WO2023155354A1 - Safe and efficient high-energy expanding agent, and preparation method therefor and use thereof - Google Patents

Safe and efficient high-energy expanding agent, and preparation method therefor and use thereof Download PDF

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Publication number
WO2023155354A1
WO2023155354A1 PCT/CN2022/100596 CN2022100596W WO2023155354A1 WO 2023155354 A1 WO2023155354 A1 WO 2023155354A1 CN 2022100596 W CN2022100596 W CN 2022100596W WO 2023155354 A1 WO2023155354 A1 WO 2023155354A1
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powder
expansion agent
energy
safe
energy expansion
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PCT/CN2022/100596
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French (fr)
Chinese (zh)
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张延松
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张延松
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
    • C06B33/08—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide with a nitrated organic compound
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/001—Fillers, gelling and thickening agents (e.g. fibres), absorbents for nitroglycerine
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/009—Wetting agents, hydrophobing agents, dehydrating agents, antistatic additives, viscosity improvers, antiagglomerating agents, grinding agents and other additives for working up
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the invention relates to the technical field of coal rock pre-splitting, in particular to a safe and efficient high-energy expansion agent and its preparation method and application.
  • pre-splitting agents or expansion agents to carry out pre-cracking of coal rocks in the prior art, but there are the following problems: as in the coal rock pre-splitting agent in CN110981660A, metal powder is not used, and the release energy is limited, which is only applicable to Coal rock with a low hardness coefficient, such as coal rock with a hardness coefficient in the range of 3 to 6; but if metal powder is directly used in the pre-cracking agent, the safety cannot be guaranteed. Therefore, the existing coal and rock pre-splitting technology has certain limitations, and a new coal and rock pre-splitting technology is still needed to achieve efficient pre-splitting of rocks and coal seams.
  • the present invention provides a safe and efficient high-energy expansion agent, which does not explode in an open space, and only in a closed space will it turn from combustion to detonation due to the generation of a large amount of high-temperature and high-pressure gas. It has dual functions of pre-splitting and detonation
  • the impact range of the fracture pore network in the coal and rock mass is 10-15 times that of the fracture pores formed by traditional industrial explosive blasting and pre-cracking agent fracturing.
  • Metal or non-metal powder 5% ⁇ 15%
  • Organic powder 10% ⁇ 20%
  • High nitrogen energetic material 10% ⁇ 25%
  • Oxidant 40% ⁇ 75%
  • Adhesive 1.5% ⁇ 3%
  • Plasticizer 1.0 ⁇ 2.0%
  • the metal powder is at least one of aluminum powder, titanium powder, and aluminum-magnesium alloy powder, the non-metallic powder is silicon powder; the organic powder is guanidine nitrate; and the high-nitrogen energetic material is LLM-105.
  • the metal powder or non-metallic powder can increase the burning rate and energy of the high-energy expansion agent, and is the main combustion agent; the organic powder guanidine nitrate is also used as a combustion agent, and its gas production is relatively large during the combustion process. Can increase the pressure in the closed space; the high nitrogen energetic material LLM-105, its chemical name is 2,6-diamino-3,5-dinitro-1-oxypyrazine, which has good high temperature resistance and insensitivity It has stable performance and certain deflagration properties.
  • LLM-105 can generate a large amount of inert nitrogen during combustion and detonation, which can not only improve the safety of natural gas and other mining processes, but also has a low viscosity coefficient of nitrogen at high temperatures. It can better expand in coal cracks and pores, and stabilize the quasi-static force of high-temperature and high-pressure gas, which can evenly and effectively break rocks.
  • the above-mentioned metal powder or non-metal powder and organic powder can act synergistically with the speed control agent to increase the pressure index and combustion speed, which can make the high-energy expansion agent burn quickly to produce a large amount of high-temperature and high-pressure gas, and improve the performance of the expansion agent.
  • Force, and then make coal rock fissures expand, and high-nitrogen energetic materials have insensitivity, which can reduce the sensitivity of the agent and reduce the burning rate of the agent, but its insensitivity can ensure the safety during use.
  • the mass ratio of the oxidant to the high-energy nitrogen-containing material is 2-5.5:1.
  • the burning rate of the expansion agent can be further adjusted. If the proportion of the material is too small, the burning rate of the expander will be greatly reduced, resulting in insufficient work ability.
  • the particle size d 50 of the metal or non-metal powder is ⁇ 200 ⁇ m; the particle size d 50 of the organic powder is ⁇ 200 ⁇ m; the particle size d 50 of the high-energy nitrogen-containing material is ⁇ 200 ⁇ m.
  • the oxidant is at least one of potassium perchlorate and potassium nitrate, and its particle size d 50 is ⁇ 200 ⁇ m.
  • the rate control agent is at least one of copper chromite and tert-butylferrocene.
  • the adhesive is at least one of ⁇ -aminopropyltriethoxysilane and polyvinyl butyral.
  • the plasticizer is at least one of 1,2,4-butanetriol phenol trinitrate and 1,1,1-triazidemethylethane.
  • the above-mentioned adhesive and plasticizer have good cohesiveness and high thermal effect, and are suitable for the high-energy expansion agent of the present invention.
  • the present invention also provides a method for preparing a safe and efficient high-energy expansion agent, comprising the following steps:
  • metal powder or non-metal powder and organic powder, high-nitrogen energetic material, oxidant, speed control agent, adhesive, and plasticizer into the mixer for processing Mix, mix evenly and discharge to obtain high-energy expansion agent; or first put metal powder or non-metal powder and organic powder, high-nitrogen energy-containing material, speed control agent, adhesive, plasticizer into the mixer Mix evenly, then add an oxidizing agent to mix, mix evenly, and then discharge to obtain a high-energy expansion agent.
  • the invention also provides the application of a safe and efficient high-energy expansion agent in coal and rock mining, natural gas mining, oil mining or mining roadway excavation, subway construction, and tunnel construction.
  • the high-energy expansion agent needs to be placed in a closed space during application and ignited by an igniter.
  • the high-energy expansion agent generates a large amount of high-temperature and high-pressure gas during the combustion process, driving the surrounding initial cracks to expand. After pressure, the high-energy expansion agent quickly turns from combustion to detonation, and the high-temperature and high-pressure gas generated during the detonation process breaks the rock and further expands the crack;
  • the main components of the high-temperature and high-pressure gas produced during combustion and detonation are 40-55% water vapor, 30-35% nitrogen, and 15%-20% carbon dioxide.
  • the high-energy expansion agent provided by the present invention is different from the energy release mode of explosives.
  • the release mode of explosives is instant detonation, and the action time is microsecond level.
  • the energy release is too fast and the effect is not good; while the high-energy expansion agent provided by the present invention It only burns and does not explode at normal pressure and temperature, and can only be converted from combustion to detonation in a closed space due to the generation of a large amount of high-temperature and high-pressure gas. It has dual functions of pre-splitting and detonation. Ignition, high-temperature and high-pressure gas is generated rapidly after combustion, and the high-temperature and high-pressure gas generated by combustion drives the initial cracks around the drill hole to expand, and the pressure continues to rise.
  • the remaining expansion agent turns from combustion to detonation, and the energy is sufficient to Coal and rock fissures are coupled to each other to further develop the fissures, and perform network-type fracturing to break up the rock blocks wrapped in the fissures to achieve the best energy release state.
  • the high-temperature and high-pressure gas has expanded the initial cracks during the initial combustion process, which can provide sufficient coupling conditions for the subsequent detonation shocks, so that the detonation shocks will not cause detonation impacts on the coal due to the narrow crack space.
  • the rock is over-crushed, reducing the consumption of explosive energy due to the crushing impact.
  • the high-energy expansion agent of the present invention cannot be detonated under normal pressure and temperature, and will automatically extinguish when the pressure in the borehole is less than 20MPa. Self-extinguishing improves safety during use; and the high-energy expansion agent of the present invention has no detonator sensitivity, can not be detonated with a detonator, and has no detonation distance; the high-energy expansion agent of the present invention has low sensitivity, and it is difficult to ignite and detonate Use a special igniter to ignite through heat transfer in the hole.
  • the high-energy expansion agent of the present invention has high safety, the danger level is 1.3-1.5, the friction sensitivity and impact sensitivity are 0-10%, and the electrostatic spark sensitivity is greater than 120mJ;
  • the high-energy expansion agent of the present invention has a high burning rate and a high pressure index, the measured burning rate of 3MPa is greater than 100mm/s, and the measured burning rate of 5MPa is greater than 200mm/s;
  • the gas production of the high-energy expansion agent of the present invention is greater than 600L/kg, the heat of combustion is greater than 3500KJ/kg, the peak pressure can be adjusted according to the specific requirements of the geological conditions of the engineering site, the range is 65Mpa ⁇ 200MPa, and the action time is 10ms ⁇ 300ms;
  • the high-energy expansion agent of the present invention does not explode in an open space, and only in a closed space will it turn from combustion to detonation due to the generation of a large amount of high-temperature and high-pressure gas, and has dual functions of pre-splitting and detonation.
  • the influence range of the network is 10 to 15 times that of the cracks and pores formed by traditional industrial explosive blasting and pre-cracking agent fracturing, which can effectively control various disasters in coal mines, improve the recovery rate of oil and natural gas, and improve the efficiency of tunnel excavation;
  • the high-energy expansion agent of the present invention is zero-oxygen balance, and the main components of the high-temperature and high-pressure gas produced during combustion and detonation are 40-55% of water vapor, 30-35% of nitrogen, and 15%-20% of carbon dioxide. %, the content of harmful gases such as carbon monoxide, nitrogen monoxide and hydrogen chloride is almost negligible, and will not pollute the environment; and because of the high content of nitrogen in the high-temperature and high-pressure gas, it is an inert gas, which can ensure the safe use of mining mines such as natural gas , to further improve security.
  • Fig. 1 is the P-t curve of the high-energy expansion agent that the embodiment of the present invention 1 makes;
  • Fig. 2 is the P-t curve of the high-energy expansion agent prepared in Example 2 of the present invention.
  • Pt curve the volume of the closed blaster is 100cm 3 , and the test is carried out according to GJB770B-2005.
  • This embodiment 1 provides a safe and efficient high-energy expansion agent, which includes the following components in mass fraction:
  • Copper chromite 0.5%
  • the particle diameters of silicon powder, guanidine nitrate, LLM-105 and potassium nitrate in the above components are all about 100 ⁇ m.
  • the above-mentioned high-energy expansion agent was tested, and its burning rate at 3MPa was 113.4mm/s, its burning rate at 5MPa was 221mm/s, its heat of combustion was 3900.6KJ/kg, its gas production was 685.9L/kg, and its friction sensitivity was 0%.
  • the impact sensitivity is 1%, and the hazard level is 1.5; the gas composition has been determined: water vapor accounts for 50%, nitrogen accounts for 33%, carbon dioxide accounts for 17%, and the content of harmful gases such as carbon monoxide, nitriding and hydrogen chloride is almost negligible.
  • the expansion agent provided in this embodiment is suitable for coal rocks with a hardness coefficient of 3 or more, including coal rocks with a hardness coefficient of 6 or more, such as coal rocks with a hardness coefficient of 8.
  • This embodiment 2 provides a safe and efficient high-energy expansion agent, which includes the following components in mass fraction:
  • Titanium powder 7%;
  • the particle diameters of titanium powder, guanidine nitrate, LLM-105 and potassium perchlorate in the above components are all about 100 ⁇ m.
  • the above-mentioned high-energy expansion agent was tested, and its burning rate at 3MPa was 124.8mm/s, its burning rate at 5MPa was 243mm/s, its heat of combustion was 5836.46KJ/kg, its gas production was 650.3L/kg, and its friction sensitivity was 2%.
  • the impact sensitivity is 3%, and the hazard level is 1.5; the gas components have been determined: water vapor accounts for 46%, nitrogen accounts for 35%, carbon dioxide accounts for 19%, and the contents of harmful gases such as carbon monoxide, nitriding and hydrogen chloride are almost negligible.
  • the expansion agent provided in this embodiment is suitable for coal rocks with a hardness coefficient of 3 or more, including 6 or more, such as coal rocks with a hardness coefficient of 8-10.
  • This embodiment 3 provides a safe and efficient high-energy expansion agent, which includes the following components in mass fraction:
  • the particle diameters of aluminum powder, guanidine nitrate, LLM-105 and potassium perchlorate in the above components are all about 100 ⁇ m.
  • the above-mentioned high-energy expansion agent is tested, and its burning rate at 3MPa is 141.3mm/s, its burning rate at 5MPa is 280.1mm/s, its heat of combustion is 6730.35KJ/kg, its gas production is 623.5L/kg, and its friction sensitivity is 4%. , the impact sensitivity is 6%, and the hazard level is 1.4.
  • the expansion agent provided in this embodiment is suitable for coal rocks with a hardness coefficient of 3 or more, including 6 or more, such as coal rocks with a hardness coefficient of 8-10.
  • This embodiment 4 provides a safe and efficient high-energy expansion agent, which includes the following components in mass fraction:
  • Aluminum-magnesium alloy powder 7%;
  • the particle diameters of aluminum-magnesium alloy powder, guanidine nitrate, LLM-105, and potassium perchlorate in the above components are all about 100 ⁇ m.
  • the above-mentioned high-energy expansion agent was tested, and its burning rate at 3MPa was 151.2mm/s, its burning rate at 5MPa was 280.3mm/s, its heat of combustion was 7400.64KJ/kg, its gas production was 619.8L/kg, and its friction sensitivity was 6%. , the impact sensitivity is 8%, and the hazard level is 1.3.
  • the expansion agent provided in this embodiment is suitable for coal rocks with a hardness coefficient of 3 or more, including 6 or more, such as coal rocks with a hardness coefficient of 8-15.
  • This embodiment 5 provides a safe and efficient high-energy expansion agent, which includes the following components in mass fraction:
  • Aluminum powder 5%;
  • the particle diameters of aluminum powder, guanidine nitrate, LLM-105 and potassium perchlorate in the above components are all about 100 ⁇ m.
  • the above-mentioned high-energy expansion agent was tested, and its burning rate at 3MPa was 118.6mm/s, its burning rate at 5MPa was 234.2mm/s, its heat of combustion was 5636.96KJ/kg, its gas production was 672.68L/kg, and its friction sensitivity was 3%.
  • the impact sensitivity is 3%, and the hazard level is 1.4.
  • the expansion agent provided in this embodiment is suitable for coal rocks with a hardness coefficient of 3 or more, including 6 or more, such as coal rocks with a hardness coefficient of 8-10.
  • This embodiment 6 provides a safe and efficient high-energy expansion agent, which includes the following components in mass fraction:
  • Aluminum powder 5%;
  • the particle diameters of aluminum powder, guanidine nitrate, LLM-105 and potassium perchlorate in the above components are all about 100 ⁇ m.
  • the above-mentioned high-energy expansion agent is tested, and its burning rate at 3MPa is 103.4mm/s, its burning rate at 5MPa is 218.7mm/s, its heat of combustion is 5648.36KJ/kg, its gas production is 668.3L/kg, and its friction sensitivity is 3%. , the impact sensitivity is 3%, and the hazard level is 1.4.
  • the expansion agent provided in this embodiment is suitable for coal rocks with a hardness coefficient of 3 or more, including 6 or more, such as coal rocks with a hardness coefficient of 8-10.
  • This embodiment 7 provides a safe and efficient high-energy expansion agent, which includes the following components in mass fraction:
  • the particle diameters of aluminum powder, guanidine nitrate, LLM-105 and potassium perchlorate in the above components are all about 100 ⁇ m.
  • the above-mentioned high-energy expansion agent is tested, and its burning rate at 3MPa is 148.6mm/s, its burning rate at 5MPa is 287.35mm/s, its heat of combustion is 6897.45KJ/kg, its gas production is 618.64L/kg, and its friction sensitivity is 5%. , the impact sensitivity is 6%, and the hazard level is 1.4.
  • the expansion agent provided in this embodiment is suitable for coal rocks with a hardness coefficient of 3 or more, including 6 or more, such as coal rocks with a hardness coefficient of 8-10.
  • This embodiment 8 provides a safe and efficient high-energy expansion agent, which includes the following components in mass fraction:
  • the particle diameters of aluminum powder, guanidine nitrate, LLM-105 and potassium perchlorate in the above components are all about 140 ⁇ m.
  • metal powder or non-metal powder and organic powder, high-nitrogen energy-containing material, speed control agent, adhesive, and plasticizer into the mixer to mix evenly, then add the oxidant and mix for 70 minutes, after mixing evenly The material is discharged to obtain a high-energy expansion agent.
  • the above-mentioned high-energy expansion agent is tested, and its burning rate at 3MPa is 160.7mm/s, its burning rate at 5MPa is 293.42mm/s, its heat of combustion is 7900.68KJ/kg, its gas production is 610.24L/kg, and its friction sensitivity is 8%. , the impact sensitivity is 9%, and the hazard level is 1.3.
  • the expansion agent provided in this embodiment is suitable for coal rocks with a hardness coefficient of 3 or more, including 6 or more, such as coal rocks with a hardness coefficient of 8-15.

Abstract

Disclosed in the present invention is a safe and efficient high-energy expanding agent. The expanding agent comprises the following components, in percentages by mass: 5-15% of a metal or nonmetal powder; 10-20% of an organic powder; 10-25% of a high-nitrogen energetic material; 40-75% of an oxidizing agent; 0.5-2.5% of a speed control agent; 1.5-3% of a solid adhesive; and 1.0-2.0% of a plasticizer, wherein the metal powder is at least one of aluminum powder, titanium powder and aluminum magnesium alloy powder; the non-metal powder is silicon powder; the organic powder is guanidine nitrate; and the high-nitrogen energetic material is LLM-105. The high-energy expanding agent of the present invention does not explode in an open space, and the combustion thereof can be converted to detonation only in a closed space due to the generation of a large amount of high-temperature and high-pressure gas, which has the dual effects of presplitting and detonation. The influence range of a fracture and pore network thereof is 10-15 times that of fracture and pores formed by the traditional industrial explosive blasting and presplitting agent fracturing. The high-energy expanding agent is suitable for coal and rock exploitation, natural gas exploitation, oil exploitation or mine roadway excavation, subway construction, tunnel construction, etc.

Description

一种安全高效的高能膨胀剂及其制备方法与应用A safe and efficient high-energy expansion agent and its preparation method and application 技术领域technical field
本发明涉及煤岩预裂技术领域，具体涉及一种安全高效的高能膨胀剂及其制备方法与应用。The invention relates to the technical field of coal rock pre-splitting, in particular to a safe and efficient high-energy expansion agent and its preparation method and application.
背景技术Background technique
目前，国内用于岩石和煤层等破碎预裂的手段主要包括炸药、水力压裂、水利冲孔、液态二氧化碳相变等，但这几种预裂方式存在一定的不足：其中，炸药主要作用是爆破而不是预裂，其能量释放方式是瞬间释放，爆轰波与少量的爆生气瞬间几乎同时作用于岩煤体钻孔，裂隙圈半径约为装药半径的10~15倍，裂隙圈往外就是原岩区，该区域的裂隙孔隙不受炸药炸的影响而变化；水力压裂具有不可控性，其无法达到较均匀的裂隙扩张；液态二氧化碳相变预裂，施工复杂，且预裂力不够，难以达到预裂效果。At present, domestic methods for pre-cracking of rocks and coal seams mainly include explosives, hydraulic fracturing, hydraulic punching, liquid carbon dioxide phase transition, etc., but there are certain deficiencies in these pre-cracking methods: Among them, the main function of explosives is Blasting instead of pre-splitting, its energy release mode is instant release, the detonation wave and a small amount of detonation gas act on the rock and coal body drilling holes almost at the same time, the radius of the crack circle is about 10~15 times the radius of the charge, and the crack circle goes outward It is the original rock area, where the fracture pores are not affected by explosives and changes; hydraulic fracturing is uncontrollable, and it cannot achieve more uniform crack expansion; liquid carbon dioxide phase change pre-cracking, complex construction, and pre-cracking force Not enough, it is difficult to achieve the pre-cracking effect.
另外，目前现有技术中也有使用预裂剂或膨胀剂对煤岩进行破碎预裂，但存在如下问题：如CN110981660A中的煤岩预裂剂中未使用金属粉，释放能量有限，仅适用于硬度系数较低的煤岩，比如硬度系数在3~6范围的煤岩；但如果在预裂剂中直接使用金属粉，安全性得不到保证。故现有煤岩预裂技术存在一定的局限性，仍需一种新型煤岩预裂技术实现岩石和煤层的高效预裂。In addition, there is also the use of pre-splitting agents or expansion agents to carry out pre-cracking of coal rocks in the prior art, but there are the following problems: as in the coal rock pre-splitting agent in CN110981660A, metal powder is not used, and the release energy is limited, which is only applicable to Coal rock with a low hardness coefficient, such as coal rock with a hardness coefficient in the range of 3 to 6; but if metal powder is directly used in the pre-cracking agent, the safety cannot be guaranteed. Therefore, the existing coal and rock pre-splitting technology has certain limitations, and a new coal and rock pre-splitting technology is still needed to achieve efficient pre-splitting of rocks and coal seams.
技术解决方案technical solution
为解决上述问题，本发明提供了一种安全高效的高能膨胀剂，在敞开空间不爆炸，只有在封闭空间才会因产生大量高温高压气体由燃烧转为爆轰，具有预裂和爆轰双重作用，其煤岩体中裂隙孔隙网络的影响范围是传统工业炸药爆破和预裂剂压裂形成裂隙孔隙影响范围的10~15倍。In order to solve the above problems, the present invention provides a safe and efficient high-energy expansion agent, which does not explode in an open space, and only in a closed space will it turn from combustion to detonation due to the generation of a large amount of high-temperature and high-pressure gas. It has dual functions of pre-splitting and detonation The impact range of the fracture pore network in the coal and rock mass is 10-15 times that of the fracture pores formed by traditional industrial explosive blasting and pre-cracking agent fracturing.
为实现上述目的，本发明具体采用如下技术方案：To achieve the above object, the present invention specifically adopts the following technical solutions:
一种安全高效的高能膨胀剂，其特征在于，包括如下质量分数的组分：A safe and efficient high-energy expansion agent is characterized in that it includes the following components in mass fraction:
金属或非金属粉末：5%~15%；Metal or non-metal powder: 5%~15%;
有机粉末：10%~20%；Organic powder: 10%~20%;
高氮含能材料：10%~25%；High nitrogen energetic material: 10%~25%;
氧化剂：40%~75%；Oxidant: 40%~75%;
控速剂：0.5~2.5%；Speed control agent: 0.5~2.5%;
固黏剂：1.5%~3%；Adhesive: 1.5%~3%;
塑化剂：1.0~2.0%；Plasticizer: 1.0~2.0%;
所述金属粉末为铝粉、钛粉、铝镁合金粉中的至少一种，所述非金属粉末为硅粉；所述有机粉末为硝酸胍；所述高氮含能材料为LLM-105。The metal powder is at least one of aluminum powder, titanium powder, and aluminum-magnesium alloy powder, the non-metallic powder is silicon powder; the organic powder is guanidine nitrate; and the high-nitrogen energetic material is LLM-105.
在上述技术方案中，所述金属粉末或非金属粉末可提升高能膨胀剂的燃速及能量，为主要燃烧剂；所述有机粉末硝酸胍也作为燃烧剂，其在燃烧过程中产气量较大，可增加封闭空间内压强；所述高氮含能材料LLM-105，其化学名称为2,6-二氨基-3,5-二硝基-1-氧吡嗪，其耐高温、钝感性好且性能稳定，具有一定的爆燃性，另外，LLM-105在燃烧及爆轰过程中可以产生大量惰性氮气，不仅可提高天然气等开采过程中的安全性，且在高温下氮气粘度系数低，可更好的在煤岩裂隙和孔隙中扩展，而且使高温高压气体的准静态作用力稳定，能够均匀有效的破碎岩石。In the above technical scheme, the metal powder or non-metallic powder can increase the burning rate and energy of the high-energy expansion agent, and is the main combustion agent; the organic powder guanidine nitrate is also used as a combustion agent, and its gas production is relatively large during the combustion process. Can increase the pressure in the closed space; the high nitrogen energetic material LLM-105, its chemical name is 2,6-diamino-3,5-dinitro-1-oxypyrazine, which has good high temperature resistance and insensitivity It has stable performance and certain deflagration properties. In addition, LLM-105 can generate a large amount of inert nitrogen during combustion and detonation, which can not only improve the safety of natural gas and other mining processes, but also has a low viscosity coefficient of nitrogen at high temperatures. It can better expand in coal cracks and pores, and stabilize the quasi-static force of high-temperature and high-pressure gas, which can evenly and effectively break rocks.
另外，上述金属粉末或非金属粉末及有机粉末可以与控速剂协同作用，起到提高压力指数与燃烧速度的作用，可使高能膨胀剂快速燃烧产生大量高温高压气体，提高膨胀剂的做功能力，进而使煤岩裂隙扩展，而高氮含能材料具有钝感性，其能够降低药剂感度，并降低药剂的燃速，但其钝感性可保证使用过程中的安全性。In addition, the above-mentioned metal powder or non-metal powder and organic powder can act synergistically with the speed control agent to increase the pressure index and combustion speed, which can make the high-energy expansion agent burn quickly to produce a large amount of high-temperature and high-pressure gas, and improve the performance of the expansion agent. Force, and then make coal rock fissures expand, and high-nitrogen energetic materials have insensitivity, which can reduce the sensitivity of the agent and reduce the burning rate of the agent, but its insensitivity can ensure the safety during use.
进一步地，所述氧化剂与高能含氮材料的质量比为2~5.5:1。Further, the mass ratio of the oxidant to the high-energy nitrogen-containing material is 2-5.5:1.
在上述技术方案中，由于高能含氮材料会在一定程度上降低膨胀剂的燃速，因此通过控制氧化剂与高能含氮材料的配比，进一步调节膨胀剂的燃速，若氧化剂与高能含氮材料的比例过小，会大幅度降低膨胀剂燃速，致使做功能力不足。In the above technical scheme, since the high-energy nitrogen-containing material will reduce the burning rate of the expansion agent to a certain extent, by controlling the proportion of the oxidant and the high-energy nitrogen-containing material, the burning rate of the expansion agent can be further adjusted. If the proportion of the material is too small, the burning rate of the expander will be greatly reduced, resulting in insufficient work ability.
进一步地，所述金属或非金属粉末的粒度d 50≤200μm；所述有机粉末的粒度d 50≤200μm；所述高能含氮材料的粒度d 50≤200μm。 Further, the particle size d 50 of the metal or non-metal powder is ≤200 μm; the particle size d 50 of the organic powder is ≤200 μm; the particle size d 50 of the high-energy nitrogen-containing material is ≤200 μm.
进一步地，所述氧化剂为高氯酸钾、硝酸钾中的至少一种，其粒度d 50≤200μm。 Further, the oxidant is at least one of potassium perchlorate and potassium nitrate, and its particle size d 50 is ≤200 μm.
进一步地，所述控速剂为亚铬酸铜、叔丁基二茂铁中的至少一种。Further, the rate control agent is at least one of copper chromite and tert-butylferrocene.
进一步地，所述固黏剂为γ-氨丙基三乙氧基硅烷、聚乙烯醇缩丁醛中的至少一种。Further, the adhesive is at least one of γ-aminopropyltriethoxysilane and polyvinyl butyral.
进一步地，所述塑化剂为1,2,4-丁三醇三硝酸酚、1,1,1-三叠氮甲基乙烷中的至少一种。上述固黏剂和塑化剂粘结性好且热效应高，适用于本发明的高能膨胀剂。Further, the plasticizer is at least one of 1,2,4-butanetriol phenol trinitrate and 1,1,1-triazidemethylethane. The above-mentioned adhesive and plasticizer have good cohesiveness and high thermal effect, and are suitable for the high-energy expansion agent of the present invention.
本发明还提供一种安全高效的高能膨胀剂的制备方法，包括如下步骤：The present invention also provides a method for preparing a safe and efficient high-energy expansion agent, comprising the following steps:
按照配方组分称量各物质并进行研磨，然后将金属粉末或非金属粉末与有机粉末、高氮含能材料、氧化剂、控速剂、固黏剂、塑化剂放入混料机中进行混合，混合均匀后出料，即得高能膨胀剂；或先将金属粉末或非金属粉末与有机粉末、高氮含能材料、控速剂、固黏剂、塑化剂放入混料机中进行混合均匀，然后再加入氧化剂进行混合，混合均匀后出料，即得高能膨胀剂。Weigh and grind each substance according to the formula components, and then put the metal powder or non-metal powder and organic powder, high-nitrogen energetic material, oxidant, speed control agent, adhesive, and plasticizer into the mixer for processing Mix, mix evenly and discharge to obtain high-energy expansion agent; or first put metal powder or non-metal powder and organic powder, high-nitrogen energy-containing material, speed control agent, adhesive, plasticizer into the mixer Mix evenly, then add an oxidizing agent to mix, mix evenly, and then discharge to obtain a high-energy expansion agent.
本发明还提供一种安全高效的高能膨胀剂在煤岩开采、天然气开采、石油开采或矿山巷道挖掘、地铁修建、隧道修建中的应用。The invention also provides the application of a safe and efficient high-energy expansion agent in coal and rock mining, natural gas mining, oil mining or mining roadway excavation, subway construction, and tunnel construction.
进一步地，所述高能膨胀剂在应用过程中需将其置于封闭空间内，并通过点火器引燃，高能膨胀剂在燃烧过程中产生大量高温高压气体，驱动周围初始裂隙扩展，当达到一定压力后，高能膨胀剂由燃烧迅速转为爆轰，爆轰过程中产生的高温高压气体使岩石破碎并使裂隙进一步扩展；Further, the high-energy expansion agent needs to be placed in a closed space during application and ignited by an igniter. The high-energy expansion agent generates a large amount of high-temperature and high-pressure gas during the combustion process, driving the surrounding initial cracks to expand. After pressure, the high-energy expansion agent quickly turns from combustion to detonation, and the high-temperature and high-pressure gas generated during the detonation process breaks the rock and further expands the crack;
燃烧及爆轰过程中产生的高温高压气体的主要组分为水蒸气40~55%、氮气30~35%、二氧化碳15%~20%。The main components of the high-temperature and high-pressure gas produced during combustion and detonation are 40-55% water vapor, 30-35% nitrogen, and 15%-20% carbon dioxide.
另外，在燃烧及爆轰过程中还产生一氧化碳、一氧化氮、氯化氢等有害气体，但含量很少，几乎可以忽略不计，因此，这种高能膨胀剂对环境污染小。In addition, harmful gases such as carbon monoxide, nitrogen monoxide, and hydrogen chloride are also produced during combustion and detonation, but the content is very small, almost negligible. Therefore, this high-energy expansion agent has little environmental pollution.
本发明所提供的高能膨胀剂，与炸药的能量释放方式不同，炸药的释放方式为瞬间爆轰，作用时间为微秒级，能量释放太快，效果不佳；而本发明所提供的高能膨胀剂，其在常压、常温下只燃烧不爆炸，只能在封闭空间内因产生大量高温高压气体由燃烧转为爆轰，具有预裂和爆轰双重作用，具体为：高能膨胀剂由点火药引燃，燃烧后迅速产生高温高压气体，燃烧生成的高温高压气体驱动钻孔周围的初始裂隙扩展，同时压力持续上升，达到一定的压力后，剩余的膨胀剂由燃烧转爆轰，能量充分与煤岩裂隙相互耦合，使裂隙进一步发育，并将裂隙间包裹的岩块进行网络型压裂破碎，达到最佳的能量释放状态。另外，正是由于燃烧初始过程中高温高压气体已将初始裂隙扩展，可以为随后的爆轰冲击提供了充分的耦合条件，使爆轰发生时不至于因为裂隙空间狭小而造成爆轰冲击对煤岩过度粉碎，减少了由于粉碎冲击造成的爆炸能量的消耗。The high-energy expansion agent provided by the present invention is different from the energy release mode of explosives. The release mode of explosives is instant detonation, and the action time is microsecond level. The energy release is too fast and the effect is not good; while the high-energy expansion agent provided by the present invention It only burns and does not explode at normal pressure and temperature, and can only be converted from combustion to detonation in a closed space due to the generation of a large amount of high-temperature and high-pressure gas. It has dual functions of pre-splitting and detonation. Ignition, high-temperature and high-pressure gas is generated rapidly after combustion, and the high-temperature and high-pressure gas generated by combustion drives the initial cracks around the drill hole to expand, and the pressure continues to rise. After reaching a certain pressure, the remaining expansion agent turns from combustion to detonation, and the energy is sufficient to Coal and rock fissures are coupled to each other to further develop the fissures, and perform network-type fracturing to break up the rock blocks wrapped in the fissures to achieve the best energy release state. In addition, it is precisely because the high-temperature and high-pressure gas has expanded the initial cracks during the initial combustion process, which can provide sufficient coupling conditions for the subsequent detonation shocks, so that the detonation shocks will not cause detonation impacts on the coal due to the narrow crack space. The rock is over-crushed, reducing the consumption of explosive energy due to the crushing impact.
另外，本发明的高能膨胀剂在常压、常温下无法引爆，当钻孔中压力小于20MPa时会自动熄灭，如封孔效果不好或煤岩破裂产生大量的缝隙与采空区连通时会自熄，提高使用过程中的安全性；且本发明的高能膨胀剂无雷管感度，不能用雷管引爆，其无殉爆距离；本发明的高能膨胀剂感度较低，点火起爆较为困难，只能采用专用的点火器通过孔内传热引燃。In addition, the high-energy expansion agent of the present invention cannot be detonated under normal pressure and temperature, and will automatically extinguish when the pressure in the borehole is less than 20MPa. Self-extinguishing improves safety during use; and the high-energy expansion agent of the present invention has no detonator sensitivity, can not be detonated with a detonator, and has no detonation distance; the high-energy expansion agent of the present invention has low sensitivity, and it is difficult to ignite and detonate Use a special igniter to ignite through heat transfer in the hole.
有益效果Beneficial effect
有益效果Beneficial effect
（1）本发明的高能膨胀剂具有较高的安全性，危险等级为1.3~1.5级，摩擦感度与撞击感度为0~10%，静电火花感度大于120mJ；(1) The high-energy expansion agent of the present invention has high safety, the danger level is 1.3-1.5, the friction sensitivity and impact sensitivity are 0-10%, and the electrostatic spark sensitivity is greater than 120mJ;
（2）本发明的高能膨胀剂在的燃速及压强指数高，3MPa的实测燃速大于100mm/s，5MPa的实测燃速大于200mm/s；(2) The high-energy expansion agent of the present invention has a high burning rate and a high pressure index, the measured burning rate of 3MPa is greater than 100mm/s, and the measured burning rate of 5MPa is greater than 200mm/s;
（3）本发明的高能膨胀剂其产气量大于600L/kg，燃烧热大于3500KJ/kg，峰值压力可随工程现场地质条件的具体要求调整，范围在65Mpa~200MPa，作用时间为10ms~300ms；(3) The gas production of the high-energy expansion agent of the present invention is greater than 600L/kg, the heat of combustion is greater than 3500KJ/kg, the peak pressure can be adjusted according to the specific requirements of the geological conditions of the engineering site, the range is 65Mpa~200MPa, and the action time is 10ms~300ms;
（4）本发明的高能膨胀剂在敞开空间不爆炸，只有在封闭空间才会因产生大量高温高压气体由燃烧转为爆轰，具有预裂和爆轰双重作用，其煤岩体中裂隙孔隙网络的影响范围是传统工业炸药爆破和预裂剂压裂形成裂隙孔隙影响范围的10~15倍，可有效治理煤矿多种灾害，提高了石油、天然气开采率，提高了隧道掘进效率；(4) The high-energy expansion agent of the present invention does not explode in an open space, and only in a closed space will it turn from combustion to detonation due to the generation of a large amount of high-temperature and high-pressure gas, and has dual functions of pre-splitting and detonation. The influence range of the network is 10 to 15 times that of the cracks and pores formed by traditional industrial explosive blasting and pre-cracking agent fracturing, which can effectively control various disasters in coal mines, improve the recovery rate of oil and natural gas, and improve the efficiency of tunnel excavation;
（5）本发明的高能膨胀剂为零氧平衡，其在燃烧及爆轰过程中产生的高温高压气体的主要组分为水蒸气40~55%、氮气30~35%、二氧化碳15%~20%，一氧化碳、一氧化氮和氯化氢等有害气体含量几乎可以忽略不计，不会对环境产生污染；而且由于高温高压气体中氮气含量高，其为惰性气体，可以保证在天然气等开采矿井的安全使用，进一步提高安全性。(5) The high-energy expansion agent of the present invention is zero-oxygen balance, and the main components of the high-temperature and high-pressure gas produced during combustion and detonation are 40-55% of water vapor, 30-35% of nitrogen, and 15%-20% of carbon dioxide. %, the content of harmful gases such as carbon monoxide, nitrogen monoxide and hydrogen chloride is almost negligible, and will not pollute the environment; and because of the high content of nitrogen in the high-temperature and high-pressure gas, it is an inert gas, which can ensure the safe use of mining mines such as natural gas , to further improve security.
附图说明Description of drawings
下面结合附图对本发明作进一步说明：The present invention will be further described below in conjunction with accompanying drawing:
图1为本发明实施例1所制得的高能膨胀剂的P-t曲线；Fig. 1 is the P-t curve of the high-energy expansion agent that the embodiment of the present invention 1 makes;
图2为本发明实施例2所制得的高能膨胀剂的P-t曲线。Fig. 2 is the P-t curve of the high-energy expansion agent prepared in Example 2 of the present invention.
本发明的实施方式Embodiments of the present invention
为了使本发明的优点、技术方案更加清楚、明确，下面结合具体实施例和附图对本发明做详细说明。In order to make the advantages and technical solutions of the present invention clearer and clearer, the present invention will be described in detail below in conjunction with specific embodiments and accompanying drawings.
另外，为便于理解，对实施例的相关检测方法等进行说明：In addition, for ease of understanding, the relevant detection methods of the embodiments are described:
P-t曲线：密闭爆发器容积为100cm 3，试验按照GJB770B-2005进行。通过连接在密闭爆发器上的压电传感器和数据处理系统记录的密闭爆发器里压力随时间变化的P-t曲线； Pt curve: the volume of the closed blaster is 100cm 3 , and the test is carried out according to GJB770B-2005. The Pt curve of the pressure in the airtight eruptor recorded by the piezoelectric sensor and the data processing system connected on the airtight eruptor;
燃烧速度的测定：测试方法按照《GJB770b方法706.燃速靶线法》；Determination of burning rate: the test method is in accordance with "GJB770b method 706. Burning rate target line method";
产气量的测定：药剂在密闭爆发器内燃烧完毕后，通过水浴系统将密闭爆发器内残余气体冷却至25℃，记录容器内压力，进而换算出残余气体体积；Measurement of gas production: After the medicament is burned in the closed detonator, the residual gas in the closed detonator is cooled to 25°C through the water bath system, the pressure in the container is recorded, and then the volume of the residual gas is converted;
气体组分测定：将铝箔采气袋通过橡胶管连接到密闭爆发器排气阀上，使燃烧气体通入元素分析仪，根据标准QJ2781A-2004检测HEEA-I燃气成分，每个试样至少进行两次平行测定；Determination of gas components: Connect the aluminum foil gas sampling bag to the exhaust valve of the airtight explosive device through the rubber tube, let the combustion gas pass into the elemental analyzer, and detect the HEEA-I gas composition according to the standard QJ2781A-2004. Each sample should be tested at least Two parallel determinations;
燃烧热的测定：试验按照GJB770B-2005进行，使用的设备为氧弹式量热计，根据标准中的公式计算出试样的燃烧热值；Determination of combustion heat: the test is carried out in accordance with GJB770B-2005, the equipment used is an oxygen bomb calorimeter, and the combustion heat value of the sample is calculated according to the formula in the standard;
摩擦感度的测定条件：3.92MPa，90°；Measurement conditions of friction sensitivity: 3.92MPa, 90°;
撞击感度的测定条件：10Kg，50cm。Determination conditions of impact sensitivity: 10Kg, 50cm.
实施例1Example 1
本实施例1提供一种安全高效的高能膨胀剂，其包括如下质量分数的组分：This embodiment 1 provides a safe and efficient high-energy expansion agent, which includes the following components in mass fraction:
硅粉：8%；Silica fume: 8%;
硝酸胍：11%；Guanidine nitrate: 11%;
LLM-105：15%；LLM-105: 15%;
硝酸钾：63%；Potassium nitrate: 63%;
亚铬酸铜：0.5%；Copper chromite: 0.5%;
聚乙烯醇缩丁醛：1.5%；Polyvinyl butyral: 1.5%;
1,2,4-丁三醇三硝酸酚：1.0%。1,2,4-Butanetriol phenol trinitrate: 1.0%.
上述组分中硅粉、硝酸胍、LLM-105、硝酸钾的粒径均为100μm左右。The particle diameters of silicon powder, guanidine nitrate, LLM-105 and potassium nitrate in the above components are all about 100 μm.
将上述组分一同加入声共振混合机中混合，混合时间为60min，即得高能膨胀剂。Put the above components into an acoustic resonance mixer and mix them for 60 minutes to obtain a high-energy expansion agent.
对上述高能膨胀剂进行检测，其在3MPa燃速为113.4mm/s，5MPa的燃速为221mm/s，燃烧热为3900.6KJ/kg，产气量为685.9L/kg，摩擦感度为0%，撞击感度为1%，危险等级为1.5级；气体组分经测定：水蒸气占50%，氮气占33%，二氧化碳占17%，一氧化碳、氮化和氯化氢等有害气体含量几乎可以忽略不计。The above-mentioned high-energy expansion agent was tested, and its burning rate at 3MPa was 113.4mm/s, its burning rate at 5MPa was 221mm/s, its heat of combustion was 3900.6KJ/kg, its gas production was 685.9L/kg, and its friction sensitivity was 0%. The impact sensitivity is 1%, and the hazard level is 1.5; the gas composition has been determined: water vapor accounts for 50%, nitrogen accounts for 33%, carbon dioxide accounts for 17%, and the content of harmful gases such as carbon monoxide, nitriding and hydrogen chloride is almost negligible.
另外，从图1中可以看出：膨胀剂在密闭爆发器内燃烧-爆轰后，会释放出大量的高温高压气体，压力迅速上升，其峰值压力可达到75Mpa，该膨胀剂在点火20ms后药剂燃烧完全。In addition, it can be seen from Figure 1 that after the expansion agent burns and detonates in the closed detonator, a large amount of high-temperature and high-pressure gas will be released, and the pressure will rise rapidly, and its peak pressure can reach 75Mpa. The potion burns completely.
本实施例所提供的膨胀剂适用于硬度系数在3以上的煤岩，包括6以上，如硬度系数为8的煤岩。The expansion agent provided in this embodiment is suitable for coal rocks with a hardness coefficient of 3 or more, including coal rocks with a hardness coefficient of 6 or more, such as coal rocks with a hardness coefficient of 8.
实施例2Example 2
本实施例2提供一种安全高效的高能膨胀剂，其包括如下质量分数的组分：This embodiment 2 provides a safe and efficient high-energy expansion agent, which includes the following components in mass fraction:
钛粉：7%；Titanium powder: 7%;
硝酸胍：10%；Guanidine nitrate: 10%;
LLM-105：13%；LLM-105: 13%;
高氯酸钾：66%；Potassium perchlorate: 66%;
亚铬酸铜：1.0%；Copper chromite: 1.0%;
聚乙烯醇缩丁醛：1.5%；Polyvinyl butyral: 1.5%;
1,1,1-三叠氮甲基乙烷：1.5%。1,1,1-Triazidomethylethane: 1.5%.
上述组分中钛粉、硝酸胍、LLM-105、高氯酸钾的粒径均为100μm左右。The particle diameters of titanium powder, guanidine nitrate, LLM-105 and potassium perchlorate in the above components are all about 100 μm.
将上述组分一同加入声共振混合机中混合，混合时间为60min，即得高能膨胀剂。Put the above components into an acoustic resonance mixer and mix them for 60 minutes to obtain a high-energy expansion agent.
对上述高能膨胀剂进行检测，其在3MPa燃速为124.8mm/s，5MPa的燃速为243mm/s，燃烧热为5836.46KJ/kg，产气量为650.3L/kg，摩擦感度为2%，撞击感度为3%，危险等级为1.5级；气体组分经测定：水蒸气占46%，氮气占35%，二氧化碳占19%，一氧化碳、氮化和氯化氢等有害气体含量几乎可以忽略不计。The above-mentioned high-energy expansion agent was tested, and its burning rate at 3MPa was 124.8mm/s, its burning rate at 5MPa was 243mm/s, its heat of combustion was 5836.46KJ/kg, its gas production was 650.3L/kg, and its friction sensitivity was 2%. The impact sensitivity is 3%, and the hazard level is 1.5; the gas components have been determined: water vapor accounts for 46%, nitrogen accounts for 35%, carbon dioxide accounts for 19%, and the contents of harmful gases such as carbon monoxide, nitriding and hydrogen chloride are almost negligible.
另外，从图2中可以看出：膨胀剂在密闭爆发器内燃烧-爆轰后，压力迅速上升，其峰值压力可达到93Mpa，该膨胀剂在点火40ms后药剂燃烧完全。In addition, it can be seen from Figure 2 that after the expansion agent burns and detonates in the closed detonator, the pressure rises rapidly, and its peak pressure can reach 93Mpa. The expansion agent burns completely after 40ms of ignition.
本实施例所提供的膨胀剂适用于硬度系数在3以上的煤岩，包括6以上，如硬度系数为8~10的煤岩。The expansion agent provided in this embodiment is suitable for coal rocks with a hardness coefficient of 3 or more, including 6 or more, such as coal rocks with a hardness coefficient of 8-10.
实施例3Example 3
本实施例3提供一种安全高效的高能膨胀剂，其包括如下质量分数的组分：This embodiment 3 provides a safe and efficient high-energy expansion agent, which includes the following components in mass fraction:
铝粉：7%；Aluminum powder: 7%;
硝酸胍：12%；Guanidine nitrate: 12%;
LLM-105：14.5%；LLM-105: 14.5%;
高氯酸钾：63.5%；Potassium perchlorate: 63.5%;
叔丁基二茂铁：1.0%；Tert-butylferrocene: 1.0%;
γ-氨丙基三乙氧基硅烷：1.0%；γ-Aminopropyltriethoxysilane: 1.0%;
1,1,1-三叠氮甲基乙烷：1.0%。1,1,1-Triazidomethylethane: 1.0%.
上述组分中铝粉、硝酸胍、LLM-105、高氯酸钾的粒径均为100μm左右。The particle diameters of aluminum powder, guanidine nitrate, LLM-105 and potassium perchlorate in the above components are all about 100 μm.
将上述组分一同加入声共振混合机中混合，混合时间为60min，即得高能膨胀剂。Put the above components into an acoustic resonance mixer and mix them for 60 minutes to obtain a high-energy expansion agent.
对上述高能膨胀剂进行检测，其在3MPa燃速为141.3mm/s，5MPa的燃速为280.1mm/s，燃烧热为6730.35KJ/kg，产气量为623.5L/kg，摩擦感度为4%，撞击感度为6%，危险等级为1.4级。The above-mentioned high-energy expansion agent is tested, and its burning rate at 3MPa is 141.3mm/s, its burning rate at 5MPa is 280.1mm/s, its heat of combustion is 6730.35KJ/kg, its gas production is 623.5L/kg, and its friction sensitivity is 4%. , the impact sensitivity is 6%, and the hazard level is 1.4.
本实施例所提供的膨胀剂适用于硬度系数在3以上的煤岩，包括6以上，如硬度系数为8~10的煤岩。The expansion agent provided in this embodiment is suitable for coal rocks with a hardness coefficient of 3 or more, including 6 or more, such as coal rocks with a hardness coefficient of 8-10.
实施例4Example 4
本实施例4提供一种安全高效的高能膨胀剂，其包括如下质量分数的组分：This embodiment 4 provides a safe and efficient high-energy expansion agent, which includes the following components in mass fraction:
铝镁合金粉：7%；Aluminum-magnesium alloy powder: 7%;
硝酸胍：12%；Guanidine nitrate: 12%;
LLM-105：14.5%；LLM-105: 14.5%;
高氯酸钾：63.5%；Potassium perchlorate: 63.5%;
叔丁基二茂铁：1.0%；Tert-butylferrocene: 1.0%;
γ-氨丙基三乙氧基硅烷：1.0%；γ-Aminopropyltriethoxysilane: 1.0%;
1,1,1-三叠氮甲基乙烷：1.0%。1,1,1-Triazidomethylethane: 1.0%.
上述组分中铝镁合金粉、硝酸胍、LLM-105、高氯酸钾的粒径均为100μm左右。The particle diameters of aluminum-magnesium alloy powder, guanidine nitrate, LLM-105, and potassium perchlorate in the above components are all about 100 μm.
将上述组分一同加入声共振混合机中混合，混合时间为60min，即得高能膨胀剂。Put the above components into an acoustic resonance mixer and mix them for 60 minutes to obtain a high-energy expansion agent.
对上述高能膨胀剂进行检测，其在3MPa燃速为151.2mm/s，5MPa的燃速为280.3mm/s，燃烧热为7400.64KJ/kg，产气量为619.8L/kg，摩擦感度为6%，撞击感度为8%，危险等级为1.3级。The above-mentioned high-energy expansion agent was tested, and its burning rate at 3MPa was 151.2mm/s, its burning rate at 5MPa was 280.3mm/s, its heat of combustion was 7400.64KJ/kg, its gas production was 619.8L/kg, and its friction sensitivity was 6%. , the impact sensitivity is 8%, and the hazard level is 1.3.
本实施例所提供的膨胀剂适用于硬度系数在3以上的煤岩，包括6以上，如硬度系数为8~15的煤岩。The expansion agent provided in this embodiment is suitable for coal rocks with a hardness coefficient of 3 or more, including 6 or more, such as coal rocks with a hardness coefficient of 8-15.
实施例5Example 5
本实施例5提供一种安全高效的高能膨胀剂，其包括如下质量分数的组分：This embodiment 5 provides a safe and efficient high-energy expansion agent, which includes the following components in mass fraction:
铝粉：5%；Aluminum powder: 5%;
硝酸胍：10%；Guanidine nitrate: 10%;
LLM-105：18%；LLM-105: 18%;
高氯酸钾：64%；Potassium perchlorate: 64%;
叔丁基二茂铁：1.0%；Tert-butylferrocene: 1.0%;
γ-氨丙基三乙氧基硅烷：1.0%；γ-Aminopropyltriethoxysilane: 1.0%;
1,1,1-三叠氮甲基乙烷：1.0%。1,1,1-Triazidomethylethane: 1.0%.
上述组分中铝粉、硝酸胍、LLM-105、高氯酸钾的粒径均为100μm左右。The particle diameters of aluminum powder, guanidine nitrate, LLM-105 and potassium perchlorate in the above components are all about 100 μm.
将上述组分一同加入声共振混合机中混合，混合时间为60min，即得高能膨胀剂。Put the above components into an acoustic resonance mixer and mix them for 60 minutes to obtain a high-energy expansion agent.
对上述高能膨胀剂进行检测，其在3MPa燃速为 118.6mm/s，5MPa的燃速234.2mm/s，燃烧热为5636.96KJ/kg，产气量为672.68L/kg，摩擦感度为3%，撞击感度为3%，危险等级为1.4级。The above-mentioned high-energy expansion agent was tested, and its burning rate at 3MPa was 118.6mm/s, its burning rate at 5MPa was 234.2mm/s, its heat of combustion was 5636.96KJ/kg, its gas production was 672.68L/kg, and its friction sensitivity was 3%. The impact sensitivity is 3%, and the hazard level is 1.4.
本实施例所提供的膨胀剂适用于硬度系数在3以上的煤岩，包括6以上，如硬度系数为8~10的煤岩。The expansion agent provided in this embodiment is suitable for coal rocks with a hardness coefficient of 3 or more, including 6 or more, such as coal rocks with a hardness coefficient of 8-10.
实施例6Example 6
本实施例6提供一种安全高效的高能膨胀剂，其包括如下质量分数的组分：This embodiment 6 provides a safe and efficient high-energy expansion agent, which includes the following components in mass fraction:
铝粉：5%；Aluminum powder: 5%;
硝酸胍：10%；Guanidine nitrate: 10%;
LLM-105：25%；LLM-105: 25%;
高氯酸钾：57%；Potassium perchlorate: 57%;
叔丁基二茂铁：1.0%；Tert-butylferrocene: 1.0%;
γ-氨丙基三乙氧基硅烷：1.0%；γ-Aminopropyltriethoxysilane: 1.0%;
1,1,1-三叠氮甲基乙烷：1.0%。1,1,1-Triazidomethylethane: 1.0%.
上述组分中铝粉、硝酸胍、LLM-105、高氯酸钾的粒径均为100μm左右。The particle diameters of aluminum powder, guanidine nitrate, LLM-105 and potassium perchlorate in the above components are all about 100 μm.
将上述组分一同加入声共振混合机中混合，混合时间为60min，即得高能膨胀剂。Put the above components into an acoustic resonance mixer and mix them for 60 minutes to obtain a high-energy expansion agent.
对上述高能膨胀剂进行检测，其在3MPa燃速为103.4mm/s，5MPa的燃速为218.7mm/s，燃烧热为5648.36KJ/kg，产气量为668.3L/kg，摩擦感度为3%，撞击感度为  3%，危险等级为1.4级。The above-mentioned high-energy expansion agent is tested, and its burning rate at 3MPa is 103.4mm/s, its burning rate at 5MPa is 218.7mm/s, its heat of combustion is 5648.36KJ/kg, its gas production is 668.3L/kg, and its friction sensitivity is 3%. , the impact sensitivity is 3%, and the hazard level is 1.4.
本实施例所提供的膨胀剂适用于硬度系数在3以上的煤岩，包括6以上，如硬度系数为8~10的煤岩。The expansion agent provided in this embodiment is suitable for coal rocks with a hardness coefficient of 3 or more, including 6 or more, such as coal rocks with a hardness coefficient of 8-10.
实施例7Example 7
本实施例7提供一种安全高效的高能膨胀剂，其包括如下质量分数的组分：This embodiment 7 provides a safe and efficient high-energy expansion agent, which includes the following components in mass fraction:
铝粉：8%；Aluminum powder: 8%;
硝酸胍：18%；Guanidine nitrate: 18%;
LLM-105：13%；LLM-105: 13%;
高氯酸钾：60%；Potassium perchlorate: 60%;
叔丁基二茂铁：1.0%；Tert-butylferrocene: 1.0%;
γ-氨丙基三乙氧基硅烷：1.0%；γ-Aminopropyltriethoxysilane: 1.0%;
1,1,1-三叠氮甲基乙烷：1.0%。1,1,1-Triazidomethylethane: 1.0%.
上述组分中铝粉、硝酸胍、LLM-105、高氯酸钾的粒径均为100μm左右。The particle diameters of aluminum powder, guanidine nitrate, LLM-105 and potassium perchlorate in the above components are all about 100 μm.
将上述组分一同加入声共振混合机中混合，混合时间为60min，即得高能膨胀剂。Put the above components into an acoustic resonance mixer and mix them for 60 minutes to obtain a high-energy expansion agent.
对上述高能膨胀剂进行检测，其在3MPa燃速为148.6mm/s，5MPa的燃速为 287.35 mm/s，燃烧热为6897.45KJ/kg，产气量为618.64L/kg，摩擦感度为5%，撞击感度为 6%，危险等级为1.4级。The above-mentioned high-energy expansion agent is tested, and its burning rate at 3MPa is 148.6mm/s, its burning rate at 5MPa is 287.35mm/s, its heat of combustion is 6897.45KJ/kg, its gas production is 618.64L/kg, and its friction sensitivity is 5%. , the impact sensitivity is 6%, and the hazard level is 1.4.
本实施例所提供的膨胀剂适用于硬度系数在3以上的煤岩，包括6以上，如硬度系数为8~10的煤岩。The expansion agent provided in this embodiment is suitable for coal rocks with a hardness coefficient of 3 or more, including 6 or more, such as coal rocks with a hardness coefficient of 8-10.
实施例8Example 8
本实施例8提供一种安全高效的高能膨胀剂，其包括如下质量分数的组分：This embodiment 8 provides a safe and efficient high-energy expansion agent, which includes the following components in mass fraction:
铝粉：15%；Aluminum powder: 15%;
硝酸胍：17%；Guanidine nitrate: 17%;
LLM-105：15%；LLM-105: 15%;
高氯酸钾：50%；Potassium perchlorate: 50%;
叔丁基二茂铁：1.0%；Tert-butylferrocene: 1.0%;
γ-氨丙基三乙氧基硅烷：1.0%；γ-Aminopropyltriethoxysilane: 1.0%;
1,1,1-三叠氮甲基乙烷：1.0%。1,1,1-Triazidomethylethane: 1.0%.
上述组分中铝粉、硝酸胍、LLM-105、高氯酸钾的粒径均为140μm左右。The particle diameters of aluminum powder, guanidine nitrate, LLM-105 and potassium perchlorate in the above components are all about 140 μm.
先将金属粉末或非金属粉末与有机粉末、高氮含能材料、控速剂、固黏剂、塑化剂放入混料机中进行混合均匀，然后再加入氧化剂进行混合70min，混合均匀后出料，即得高能膨胀剂。Put the metal powder or non-metal powder and organic powder, high-nitrogen energy-containing material, speed control agent, adhesive, and plasticizer into the mixer to mix evenly, then add the oxidant and mix for 70 minutes, after mixing evenly The material is discharged to obtain a high-energy expansion agent.
对上述高能膨胀剂进行检测，其在3MPa燃速为160.7mm/s，5MPa的燃速为293.42mm/s，燃烧热为7900.68KJ/kg，产气量为610.24L/kg，摩擦感度为8%，撞击感度为9%，危险等级为1.3级。The above-mentioned high-energy expansion agent is tested, and its burning rate at 3MPa is 160.7mm/s, its burning rate at 5MPa is 293.42mm/s, its heat of combustion is 7900.68KJ/kg, its gas production is 610.24L/kg, and its friction sensitivity is 8%. , the impact sensitivity is 9%, and the hazard level is 1.3.
本实施例所提供的膨胀剂适用于硬度系数在3以上的煤岩，包括6以上，如硬度系数为8~15的煤岩。The expansion agent provided in this embodiment is suitable for coal rocks with a hardness coefficient of 3 or more, including 6 or more, such as coal rocks with a hardness coefficient of 8-15.
上述未述及的部分借鉴现有技术即可实现。The parts not mentioned above can be realized by referring to the prior art.
当然，上述说明并非是对本发明的限制，本发明也并不仅限于上述举例，本技术领域的技术人员在本发明的实质范围内所做出的变化、改型、添加或替换，也应属于本发明的保护范围。Of course, the above descriptions are not intended to limit the present invention, and the present invention is not limited to the above examples. Changes, modifications, additions or replacements made by those skilled in the art within the scope of the present invention shall also belong to the present invention. protection scope of the invention.

Claims (10)

  1. 一种安全高效的高能膨胀剂，其特征在于，包括如下质量分数的组分：A safe and efficient high-energy expansion agent is characterized in that it includes the following components in mass fraction:
    金属或非金属粉末：5%~15%；Metal or non-metal powder: 5%~15%;
    有机粉末：10%~20%；Organic powder: 10%~20%;
    高氮含能材料：10%~25%；High nitrogen energetic material: 10%~25%;
    氧化剂：40%~75%；Oxidant: 40%~75%;
    控速剂：0.5~2.5%；Speed control agent: 0.5~2.5%;
    固黏剂：1.5%~3%；Adhesive: 1.5%~3%;
    塑化剂：1.0~2.0%；Plasticizer: 1.0~2.0%;
    所述金属粉末为铝粉、钛粉、铝镁合金粉中的至少一种，所述非金属粉末为硅粉；所述有机粉末为硝酸胍；所述高氮含能材料为LLM-105。The metal powder is at least one of aluminum powder, titanium powder, and aluminum-magnesium alloy powder, the non-metallic powder is silicon powder; the organic powder is guanidine nitrate; and the high-nitrogen energetic material is LLM-105.
  2. 根据权利要求1所述的一种安全高效的高能膨胀剂，其特征在于，所述氧化剂与高能含氮材料的质量比为2~5.5:1。A safe and efficient high-energy expansion agent according to claim 1, wherein the mass ratio of the oxidant to the high-energy nitrogen-containing material is 2-5.5:1.
  3. 根据权利要求1所述的一种安全高效的高能膨胀剂，其特征在于，所述金属或非金属粉末的粒度d 50≤200μm；所述有机粉末的粒度d 50≤200μm；所述高能含氮材料的粒度d 50≤200μm。 A safe and efficient high-energy expansion agent according to claim 1, characterized in that, the particle size d 50 of the metal or non-metal powder is ≤200 μm; the particle size d 50 of the organic powder is ≤200 μm; the high-energy nitrogen-containing The particle size d 50 of the material is ≤200 μm.
  4. 根据权利要求1所述的一种安全高效的高能膨胀剂，其特征在于，所述氧化剂为高氯酸钾、硝酸钾中的至少一种，其粒度d 50≤200μm。 A safe and efficient high-energy expansion agent according to claim 1, characterized in that the oxidizing agent is at least one of potassium perchlorate and potassium nitrate, and its particle size d 50 ≤ 200 μm.
  5. 根据权利要求1所述的一种安全高效的高能膨胀剂，其特征在于，所述控速剂为亚铬酸铜、叔丁基二茂铁中的至少一种。A safe and efficient high-energy expansion agent according to claim 1, characterized in that the rate control agent is at least one of copper chromite and tert-butyl ferrocene.
  6. 根据权利要求1所述的一种安全高效的高能膨胀剂，其特征在于，所述固黏剂为γ-氨丙基三乙氧基硅烷、聚乙烯醇缩丁醛中的至少一种。A safe and efficient high-energy expansion agent according to claim 1, characterized in that the adhesive is at least one of γ-aminopropyltriethoxysilane and polyvinyl butyral.
  7. 根据权利要求1所述的一种安全高效的高能膨胀剂，其特征在于，所述塑化剂为1,2,4-丁三醇三硝酸酚、1,1,1-三叠氮甲基乙烷中的至少一种。A safe and efficient high-energy expansion agent according to claim 1, wherein the plasticizer is 1,2,4-butanetriol phenol trinitrate, 1,1,1-triazidemethyl at least one of ethane.
  8. 根据权利要求1-7任一项所述的一种安全高效的高能膨胀剂的制备方法，其特征在于，包括如下步骤：The preparation method of a kind of safe and efficient high-energy expansion agent according to any one of claims 1-7, is characterized in that, comprises the steps:
    按照配方组分称量各物质并进行研磨，然后将金属粉末或非金属粉末与有机粉末、高氮含能材料、氧化剂、控速剂、固黏剂、塑化剂放入混料机中进行混合，混合均匀后出料，即得高能膨胀剂；或先将金属粉末或非金属粉末与有机粉末、高氮含能材料、控速剂、固黏剂、塑化剂放入混料机中进行混合均匀，然后再加入氧化剂进行混合，混合均匀后出料，即得高能膨胀剂。Weigh and grind each substance according to the formula components, and then put the metal powder or non-metal powder and organic powder, high-nitrogen energetic material, oxidant, speed control agent, adhesive, and plasticizer into the mixer for processing Mix, mix evenly and discharge to obtain high-energy expansion agent; or first put metal powder or non-metal powder and organic powder, high-nitrogen energy-containing material, speed control agent, adhesive, plasticizer into the mixer Mix evenly, then add an oxidizing agent to mix, mix evenly, and then discharge to obtain a high-energy expansion agent.
  9. 根据权利要求1-7任一项所述的一种安全高效的高能膨胀剂在煤岩开采、天然气开采、石油开采或矿山巷道挖掘、地铁修建、隧道修建中的应用。The application of a safe and efficient high-energy expansion agent according to any one of claims 1-7 in coal and rock mining, natural gas mining, oil mining or mine roadway excavation, subway construction, and tunnel construction.
  10. 根据权利要求9所述的一种安全高效的高能膨胀剂在煤岩开采、天然气开采、石油开采或矿山巷道挖掘、地铁修建、隧道修建中的应用，其特征在于，所述高能膨胀剂在应用过程中需将其置于封闭空间内，并通过专用点火器引燃，高能膨胀剂在燃烧过程中产生大量高温高压气体，驱动周围初始裂隙扩展，当达到一定压力后，高能膨胀剂由燃烧迅速转为爆轰，爆轰过程中产生的高温高压气体使岩石破碎并使裂隙进一步扩展；According to claim 9, the application of a safe and efficient high-energy expansion agent in coal mining, natural gas extraction, oil extraction or mine roadway excavation, subway construction, and tunnel construction is characterized in that the high-energy expansion agent is used in the application During the process, it needs to be placed in a closed space and ignited by a special igniter. The high-energy expansion agent generates a large amount of high-temperature and high-pressure gas during the combustion process, which drives the initial cracks around it to expand. When a certain pressure is reached, the high-energy expansion agent burns rapidly. Turning into detonation, the high-temperature and high-pressure gas generated during the detonation process breaks the rock and further expands the cracks;
    燃烧及爆轰过程中产生的高温高压气体的主要组分为水蒸气40~55%、氮气30~35%、二氧化碳15%~20%。The main components of the high-temperature and high-pressure gas produced during combustion and detonation are 40-55% water vapor, 30-35% nitrogen, and 15%-20% carbon dioxide.
PCT/CN2022/100596 2022-02-21 2022-06-23 Safe and efficient high-energy expanding agent, and preparation method therefor and use thereof WO2023155354A1 (en)

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