Special composite wax for powdery emulsion explosive as well as preparation method and application of special composite wax

Abstract

The invention belongs to the technical field of petrifaction, and discloses special composite wax for powdery emulsion explosives as well as a preparation method and application of the special composite wax. Comprising hydrogenated oil, distillate oil, paraffin, light deoiled oil and a thickening agent. All the raw materials are weighed according to the formula proportion and then heated to be in a complete melting state. Heating the hydrogenated grease to 80 DEG C, heating the distillate oil to 80 DEG C, heating the paraffin to 80 DEG C, heating the light deoiling oil to 90 DEG C, mixing the four raw materials, then adding the weighed rosin, stirring for 20 minutes at the temperature of 130 DEG C, and cooling to room temperature. The amount of the hydrogenated grease is specifically limited, and the hardness of the composition can be improved and controlled not to be too high through a specific preparation method, so that the composition is beneficial to transportation, storage and use to a certain extent. And a better use effect is achieved.

Description

Technical Field

[0001] The invention belongs to the technical field of petrochemicals and relates to a special composite wax for powdered emulsion explosives and a preparation method and application thereof. Background Art

[0002] Powdered emulsion explosive is a new type of explosive with excellent performance developed in recent years. It is also called powdered emulsion explosive. It has the advantages of both powdered explosive and emulsion explosive. It is a powdered ammonium nitrate explosive made by atomizing powder and other methods, with fine droplets of oxidant solution with low water content as dispersed phase and oil phase solution composed of specific carbonaceous fuel and emulsifier as continuous phase. Under certain process conditions, it forms an oil-in-water type emulsion through strong shearing. Because emulsion explosive has a thermodynamically unstable latex structure at the microscopic level, its storage period is short. At the same time, its ointment-like form makes it difficult to fill the blasthole in small-diameter blasting operations. In addition, the high water content causes the emulsion explosive to lose part of its energy due to water vaporization during detonation. It is under this situation that, in order to overcome these shortcomings of emulsion explosives, people have developed solid emulsion explosives that have both the excellent performance of emulsion explosives and the characteristics of general industrial explosives. Solid emulsion explosives are first formed into water-in-oil emulsions using emulsification technology, and then different solid products are obtained using different methods. Solid emulsion explosives mainly include powdered emulsion explosives, emulsified granular explosives and cast emulsion explosives. Among the three, powdered emulsion explosives are the most widely used.

[0003] The research on powdered emulsion explosives began in 1989. The former Explosive Bureau of the General Corps organized scientific researchers to set up a research project. After more than two years of hard work, the laboratory preparation was completed in 1991, and the invention patent was applied for in 1992. In 1994, the Beijing Research Institute of Mining and Metallurgy disclosed the patent for the manufacture of powdered emulsion explosives by rotary flash evaporation. Shortly after the completion of the laboratory preparation, the expanded test of powdered emulsion explosives was started under the organization of the Explosive Bureau of the General Corps to apply the scientific research results to production as soon as possible. In January 1997, the powdered emulsion explosive passed the production appraisal at the Jiangsu Piaoyang Mining Chemical Material Factory, marking the official transformation of this scientific and technological achievement into productivity. Due to the advantages of low production cost, good explosive performance, strong water resistance, non-toxicity, and low environmental pollution, this product was quickly promoted and used. At present, more than 20 factories in China have invested in the production of powdered emulsion explosives. After several years of production practice, powdered emulsion explosives have achieved continuous and automated production, with an annual production capacity of 7,000 tons per line.

[0004] The main raw material of emulsion explosives is ammonium nitrate, which is a high-energy surface substance. Due to the electrostatic effect between polar molecules, it is easy to absorb and wet water, and its hygroscopicity is extremely strong. According to the "salt bridge" theory, the solubility of ammonium nitrate in water varies greatly with temperature. After absorbing moisture, a saturated solution film is formed on the surface. Under the action of surface tension, a "salt bridge" is formed between adjacent particles. When the air temperature or humidity decreases, the ammonium nitrate dissolved in the "salt bridge" will crystallize into small rhombus polyhedral crystals, forming a "salt bridge" to make its particles tightly combined together to form a dense hard block, resulting in reduced explosive performance of explosives, difficulty in detonation, and even explosion refusal. The finer the ammonium nitrate particles, the higher the explosive performance of the explosive produced with it, but the stronger its agglomeration.

[0005] Petroleum wax is a non-polar material. It is evenly coated on the surface of ammonium nitrate particles to form a hydrophobic layer, which changes the surface energy of ammonium nitrate from high polarity to low non-polarity, reduces its adsorption and wettability to water vapor, and effectively improves its hygroscopicity. Cutting off the intermediate link of ammonium nitrate adsorption of water, preventing water from entering the interior of ammonium nitrate, and improving the water resistance and anti-caking properties of emulsion explosives. In addition, in the explosive formula, petroleum wax materials are reducing agents, which are in close contact with the oxidant ammonium nitrate, increasing the explosive performance of the explosive. Therefore, emulsion explosive wax is one of the main factors affecting the performance of explosives. The main basis for the selection of emulsion explosive oil phase materials is the carbon distribution and distillation range of each component. When the emulsion explosive wax has a more reasonable carbon distribution and distillation range, an oil film with better density, higher strength and better stability can be formed during emulsification, and the emulsion explosive can have a longer storage period.

[0006] If the oil content of the oil phase material is too high and the needle penetration is too high, the explosive will be too sensitive and unsafe to store; the explosive will be too thin and soft, making it difficult to sensitize; and the explosive will be difficult to load into the tube and the weight will be insufficient, affecting the explosive performance. If the oil content is too low and the needle penetration is too small, the sympathetic detonation performance of the explosive will be affected, and the density of the explosive roll will be too high, resulting in poor explosive performance of the equivalent explosive, especially in winter, where the impact is more serious.

[0007] Emulsion explosives are water-resistant, non-toxic, and have low smoke. However, they also have disadvantages such as being soft, difficult to load, inconvenient to use, and less powerful than ammonium nitrate explosives.

[0008] Powdered emulsion explosives have a microstructure similar to that of emulsion explosives, with an outer layer of oil film and loose ammonium nitrate crystals inside. There is a saturated ammonium nitrate aqueous solution between the oil film and the ammonium nitrate structure.

[0009] Due to its powdery appearance and low water content, compared with emulsion explosives, while maintaining the good water resistance and ideal detonation performance of emulsion explosives, powdered emulsion explosives have better stability, are more convenient to produce, transport and use, are more in line with people's usage habits, and have greater explosive power. At the same time, since powdered emulsion explosives do not contain toxic single-element high explosives such as TNT, the production environment is good, the environment is not polluted during use, and it is easy to achieve continuous and automated production, with high production efficiency and low labor intensity for workers. Therefore, it is an ideal new type of explosive to replace ammonium-tNT explosives.

[0010] The organic oil phase material of the powdered emulsion explosive forms the continuous phase of the emulsified matrix together with the emulsifier. The organic oil phase material should not only be conducive to the formation and stability of the emulsified matrix, but also have a certain fluidity and softness during the cooling, solidification and dispersion of the latex, so that the continuous phase oil film can repair the coating defects of the oxidant grains to a certain extent. At the same time, the continuous phase oil film composed of the organic oil phase material and the emulsifier must also have a certain strength to prevent the oxidant phase grains from breaking through the oil film barrier layer and connecting into pieces.

[0011] As a powdered ammonium nitrate explosive with a special structure, powdered emulsion explosive is a fluid emulsion product at the beginning of production and the final form is a solid powder. Therefore, the physical properties of the raw materials used must be able to meet the needs of this transformation. Compared with the oil phase material of emulsion explosive, the oil phase material of powdered emulsion explosive has greater hardness, lower oil content and higher drop melting point.

[0012] However, these existing formulas and preparation methods have the following main disadvantages: the oil content of the raw materials generally used to prepare powdered emulsion explosive wax is uncontrolled, resulting in a large needle penetration, which can only be adjusted by using paraffin products with a lower oil content. However, paraffin products are limited in resources and relatively expensive, and the improvement in needle penetration is not obvious. A large amount of paraffin products needs to be added to achieve some improvement, which results in a large waste of non-renewable resources. Summary of the invention

[0013] In order to overcome the shortcomings of the prior art, the present invention provides a special composite wax for powdered emulsion explosives and a preparation method and application thereof, wherein hydrogenated fat is introduced into the formula of the composite wax for powdered emulsion explosives, the amount of hydrogenated fat is specifically limited, and a specific preparation method is used to increase its hardness and control its hardness not to be too high, which is beneficial to transportation, storage and use to a certain extent, and achieves better use effect.

[0014] The above object of the present invention is achieved through the following technical solutions:

[0015] A special composite wax for powdered emulsion explosives comprises hydrogenated grease, distillate oil, paraffin, light deoiling and thickener.

[0016] The weight percentages of hydrogenated fat, distillate oil, paraffin, light deoiling and thickener are as follows: hydrogenated fat is 5-15%, distillate oil is 5-15%, paraffin is 40-48%, light deoiling is 30-39% and thickener is 4-8%.

[0017] Furthermore, the thickener is rosin, which is a yellow transparent solid with a softening point of not less than 75°C, an acid value of not less than 165 mgKOH / g, an unsaponifiable matter content of not more than 5%, an ethanol infusible matter of not more than 0.03%, and an ash content of not more than 0.03%.

[0018] Furthermore, the penetration of hydrogenated oil is 4.21 / 10mm, the melting point is 59.9℃, and the viscosity is 9.38mm 2 / s, oil content is 0.72%, no trace of moisture, no mechanical impurities.

[0019] Furthermore, the distillate oil has a needle penetration of 1771 / 10 mm, a drop melting point of 63.6 °C, and a viscosity of 10.55 mm 2 / s, oil content is 56.6%, no trace of moisture, no mechanical impurities.

[0020] Furthermore, the paraffin wax has a needle penetration of 381 / 10 mm, a drop melting point of 66.7 °C, and a viscosity of 5.61 mm 2 / s, oil content is 0.98%, no trace of moisture, no mechanical impurities.

[0021] Furthermore, the light deoiling needle penetration is 1541 / 10mm, the drop melting point is 78.0℃, and the viscosity is 25.74mm 2 / s, oil content is 46.07%, no trace of moisture, no mechanical impurities.

[0022] The preparation method of the above-mentioned special composite wax for powdered emulsion explosives is as follows: raw materials are weighed according to the formula, heated until completely melted, and then stirred to mix, so as to produce hydrogenated oil type powdered emulsion explosive wax.

[0023] Furthermore, the specific preparation method is as follows: weigh each raw material according to the formula ratio, and then heat it to a completely melted state. Heat the hydrogenated fat to 80°C, the distillate oil to 80°C, the paraffin to 80°C, and the light deoiling to 90°C, mix the above four raw materials, then add the weighed rosin, stir at 130°C for 20 minutes, and cool to room temperature.

[0024] The present invention also claims to protect the use of the special composite wax for powdered emulsion explosive prepared by the preparation method in preparing powdered emulsion explosive.

[0025] The special composite wax for powdered emulsion explosive provided by the present invention is mainly used in the production of powdered emulsion explosive. Ammonium nitrate, as the main raw material of emulsion explosive, belongs to high-energy surface material. Because of the electrostatic effect between its polar molecules, it has strong hygroscopicity and is particularly easy to absorb moisture in the surrounding environment. According to the "salt bridge" theory, as the temperature rises, the solubility of ammonium nitrate in water also increases. As the solubility increases, a layer of solution film will be attached to the surface of ammonium nitrate. Adjacent particles will form a "salt bridge" under the action of surface tension. When the air temperature decreases or the humidity decreases, ammonium nitrate will dissolve and crystallize in the "salt bridge" to form rhombus-shaped polyhedral fine crystals, forming a new "salt bridge". The internal particles are closely combined to form a dense hard block, thereby causing the explosive to agglomerate and affect the explosive performance. In severe cases, even explosion refusal occurs. Due to the above reasons, the finer the ammonium nitrate particles, the stronger the agglomeration, but the higher the explosive performance of the explosive produced by it. There are many types of organic compounds as oil phase materials for emulsion explosives, and the range of options is quite wide. Generally speaking, the selection of oil phase materials is closely related to the role played by these materials in emulsion explosives. Although the final product of emulsion explosives can have a solid or nearly solid appearance, the external phase of the initially prepared emulsion system must be liquid or have sufficient fluidity to form an emulsion at the temperature of emulsification and mixing. That is to say, the oil phase material component should have the ability to provide different viscosities as the temperature changes. For example, diesel, motor oil, paraffin and waxy polymers are all commonly used oil phase materials in emulsion explosives. Although they have different appearances at room temperature, they can easily form a fluid state when heated, which is convenient for emulsification and mixing with emulsifiers and oxidizer aqueous solutions.

[0026] As the component of the oil phase material of the external phase of the emulsion explosive, its consistency is usually very important for maintaining tiny sensitized bubbles, which are necessary for the emulsion explosive product to have the required sensitivity. If the viscosity of the product is too large during production, storage and use, the sensitized bubbles will tend to coalesce and escape, which is obviously unfavorable for the detonation sensitivity of the emulsion explosive. In addition, if the viscosity is too high, the emulsion system formed is easy to "age", which is unfavorable to the storage stability.

[0027] The beneficial effects of the present invention compared with the prior art are:

[0028] The present invention provides a special composite wax for powdered emulsion explosives. The present invention adds hydrogenated oil to improve the hardness of the powdered emulsion explosive composite wax to a certain extent. However, once the hardness of the powdered emulsion explosive composite wax is too high (the needle penetration is too small), the coating film will become brittle and easy to break, especially in the mechanical crushing and powder making process, which seriously affects the water resistance and stability of the emulsion explosive. The present application can solve the above problems by limiting the specific ratio and the specific preparation method, and the prepared powdered emulsion explosive special composite wax has good overall physical and chemical properties. DETAILED DESCRIPTION

[0029] The present invention is described in detail below through specific examples, but the protection scope of the present invention is not limited. Unless otherwise specified, the experimental methods adopted in the present invention are all conventional methods, and the experimental equipment, materials, reagents, etc. used can be obtained from commercial channels. The percentages of raw materials used in the embodiments and comparative examples are all weight percentages. The specific preparation method is: weigh each raw material according to the formula ratio, and then heat it to a completely melted state. Heat the hydrogenated oil to 80°C, the distillate oil to 80°C, the paraffin to 80°C, and the light deoiling to 90°C. Mix the above four raw materials, then add the weighed rosin, stir at 130°C for 20 minutes, and cool to room temperature.

[0030] Example 1

[0031] A composite wax for powdered emulsion explosives, wherein the amount of hydrogenated oil is 5%, the amount of distillate oil is 10%, the amount of paraffin is 45%, the amount of light deoiling is 35%, and the amount of thickener is 5%. The obtained composite wax for powdered emulsion explosives has a needle penetration of 361 / 10mm, a drop melting point of 60.0℃, and a viscosity of 8.34mm 2 / s, oil content is 26.0%, no trace of moisture, no mechanical impurities, and flash point is 276℃.

[0032] Example 2

[0033] A special composite wax for powdered emulsion explosives, wherein the amount of hydrogenated oil is 8%, the amount of distillate oil is 10%, the amount of paraffin is 42%, the amount of light deoiling is 35%, and the amount of thickener is 5%. The obtained special composite wax for powdered emulsion explosives has a needle penetration of 381 / 10mm, a drop melting point of 60.0℃, and a viscosity of 8.46mm 2 / s, oil content is 25.8%, no trace of moisture, no mechanical impurities, and flash point is 275℃.

[0034] Example 3

[0035] A special composite wax for powdered emulsion explosives, wherein the amount of hydrogenated oil is 14%, the amount of distillate oil is 12%, the amount of paraffin is 40%, the amount of light deoiling is 30%, and the amount of thickener is 4%. The obtained special composite wax for powdered emulsion explosives has a needle penetration of 341 / 10mm, a drop melting point of 58.9℃, and a viscosity of 7.58mm 2 / s, oil content is 25.1%, no trace of moisture, no mechanical impurities, and flash point is 277℃.

[0036] Example 4

[0037] A special composite wax for powdered emulsion explosives, wherein the amount of hydrogenated oil is 9%, the amount of distillate oil is 8%, the amount of paraffin is 48%, the amount of light deoiling is 30%, and the amount of thickener is 5%. The obtained special composite wax for powdered emulsion explosives has a needle penetration of 311 / 10mm, a drop melting point of 58.9℃, and a viscosity of 8.03mm 2 / s, oil content is 22.2%, no trace of moisture, no mechanical impurities, and flash point is 273℃.

[0038] Example 5

[0039] A special composite wax for powdered emulsion explosives, wherein the amount of hydrogenated oil is 9%, the amount of distillate oil is 15%, the amount of paraffin is 41%, the amount of light deoiling is 30%, and the amount of thickener is 5%. The obtained special composite wax for powdered emulsion explosives has a needle penetration of 351 / 10mm, a drop melting point of 59.6℃, and a viscosity of 8.17mm 2 / s, oil content is 26.2%, no trace of moisture, no mechanical impurities, and flash point is 275℃.

[0040] Comparative Example 1

[0041] A special composite wax for powdered emulsion explosives, wherein the amount of hydrogenated oil is 16%, the amount of distillate oil is 5%, the amount of paraffin is 41%, the amount of light deoiling is 30%, and the amount of thickener is 8%. The obtained special composite wax for powdered emulsion explosives has a needle penetration of 291 / 10mm, a drop melting point of 58.2℃, and a viscosity of 7.38mm 2 / s, oil content is 19.5%, no trace of moisture, no mechanical impurities, and flash point is 274℃.

[0042] Comparative Example 2

[0043] A special composite wax for powdered emulsion explosives, wherein the amount of hydrogenated oil is 6%, the amount of distillate oil is 10%, the amount of paraffin is 34%, the amount of light deoiling is 40%, and the amount of thickener is 10%. The obtained special composite wax for powdered emulsion explosives has a needle penetration of 371 / 10mm, a drop melting point of 58.2℃, and a viscosity of 9.12mm 2 / s, oil content is 19.8%, no trace of moisture, no mechanical impurities, and flash point is 274℃.

[0044] Comparative Example 3

[0045] A special composite wax for powdered emulsion explosives, wherein the amount of hydrogenated oil is 40%, the amount of distillate oil is 10%, the amount of paraffin is 5%, the amount of light deoiling is 40%, and the amount of thickener is 5%. The obtained special composite wax for powdered emulsion explosives has a needle penetration of 331 / 10mm, a drop melting point of 58.8℃, and a viscosity of 9.03mm 2 / s, oil content is 28.3%, no trace of moisture, no mechanical impurities, and flash point is 274℃.

[0046] Application Example 1

[0047] The plant-based powdered emulsion explosive wax product produced by the first petroleum plant of Fushun Petrochemical Company according to Example 1 has a yellow-brown appearance; it is used in the production of powdered emulsion explosives by Nanjing Qunfeng Composite Materials Co., Ltd., and has good compatibility with the emulsifier of Nanjing Qunfeng Composite Materials Co., Ltd., and the produced emulsion explosive has excellent quality, good stability, and strong bombing performance. It is odorless, safe and environmentally friendly.

[0048] The above-described embodiments are only preferred embodiments of the present invention, but not all feasible embodiments of the present invention. For those skilled in the art, any obvious changes made thereto without departing from the principles and spirit of the present invention should be considered to be included in the scope of protection of the claims of the present invention.

Claims

1. A composite wax for powdered emulsion explosives, Its characteristics are: Including hydrogenated oils, distillate oils, paraffin, light deoiling, and thickeners.

2. A composite wax for powdered emulsion explosive as claimed in claim 1, Its characteristics are: The weight percentages of hydrogenated fat, distillate oil, paraffin, light deoiling and thickener are as follows: hydrogenated fat is 5-15%, distillate oil is 5-15%, paraffin is 40-48%, light deoiling is 30-39% and thickener is 4-8%.

3. A composite wax for powdered emulsion explosive as claimed in claim 2, Its characteristics are: The thickener is rosin, which is a yellow transparent solid with a softening point of not less than 75°C, an acid value of not less than 165 mgKOH / g, an unsaponifiable matter content of not more than 5%, an ethanol insoluble matter of not more than 0.03%, and an ash content of not more than 0.03%.

4. A composite wax for powdered emulsion explosive as claimed in claim 3, Its characteristics are: The penetration of hydrogenated oil is 4.21 / 10mm, the melting point is 59.9℃, and the viscosity is 9.38mm 2 / s, oil content is 0.72%, no trace of moisture, no mechanical impurities.

5. A composite wax for powdered emulsion explosive as claimed in claim 4, Its characteristics are: The penetration of the distillate oil is 1771 / 10mm, the melting point is 63.6℃, ​​and the viscosity is 10.55mm 2 / s, oil content is 56.6%, no trace of moisture, no mechanical impurities.

6. A composite wax for powdered emulsion explosive as claimed in claim 5, Its characteristic is that paraffin The needle penetration is 381 / 10mm, the melting point is 66.7℃, and the viscosity is 5.61mm 2 / s, oil content is 0.98%, no trace of moisture, no mechanical impurities.

7. A composite wax for powdered emulsion explosive as claimed in claim 6, Its characteristics are: The light deoiling needle penetration is 1541 / 10mm, the melting point is 78.0℃, and the viscosity is 25.74mm 2 / s, oil content is 46.07%, no trace of moisture, no mechanical impurities.

8. A composite wax for powdered emulsion explosive as claimed in claim 7, Its characteristics are: The preparation method of the special composite wax for powdered emulsion explosive is as follows: raw materials are weighed according to the formula, heated until completely melted, and then mixed by stirring to produce the hydrogenated oil type powdered emulsion explosive wax.

9. A composite wax for powdered emulsion explosive as claimed in claim 8, Its characteristics are: Weigh each raw material according to the formula ratio, and then heat it until it is completely melted. Heat the hydrogenated oil to 80℃, the distillate oil to 80℃, the paraffin to 80℃, and the light deoiling to 90℃, mix the above four raw materials, then add the weighed rosin, stir at 130℃ for 20 minutes, and cool to room temperature.