Emulsification demolition agent for complex deflagration environment, and preparation method therefor
Patent Information
- Application Number
- PCT/CN2025/087216
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2025-03-25
- Filing Date
- 2025-04-03
- Publication Date
- 2026-10-01
Smart Images
Figure CN2025087216_01102026_PF_FP_ABST
Abstract
Description
An emulsifying and destructive agent for complex deflagration environments and its preparation method Technical Field
[0001] This invention belongs to the field of industrial destructive agent technology, and more specifically relates to an emulsified destructive agent for complex deflagration environments and its preparation method. Background Technology
[0002] In complex environments, the application of emulsion detonators is gaining increasing attention, particularly in the petroleum, chemical, and mining industries. Complex environments typically refer to those with extreme temperatures, pressures, pH levels, ionic strengths, or the presence of multiple interfering substances. In such environments, the performance of conventional detonators is affected, necessitating the selection of detonators with better stability and adaptability. Emulsion detonators for complex environments can also be applied to metal welding. Utilizing the enormous energy generated by the detonator's explosion, it drives metal plates to collide at high speed, creating high pressure at the contact surface and forming a metal jet, thus achieving a metallurgical bond. The application of emulsion detonators for complex environments can improve the welding effect of metal materials with vastly different physical properties. Therefore, emulsion detonators for complex environments hold an extremely important position in the explosive processing industry. Due to the special requirements of complex environment technology, the deflagration velocity of detonators used in complex environments must be controlled within the range of 1300 m / s to 2800 m / s to achieve better results, while the deflagration velocity of commonly used civilian detonators is generally between 3000 m / s and 6000 m / s. Therefore, reducing the deflagration velocity of detonators used in complex environments is of great practical significance.
[0003] Currently, detonating agents for complex environments, both domestically and internationally, are mainly prepared by mixing diluents such as salt, talc, and expanded perlite with powdered detonating agents such as expanded ammonium nitrate detonating agents, powdered modified ammonium oil detonating agents (ANFO), and powdered emulsified detonating agents in complex environments. Some researchers use oil and diluents to produce expanded ammonium oil detonating agents for complex environments, which exhibit excellent performance. However, these detonating agents are energy-intensive, generate significant dust, and are prone to moisture absorption and clumping in humid environments. Furthermore, diluents such as salt can corrode welded metals, and mixing diluents on-site increases safety hazards. Therefore, the prepared detonating agents must possess a suitable detonation rate, along with good flowability, stability, and processability, to be effectively applied in industrial applications.
[0004] Furthermore, current improved fracturing agent solutions still have many shortcomings. For example, Chinese patent CN102010169A discloses a static fracturing agent composed of the following raw materials by weight: 60-90 parts of hydrated expansive substance; 4-10 parts of hydraulic substance; 2-4 parts of hydration retarder; 1-2 parts of water-reducing agent; 2-4 parts of expansion enhancer; and 1-31 parts of cementing enhancer. Although this method can statically blast marble, the reaction time is long, which is time-consuming and labor-intensive. Chinese patent CN116199479A discloses a novel static fracturing agent and its preparation method. The main ingredient of this novel static fracturing agent, calcium oxide, has a high calcination temperature and a long isothermal time, and short-term exposure to air directly affects its performance. Meanwhile, existing technologies such as Chinese patents CN114163285A, CN112409111A, CN104341253A, and CN109369314A disclose emulsion explosives, whose raw materials include ammonium nitrate, sodium nitrate, and certain rare earth materials. However, these technologies fail to provide a comprehensive formulation scheme for fracturing agents in complex environments, particularly regarding deflagration rate control and the use of isooctanoic acid rare earth materials. They do not address the technical effects of reducing deflagration rate, and improvements in stability and adaptability under complex environmental conditions remain insufficient. Therefore, existing fracturing agents still have many drawbacks when applied to complex environments, including excessively high deflagration rates, excessive energy consumption, poor flowability, and safety hazards, requiring further optimization. Under complex environmental conditions, emulsion fracturing agents need to possess good thermal and chemical stability to ensure effectiveness during use. The aforementioned technical solutions do not meet the applicability requirements of fracturing agents in complex environments.
[0005] Therefore, how to provide an emulsifying and breaking agent for complex deflagration environments and its preparation method is a technical problem that urgently needs to be solved by those skilled in the art. Summary of the Invention
[0006] To overcome the shortcomings and deficiencies of existing technologies, this invention provides an emulsified detonator for complex deflagration environments with good explosive and safety performance, and its preparation method. It has the advantages of simple preparation process, high safety, high stability, and low sensitivity. To further optimize the performance of the detonator, research has found that adjusting the proportion of key raw materials, such as increasing the proportion of expanded graphite, can effectively control the deflagration rate and improve its stability.
[0007] To achieve the above objectives, the present invention adopts the following technical solution:
[0008] An emulsifying and breaking agent for complex deflagration environments comprises the following raw materials in parts by weight: 10-20 parts ammonium nitrate, 39-45 parts porous granular ammonium nitrate, 5-10 parts sodium nitrate, 10-20 parts water, 4-7 parts oil, 2-4 parts emulsifier, 2-10 parts nano aluminum powder, and 1-3 parts rare earth materials.
[0009] The beneficial effects of the above technical solution are as follows: adding aluminum powder to the fracturing agent can effectively enhance the total energy released during the explosion, and improve the fracturing agent's work capacity and explosive power. Aluminum has a high energy level in its oxidation reaction, but its reaction rate is usually much lower than that of a pure matrix fracturing agent. This results in the aluminum powder's reaction being completed and releasing energy during the expansion of the detonation products after the CJ plane. The detonation consists of two processes: the first process is the direct detonation reaction between the aluminum powder and the fracturing agent components, forming detonation products; the second process is the secondary reaction between the unreacted aluminum powder and the detonation gas products, forming the final detonation products.
[0010] Preferably, the raw material further includes expanded graphite.
[0011] The beneficial effects of the above technical solution are as follows: Expanded graphite has a loose and porous structure, is non-toxic and harmless, has a strong adsorption capacity for organic compounds, and also possesses properties such as high temperature resistance, low temperature resistance, corrosion resistance, and unique mechanical properties. Expanded graphite does not react with other raw materials in the formulation and can better mix with the emulsion matrix to form a more stable substance. Due to the unique physical properties of expanded graphite, when the emulsion matrix is mixed with expanded graphite, the volume of the resulting substance increases, and the water-in-oil emulsion matrix is not easily hygroscopic and has good flowability, allowing expanded graphite to be fully mixed into the substance, thereby forming a deflagration emulsion destructive agent.
[0012] Expanded graphite has good heat resistance and flame retardant properties, which makes deflagration emulsion detonators more sensitive and safer. The special structure of expanded graphite can effectively reduce the density of the emulsion detonator, thereby reducing the detonation propagation speed of the detonator.
[0013] Expanded graphite has a network-like internal structure, which plays an important role in improving the detonation sensitivity of the detonating agent. When a high-temperature emulsion matrix is mixed with expanded graphite, the emulsion matrix coats the surface of the expanded graphite and seals microbubbles, which can form "hot spots" during the explosion reaction, thereby improving the initiation and detonation propagation sensitivity of the detonating agent.
[0014] Preferably, the bulk density of the ammonium nitrate is 2.26 g / cm³. 3 .
[0015] Preferably, the porous granular ammonium nitrate has the chemical formula NH4NO3·nH2O, where n = 0.2 to 0.3.
[0016] Preferably, the porous granular ammonium nitrate has a bulk density of 0.8 g / cm³. 3 .
[0017] The beneficial effects of the above technical solution are as follows: Porous granular ammonium nitrate is a white granule with a porous appearance, loose texture, easy moisture absorption, contains water of crystallization in its molecules, has a lower melting point than ammonium nitrate, and is more prone to deliquescence and decomposition than ammonium nitrate. It can be directly added to the emulsion matrix. The large particle size of porous granular ammonium nitrate can better reduce the density of the decomposition agent, thereby reducing the deflagration rate.
[0018] Preferably, the oil is selected from one or more of engine oil, diesel oil, mineral oil, corn oil, soybean oil, paraffin wax, petrolatum wax, microcrystalline wax, and beeswax.
[0019] Preferably, the emulsifier is selected from one of polyisobutylene succinic anhydride derivatives, polyisobutylene succinic anhydride derivatives and a mixture of Span 80.
[0020] Preferably, the polyisobutylene succinic anhydride derivative is selected from one of the grades T151, T152, and T154.
[0021] Preferably, the rare earth material is rare earth isooctanoate.
[0022] The beneficial effects of the above technical solution are as follows: rare earth isooctanoate is safe, non-toxic, inexpensive, and possesses unique physical and chemical properties. It can be compounded with other metal salts to form a composite stabilizer, which can play a synergistic role and can better mix with the aqueous and oil phases to form a more stable substance. At the same time, rare earth materials can interact with the material surface to change the surface energy of the material, enabling the deflagration agent to be effectively dispersed, reducing the density and thus lowering the deflagration rate.
[0023] Preferably, the deflagration velocity of the emulsified destructive agent is 1800-2500 m / s.
[0024] This invention also provides a method for preparing the above-mentioned emulsifying and destructive agent for complex deflagration environments, comprising the following steps:
[0025] S1: At room temperature, ammonium nitrate, sodium nitrate, nano aluminum powder and water are mixed and stirred thoroughly to dissolve them, thus obtaining an aqueous phase;
[0026] S2: At room temperature, mix the emulsifier and oil thoroughly and stir until dissolved to obtain the oil phase;
[0027] S3: Slowly add the rare earth material and the aqueous phase obtained in step S1 into the oil phase, and stir in a mixer to obtain a water-in-oil emulsion matrix.
[0028] S4: The emulsified matrix obtained in step S3 is thoroughly mixed with porous granular ammonium nitrate to obtain a gel-like matrix;
[0029] S5: Add the colloidal matrix obtained in step S4 to the expanded graphite and disperse and mix evenly to obtain the emulsified fracturing agent.
[0030] Preferably, the stirring speed in step S3 is 1500 r / min and the stirring time is 6 min.
[0031] Preferably, the mass ratio of the colloidal matrix to the expanded graphite in step S5 is 80-90:10-20.
[0032] The beneficial effects of the above technical solution are as follows: Because the colloidal matrix has a certain degree of fluidity and adhesiveness, and expanded graphite has a certain degree of self-adhesion, it is easy to disperse and mix with expanded graphite. Thoroughly dispersing and mixing the freshly prepared colloidal matrix with expanded graphite plays an important role in improving stability.
[0033] As can be seen from the above technical solution, compared with the prior art, the present invention provides an emulsifying and destructive agent for complex deflagration environments and its preparation method, which has the following beneficial effects:
[0034] 1. The emulsified debriding agent obtained by the present invention has the advantages of simple preparation process, high safety, high stability and low sensitivity. It has a low deflagration rate and can meet the requirements of debriding agents for complex environments with dissimilar metals. It can be applied to different complex environments by adjusting the material ratio and dosage.
[0035] 2. Rare earth isooctanoate can be compounded with its metal salts to form a composite heat stabilizer, exhibiting a synergistic effect and enabling better mixing with the aqueous and oil phases to form a more stable substance. The emulsion matrix can form a stable W / O structure, and the emulsion matrix and expanded graphite are miscible, resulting in a fracturing agent that is not easily hygroscopic and has good flowability. Expanded graphite is a non-toxic substance, widely available, and moderately priced, reducing the cost of the fracturing agent. By adjusting the ratio of expanded graphite to porous granular ammonium nitrate, the density, deflagration rate, and sensitivity of the fracturing agent can be altered, thereby optimizing its application in specific environments. Increasing the proportion of expanded graphite significantly improves the hygroscopicity and flowability of the fracturing agent, reduces the deflagration rate, and increases the detonation sensitivity of the fracturing agent. Attached Figure Description
[0036] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.
[0037] Figure 1 is a process flow diagram of the present invention. Detailed Implementation
[0038] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0039] The process flow diagram of the present invention is shown in Figure 1, and the final product is the emulsified destructive agent, i.e., the explosive product.
[0040] Example 1
[0041] A method for preparing an emulsion-breaking agent for complex deflagration environments includes the following steps:
[0042] S1: At room temperature, mix 15 parts water, 5 parts nano aluminum powder, 15 parts ammonium nitrate, and 6 parts sodium nitrate, add them to an aqueous phase mixing tank and stir thoroughly to dissolve them, thus obtaining an aqueous phase;
[0043] S2: At room temperature, mix 4.5 parts of diesel and engine oil by equal proportion and 2.5 parts of emulsifier T-154, add them to the oil phase mixing tank, stir and mix to obtain the oil phase;
[0044] S3: At room temperature, slowly add the aqueous phase and 2 parts of rare earth isooctanoate to the oil phase, and continuously increase the speed to 1500 r / min and stir for 6 min in a stirrer to obtain a water-in-oil (W / O) emulsion matrix.
[0045] S4: Thoroughly mix the emulsified matrix with 40 parts of porous granular ammonium nitrate to obtain a gel-like matrix;
[0046] S5: Expanded graphite is added to the colloidal matrix. Under the continuous and thorough stirring and dispersion of the mixer, the expanded graphite and the colloidal matrix are fully combined to obtain the emulsified cleavage agent.
[0047] Example 2
[0048] A method for preparing an emulsion-disrupting agent for complex deflagration environments includes the following steps:
[0049] S1: At room temperature, mix 14 parts water, 6 parts nano aluminum powder, 14 parts ammonium nitrate, and 6 parts sodium nitrate, add them to an aqueous phase mixing tank and stir thoroughly to dissolve them, thus obtaining an aqueous phase;
[0050] S2: At room temperature, mix 4.5 parts of diesel and engine oil by equal proportion and 2 parts of emulsifier T-1542, add them to the oil phase mixing tank, stir and mix to obtain the oil phase;
[0051] S3: At room temperature, the aqueous phase and 1.5 parts of rare earth isooctanoate are slowly added to the oil phase, and the stirring speed is continuously increased to 1500 r / min and stirred for 6 min in a stirrer to obtain a water-in-oil (W / O) emulsion matrix.
[0052] S4: Mix the emulsified matrix thoroughly with 40 parts of porous granular ammonium nitrate to obtain a gel-like matrix.
[0053] S5: Expanded graphite is added to the colloidal matrix. Under the continuous and thorough stirring and dispersion of the mixer, the expanded graphite and the colloidal matrix are fully combined to obtain the emulsified cleavage agent.
[0054] Example 3
[0055] A method for preparing an emulsion-disrupting agent for complex deflagration environments includes the following steps:
[0056] S1: At room temperature, mix 13 parts water, 5.5 parts nano aluminum powder, 14 parts ammonium nitrate, and 6 parts sodium nitrate in an aqueous phase mixing tank and stir thoroughly to dissolve them to obtain an aqueous phase;
[0057] S2: At room temperature, mix 4.5 parts of diesel and engine oil by equal proportion and 2 parts of emulsifier T-1542, add them to the oil phase mixing tank, stir and mix to obtain the oil phase;
[0058] S3: At room temperature, slowly add the aqueous phase and 2 parts of rare earth isooctanoate to the oil phase, and continuously increase the speed to 1500 r / min and stir for 6 min in a stirrer to obtain a water-in-oil (W / O) emulsion matrix.
[0059] S4: The emulsified matrix was thoroughly mixed with 39 parts of porous granular ammonium nitrate to obtain a gel-like matrix;
[0060] S5: Expanded graphite is added to the colloidal matrix. Under the continuous and thorough stirring and dispersion of the mixer, the expanded graphite and the colloidal matrix are fully combined to finally obtain the emulsified cleavage agent.
[0061] Test Experiment
[0062] The deflagration rate was measured using a BSW-3A deflagration rate tester. The emulsion deactivating agent prepared in each embodiment was poured into a container with dimensions of 30cm in length, 3cm in width, and 3cm in height, and the deactivating agent thickness was 20mm. The distance between the two probes measuring the deflagration rate was 8cm. Each embodiment was tested three times, and the average value was taken. The results are shown in Table 1.
[0063] Table 1
[0064] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims
1. An emulsifying and destructive agent for complex deflagration environments, characterized in that, The raw materials include the following parts by weight: 10-20 parts ammonium nitrate, 39-45 parts porous granular ammonium nitrate, 5-10 parts sodium nitrate, 10-20 parts water, 4-7 parts oil, 2-4 parts emulsifier, 2-10 parts nano aluminum powder, and 1-3 parts rare earth materials.
2. The deflagration-prone complex environment emulsifying and breaking agent according to claim 1, characterized in that, The raw materials also include expanded graphite.
3. The deflagration-prone complex environment emulsifying and breaking agent according to claim 1, characterized in that, The porous granular ammonium nitrate has the chemical formula NH4NO3·nH2O, where n = 0.2–0.
3.
4. The deflagration-prone complex environment emulsifying and breaking agent according to claim 1, characterized in that, The oil is selected from one or more of the following: engine oil, diesel oil, mineral oil, corn oil, soybean oil, paraffin wax, petrolatum wax, microcrystalline wax, and beeswax.
5. The deflagration-prone complex environment emulsifying and breaking agent according to claim 1, characterized in that, The emulsifier is selected from one of polyisobutylene succinic anhydride derivatives, polyisobutylene succinic anhydride derivatives and a mixture of Span 80.
6. The deflagration-prone complex environment emulsifying and breaking agent according to claim 1, characterized in that, The rare earth material is rare earth isooctanoate.
7. A method for preparing an emulsified destructive agent for complex deflagration environments according to any one of claims 1-6, characterized in that, Includes the following steps: S1: At room temperature, ammonium nitrate, sodium nitrate, nano aluminum powder and water are mixed and stirred thoroughly to dissolve them, thus obtaining an aqueous phase; S2: At room temperature, mix the emulsifier and oil thoroughly and stir until dissolved to obtain the oil phase; S3: Slowly add the rare earth material and the aqueous phase obtained in step S1 into the oil phase, and stir in a mixer to obtain a water-in-oil emulsion matrix. S4: The emulsified matrix obtained in step S3 is thoroughly mixed with porous granular ammonium nitrate to obtain a gel-like matrix; S5: Add the colloidal matrix obtained in step S4 to the expanded graphite and disperse and mix evenly to obtain the emulsified fracturing agent.
8. A method for preparing an emulsified destructive agent for complex deflagration environments according to any one of claims 7, characterized in that, The stirring speed in step S3 is 1500 r / min, and the stirring time is 6 min.
9. A method for preparing an emulsified destructive agent for complex deflagration environments according to any one of claims 7, characterized in that, The mass ratio of the colloidal matrix to the expanded graphite in step S5 is 80-90:10-20.