阅读说明：本技术 一种多孔粒状铵油***用表面活性剂、性能增强剂及*** (Porous granular ammonium surfactant for oil-frying, performance enhancer and explosive ) 是由 叶辉 崔刚 马平 谭本岭 王肇中 郝会娟 查正清 李国仲 龚兵 田丰 于 2020-06-18 设计创作，主要内容包括：本发明属于功能化学品领域,具体涉及一种多孔粒状铵油炸药用表面活性剂、一种多孔粒状铵油炸药用性能增强剂及其制备方法和一种多孔粒状铵油炸药。其中,所述表面活性剂包含通式I、通式II和通式III所代表的化合物中的至少一种。将本发明的表面活性剂进一步制成用于多孔粒状铵油炸药的性能增强剂,使用后ANFO具有优异的爆轰性能和储存稳定性。<Image he="468" wi="700" file="DDA0002545908260000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention belongs to the field of functional chemicals, and particularly relates to a porous granular ammonium nitrate-fuel oil explosive surfactant, a porous granular ammonium nitrate-fuel oil explosive performance enhancer and a preparation method thereof, and a porous granular ammonium nitrate-fuel oil explosive. Wherein the surfactant comprises at least one of the compounds represented by the general formula I, the general formula II and the general formula III. The surfactant of the invention is further prepared into a performance enhancer for porous granular ammonium nitrate fuel oil explosives, and the ANFO has excellent detonation performance and storage stability after being used.)

1. A porous granular surfactant for ammonium oil-fried medicines, characterized by comprising at least one of compounds represented by general formula I, general formula II and general formula III;

the general formula I is specifically as follows:

in the general formula I, R₁Represents C₈～C₂₀Alkyl or C₈～C₂₀An alkenyl group; r₂Representative H, CH₃、CH₃CH₂、CH₂OH、CH₂CH₂OH or CH₂CH(CH₃)OH；R₃Represents CH₂，CH₂CH₂、CH₂CH(CH₃) Or C (CH)₃)₂CH₂；

The general formula II is specifically:

in the general formula II, R₄Represents C₈～C₂₀Alkyl or C₈～C₂₀An alkenyl group; r₅Represents CH₂，CH₂CH₂、CH₂CH(CH₃) Or C (CH)₃)₂CH₂；R₆And R₇Same or different, each independently represent H, CH₃、CH₃CH₂、CH₂OH、CH₂CH₂OH or CH₂CH(CH₃)OH；

The general formula III is specifically:

in the general formula III, R₈Represents C₈～C₂₀Alkyl or C₈～C₂₀An alkenyl group; r₉Represents CH₂，CH₂CH₂、CH₂CH(CH₃) OrC(CH₃)₂CH₂；R₁₀And R₁₁Same or different, each independently represent H, CH₃、CH₃CH₂、CH₂OH、CH₂CH₂OH or CH₂CH(CH₃)OH。

2. A performance enhancer for porous granular ammonium fried food, characterized by comprising, by weight, 1 to 30 parts of the surfactant according to claim 1, 1 to 30 parts of a lower alcohol, 0 to 5 parts of an organic amine, 1 to 100 parts of water, and 0 to 5 parts of an auxiliary agent.

3. The performance enhancer for porous granular ammonium nitrate fuel oil explosives according to claim 2, characterized by comprising 1 to 10 parts by weight of the surfactant, 10 to 30 parts by weight of a lower alcohol, 0.1 to 1 part by weight of an organic amine, 50 to 100 parts by weight of water and 0 to 1 part by weight of an auxiliary agent.

4. The porous particulate ammonium fryer pharmaceutical performance enhancer according to claim 2 or 3, wherein the lower alcohol is at least one selected from the group consisting of methanol, ethanol, ethylene glycol, isopropanol, n-propanol, propylene glycol, glycerol and butanediol.

5. The porous particulate ammonium fryer performance enhancer according to any one of claims 2 to 4, wherein the organic amine is at least one selected from the group consisting of fatty amines, alcamines, and amides.

6. The performance enhancer for porous particulate ammonium nitrate fuel oil explosives according to claim 5, characterized in that the organic amine is selected from at least one of triethylamine, tripropylamine, N-butylamine, diisopropylamine, ethylenediamine, butanediamine, hexanediamine, ethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, N-methyldiethanolamine, N-dimethylethanolamine, N-diethylethanolamine, isobutanolamine, formamide, acetamide, propionamide, butyramide, isobutyramide, acrylamide, N-dimethylacetamide, N-dimethylformamide, and caprolactam.

7. The porous particulate ammonium fryer performance enhancer according to any one of claims 2 to 6, wherein the auxiliary agent is at least one selected from the group consisting of higher fatty acid salts, polyoxyethylene ether-type antifoaming agents, and polyether-modified silicone antifoaming agents.

8. A process for the preparation of a performance enhancer for a porous particulate ammonium nitrate-fuel oil explosive according to any of claims 2 to 7, characterized in that it comprises the following steps:

keeping the temperature of the surfactant to 20-60 ℃;

sequentially adding the organic amine, the low-carbon alcohol and the water, and uniformly mixing; and

and adding the auxiliary agent into the mixture, and uniformly mixing to obtain the additive for the porous granular ammonium nitrate fuel oil explosive.

9. A porous granular ammonium nitrate fuel oil explosive, which is characterized by comprising 90-100 parts by weight of porous granular ammonium nitrate, 1-10 parts by weight of fuel oil, and 0.1-5 parts by weight of a performance enhancer for porous granular ammonium explosives for oil explosives according to any one of claims 2-7 or a performance enhancer for porous granular ammonium nitrate fuel oil explosives prepared by the preparation method according to claim 8.

10. The porous particulate ammonium nitrate-oil explosive according to claim 9, characterized in that the fuel oil is selected from at least one of mineral oil distillates, biofuels, synthetic fuel oils and oily liquids derived from plant sources, animal sources and synthetic equivalents thereof, preferably diesel oil, ethylene glycol, higher fatty alcohols or lower esters of higher fatty acids.

Technical Field

The invention belongs to the field of functional chemicals, and particularly relates to a porous granular ammonium nitrate-fuel oil explosive surfactant, a porous granular ammonium nitrate-fuel oil explosive performance enhancer and a preparation method thereof, and a porous granular ammonium nitrate-fuel oil explosive.

Background

The porous granular ammonium nitrate fuel oil explosive, called ANFO for short, is a common on-site mixed explosive, is prepared by physically mixing porous granular ammonium nitrate and an oil phase, and has the advantages of simple production process, low cost, high cost performance and the like. ANFO is a typical heterogeneous mixed explosive, and the porous granular ammonium nitrate used is a substance with high porosity and high specific surface area, and the specific surface area can reach as high as 1000cm²·g^-1In general, the weight ratio is preferably 94% to 95% in order to satisfy the "zero oxygen balance" of the oxidizing agent and the reducing agent required for explosion. There is a great deal of research on the oil phase used in ANFO, and theoretically, all hydrocarbon fuels that can produce carbon dioxide and water after combustion can be used as the oil phase component of ANFO. The most commonly used oil phase component in practical production is diesel oil, which has a high calorific value and excellent flow propertiesThe ammonium nitrate can be formed into a stable substance through physical adsorption and full contact, and has good detonation performance. However, diesel fuel has the same obvious disadvantages: the flash point is low, the volatility is high, and strong pungent smell can be generated in field operation. And microscopically, in the adsorption process, diesel oil can spread on the surface layer of the porous granular ammonium nitrate, and the diesel oil and the porous granular ammonium nitrate have large surface tension difference and are easy to desorb under external vibration and bump, so that the oil spilling phenomenon of ANFO is caused, and the stability of the service performance of the ANFO is influenced. Therefore, in recent years, in order to improve various performance properties of ANFO, many materials have been applied to the oil phase component of ANFO, and there are several major categories:

the first type is waste oil: in recent years, with the increasing energy crisis, the energy is in shortage, and the petroleum derived products are frequently in short supply, which corresponds to the situation that a large amount of waste oil, such as waste mineral oil, waste edible oil, etc., is generated in China every year. If the post-treatment of a large amount of waste oil is not proper, not only is a large energy waste caused, but also the environment is inestimably polluted. Many researchers have therefore introduced waste oil into ANFO applications, enabling recycling of waste oil regeneration. Such as Song Ri, 2016,45(03):51-54.]The produced waste mineral oil replaces part of diesel oil, the oil phase components comprise 2.75 percent of waste mineral oil and 2.75 percent of diesel oil, and the kinematic viscosity at 40 ℃ is 12.0-17.7 mm²·s^-1The oil absorption was 9.8%. The composition of the waste mineral oil and the diesel oil ensures the appropriate viscosity and oil absorption rate of oil phase components, and the prepared ANFO meets the regulations of GB 17583-1998. CN 107311828A discloses that the viscosity of oil phase components prepared from waste mineral oil (waste engine oil, hydraulic oil, gear oil, etc.), heat value increaser (ferrocene, zinc peroxide, nitrate, etc.) and antifreeze (alcohols, naphthenic acid, aviation kerosene, etc.) is adjusted to be as low as 0.82g cm^-3The calorific value is as high as 4200 kJ.kg^-1The anti-freezing performance is good, the anti-freezing agent is suitable for being used for on-site mixed loading ANFO in northern cold areas, and the detonation velocity can reach 3612m & s at most^-1. Yue Chinese et al [ Yue Chinese, Yuqiang, Liyuqing, et al. engineering blasting 2015,21(04):1-5,44.]By utilizing the good compatibility of the grease and the diesel oil according to the wasteThe ratio of the edible oil to the diesel oil is 1:1, the kinematic viscosity is proper, the oil absorption rate of the porous granular ammonium nitrate is ensured, and the explosion velocity of the produced ANFO reaches 3287 m.s^-1. In a word, the application of the reclaimed oil in the ANFO not only greatly reduces the production cost and improves the economic benefit, but also plays a certain role in the cyclic utilization and the environmental protection of a large amount of generated waste oil, and has stronger social significance.

The second type is biomass fuel: the fuel oil has the advantages of low pollution, reproducibility, high heat value and the like, belongs to high-quality energy which is vigorously advocated and developed by the nation, and is also applied to ANFO. (1) Biodiesel oil: has higher heat value (close to that of diesel oil), has small difference in viscosity, flow property and diffusion property from diesel oil, can completely or partially replace diesel oil, has a flash point of more than 130 ℃, has no irritant and volatile smell, and has safety far higher than that of diesel oil. For example, CN 106316727 a discloses a method for preparing biodiesel, which is a biomass fuel oil prepared by subjecting hydrogenated oil (hydrogenated soybean oil, hydrogenated palm oil or hydrogenated rapeseed oil, etc.) to high-temperature catalytic cracking (350-450 ℃) in a catalyst (carbonate, alkali metal hydroxide, metal oxide, etc.), collecting petroleum ether, cooling the cracked product, distilling, collecting, etc., thereby improving the flash point and production safety of oil phase, suppressing the oil overflow defect of porous granular ammonium nitrate mixed with diesel oil, and significantly improving the performance of the prepared novel ANFO explosive. (2) Wood powder: the crushed natural material has high carbon-hydrogen mass fraction and large negative oxygen balance, can adjust the loosening degree of an explosive system, and is an excellent combustible agent, sensitizer and loosening agent. 22-24 parts of Guo Zhang Jiangjiang et al (Guo Zhang Jiangtang Zhang Tandong open-cast mining technology, 2009 (06)).]And Liuwanrong et al [ Liuwanrong, Zhang Jun, Zhang Chi Jun. open-air mining technology, 2005(2):13-14.]The ANFO was prepared by premixing 93% porous prill ammonium nitrate with 3% wood flour and blending with 4% diesel. The ANFO added with the wood powder reduces the explosive density, and the detonation velocity can reach 3486m & s^-1The blast hole explosive loading is reduced, the blasting unit consumption is reduced, and the method is suitable for blasting open-pit mines and soft rock stratums. (3) Bamboo charcoal powder: the bamboo is a natural product, and the bamboo is carbonized and crushed at 700-800 ℃ to prepare bamboo charcoal powder with the characteristics ofHigh specific surface area (the diameter of the bamboo charcoal powder with the particle diameter of 0.5 mm-1 mm can reach 350 m)²·g^-1) After the ANFO is mixed with diesel oil and porous granular ammonium nitrate, the volatilization of diesel oil components can be reduced to a certain degree, the external moisture can be prevented from entering, the stability of the ANFO is improved, hot spots are formed by a plurality of pores on the surface of the ANFO, and the explosive sensitivity of the ANFO can be improved to a certain degree. CN 103435428A discloses a preparation method of ANFO: after 93-95% of porous granular ammonium nitrate, 2.5-3% of light diesel oil and 1.5-4% of bamboo charcoal powder are mixed, the detonation velocity can reach 3486 m.s^-1. After the bamboo charcoal powder is added, the physical and chemical properties and detonation performance of ANFO can be changed to a certain extent, and the production cost is greatly reduced.

The third type is pulverized coal: coal is pulverized to form coal powder with a certain particle size, the coal powder is an energetic fuel mainly containing carbon elements, has high heat value and stable market source, and can be prepared into a good composite combustible agent by compounding with diesel oil.

Shenhua quanieng group company applies coal powder to ANFO field, Zhang Chijun et al (Zhang Chijun, Liuwanrong, Zhang Jun. blasting equipment, 2005(02): 10-11).]After tests, the mixture ratio of 94 percent of porous granular ammonium nitrate, 3.5 percent of diesel oil and 2.5 percent of coal powder is determined, and the detonation velocity of ANFO can reach 3061 m.s^-1The brisance is 18.5 mm; patent CN 105646113a of songi et al discloses that after fine coal powder is mixed with porous granular ammonium nitrate, good contact and uniform coverage can be formed on the surface of the fine coal powder due to the fact that the particle size of the fine coal powder is close to the pore size of the porous granular ammonium nitrate, and after 2.5% -3% of coal powder is used for replacing diesel oil, the detonation performance of ANFO is greatly improved, the blasting effect is good, the wave impedance is close to the wave impedance of rocks, and the maximum power of ANFO is exerted. Because the unit consumption of the explosive is low, the production cost is reduced, and the application range of the pulverized coal is expanded.

The fourth type is emulsified diesel oil: the emulsified diesel oil is W/O emulsion formed by shearing diesel oil and water or alcohol under the action of emulsifier and is homogeneous effective process for forming incompatible diesel oil and water or alcohol with great difference in polarity and surface tension. Such as Diehai Peak (Diehai Peak. coal and chemical, 2018,41(07):135-137, 15)1.]The stable water-containing emulsified diesel oil is prepared by emulsifying the emulsifier such as Span 80, sodium dodecyl benzene sulfonate, sodium methylene cellulose and the like by ultrasonic waves. When the prepared ANFO is under the explosion shock wave, the rapid thermal expansion can be generated, the high-temperature and high-pressure effect is formed, the water molecule particles can be rapidly vaporized under the system condition, the formed secondary atomization promotes the full reaction of the oil film, and the experimental result proves that: after the emulsified diesel oil is tightly fused with the porous granular ammonium nitrate, the manganese nitrate (ANFO) has the brisance and the detonation velocity (2870-3200 mS)^-1) Obviously improved and the storage period is obviously improved. Liu Xiao Ming, etc. [ Liu Xiao Ming, Qiluofu, original Wenji. coal science and technology, 2018,46(S2): 272-.]The composite oil-phase microemulsion is prepared from 75-85% of fuel oil, 5-10% of composite emulsifier and 0-5% of water, and is difficult to be compatible due to high surface tension of oil-water in general conditions, but oil-water solubilization can be carried out under the action of a proper emulsifier, so that a stable oil-water compatible state can be realized, the particles can reach the nanometer level, the flash point is 15 ℃ higher than that of common diesel oil, and tests show that: compared with the conventional ANFO, the explosion velocity of the ANFO prepared by the novel oil phase is improved by 20.7 percent, the work capacity is improved by 11 percent, and the emission of toxic gases is reduced by 12 percent. Nieuqi et al CN 103382143A discloses that ANFO prepared by mixing conventional fuel oil (diesel oil, lubricating oil, gasoline, vegetable oil, animal oil, coal oil, etc.), emulsifier (oleate, polyisobutylene succinimide, polyoxyethylene ether, Tween, triton, sodium dodecyl benzene sulfonate, etc.), low carbon alcohol solution and inorganic salt solution (nitrate, carbonate, sulfate, sulfonate, etc.) has higher detonation velocity (3300 m.s.^-1) And the work-doing ability, the content of toxic gas is reduced by about one third, and the method has stronger environmental protection significance.

In conclusion, the basic requirements of the oil phase material for the ANFO are high safety (high flash point, nonflammable and explosive property, lower saturated vapor pressure), low cost (abundant market sources and low cost), high performance (capable of effectively improving the explosion speed, the explosion speed and the work capacity of the ANFO), and the performance requirements are that the oil phase material has better fluidity, can have higher adsorption rate, higher saturated adsorption amount and lower oil-escaping desorption rate with porous granular ammonium nitrate. The waste oil, the biomass fuel, the coal powder, the emulsified diesel oil and the like are applied to ANFO, so that the problems of low flash point, high volatility, odor stimulation and the like of the existing diesel oil can be solved to a certain extent, the dependence of explosive production on the diesel oil is effectively relieved, and the explosive performance is improved.

However, many problems still exist in the using process, such as unstable waste oil source and large performance difference, and the harmful gas of the ANFO prepared by the method exceeds the standard after explosion; coal powder, wood powder, bamboo powder and the like are required to be crushed into smaller particles to have a good mixing effect with porous granular ammonium nitrate, so that dust pollution and environmental damage caused by the mixing effect cannot be ignored; the emulsified diesel oil needs to prepare immiscible diesel oil, alcohols and the like into emulsion by using a surfactant, a large amount of surfactant is used for thermodynamic stability of the emulsion, the cost advantage is not achieved, and the detonation performance of the explosive is not obviously improved.

Theoretically, porous granular ammonium nitrate is a hydrophilic substance having strong polarity, and the oil phase is a non-polar lipophilic substance. Surface tension gamma of diesel oil at 20 DEG C^l26.8mN · m^-1Surface tension of ammonium nitrate gamma^sUp to 90 mN.m^-1The contact angle theta between diesel oil and ammonium nitrate is about 114 degrees, and the diesel oil cannot be wetted and spread on the interface of the ammonium nitrate because the theta is more than 90 degrees. According to the Young's equation gamma^s＝γ^l-s+γ^lcos theta, calculating to obtain the diesel oil-ammonium nitrate interfacial tension gamma^l-sUp to 101.4 mN.m^-1Therefore, the diesel oil is easy to escape from the surface of the ammonium nitrate, the mixing uniformity of the porous granular ammonium nitrate and the diesel oil is difficult to obviously improve when the explosive is used on site, and the detonation performance of the explosive is not effectively improved.

Disclosure of Invention

The invention provides a porous granular ammonium nitrate explosive surfactant, which is prepared into a performance enhancer for porous granular ammonium nitrate oil explosives through a specific formula, and based on the difference of interfacial properties of porous granular ammonium nitrate and oil phase components, the surfactant overcomes the defects of slow mixing rate, nonuniform mixing, low explosive detonation performance and the like of porous granular ammonium nitrate oil explosives in the preparation process of the existing porous granular ammonium nitrate oil explosives.

Specifically, the invention provides the following technical scheme:

a porous granular ammonium surfactant for deep-fry use comprising at least one of compounds represented by the general formulae I, II and III;

the general formula I is specifically as follows:

in the general formula I, R₁Represents C₈～C₂₀Alkyl or C₈～C₂₀An alkenyl group; r₂Representative H, CH₃、CH₃CH₂、CH₂OH、CH₂CH₂OH or CH₂CH(CH₃)OH；R₃Represents CH₂，CH₂CH₂、CH₂CH(CH₃) Or C (CH)₃)₂CH₂；

The general formula II is specifically:

in the general formula II, R₄Represents C₈～C₂₀Alkyl or C₈～C₂₀An alkenyl group; r₅Represents CH₂，CH₂CH₂、CH₂CH(CH₃) Or C (CH)₃)₂CH₂；R₆And R₇Same or different, each independently represent H, CH₃、CH₃CH₂、CH₂OH、CH₂CH₂OH or CH₂CH(CH₃)OH；

The general formula III is specifically:

in the general formula III, R₈Represents C₈～C₂₀Alkyl or C₈～C₂₀An alkenyl group; r₉Represents CH₂，CH₂CH₂、CH₂CH(CH₃) Or C (CH)₃)₂CH₂；R₁₀And R₁₁Same or different, each independently represent H, CH₃、CH₃CH₂、CH₂OH、CH₂CH₂OH or CH₂CH(CH₃)OH。

The invention also provides a performance enhancer for the porous granular ammonium nitrate fuel oil explosive, which comprises 1-30 parts of the surfactant, 1-30 parts of low carbon alcohol, 0-5 parts of organic amine, 1-100 parts of water and 0-5 parts of an auxiliary agent in parts by weight.

Preferably, the performance enhancer for porous granular ammonium fried medicines comprises, by weight, 1-10 parts of the surfactant, 10-30 parts of low carbon alcohol, 0.1-1 part of organic amine, 50-100 parts of water and 0-1 part of an auxiliary agent.

Preferably, in the performance enhancer for porous granular ammonium nitrate fuel oil explosives, the lower alcohol is at least one selected from methanol, ethanol, ethylene glycol, isopropanol, n-propanol, propylene glycol, glycerol and butanediol.

Preferably, in the performance enhancer for porous granular ammonium nitrate fuel oil explosives, the organic amine is at least one selected from the group consisting of fatty amines, alcamines, and amides; further preferably, the organic amine is at least one selected from the group consisting of triethylamine, tripropylamine, N-butylamine, diisopropylamine, ethylenediamine, butanediamine, hexanediamine, ethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, N-methyldiethanolamine, N-dimethylethanolamine, N-diethylethanolamine, isobutanolamine, formamide, acetamide, propionamide, butyramide, isobutyramide, acrylamide, N-dimethylacetamide, N-dimethylformamide, and caprolactam.

Preferably, in the performance enhancer for porous granular ammonium nitrate fuel oil explosives, the auxiliary agent is at least one selected from higher fatty acid salts, polyoxyethylene ether defoaming agents, and polyether-modified silicone defoaming agents.

The invention also provides a preparation method of the performance enhancer for the porous granular ammonium nitrate fuel oil explosive, which comprises the following steps:

keeping the temperature of the surfactant to 20-60 ℃;

sequentially adding the organic amine, the low-carbon alcohol and the water, and uniformly mixing; and

and adding the auxiliary agent into the mixture, and uniformly mixing to obtain the additive for the porous granular ammonium nitrate fuel oil explosive.

Preferably, in the preparation method, as shown in fig. 1, the dosage of the surfactant can be determined according to the predetermined kinematic viscosity of the porous granular ammonium nitrate fuel oil explosive performance enhancer in practical application; the amount of the adjuvant may be determined in accordance with the predetermined foaming properties of the porous particulate anfo explosive property enhancer.

The invention also provides a porous granular ammonium nitrate fuel oil explosive which comprises 90-100 parts by weight of porous granular ammonium nitrate, 1-10 parts by weight of fuel oil and 0.1-5 parts by weight of performance enhancer for the porous granular ammonium nitrate fuel oil explosive or the performance enhancer for the porous granular ammonium nitrate fuel oil explosive prepared by the preparation method.

Preferably, in the above porous granular ammonium nitrate fuel oil explosive, the fuel oil is at least one selected from the group consisting of mineral oil distillate, biofuel, synthetic fuel oil, and oily liquid derived from plant sources, animal sources, and synthetic equivalents thereof, and more preferably diesel oil, ethylene glycol, higher fatty alcohol, or higher fatty acid lower ester.

Compared with the prior art, the invention has at least one of the following advantages and effects:

(1) the performance enhancer for the porous granular ammonium nitrate fuel oil explosive provided by the invention contains high-activity fatty acid alcohol amide, fatty acid alcohol amine ester or fatty acid alcohol amine salt surfactant, the hydrophilic part of the surfactant can be combined with the surface of ammonium nitrate, and the lipophilic part of the surfactant extends to diesel oil, so that the function of bridge connection is achieved, the extremely high interfacial tension of the diesel oil and the ammonium nitrate is reduced, the adsorption strength and the spreading degree of the diesel oil on the ammonium nitrate interface are improved, the diesel oil and the porous granular ammonium nitrate are tightly combined, and the explosion reaction performance is optimal;

(2) the performance enhancer for the porous granular ammonium nitrate fuel oil explosive contains low-carbon alcohol and organic amine, and polar groups such as hydroxyl, amino, imino, secondary amino and the like in the molecule of the performance enhancer are easier to be matched with NH in porous granular ammonium nitrate₄ ⁺、NO₃ ^-Combining to form a more stable structure; the low-carbon alcohol has higher heat value, and can promote the reaction to be rapidly carried out in the detonation process;

(3) in the porous granular ammonium nitrate fuel oil explosive containing the performance enhancer, water molecules are vaporized into tiny water vapor particles in the detonation process, more OH active groups are generated, the rapid progress of the detonation reaction is facilitated, the detonation of the explosive is promoted to be complete and sufficient, and the generation of smoke and harmful gases is reduced;

(4) the performance enhancer for the porous granular ammonium nitrate fuel oil explosive provided by the invention has the advantages that after 25-42% of diesel oil is replaced, the detonation performance (detonation velocity, brisance and work capacity) of the prepared porous granular ammonium nitrate fuel oil explosive is greatly improved, the dependence of explosive production on the diesel oil is effectively relieved, and the production cost is greatly reduced.

Drawings

Fig. 1 is a flow chart of the preparation of the performance enhancer for porous granular ammonium nitrate fuel oil explosives of the invention.

FIG. 2 is a schematic representation of the surfactant of the present invention acting at the interface between ammonium nitrate and diesel fuel;

FIG. 3 is a graph showing the results of the resistance to water erosion of the ANFO of the present invention.

Detailed Description

The inventor of the application aims at the problems that in the existing preparation process of the porous granular ammonium nitrate fuel oil explosive, the mixed adsorption strength of diesel oil and porous granular ammonium nitrate is low, the adsorption rate is low, the detonation performance is unstable, and the like, and provides the performance enhancer for the porous granular ammonium nitrate fuel oil explosive.

As shown in FIG. 2, the performance enhancer for porous granular ammonium nitrate fuel oil explosive provided by the invention contains high-activity fatty acid alcohol amide, fatty acid alcohol amine ester or fatThe acid alkanolamine salt surfactant contains hydrophilic groups such as hydroxyl, amido, amino, imino, ammonium salt and the like in the molecule, and lone pair electrons on O atom and N atom of the groups can react with NH₄ ⁺The diesel oil and the porous granular ammonium nitrate are tightly combined, so that the explosion reaction performance is optimal.

The surfactant is amide, carboxylic acid alcohol amine ester or carboxylic acid alcohol amine salt formed by fatty carboxylic acid and alcohol amine, and is respectively represented by a general formula I, a general formula II and a general formula III:

the general formula I is specifically as follows:

in the general formula I, R₁Represents C₈～C₂₀Alkyl or C₈～C₂₀An alkenyl group; r₂Representative H, CH₃、CH₃CH₂、CH₂OH、CH₂CH₂OH or CH₂CH(CH₃)OH；R₃Represents CH₂，CH₂CH₂、CH₂CH(CH₃) Or C (CH)₃)₂CH₂；

The general formula II is specifically:

in the general formula II, R₄Represents C₈～C₂₀Alkyl or C₈～C₂₀An alkenyl group; r₅Represents CH₂，CH₂CH₂、CH₂CH(CH₃) Or C (CH)₃)₂CH₂；R₆And R₇Same or different, each independently represent H, CH₃、CH₃CH₂、CH₂OH、CH₂CH₂OH or CH₂CH(CH₃)OH；

The general formula III is specifically:

in the general formula III, R₈Represents C₈～C₂₀Alkyl or C₈～C₂₀An alkenyl group; r₉Represents CH₂，CH₂CH₂、CH₂CH(CH₃) Or C (CH)₃)₂CH₂；R₁₀And R₁₁Same or different, each independently represent H, CH₃、CH₃CH₂、CH₂OH、CH₂CH₂OH or CH₂CH(CH₃)OH。

The performance enhancer for the porous granular ammonium nitrate fuel oil explosive contains low-carbon alcohol and organic amine, and polar groups such as hydroxyl, amino, imino, sub-amino and the like in the molecule of the performance enhancer are easier to be matched with NH in porous granular ammonium nitrate₄ ⁺、NO₃ ^-Combining to form a more stable structure; and the low-carbon alcohol has higher heat value, and can promote the reaction to be rapidly carried out in the detonation process.

In a preferred embodiment, the lower alcohol comprises at least one of methanol, ethanol, ethylene glycol, isopropanol, n-propanol, propylene glycol, glycerol, and butanediol.

In a preferred embodiment, the organic amine includes at least one of fatty amines, alcohol amines, and amides. The aliphatic amines, alkanolamines and amides include triethylamine, tripropylamine, N-butylamine, diisopropylamine, ethylenediamine, butanediamine, hexanediamine, ethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, N-methyldiethanolamine, N-dimethylethanolamine, N-diethylethanolamine, isobutanolamine, formamide, acetamide, propionamide, butyramide, isobutyramide, acrylamide, N-dimethylacetamide, N-dimethylformamide or caprolactam.

The porous granular ammonium nitrate fuel oil explosive prepared by the performance enhancer for the porous granular ammonium nitrate fuel oil explosive contains free water molecules, on one hand, the water molecules are vaporized into tiny water vapor particles in the detonation process to generate more OH active groups, which is beneficial to the rapid proceeding of the detonation reaction, promotes the detonation of the explosive to be complete and sufficient as possible, and reduces the generation of smog and harmful gases; on the other hand, theoretically, the existence of water molecules can erode porous granular ammonium nitrate and accelerate agglomeration and hardening of the porous granular ammonium nitrate fuel oil explosive, so that the internal particle size composition is changed, and the shelf life is greatly reduced, so that the influence of the performance enhancer of the porous granular ammonium nitrate fuel oil explosive on the erodibility of the porous granular ammonium nitrate fuel oil explosive needs to be examined.

In a preferred embodiment, the auxiliary agent includes at least one of a higher fatty acid salt, a polyoxyethylene ether type defoaming agent, a polyether modified silicone defoaming agent.

In a preferred embodiment, the performance enhancer for porous granular ammonium oil explosives provided by the invention is a flowable liquid at normal temperature, has a low kinematic viscosity, and has a freezing point at least below-20 ℃, so that the performance enhancer for porous granular ammonium oil explosives and porous granular ammonium nitrate still have a high adsorption rate in a low-temperature environment, and the specific technical parameters are shown in table 1.

TABLE 1

Technical project	Technical parameters	Test method
			Appearance of the product	Clear liquid easy to flow at normal temperature	Observation of
pH	6～10	GB/T 23769-2009
			Density (20 ℃ C.)/g-cm-3	0.90～1.10	GB/T 1884-2000
Kinematic viscosity (20 ℃ C.)/mm2·s-1	1.0～30.0	GB/T 265-1988
			Freezing point/. degree.C	≤-20.0	GB/T 2430-2008

It can be seen from table 1 that the performance index of the performance enhancer for porous granular ammonium nitrate fuel oil explosives of the invention can meet the requirements for producing porous granular ammonium nitrate fuel oil explosives.

The present invention will be described in further detail with reference to specific examples, but the scope of the present invention is not limited thereto. The features and advantages of the present invention will become more apparent as the description proceeds.

The experimental procedures used in the following examples are conventional unless otherwise specified. The experimental raw materials and the related equipments used in the following examples are commercially available unless otherwise specified.