Hydrogenated grease type emulsion explosive wax as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of petrifaction, and discloses hydrogenated grease type emulsion explosive wax as well as a preparation method and application thereof. Comprising hydrogenated oil, distillate oil, deoiled wax, foots oil and a thickening agent. Wherein the weight percentages of the hydrogenated grease, the distillate oil, the deoiled wax, the foots oil and the thickening agent are as follows: the use amount of the hydrogenated grease is 21-33%, the use amount of the distillate oil is 15-25%, the use amount of the deoiled wax is 28-38%, the use amount of the foots oil is 15-25%, and the use amount of the thickening agent is 2-8%. The emulsion explosive wax solves the problem of high unsaturated degree of the existing emulsion explosive wax, improves the melting point, reduces the oil content, improves the stability of grease to oxygen and heat, is convenient to store and transport, can improve the properties of the emulsion explosive wax, can reduce the cost, and improves the use performance of the product.

Description

Technical Field

[0001] The invention belongs to the technical field of petrochemicals and relates to a hydrogenated grease type emulsion explosive wax and a preparation method and application thereof. Background Art

[0002] Emulsion explosives first appeared in 1961, when Egly RS and others from the American Industrial Solvents Corp. mixed W / O emulsions with ordinary water-containing slurry explosives. In 1963, Gehrig NE of Atlas Chemical Industries in the United States further designed an emulsion explosive with only W / O emulsions and published a patent. In the development history of emulsion explosives, the first person to comprehensively explain the technology of emulsion explosives was Bluhm HF of Atlas, who first announced the water-in-oil emulsion explosive in 1969. At that time, the sensitivity of emulsion explosives was relatively low (non-detonator sensitive), and they needed to be detonated by detonating charges. Obviously, this large-diameter non-detonator sensitive emulsion explosive is very inconvenient to use. With the successful development of new products, new processes and new emulsifiers for emulsion explosives, the sensitivity of emulsion explosives has gradually improved. In 1972, Cattermole GR of DuPont proposed a formula and preparation process for improving detonation sensitivity by using organic amine nitrates (such as methylamine nitrates), and provided an emulsion explosive that can stably transmit detonation in small-diameter blastholes. In 1973, Tomic EA of DuPont used ammonium stearate or metal stearate as an emulsifier to prepare oil-in-water emulsion explosives that do not stick to bags. In 1977, Charles Wade G of Atlas invented an emulsion explosive that can be reliably detonated with a No. 6 detonator without adding explosive sensitizers and other organic amine nitrate sensitizers. Its main feature is that it uses the sensitization effect of hollow glass microspheres with appropriate particle size to make the emulsion explosive have detonator sensitivity. In 1978, Charles Wade G announced a US patent for the continuous production process and equipment of oil-in-water emulsion explosives, marking the entry of emulsion explosives into the stage of industrial production and field application.

[0003] In 1978, Atlas Powder Company of the United States began the industrial production of oil-in-water emulsion explosives. Due to the advantages of emulsion explosives such as excellent explosive performance and water resistance, wide sources of raw materials and low production costs, they have attracted the attention of industrial explosives in various countries and have begun to develop and produce emulsion explosives. my country began to develop emulsion explosives in the late 1970s and soon turned to industrial production. In September 1980, the "EL series emulsion explosives" developed by Beijing Research Institute of Mining and Metallurgy were the first to pass the technical appraisal hosted by the Ministry of Metallurgy and officially put into industrial production. More than ten years later, through the joint efforts of technical personnel, significant progress has been made in the varieties, performance, process equipment and safe production of emulsion explosives. At present, there are about dozens of explosives factories in China that produce emulsion explosives, with an annual output of more than 400,000 tons, accounting for more than 25% of the entire industrial explosives. my country is at the forefront of the world in the application and research of emulsion explosives. It can now produce explosives with different performances for open-pit mining, underground mining, coal mining, underwater blasting and oil seismic sources, basically meeting the needs of various blasting projects. Emulsion explosives products have been exported to neighboring countries, and the export volume has increased year by year. Certain production technologies have also been introduced to the international market.

[0004] Emulsion explosive is a kind of aqueous ammonium nitrate explosive and a new type of water-resistant explosive. It has been widely used due to its excellent detonation performance, stable storage performance, environmental friendliness, low processing cost, etc., and its application prospects are very broad. Emulsion explosive wax is the key component of emulsion explosive. As a continuous phase, due to the limitation of oxygen balance and the requirements of explosive performance, emulsion explosive wax is coated with more than 95% oxidant aqueous solution at a content of less than 5%, forming closely arranged polyhedral structure emulsified particles, so the viscosity, chain length, molecular structure, etc. of emulsion explosive wax are very important.

[0005] Choosing the right emulsion explosive wax can often greatly improve the performance of emulsion explosives, making it produce a very suitable application effect. The emulsion explosive wax commonly used at present is a hydrocarbon with a suitable viscosity, including all waxes, oils and various polymers. Polymers are often used to thicken oil phase materials and improve the appearance of the finished product. Any liquid petroleum product with a suitable viscosity can also be used as emulsion explosive wax, which includes various oils with viscosities ranging from thin liquids to non-flowing at room temperature, such as various brands of diesel, motor oil and white oil.

[0006] It is composed of oxidant aqueous solution, oil phase, emulsifier, stabilizer, sensitizer, high heat agent and other components, and belongs to the water-in-oil (W / O) type structure. The main components of emulsion explosives are as follows:

[0007] 1) The aqueous solution component of the inorganic oxidant that forms the dispersed phase. It is the basis for preparing emulsion explosives and is basically composed of ammonium nitrate dissolved in water by heating. Of course, it also includes other water-soluble oxidants that are compatible with latex, such as sodium nitrate, calcium nitrate, potassium nitrate, barium nitrate, zinc nitrate, ammonium perchlorate, sodium perchlorate, calcium perchlorate, methylammonium nitrate, urea nitrate, etc.

[0008] 2) A carbonaceous fuel component that forms a continuous phase. Generally speaking, any petroleum product with a suitable viscosity can be selected as a carbonaceous fuel component for emulsion explosives. The selection principle is to form a stable water-in-oil latex and to make the emulsified system thick and unable to flow at a certain temperature. This requires the carbonaceous fuel component to have the ability to provide different viscosities as the temperature changes. Diesel, heavy oil, motor oil, white oil, vaseline, composite wax, paraffin, microcrystalline wax, lignite wax, beeswax, spermaceti or mixtures thereof are all available fuels. Undoubtedly, many other organic compounds, such as olefins, aromatics, cycloalkanes, higher alcohols, saturated fatty acids, etc. are also available.

[0009] 3) Sensitizing gas component that forms the dispersed phase. Generally speaking, this component is added as the third phase, which can be air in the form of an envelope, tiny bubbles generated by decomposition reaction by adding certain chemicals (such as sodium nitrite, etc.), or solid particles enclosed with gas (such as hollow broken glass microspheres, expanded perlite particles, hollow resin microspheres, etc.).

[0010] 4) Water-in-oil emulsifier. Experience shows that most emulsifiers with HLB (Hydrophile Lipophile Balance) values ​​of 3 to 7 can be selected as emulsifiers for emulsion explosives. It can be a single emulsifier or a composite emulsifier composed of two or more emulsifiers. For example, sorbitan monooleate, xylitol monooleate (or mixed acid esters), etc.

[0011] The oil phase material of emulsion explosives can be broadly understood as a class of organic compounds that are insoluble in water. When an emulsifier is present, it forms a W / O type emulsion together with an oxidant salt solution. Obviously, it is one of the key components of this type of explosive. Because without these oil phase materials that constitute the continuous phase, the water-in-oil emulsion system will no longer exist.

[0012] Since the emulsion explosive wax is mainly prepared by blending paraffin wax, ozokerite wax, motor oil, diesel oil, etc., they are all products in the crude oil refining process. When preparing the emulsion explosive wax, they are compounded together, the process is repeated and the cost is increased. Therefore, if several raw materials can be directly extracted in the oil refining process to prepare the emulsion explosive wax, the refining process is reduced and the cost is reduced. Based on this consideration, methods for blending with petroleum refining intermediates as the main raw materials have emerged one after another. The raw materials they use are mainly normal and vacuum distillate oils, vacuum wax pastes, residual oil wax pastes, light deasphalted oils and heavy deasphalted oils. However, these existing formulas and preparation methods mainly have the following disadvantages: the oil content of the raw materials is relatively high, the needle penetration is too large, which will cause the explosives to be too sensitive and unsafe to store; the explosives are too thin and soft, and sensitization is difficult; the explosives are difficult to load into barrels, and the weight is insufficient, which affects the explosive performance. Summary of the invention

[0013] In order to overcome the deficiencies of the prior art, the present invention provides a hydrogenated oil-based emulsion explosive wax and a preparation method and application thereof, which solve the problem of high unsaturation of the prior emulsion explosive wax, increase the melting point, reduce the oil content, improve the stability of the oil to oxygen and heat, facilitate storage and transportation, and improve the properties of the emulsion explosive wax, reduce costs, and improve the performance of the product.

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

[0015] A hydrogenated grease type emulsion explosive wax comprises hydrogenated grease, distillate oil, deoiled wax, wax lower oil and thickener.

[0016] The weight percentages of hydrogenated fat, distillate oil, deoiled wax, wax oil and thickener are as follows: hydrogenated fat is 21-33%, distillate oil is 15-25%, deoiled wax is 28-38%, wax oil is 15-25% and thickener is 2-8%.

[0017] Furthermore, the thickener is a petroleum resin, the softening point of which is 100-110° C., the acid value is less than 1.0 mgKOH / g, and the ash content is less than 0.1%.

[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 viscosity of the oil under wax is 5.96 mm 2 / s, oil content is 34.9%, no trace of moisture, no mechanical impurities.

[0020] Furthermore, the deoiled wax has a needle penetration of 38.11 / 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 distillate oil has a needle penetration of 1771 / 10 mm, a drop melting point of 57.8 °C, and a viscosity of 10.55 mm 2 / s, oil content is 58.6%, no trace of moisture, no mechanical impurities.

[0022] The preparation method of the hydrogenated grease type emulsion explosive wax is as follows: raw materials are weighed according to the formula, heated until completely melted, and then stirred to mix, so as to produce the hydrogenated grease type 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 70°C, the deoiled wax to 80°C, the wax oil to 60°C, and the petroleum resin to 130°C. Mix all the raw materials, stir at 120°C for 20 minutes, and cool to room temperature.

[0024] The present invention also claims to protect the use of the hydrogenated grease type emulsion explosive wax prepared by the above preparation method in preparing emulsion explosives, and the oil phase material used in preparing emulsion explosives.

[0025] The hydrogenated grease type emulsion explosive wax prepared by the present invention is an important component for preparing emulsion explosives, and belongs to the oil phase material of emulsion explosives. It works together with oxidant aqueous solution, emulsifier, stabilizer, sensitizer, high heat agent and other components to form a continuous phase carbonaceous fuel component, that is, a water-in-oil (W / O) type structure. Since emulsion explosives have excellent explosion performance and water resistance, they can currently produce explosives with various different performances such as open-pit mines, underground mines, coal mines, underwater blasting and oil seismic sources, which can basically meet the needs of various blasting projects; emulsion explosive products have been exported to neighboring countries, and the export volume has increased year by year, and some production technologies have also been promoted to the international market.

[0026] The beneficial effects of the present invention compared with the prior art are:

[0027] The hydrogenated grease type emulsion explosive wax provided by the present invention solves the problems of narrow adjustable range of oil content of oil phase material and large needle penetration compared with the traditional emulsion explosive wax. The traditional emulsion explosive wax cannot be accurately regulated because the raw materials are mostly intermediate products and the oil content is not a key control index. If the oil content is too high, the explosive will be too sensitive and unsafe to store; the explosive is too thin and soft, and sensitization is difficult; the explosive is difficult to load into the barrel, the weight is insufficient, and the explosion performance is affected. If the oil content is too low and the needle penetration is too small, the sympathetic detonation performance of the explosive is affected, and the density of the drug roll is too large, and the explosion performance of the equivalent explosive is poor, especially in winter, the impact is more serious. Therefore, hydrogenated grease is introduced into the emulsion explosive wax as a raw material with a relatively stable oil content, which can effectively control the oil content of the product, so that it can achieve the purpose of formula optimization, improving the use effect, etc. In addition, hydrogenated grease belongs to a renewable resource, has a short regeneration cycle and is environmentally friendly, and can reduce the amount of products used in the crude oil refining process, that is, reduce the unnecessary use of non-renewable resources. DETAILED DESCRIPTION

[0028] 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. Hydrogenated fats are heated to 80°C, distillate oils are heated to 70°C, deoiled wax is heated to 80°C, wax oil is heated to 60°C, and petroleum resin is heated to 130°C. Mix all the raw materials, stir at 120°C for 20 minutes, and cool to room temperature.

[0029] Example 1

[0030] A hydrogenated oil type emulsion explosive wax, wherein the amount of hydrogenated oil is 28%, the amount of distillate oil is 19%, the amount of deoiled wax is 34%, the amount of wax oil is 15%, and the amount of thickener is 4%. The obtained plant type emulsion explosive wax has a needle penetration of 681 / 10mm, a drop melting point of 58.5℃, and a viscosity of 7.24mm 2 / s, oil content is 20.1%, no trace of moisture, no mechanical impurities, and flash point is 264℃.

[0031] Example 2

[0032] A hydrogenated oil type emulsion explosive wax, wherein the amount of hydrogenated oil is 21%, the amount of distillate oil is 25%, the amount of deoiled wax is 35%, the amount of wax oil is 15%, and the amount of thickener is 4%. The obtained plant type emulsion explosive wax has a needle penetration of 791 / 10mm, a drop melting point of 60.3℃, and a viscosity of 7.26mm 2 / s, oil content is 23.4%, no trace of moisture, no mechanical impurities, and flash point is 262℃.

[0033] Example 3

[0034] A hydrogenated oil type emulsion explosive wax, wherein the amount of hydrogenated oil is 30%, the amount of distillate oil is 20%, the amount of deoiled wax is 31%, the amount of wax oil is 15%, and the amount of thickener is 4%. The obtained plant type emulsion explosive wax has a needle penetration of 691 / 10mm, a drop melting point of 58.2℃, and a viscosity of 7.35mm 2 / s, oil content is 20.5%, no trace of moisture, no mechanical impurities, and the flash point is 263℃.

[0035] Example 4

[0036] A hydrogenated oil type emulsion explosive wax, wherein the amount of hydrogenated oil is 27%, the amount of distillate oil is 25%, the amount of deoiled wax is 28%, the amount of wax oil is 15%, and the amount of thickener is 5%. The obtained plant type emulsion explosive wax has a needle penetration of 761 / 10mm, a drop melting point of 57.9℃, and a viscosity of 7.43mm 2 / s, oil content is 23.4%, no trace of moisture, no mechanical impurities, and flash point is 263℃.

[0037] Example 5

[0038] A hydrogenated oil type emulsion explosive wax, wherein the amount of hydrogenated oil is 33%, the amount of distillate oil is 23%, the amount of deoiled wax is 28%, the amount of wax oil is 15%, and the amount of thickener is 1%. The obtained plant type emulsion explosive wax has a needle penetration of 681 / 10mm, a drop melting point of 58.1℃, and a viscosity of 7.72mm 2 / s, oil content is 22.4%, no trace of moisture, no mechanical impurities, and flash point is 261℃.

[0039] Comparative Example 1

[0040] A hydrogenated oil type emulsion explosive wax, wherein the amount of hydrogenated oil is 35%, the amount of distillate oil is 21%, the amount of deoiled wax is 28%, the amount of wax oil is 15%, and the amount of thickener is 1%. The obtained plant type emulsion explosive wax has a needle penetration of 681 / 10mm, a drop melting point of 59.0℃, and a viscosity of 7.86mm 2 / s, oil content is 18.1%, no trace of moisture, no mechanical impurities, and flash point is 263℃.

[0041] Comparative Example 2

[0042] A hydrogenated oil type emulsion explosive wax, wherein the amount of hydrogenated oil is 20%, the amount of distillate oil is 25%, the amount of deoiled wax is 30%, the amount of wax oil is 17%, and the amount of thickener is 8%. The obtained plant type emulsion explosive wax has a needle penetration of 791 / 10mm, a drop melting point of 56.1℃, and a viscosity of 9.21mm 2 / s, oil content is 24.1%, no trace of moisture, no mechanical impurities, and flash point is 261℃.

[0043] Comparative Example 3

[0044] A hydrogenated oil type emulsion explosive wax, wherein the amount of hydrogenated oil is 10%, the amount of distillate oil is 25%, the amount of deoiled wax is 38%, the amount of wax oil is 24%, and the amount of thickener is 3%. The obtained plant type emulsion explosive wax has a needle penetration of 911 / 10mm, a drop melting point of 58.0℃, and a viscosity of 6.97mm 2 / s, oil content is 26.5%, no trace of moisture, no mechanical impurities, and flash point is 261℃.

[0045] Application Example 1

[0046] Proof of application of "Plant-based emulsion explosive wax series products"

[0047] The plant-based emulsion explosive wax product produced by the First Oil Plant of Fushun Petrochemical Company according to Example 1 has a dark yellow appearance; it is applied to the production of 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.

[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 hydrogenated grease type emulsion explosive wax, Its characteristics are: Including hydrogenated oils, distillate oils, deoiled waxes, wax oils, and thickeners.

2. A hydrogenated oil type emulsion explosive wax as claimed in claim 1, Its characteristics are: The weight percentages of hydrogenated fat, distillate oil, deoiled wax, wax oil and thickener are as follows: hydrogenated fat is 21-33%, distillate oil is 15-25%, deoiled wax is 28-38%, wax oil is 15-25% and thickener is 2-8%.

3. A hydrogenated oil type emulsion explosive wax as claimed in claim 1, Its characteristics are: The thickener is a petroleum resin, the softening point of which is 100-110°C, the acid value is less than 1.0 mgKOH / g, and the ash content is less than 0.1%.

4. A hydrogenated oil type emulsion explosive wax as claimed in claim 1, 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 hydrogenated oil type emulsion explosive wax as claimed in claim 1, Its characteristic is that wax The viscosity of the lower oil is 5.96 mm 2 / s, the oil content is 34.9%, there are traces of moisture, and there are no mechanical impurities.

6. A hydrogenated oil type emulsion explosive wax as claimed in claim 1, Its characteristics are: The needle penetration of deoiled wax is 38.11 / 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 hydrogenated oil-based emulsion explosive wax as claimed in claim 1, Its characteristics are: The penetration of distillate oil is 1771 / 10mm, the melting point is 57.8℃, and the viscosity is 10.55mm 2 / s, oil content is 58.6%, no trace of moisture, no mechanical impurities.

8. A method for preparing a hydrogenated oil-based emulsion explosive wax as claimed in claim 2, Its characteristics are: The raw materials are weighed according to the formula, heated until completely melted, and then mixed by stirring to produce the hydrogenated oil type emulsion explosive wax.

9. A method for preparing a hydrogenated oil-based emulsion explosive wax as claimed in claim 8, Its characteristics are: Weigh each raw material according to the formula ratio, and then heat them until they are completely melted; heat the hydrogenated oil to 80°C, the distillate oil to 70°C, the deoiled wax to 80°C, the wax oil to 60°C, and the petroleum resin to 130°C; mix all the raw materials, stir at 120°C for 20 minutes, and cool to room temperature.