO (sorbitan monooleate) may be used in an amount of 20 wt% or less based on the total weight of the emulsifier.
[0035] In the present invention, to enable the use of ammonium nitrate including a solidification inhibitor and other organic or inorganic materials, such as agricultural ammonium nitrate, porous ammonium nitrate for an ammonium nitrate fuel oil explosive or high-specific-gravity ammonium nitrate, which is granular ammonium nitrate, without an additional filtration or removal process, 100 wt% of a PIBSA (polyisobutylene succinic anhydride) amine salt is preferably used as an emulsifier. For the purpose of sensitizing an emulsion through a chemical reaction or of reducing material costs, SMO (sorbitan monooleate) may be added in a small amount, but is preferably used in an amount of 20 wt% or less based on the total weight of the emulsifier. If the amount of SMO exceeds 20 wt%, storage stability after emulsion preparation may be insufficient and thus the emulsion may break down when mixed with a material such as a sensitizer and an ammonium nitrate fuel oil explosive or during emulsion storage, whereby the oxidizing agent may precipitate and the emulsion may undesirably become nonexplosive.
[0036] Moreover, in the present invention, the PIBSA amine salt emulsifier may be any example thereof having an acid value of 30 or less and an amine value of 45 or more. If the acid value exceeds 30 or if the amine value is less than 45 under the condition that the acid value is 30 or less, the emulsion cannot be formed, or even when the emulsion is formed, the stability thereof may deteriorate, whereby the oxidizing agent undesirably precipitates during storage. Most preferably, a PIBSA amine salt emulsifier having chemical properties of an acid value of 30 or less and an amine value of 45 to 65 is used in the present invention. If these values fall out of the above ranges, the long-term storage stability and mixing stability of the prepared emulsion composition for an explosive may drastically deteriorate, which is undesirable.
[0037] [0038] The fuel oil may be at least one selected from the group consisting of mineral oil and light oil. In an explosive phase, convenience in use and long-term stability may be improved through the use of continuous-phase oil (fuel), which is exposed to the outside and comes into contact with air. Light oil or mineral oil, which is a constituent of the oil, is liquid at room temperature and remains in an appropriate explosive phase when combined at a suitable ratio with the emulsifier, thus providing convenience in use and increasing long-term storage stability.
[0039] [0040] The fuel solution preferably includes, based on the total weight thereof, 2 to 35 wt% of the emulsifier and 65 to 98 wt% of the fuel oil. If the amount of the emulsifier falls out of the above range, the emulsion may not be formed or an explosion may not occur. If the amount of the fuel oil falls out of the above range, the emulsion may not be formed or an explosion may not occur.
[0041] [0042] In the present invention, the oxidizing agent aqueous solution and the fuel solution are mixed together, thus forming an emulsion solution. Here, the emulsion composition preferably includes, based on the total weight thereof, 85 to 95 wt% of the oxidizing agent aqueous solution including the ammonium nitrate and 5 to 15 wt% of the fuel solution including the emulsifier and the fuel oil, which are mixed together. If the amount of the oxidizing agent aqueous solution falls out of the above range, the power of the resulting explosive is high and thus booster explosiveness necessary for a bulk emulsion explosive may not be realized. If the amount thereof is small, an explosion may not occur.
[0043] [0044] The emulsion of the present invention preferably has a bulk density of
1.20 to 1.50 g/cc, which is determined by the weight ratio of ammonium nitrate and water or the weight ratio of potassium nitrate or calcium nitrate that is additionally added.
[0045] [0046] Moreover, when the viscosity of the emulsion is high in manufacturing and blasting fields, problems related to transport or mixing with other materials may occur. Hence, the emulsion preferably has a viscosity of 40,000 or less. To this end, the emulsifier has to be used within the above amount range. If the amount of the emulsifier is high, the viscosity may increase and manufacturing costs may also be increased.
[0047] [0048] In addition, the present invention pertains to a method of preparing an emulsion composition for an explosive, the method comprising: preparing an oxidizing agent aqueous solution including ammonium nitrate without additional filtration or removal of impurities; and preparing an emulsion by emulsifying the oxidizing agent aqueous solution using a fuel solution including an emulsifier and fuel oil.
[0049] In the method of preparing the emulsion composition for an explosive according to the present invention, for the description of the oxidizing agent aqueous solution and the fuel solution, reference may be made to the above description of the emulsion composition for an explosive.
[0050] [0051] Specifically, the method of preparing the emulsion composition for an explosive according to the present invention includes preparing an oxidizing agent aqueous solution including ammonium nitrate at 50°C to 95° C and preparing an emulsion by emulsifying the oxidizing agent aqueous solution at 50°C to 95° C using a fuel solution including an emulsifier and fuel oil, without removal of impurities other than the ammonium nitrate through additional filtration, in which the emulsifier includes a PIBSA (polyisobutylene succinic anhydride) amine salt having an acid value of 30 or less and an amine value of 45 to 65.
[0052] [0053] The emulsifier may further include SMO (sorbitan monooleate), the amount of which is preferably 20 wt% or less based on the total weight of the emulsifier. If the amount of SMO exceeds 20 wt%, storage stability is insufficient after emulsion preparation, and thus the emulsion may break down when mixed with a material such as a sensitizer and ammonium nitrate fuel oil explosive or during emulsion storage, whereby the oxidizing agent may precipitate and the emulsion may undesirably become nonexplosive.
[0054] [0055] A better understanding of the present invention will be given through the following Examples, which are merely set forth to illustrate the present invention but are not to be constmed as limiting the scope of the present invention. The following Examples may be appropriately modified or altered by those skilled in the art within the scope of the present invention.
[0056] [0057] Example 1.
[0058] An emulsion was prepared by emulsifying 93 wt% of an oxidizing agent aqueous solution at 80°C comprising 80 wt% of ammonium nitrate and 20 wt% of water and 7 wt% of a fuel solution at 70° C comprising 71 wt% of light oil and 29 wt% of a PIBSA amine salt emulsifier using an emulsifying machine.
[0059] Here, the PIBSA amine salt emulsifier that was used was an emulsifier having an amine value of 50 and an acid value of 8.
[0060] [0061] Example 2.
[0062] An emulsion was prepared using the composition in the same wt% as in
Example 1. Here, the PIBSA amine salt emulsifier that was used upon emulsion preparation was an emulsifier having an amine value of 63 and an acid value of 24.
[0063] [0064] Example 3.
[0065] An emulsion was prepared by emulsifying 93 wt% of the same oxidizing agent aqueous solution as in Example 1 and 7 wt% of a fuel solution at 70° C comprising 79 wt% of mineral oil and 21 wt% of a PIBSA amine salt emulsifier using an emulsifying machine. Here, the PIBSA amine salt emulsifier that was used was an emulsifier having an amine value of 50 and an acid value of 8.
[0066] [0067] Example 4.
[0068] An emulsion was prepared by emulsifying 93 wt% of the same oxidizing agent aqueous solution as in Example 1 and 7 wt% of a fuel solution at 70° C comprising 79 wt% of mineral oil, 18 wt% of a PIBSA amine salt emulsifier and 3 wt% of an SMO emulsifier using an emulsifying machine. Here, the PIBSA amine salt emulsifier that was used was an emulsifier having an amine value of 50 and an acid value of 8.
[0069] [0070] Example 5.
[0071] An emulsion was prepared by emulsifying 91.5 wt% of an oxidizing agent aqueous solution at 80°C comprising 50 wt% of ammonium nitrate, 30 wt% of calcium nitrate and 20 wt% of water and 8.5 wt% of a fuel solution at 70°C comprising 94 wt% of mineral oil and 6 wt% of a PIBSA amine salt emulsifier using an emulsifying machine.
Here, the PIBSA amine salt emulsifier that was used was an emulsifier having an amine value of 50 and an acid value of 8.
[0072] [0073] Comparative Example 1.
[0074] An emulsion solution was prepared using the composition in the same wt% as in Example 1. Here, the PIBSA amine salt emulsifier that was used for the emulsion solution was an emulsifier having an amine value of 15 and an acid value of 22.
[0075] [0076] Comparative Example 2.
[0077] An emulsion was prepared by emulsifying 93 wt% of the same oxidizing agent aqueous solution as in Example 1 and 7 wt% of a fuel solution at 70° C comprising 79 wt% of mineral oil, 14 wt% of a PIBSA amine salt emulsifier and 7 wt% of an SMO emulsifier using an emulsifying machine. Here, the PIBSA amine salt emulsifier that was used was an emulsifier having an amine value of 50 and an acid value of 8.
[0078] [0079] Comparative Example 3.
[0080] An emulsion solution was prepared using the composition in the same wt% as in Example 5. Here, the PIBSA amine salt emulsifier that was used for the emulsion solution was an emulsifier having an amine value of 15 and an acid value of 22.
[0081] [0082] Comparative Example 4.
[0083] An emulsion was prepared by emulsifying 93 wt% of the same oxidizing agent aqueous solution as in Example 1 and 7 wt% of a fuel solution at 70° C comprising 79 wt% of light oil, 14 wt% of a PIBSA amine salt emulsifier and 7 wt% of an SMO emulsifier using an emulsifying machine. Here, the PIBSA amine salt emulsifier that was used was an emulsifier having an amine value of 15 and an acid value of 22.
[0084] [0085] Test Example 1.
[0086] The properties and stability of the emulsion compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were measured through typical methods in the art. The results are shown in Tables 1 and 2 below.
[0087] [0088] [Table 1]
No. Example 1 Example 2 Example 3 Example 4 Example 5
Oxidizing agent Ammonium nitrate1* Ammonium nitrate Ammonium nitrate Ammonium nitrate Ammonium nitrate Calcium nitrate
PIBSA amine salt emulsifier Amount (%)2) 2 2 1.5 1.25 0.5
Amine value 50 63 50 50 50
Acid value 8 24 8 8 8
SMO emulsifier Amount (wt%)2) - - - 0.25 -
Fuel oil Kind Light oil Light oil Mineral oil Mineral oil Mineral oil
Emulsion long-term storage stability 12 weeks or more 12 weeks or more 12 weeks or more 12 weeks or more 12 weeks or more
Mixing stability 3 weeks or more 3 weeks or more 3 weeks or more 3 weeks or more 3 weeks or more
[0089] ^Kind of ammonium nitrate used [0090] 1. Granular agricultural ammonium nitrate (UN No. 2067) [0091] A. available from SBU Azot, Russia [0092] B. available from Acron, Russia [0093] 2. Granular porous ammonium nitrate for ammonium nitrate fuel oil explosive (UN No. 1942) [0094] A. available from Hubei, China, bulk density of 0.795 g/cc [0095] B. available from Eurochem, Russia, bulk density of 0.709 g/cc [0096] 3. Granular high-specific-gravity ammonium nitrate (UN No. 1942) [0097] A. available from Acron, Russia, bulk density of 1.023 g/cc [0098] ^Emulsifier wt% contained in emulsion composition [0099] [Table 2]
No. Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4
Oxidizing agent Ammonium nitrate1’ Ammonium nitrate Ammonium nitrate Calcium nitrate Ammonium nitrate2’
P1BSA amine salt emulsifier Amount (wt%)3) 2 1.0 0.5 1.0
Amine value 15 50 15 15
Acid value 22 8 22 22
SMO Emulsifier Amount (wt%)3’ - 0.5 - 0.5
Fuel oil Kind Light oil Mineral oil Mineral oil Light oil
Emulsion long-term storage stability Less than 3 weeks Less than 3 weeks Less than 3 weeks 12 weeks or more
Mixing stability Less than 1 week Less than 1 week Less than 1 week 3 weeks or more
[00100] Kind of ammonium nitrate used [00101] 1. Granular agricultural ammonium nitrate (UNNo. 2067) [00102] A. available from SBU Azot, Russia [00103] B. available from Acron, Russia [00104] 2. Granular porous ammonium nitrate for ammonium nitrate fuel oil explosive (UN No. 1942) [00105] A. available from Hubei, China, bulk density of 0.795 g/cc [00106] B. available from Eurochem, Russia, bulk density of 0.709 g/cc [00107] 3. Granular high-specific-gravity ammonium nitrate (UN No. 1942) [00108] A. available from Acron, Russia, bulk density of 1.023 g/cc [00109] ^Liquid ammonium nitrate: pure ammonium nitrate synthesized, Hanwha [00110] ^Emulsifier wt% contained in emulsion composition [00111] [00112] As is apparent from the results of Tables 1 and 2, the long-term storage stability of the emulsion compositions of Examples 1 to 5 of the present invention was 12 weeks or more, which is evaluated to be very high compared to the emulsion compositions of Comparative Examples 1 to 3 (less than 3 weeks), and the mixing stability with a sensitizer and an ammonium nitrate fuel oil explosive was 3 weeks or more, which is evaluated to be notably different from the emulsion compositions of Comparative Examples 1 to 3 (less than 1 week).
[00113] In the emulsion composition of Comparative Example 1, an emulsifying machine was used to realize the desired viscosity of the emulsion, but even when the emulsifying machine was used for a period of time at least 5 times the time of operation of the emulsifying machine in Examples 1 to 5, the viscosity of the emulsion did not reach a desired level, and thus the resulting emulsion was unsuitable for use in bulk emulsion explosives. When the explosive compositions of Comparative Examples 2 and 3 were mixed with a sensitizer and an ammonium nitrate fuel oil explosive, the oxidizing agent in the emulsion was precipitated 2 days after mixing, and thus partial explosion occurred, indicating that the resulting emulsions were unsuitable for use in explosives.
[00114] In the emulsion of Comparative Example 4, using the synthesized ammonium nitrate, even when the PIBSA amine salt emulsifier having a low amine value was used and the SMO emulsifier was used in an amount exceeding 20 wt% based on the total weight of the emulsifier, the emulsion composition exhibited long-term storage stability of 12 weeks or more and mixing stability of 3 weeks or more, which is evaluated to be different from the emulsions using other ammonium nitrates.
[00115] [00116] The bulk density of the emulsion preferably falls in the range of 1.20 to 1.50 g/cc. In the following Examples 6 to 8 and Comparative Examples 4 and 5, the reason why the emulsion having a bulk density of 1.20 to 1.50 g/cc is preferable in the present invention is described in detail.
[00117] [00118] Example 6.
[00119] An emulsion was prepared by emulsifying 93 wt% of an oxidizing agent aqueous solution at 80°C comprising 70 wt% of ammonium nitrate and 30 wt% of water and 7 wt% of a fuel solution at 70° C comprising 71 wt% of light oil and 29 wt% of a PIBSA amine salt emulsifier using an emulsifying machine. Here, the PIBSA amine salt emulsifier that was used was an emulsifier having an amine value of 50 and an acid value of8.
[00120] [00121] Example 7.
[00122] An emulsion was prepared using the composition including an oxidizing agent aqueous solution at 80° C comprising 80 wt% of ammonium nitrate and 20 wt% of water, light oil, and a PIBSA amine salt emulsifier in the same wt% as in Example 1.
Here, the PIBSA amine salt emulsifier that was used upon emulsion preparation was the same emulsifier as in Example 1.
[00123] [00124] Example 8.
[00125] An emulsion was prepared using the composition including an oxidizing agent aqueous solution at 80°C comprising 46 wt% of ammonium nitrate, 38 wt% of calcium nitrate and 16 wt% of water, light oil, and a PIBSA amine salt emulsifier in the same wt% as in Example 1. Here, the PIBSA amine salt emulsifier that was used upon emulsion preparation was the same emulsifier as in Example 1.
[00126] [00127] Comparative Example 4.
[00128] An emulsion was prepared using the composition including an oxidizing agent aqueous solution at 80° C comprising 60 wt% of ammonium nitrate and 40 wt% of water, light oil, and a PIBSA amine salt emulsifier in the same wt% as in Example 1. Here, the PIBSA amine salt emulsifier that was used upon emulsion preparation was the same emulsifier as in Example 1.
[00129] [00130] Comparative Example 5.
[00131] An emulsion was prepared using the composition including an oxidizing agent aqueous solution at 80° C comprising 20 wt% of ammonium nitrate, 70 wt% of calcium nitrate and 10 wt% of water, light oil, and a PIBSA amine salt emulsifier in the same wt% as in Example 1. Here, the PIBSA amine salt emulsifier that was used upon emulsion preparation was the same emulsifier as in Example 1.
[00132] [00133] Test Example 2.
[00134] An emulsion explosive was manufactured by adding the emulsion composition of each of Examples 1 to 5 with 2.0 wt% of hollow glass microspheres (K-15, available from 3M), and the properties and stability thereof were measured through typical methods in the art. The results are shown in Table 3 below.
[00135] [00136] [Table 3]
No. Example 6 Example 7 Example 8 Comparative Example 4 Comparative Example 5
Oxidizing agent Ammonium nitrate1’ Ammonium nitrate1’ Ammonium nitrate1’ Ammonium nitrate1’ Ammonium nitrate1’ Calcium nitrate
Water (wt%)2’ 30 20 16 40 10
Emulsion bulk density (g/cc) 1.20 1.35 1.50 1.10 1.60
Emulsion long-term storage stability 12 weeks or more 12 weeks or more 12 weeks or more 12 weeks or more Less than 5 weeks
Speed of explosion of emulsion explosive3’ (m/sec) 2500 3500 3500 Partial explosion 4000
Explosion heat (kcal/ 1683 2327 2487 1039 1609
[00137] [00138] Kind of ammonium nitrate used [00139] 1. Granular agricultural ammonium nitrate (UNNo. 2067) [00140] A. available from SBU Azot, Russia [00141] B. available from Acron, Russia [00142] 2. Granular porous ammonium nitrate for ammonium nitrate fuel oil explosive (UN No. 1942) [00143] A. available from Hubei, China, bulk density of 0.795 g/cc [00144] B. available from Eurochem, Russia, bulk density of 0.709 g/cc [00145] 3. Granular high-specific-gravity ammonium nitrate (UN No. 1942) [00146] A. available from Acron, Russia, bulk density of 1.023 g/cc [00147] 21Water wt% contained in oxidizing agent aqueous solution [00148] 3)Speed of explosion of explosive, resulting from testing in the state of sealed in a carbon steel pipe having a diameter of 50 mm and a length of 350 mm.
[00149] [00150] As is apparent from the results of Table 3, the long-term storage stability of the emulsion compositions of Examples 6 to 8 of the present invention was 12 weeks or more, which is evaluated to be notably different from the emulsion composition of Comparative Example 5 (less than 5 weeks).
[00151] In the emulsion composition of Comparative Example 4, when the emulsion explosive was manufactured and subjected to an explosion speed test, partial explosion occurred, and the calculated explosion heat energy was very low, and thus the resulting emulsion was unsuitable for use in explosives.
[00152] Based on the test results, in order to prepare an emulsion having a bulk density of less than 1.2 g/cc, when water, having relatively low specific gravity, was used in an increased amount, the resulting emulsion only partially exploded when used as an emulsion explosive. On the other hand, in order to prepare an emulsion having a bulk density exceeding 1.5 g/cc, when ammonium nitrate or calcium nitrate was used in an increased amount as the oxidizing agent, there was a significant difference in stability.
Hence, the bulk density of the emulsion for an emulsion explosive according to the present invention is preferably limited to the range of 1.2 to 1.5 g/cc.
[00153] [00154] According to the present invention, an emulsion composition for an emulsion explosive can be manufactured at low cost and can exhibit superior stability compared to conventional emulsions for emulsion explosives.
[00155] In particular, the emulsion composition for an emulsion explosive according to the present invention is capable of exhibiting superior long-term storage stability and mixing stability and also of reducing material costs by about 12% by virtue of the use of ammonium nitrate including a solidification inhibitor and other organic or inorganic materials, such as agricultural ammonium nitrate, porous ammonium nitrate for an ammonium nitrate fuel oil explosive or high-specific-gravity ammonium nitrate, which is granular ammonium nitrate having a price, on average, of about 80% compared to conventional liquid ammonium nitrate.
[00156] [00157] While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments and that various changes and modifications may be made therein without departing from the spirit of the present invention, and are thus incorporated in the present invention.

Claims (13)

1. An emulsion composition for an explosive, comprising an oxidizing agent aqueous solution including, as granular ammonium nitrate added with an organic or inorganic material including a phase-transition inhibitor, a solidification inhibitor or a coating agent, at least one of agricultural ammonium nitrate, porous ammonium nitrate for an ammonium nitrate fuel oil explosive and high-specific-gravity ammonium nitrate, and a fuel solution including an emulsifier and an oil, wherein the emulsifier includes a PIBSA (polyisobutylene succinic anhydride) amine salt having an acid value of 30 or less and an amine value of 45 to 65.
2. The emulsion composition of claim 1, comprising 85 to 95 wt% of the oxidizing agent aqueous solution, 0.3 to 5 wt% of the emulsifier, and 3 to 10 wt% of the oil, based on a total weight of an emulsion.
3. The emulsion composition of claim 1, wherein the oxidizing agent aqueous solution further includes at least one of potassium nitrate and sodium nitrate.
4. The emulsion composition of claim 1, wherein the emulsifier further includes 20 wt% or less of SMO (sorbitan monooleate) based on a total weight of the emulsifier.
5. The emulsion composition of claim 1, wherein the oil is at least one selected from the group consisting of mineral oil and light oil.
6. The emulsion composition of claim 1, wherein an emulsion has a bulk density of
1.20 to 1.50 g/cc.
7. The emulsion composition of claim 1, wherein the PIBSA amine salt is contained in an amount of 100 wt% or less but exceeding 80 wt% based on a total weight of the emulsifier.
8. The emulsion composition of claim 1, wherein the organic or inorganic material including the phase-transition inhibitor, the solidification inhibitor or the coating agent includes at least one selected from among magnesium nitrate, silicate, clay, aluminum sulfate, diatomaceous earth, talc, and an amine salt.
9. A method of preparing an emulsion composition for an explosive, the method comprising:
preparing an oxidizing agent aqueous solution including ammonium nitrate added with an organic or inorganic material including a phase-transition inhibitor, a solidification inhibitor or a coating agent at 50°C to 95°C; and preparing an emulsion by emulsifying the oxidizing agent aqueous solution at 50°C to 95° C using a fuel solution including an emulsifier and a fuel oil, without an additional filtration or purification process, wherein the emulsifier includes a PIBSA (polyisobutylene succinic anhydride) amine salt having an acid value of 30 or less and an amine value of 45 to 65.
10. The method of claim 9, wherein the emulsion composition has a bulk density of 1.20 to 1.50 g/cc.
11. The method of claim 9, wherein the emulsion composition comprises 85 to 95 wt% of the oxidizing agent aqueous solution, 0.3 to 5 wt% of the emulsifier, and 3 to 10 wt% of the oil, based on a total weight of the emulsion.
12. The method of claim 9, wherein the PIBSA amine salt is contained in an amount of 100 wt% or less but exceeding 80 wt% based on a total weight of the emulsifier.
13. The method of claim 9, wherein the organic or inorganic material including the phase-transition inhibitor, the solidification inhibitor or the coating agent includes at least one selected from among magnesium nitrate, silicate, clay, aluminum sulfate, diatomaceous earth, talc, and an amine salt.
AU2017382081A 2016-12-19 2017-12-13 Emulsion explosive composition and preparation method therefor Active AU2017382081B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR1020160173641A KR101796724B1 (en) 2016-12-19 2016-12-19 Composition of emulsion explosives and manufacturing method therefor
KR10-2016-0173641 2016-12-19
PCT/KR2017/014650 WO2018117531A1 (en) 2016-12-19 2017-12-13 Emulsion explosive composition and preparation method therefor

Publications (2)

Publication Number Publication Date
AU2017382081A1 true AU2017382081A1 (en) 2019-07-04
AU2017382081B2 AU2017382081B2 (en) 2020-01-16

Family

ID=60386330

Family Applications (1)

Application Number Title Priority Date Filing Date
AU2017382081A Active AU2017382081B2 (en) 2016-12-19 2017-12-13 Emulsion explosive composition and preparation method therefor

Country Status (5)

Country Link
US (1) US20200109093A1 (en)
KR (1) KR101796724B1 (en)
AU (1) AU2017382081B2 (en)
CL (1) CL2019001688A1 (en)
WO (1) WO2018117531A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101991239B1 (en) * 2018-02-01 2019-06-20 주식회사 한화 High speed tunnelling method using low density bulk emulsion explosive
CN111704515A (en) * 2020-07-02 2020-09-25 安徽金奥博化工科技有限公司 Integrated composite oil phase for emulsion explosive and preparation method thereof
CN112358372A (en) * 2020-11-27 2021-02-12 山西江阳兴安民爆器材有限公司 Underground on-site mixed emulsion explosive and preparation method thereof
CN112961015A (en) * 2021-03-11 2021-06-15 辽宁红山化工股份有限公司 Low-viscosity low-condensation liquid composite oil phase for emulsion explosive and preparation method thereof
KR102674075B1 (en) * 2021-12-07 2024-06-10 주식회사 한화 Emulsion explosive composition comprising Porous Prilled Ammonium Nitrate

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4475965A (en) * 1983-10-24 1984-10-09 Standard Oil Company (Indiana) Shale oil explosives
US6808573B2 (en) * 2002-09-23 2004-10-26 Dyno Nobel Inc. Emulsion phase having improved stability
JP2007008753A (en) * 2005-06-30 2007-01-18 Nippon Kayaku Co Ltd Explosive composition
KR20070023949A (en) * 2005-08-25 2007-03-02 대림산업 주식회사 Method for producing polybutene for emulsion explosive having high storage stability
KR101272390B1 (en) * 2012-06-15 2013-06-07 주식회사 한화 Composition of low vibration emulsion explosives
KR20170062952A (en) * 2015-11-30 2017-06-08 휴켐스주식회사 Prill or granule type anticaking agent comprising double nitrate salts and method of preventing the caking of Ammonium Nitrate or Fertilizer Thereby

Also Published As

Publication number Publication date
AU2017382081B2 (en) 2020-01-16
US20200109093A1 (en) 2020-04-09
WO2018117531A1 (en) 2018-06-28
CL2019001688A1 (en) 2019-10-04
KR101796724B1 (en) 2017-11-10

Similar Documents

Publication Publication Date Title
AU2017382081B2 (en) Emulsion explosive composition and preparation method therefor
JP7118514B2 (en) Use of compounds as energy materials
US2836484A (en) Aqueous metal powder explosive
US4394198A (en) Water-in-oil emulsion explosive composition
KR20080083664A (en) Compositions comprising ammonium nitrate double salts
CA2636486A1 (en) Stabilized compositions comprising ammonium nitrate
JPH05500795A (en) Dinitramid salt and its manufacturing method
US4764230A (en) Explosive composition
NZ202647A (en) Melt explosive composition containing napthalene sulfonate derivatives
NO125443B (en)
CA1214471A (en) Explosive double salts and preparation
US5675119A (en) Granular ammonium nitrate explosive
EP1292537A1 (en) Process for stabilizing ammonium nitrate
CA1063356A (en) Nitroparaffin explosive composition
KR20210127174A (en) Phase stabilized ammonium nitrate prills and related products and methods
US3306789A (en) Nitric acid explosive composition containing inorganic nitrate oxidizer and nitrated aromatic compound
US5145535A (en) Method for intermolecular explosive with viscosity modifier
US3966516A (en) Slurry explosive composition containing a nitroparaffin and an amide
US3201291A (en) Dispersion-type blasting explosives
US4039361A (en) Dry blasting agents
Gordin ON THE CRYSTALLINE ALKALOID OF CALYCANTHUS GLAUCUS. THIRD PAPER.—ON ISOCALYCANTHINE, ISOMERIC WITH CALYCANTHINE.
US9890090B2 (en) Melt-castable nitramine binders for high energy compositions
RU2701934C1 (en) Explosive composition granomon for breaking of rocks
CH543463A (en) Use of salts as sensitizers in water-containing explosives mixtures
AU2009311605B2 (en) Weakly oxidizing ammonium nitrate composite materials and methods for preparing such compositions

Legal Events

Date Code Title Description
FGA Letters patent sealed or granted (standard patent)