Low-temperature composite oil phase for emulsion explosive, preparation method of low-temperature composite oil phase and emulsion explosive

Abstract

The invention provides a low-temperature composite oil phase for an emulsion explosive, a preparation method of the low-temperature composite oil phase and the emulsion explosive. The low-temperature composite oil phase for the emulsion explosive comprises the following raw materials in parts by weight: 50-55% of wax special for explosives, 0-6% of engine oil, 1-3% of vaseline, 22-38% of a composite emulsifier and 1-6% of soybean lecithin. The compound emulsifier comprises 1%-5% of an H1507C type polymer emulsifier, 1%-3% of a KL-118b type compound emulsifier and 20%-30% of an Sp-80 emulsifier. According to the low-temperature composite oil phase for the emulsion explosive, the composite emulsifier compounded in the low-temperature composite oil phase is optimized and is comprehensively blended with other components, so that the oil film stability of the emulsion explosive can be remarkably enhanced, and the emulsion explosive with high stability can be prepared.

Description

Technical Field

[0001] The invention belongs to the field of emulsion explosives, and in particular relates to a low-temperature composite oil phase for emulsion explosives, a preparation method thereof, and the emulsion explosive. Background Art

[0002] Emulsion explosives are mainly oil-in-water structures. During use, they have the advantages of simple production process and equipment, excellent explosive performance, good resistance, and a wide range of raw material sources. For this reason, emulsion explosives have always been favored by people. The oil phase is a continuous phase and is one of the main components of emulsion explosives. Research on oil phase materials has always been the center of research in the blasting industry. In recent years, new composite oil phases have appeared in people's vision and attracted the attention of the masses. Therefore, the formula of the composite oil phase and the material composition and properties in the composite oil phase have become the focus of research. In the industrial production of emulsion explosives, choosing the right oil phase formula and oil phase materials can not only reduce production costs but also prepare emulsion explosives with stable properties and good explosiveness.

[0003] However, the existing composite oil phase technology uses a relatively single emulsifier component, which often makes it difficult to prepare emulsion explosives with stable properties. Controlling the components of the composite oil phase of emulsion explosives has become a key problem in improving their performance. Summary of the invention

[0004] The technical problem to be solved by the present invention is that the emulsifier component used in the existing composite oil phase technology is relatively single, and the shortcomings and defects mentioned in the above background technology are overcome to provide a low-temperature composite oil phase for emulsion explosives, a preparation method thereof and an emulsion explosive.

[0005] In order to solve the above technical problems, the technical solution proposed by the present invention is:

[0006] A low-temperature composite oil phase for emulsion explosives comprises the following raw materials in parts by weight:

[0007] 50% to 55% of special wax for explosives, 0% to 6% of engine oil, 1% to 3% of vaseline, 22% to 38% of compound emulsifier, and 1% to 6% of soybean lecithin;

[0008] The composite emulsifier comprises 1% to 5% of H1507C polymer emulsifier, 1% to 3% of KL-118b composite emulsifier and 20% to 30% of Sp-80 emulsifier.

[0009] Emulsifier is the most critical component of emulsion explosives. When a single emulsifier is used, it is often not possible to prepare an emulsion explosive with stable properties. Therefore, the present application designs a composite emulsifier, which contains three surfactant components: H1507C polymer emulsifier, KL-118b composite emulsifier and Sp-80 emulsifier, which are mixed in a specific ratio to achieve a better emulsification effect. Compared with a single emulsifier, the composite emulsifier of the present application has at least the following advantages:

[0010] (1) The composite emulsifier has stronger emulsifying performance, which improves the oil film thickness and strength of the composite emulsifier emulsion explosive, thereby improving the storage stability of the emulsion explosive and extending the effective service life of the emulsion explosive;

[0011] (2) The viscous resistance of the composite emulsifier in the emulsion explosive is significantly greater than that of the single emulsifier, which hinders the flocculation of the emulsion explosive and is beneficial to improving the stability of the emulsion explosive.

[0012] (3) By using composite emulsifiers, the membrane strength of each molecule of the emulsion explosive is increased, and it is easiest to achieve close stacking. Therefore, the molecules of the emulsion explosive are not easy to coagulate, and the stability of the emulsion explosive is greatly improved.

[0013] (4) Composite emulsifiers can increase the starting temperature and activation energy of thermal decomposition of emulsion explosives, and can also optimize the detonation performance of emulsion explosives.

[0014] Soybean lecithin acts as an auxiliary emulsifier and works together with the composite emulsifier to further enhance the emulsification effect of the oil-water phase. Soybean lecithin is an amphoteric surfactant containing polar and non-polar groups. In emulsion explosives, its non-polar part is arranged in rows in the oil phase, and the polar end is arranged in rows on the surface of the water phase. These oil droplets repel each other and decompose in the two phases, thus forming a stable emulsion with good emulsification, dispersibility, wettability and permeability. In addition, the structure of soybean lecithin is similar to that of triglycerides, and it is easy to complex with other small molecules to form a stable network structure, which is beneficial to enhance the stability of the emulsification system.

[0015] Explosive wax, engine oil and vaseline are used as composite wax materials to increase the film-forming strength of the emulsified matrix and extend the storage period of the emulsion explosive. The components of the present application cooperate with each other to jointly improve the stability and performance of the emulsion explosive.

[0016] Preferably, the active ingredients of the KL-118b type composite emulsifier include Sp-80 emulsifier and lecithin.

[0017] The active ingredients of KL-118b composite emulsifier are phospholipids and lecithin. The phospholipid molecules have a lipophilic part (including two fatty acid chains attached to the glycerol main frame structure) and a hydrophilic part composed of choline phosphate, choline or inositol. This molecular structure makes lecithin emulsifying and dispersing. It is a pure natural surfactant. As a surfactant, it has two groups, hydrophilic and lipophilic; therefore, lecithin is a good fat emulsifier. In the production process of emulsified explosives, lecithin can help form the emulsion and stabilize it. Lecithin can easily form a network structure with other molecules and be "embedded" into the bulky voids to form a thick and tightly packed "complex" film on the interface. The packing density and strength of the film and the apparent viscosity of the emulsion are greatly improved, overcoming the swelling phenomenon of a single emulsifier and inhibiting the movement of latex particles. Even under adverse conditions, the W / O structure can be maintained, thereby improving the stability of the emulsion explosive. At the same time, the latex particles formed are miniaturized and evenly distributed, and the contact area between the aqueous solution of oxidants such as ammonium nitrate and the oil phase is large, which is beneficial to improving the explosive performance.

[0018] Preferably, the active ingredient of the H1507C polymer emulsifier comprises polyisobutylene succinimide.

[0019] Polyisobutylene succinimide, the active ingredient of polymer emulsifier, has the following advantages:

[0020] ① Both ends of the polyisobutylene succinimide emulsifier molecule are lipophilic polyisobutylene segments, and the middle part is a polar group of succinimide structure, which accounts for less than 6% of the entire molecule. It is completely different from ordinary water-in-oil emulsifiers. It cannot form emulsified micelles in the oil phase, resulting in the polyisobutylene succinimide emulsifier being able to form a single molecule dispersion state in the oil phase;

[0021] ② The effect of polyisobutylene succinimide emulsifier between oil and water phases is not only physical, but also chemical adsorption. The imide part in the emulsifier has hydrogen bonding with nitrate and water in the water phase, thereby reducing the interfacial tension between the two phases of emulsion explosives and improving the stability of emulsion explosives.

[0022] ③ In the latex particle oil film, the molecules of polyisobutylene succinimide emulsifier are freely stretched macromolecular segments, which can firmly adsorb small molecular substances in the oil phase around themselves, spread on the surface of the latex particles, and form a continuous and tough oil film. In addition, the macromolecular chain inhibits the crystallization of nitrates internally and enhances the water resistance of the latex particles externally, which is conducive to the formation of a dense protective film.

[0023] Sp-80 emulsifier is sorbitan monooleate, whose main raw materials are oleic acid and sorbitol. It is synthesized by chemical reaction under catalyst conditions. It is a typical polyol low-molecular non-ionic surfactant. From the chemical structure point of view, one end of it is a polar hydrophilic group, and the carbon-hydrogen bond at the other end is a non-polar hydrophobic group. It is an excellent oil-in-water surfactant with good emulsification, dispersion, penetration and solubilization properties.

[0024] Preferably, the synthesis method of the H1507C polymer emulsifier comprises a two-step synthesis by chlorination, wherein the first step is the hydrocarbonization reaction of polyisobutylene and maleic anhydride under the catalytic action of chlorine to generate an olefin anhydride intermediate, and the second step is the reaction of the olefin anhydride intermediate with polyene polyamine to generate polyisobutylene succinimide.

[0025] Under the same technical concept, the present invention also provides a method for preparing a low-temperature composite oil phase for emulsion explosives, which specifically comprises the following steps:

[0026] The weighed solid raw materials of the low-temperature composite oil phase are heated and melted respectively, and the melted solid raw materials are mixed with the composite emulsifier and soybean lecithin in sequence;

[0027] The mixing and preparing sequence is: firstly, melted wax for explosives, vaseline and engine oil are mixed, cooled to 80-85° C., and composite emulsifier and soybean lecithin are added in sequence to obtain a low-temperature composite oil phase for emulsified explosives.

[0028] Different materials have different carbonization temperatures. In order to reduce the carbonization of materials during the oil phase preparation process and reduce the loss of components in the materials, this application strictly limits the order of adding materials to ensure the final composite and effective active ingredient effect.

[0029] Preferably, the heating and melting are as follows: the heating temperature of the special wax for explosives and vaseline is 95-105°C, the heating temperature of soybean lecithin is 55-60°C, and the heating temperature of Sp-80 emulsifier and composite emulsifier is 70-80°C.

[0030] Under the same technical concept, the present invention also provides an emulsion explosive, the raw materials of which include the low-temperature composite oil phase for emulsion explosive or are prepared by the method for preparing the low-temperature composite oil phase for emulsion explosive.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] (1) The present application provides a low-temperature composite oil phase for emulsion explosives. By optimizing the composite emulsifier therein and comprehensively formulating it with other components, the oil film stability of the emulsion explosive can be significantly enhanced, which helps to prepare an emulsion explosive with strong stability.

[0033] (2) The present application provides a method for preparing a low-temperature composite oil phase for emulsion explosives. The low-temperature composite oil phase is prepared at low temperature throughout the entire process. The preparation method is simple, the preparation environment is good, and it has high industrial value.

[0034] (3) The emulsion explosive provided by the present application has excellent stability and explosion performance. DETAILED DESCRIPTION

[0035] In order to facilitate the understanding of the present invention, the present invention will be described more comprehensively and carefully in combination with preferred embodiments below, but the protection scope of the present invention is not limited to the following specific embodiments.

[0036] Unless otherwise defined, all professional terms used below have the same meanings as those generally understood by those skilled in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0037] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0038] Embodiment: 1:

[0039] This embodiment provides a low-temperature composite oil phase for emulsion explosives, comprising the following raw materials in parts by weight:

[0040] 52.6% 2# wax for explosives, 4.5% engine oil, 2% vaseline, 6% soybean lecithin, and 34.9% composite emulsifier; among them, 2# wax for explosives is 2# wax for explosives from Nanyang Xinrun New Energy Co., Ltd.; the composite emulsifier includes 5% H1507C polymer emulsifier from Gansu Herui Petrochemical Technology Co., Ltd. and 2.5% KL-118b composite emulsifier and 27.4% Sp-80 emulsifier from Hunan Nanling Fine Chemical Co., Ltd. The active ingredients of KL-118b composite emulsifier include Sp-80 and lecithin, and the active ingredients of H1507C polymer emulsifier include polyisobutylene succinimide.

[0041] This embodiment provides a method for preparing the low-temperature composite oil phase for the emulsion explosive, comprising the following steps:

[0042] The above-mentioned raw materials are weighed and measured by weight ratio, and then put into their respective melting tanks for heating and melting. In order to prevent the carbonization of each material due to excessive heating time, the melting temperature of each material is strictly controlled; the heating and melting temperature of 2# explosive compound wax and vaseline is 95-105°C, the heating temperature of soybean lecithin is 55-60°C, and the heating temperature of Sp-80 emulsifier, H1507C polymer emulsifier, and KL-118b compound emulsifier is 70-80°C;

[0043] After melting, the materials are pumped into the preparation tank for the preparation of the composite oil phase. During the preparation process, the order of adding materials is to first add 2# composite wax, vaseline, and engine oil for explosives, and then add Sp-80 emulsifier, H1507C polymer emulsifier, KL-118b composite emulsifier and soybean lecithin when the temperature drops to 80℃-85℃ to obtain a low-temperature composite oil phase for emulsified explosives.

[0044] This embodiment provides an emulsion explosive, which is prepared from the emulsion explosive using the low-temperature composite oil phase. The performance of the emulsion explosive sample was tested, and the test results are shown in Tables 1 and 2.

[0045] Embodiment 2:

[0046] This embodiment provides a low-temperature composite oil phase for emulsion explosives, comprising the following raw materials in parts by weight:

[0047] 52.6% 2# special wax for explosives, 4.5% motor oil, 2% vaseline, 6% soybean lecithin and 34.9% compound emulsifier; among them, 2# special wax for explosives is the No. 2 special wax for explosives produced by Nanyang Xinrun New Energy Co., Ltd.; the compound emulsifier includes 4.5% H1507C polymer emulsifier produced by Gansu Herui Petrochemical Technology Co., Ltd. and 3% KL-118b compound emulsifier and 27.4% Sp-80 emulsifier produced by Hunan Nanling Fine Chemical Co., Ltd.

[0048] This embodiment provides a method for preparing the low-temperature composite oil phase for the emulsion explosive, comprising the following steps:

[0049] The above-mentioned raw materials are weighed and measured by weight ratio, and then put into their respective melting tanks for heating and melting. In order to prevent the carbonization of each material due to excessive heating time, the melting temperature of each material is strictly controlled; the heating and melting temperature of 2# explosive compound wax and vaseline is 95-105°C, the heating temperature of soybean lecithin is 55-60°C, and the heating temperature of Sp-80 emulsifier, H1507C polymer emulsifier, and KL-118b compound emulsifier is 70-80°C;

[0050] After melting, the materials are pumped into the preparation tank for the preparation of the composite oil phase. During the preparation process, the order of adding materials is to first add 2# composite wax, vaseline, and engine oil for explosives, and then add Sp-80 emulsifier, H1507C polymer emulsifier, KL-118b composite emulsifier and soybean lecithin when the temperature drops to 80℃-85℃ to obtain a low-temperature composite oil phase for emulsified explosives.

[0051] This embodiment provides an emulsion explosive, which is prepared from the emulsion explosive using the low-temperature composite oil phase. The performance of the emulsion explosive sample was tested, and the test results are shown in Tables 1 and 2.

[0052] Comparative Example 1:

[0053] This comparative example provides a low-temperature composite oil phase for emulsion explosives, comprising the following raw materials in parts by weight:

[0054] 2# dynamite wax 52.6%, engine oil 4.5%, vaseline 2%, Sp-80 emulsifier 34.9%, soybean lecithin 6%; among them, 2# dynamite wax is the 2# dynamite wax of Nanyang Xinrun New Energy Co., Ltd.;

[0055] This comparative example provides a method for preparing the low-temperature composite oil phase for the emulsion explosive, comprising the following steps:

[0056] The above-mentioned raw materials are weighed and measured by weight, and then put into their respective melting tanks for heating and melting. In order to prevent the carbonization of each material due to excessive heating time, the melting temperature of each material is strictly controlled; the heating and melting temperature of 2# explosive compound wax and vaseline is 95-105°C, the heating temperature of soybean lecithin is 55-60°C, and the heating temperature of Sp-80 emulsifier is 70-80°C;

[0057] After melting, the materials are pumped into the preparation tank for the preparation of the composite oil phase. During the preparation process, the order of adding materials is to first add 2# composite wax, vaseline, and engine oil for explosives, and then add Sp-80 emulsifier and soybean lecithin when the temperature drops to 80℃-85℃ to obtain a low-temperature composite oil phase for emulsified explosives.

[0058] This comparative example provides an emulsion explosive prepared by using the low-temperature composite oil phase for the emulsion explosive. The performance of the emulsion explosive sample was tested using the GB / T 12440 lead column compression method for explosive intensity test, the GB / T 13228 industrial explosive detonation velocity determination method, and the WJ / T9055 industrial explosive sympathetic detonation distance test method. The test results are shown in Tables 1 and 2.

[0059] Table 1 is the performance index of the finished composite oil phase of the present invention

[0060]

[0061]

[0062] Table 2 Initial explosion performance of emulsion explosive prepared by the present invention

[0063]

[0064] From Table 1 and Table 2, it can be seen that the kinematic viscosity of the oil phase prepared by using the composite emulsifier is greater than that of the single emulsifier SP-80, and the sympathetic detonation, intensity (the lead column compression of the explosive sample with the composite emulsifier is greater than the lead column compression of the single emulsifier) ​​and detonation velocity of the prepared emulsion explosive are all improved to a certain extent.

[0065] Table 3 Detonation performance of Example 1 after high and low temperature cycles

[0066] Cycle times Sympathetic explosion (cm) Sharpness(mm) Explosive speed (m / s) 0 7 17.14 5196 4 6 16.65 4977 8 6 16.54 4862 12 5 15.16 4690

[0067] Table 4 Detonation performance of comparative example 1 after high and low temperature cycles

[0068] Cycle times Sympathetic explosion (cm) Sharpness(mm) Explosive speed (m / s) 0 6 15.46 4818 4 5 14.86 4649 8 3 14.16 4344 12 3 12.82 3581

[0069] In order to evaluate the storage stability of emulsion explosives in a simple, fast, accurate and reliable manner, this patent uses a high and low temperature cycle method to reflect the effect of temperature changes on the stability of explosives. This method is relatively intuitive, simple and easy to implement. Its basic principle is to artificially create an environment with continuous changes in high and low temperatures, and freeze the emulsion explosive sample at low temperature for a period of time, and then place it at a higher temperature for a period of time. The cold and hot cycles are regarded as a cycle to accelerate the aging of the emulsion explosive, so that the storage stability of the emulsion explosive can be predicted in a shorter time, and the advantages and disadvantages of the patented formula can be relatively compared. The experiment of this application is to place the emulsion explosive sample at a high temperature of 50°C for 8 hours and at a low temperature of -15°C for 16 hours as a complete cycle of temperature change.

[0070] When the high and low temperature cycle test was carried out for Example 1 and Comparative Example 1, the detonation performance of both of them decreased to a certain extent as the number of high and low temperature cycle tests increased. The results show that the detonation velocity of the emulsion explosive is constantly decreasing with the increase of the number of high and low temperature tests. This shows that during the high and low temperature cycle test, the severe change of the ambient temperature will inevitably affect the physical state of the system, and finally destroy the emulsified colloid, resulting in crystal precipitation and deterioration of the explosion performance.

[0071] It can be seen from Tables 3 and 4 that the detonation performance of Example 1 is relatively stable when it undergoes high and low temperature cycles. After 12 cycles, the detonation is still maintained at 5 cm, while the intensity and detonation velocity are 15.16 mm and 4690 m / s. Compared with a single emulsifier, the use of a composite emulsifier effectively improves the storage stability of the emulsion explosive.

Claims

1. A low-temperature composite oil phase for emulsion explosives, characterized in that: The invention comprises the following raw materials in parts by weight: 50% to 55% of special wax for explosives, 0% to 6% of engine oil, 1% to 3% of vaseline, 22% to 38% of compound emulsifier, and 1% to 6% of soybean lecithin; The composite emulsifier comprises 1% to 5% of H1507C polymer emulsifier, 1% to 3% of KL-118b composite emulsifier and 20% to 30% of Sp-80 emulsifier.

2. The low-temperature composite oil phase for emulsion explosive according to claim 2, characterized in that: The effective ingredients of the KL-118b composite emulsifier include Sp-80 and lecithin.

3. The low-temperature composite oil phase for emulsion explosive according to claim 2, characterized in that: The effective component of the H1507C polymer emulsifier includes polyisobutylene succinimide.

4. The low-temperature composite oil phase for emulsion explosive according to claim 3, characterized in that: The synthesis method of the H1507C polymer emulsifier comprises a two-step synthesis by chlorination, wherein the first step is the hydrocarbonization reaction of polyisobutylene and maleic anhydride under the catalytic action of chlorine to generate an olefin anhydride intermediate, and the second step is the olefin anhydride intermediate and polyene polyamine to generate polyisobutylene succinimide.

5. A method for preparing a low-temperature composite oil phase for emulsion explosive according to any one of claims 1 to 4, characterized in that: The specific steps include: The weighed solid raw materials of the low-temperature composite oil phase are heated and melted respectively, and the melted solid raw materials are mixed with the composite emulsifier and soybean lecithin in sequence; The mixing and preparing sequence is: firstly, melted wax for explosives, vaseline and engine oil are mixed, cooled to 80-85° C., and composite emulsifier and soybean lecithin are added in sequence to obtain a low-temperature composite oil phase for emulsified explosives.

6. The preparation method according to claim 5, characterized in that: The melting temperatures of the heated and melted materials are as follows: the heating temperature of the wax for explosives and vaseline is 95-105°C, the heating temperature of soybean lecithin is 55-60°C, and the heating temperature of the composite emulsifier is 70-80°C.

7. An emulsion explosive, characterized in that: The raw material of the emulsion explosive comprises the low-temperature composite oil phase for emulsion explosive as claimed in any one of claims 1 to 4 or is prepared by the method for preparing the low-temperature composite oil phase for emulsion explosive as claimed in any one of claims 5 to 6.

Images