Composite sensitizer and preparation method thereof, and preparation method of mixed emulsion explosive
By using a composite sensitizer composed of sodium nitrite, fluorinated graphite microspheres and foaming agent, the problems of poor detonation performance and safety risks in emulsified explosives are solved, and the efficient detonation and long-term stability of emulsified explosives are achieved.
Patent Information
- Application Number
- CN202510055857.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-14
- Publication Date
- 2025-04-18
AI Technical Summary
The existing sensitizers have problems such as poor detonation performance, flammability, and difficult to control the sensitization quality in emulsified explosives, resulting in safety risks and unstable performance.
Compound sensitizers including sodium nitrite, fluorinated graphite microspheres and foaming agents are used to mix them with the emulsified matrix through a specific preparation method to form an efficient mixed emulsified explosive.
It improves the detonation performance and long-term storage stability of emulsified explosives, enhances safety performance, is stable in density and has no foaming after-effect.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of emulsion explosive sensitization, and more specifically, to a composite sensitizer and a preparation method thereof and a preparation method of a mixed emulsion explosive. Background Art
[0002] Mixed emulsion explosives are suitable for blasting operations in underground mining, such as underground tunnel excavation and small-section mining in underground mines. They can reduce the transportation and storage risks of finished explosives and improve the safety of underground blasting operations.
[0003] Mixed emulsion explosives are composed of emulsified matrix, sensitizer and other components. The role of the sensitizer is to introduce tiny bubbles into the emulsified matrix to adjust the density and energy of the explosive. At present, there are two methods to introduce uniform tiny bubbles: one is physical introduction, which is to add microporous materials containing bubbles such as perlite and glass microspheres, and use the gas in the cavities of the microporous materials to form "hot spots" under the action of the detonator to achieve sensitization; the other is chemical sensitization, which is to add chemical materials to the emulsified matrix to make it react chemically during the cooling and mixing process to release gas, which is retained inside to form bubbles and evenly distributed in the emulsified matrix, thereby achieving the purpose of sensitization.
[0004] There are many problems with the sensitizers currently in use. For example, expanded perlite is a widely used physical sensitizer, but the detonation performance of emulsion explosives is unsatisfactory. Organic chemical sensitizers have good foaming quality but are flammable. During the high temperatures in summer, domestic explosives produced using foaming agent H have spontaneously combusted many times, posing a huge safety risk. Although inorganic chemical sensitizers have fast foaming and large bubbles, the sensitization quality is difficult to control and can easily cause local energy anomalies due to uneven bubble distribution.
[0005] Therefore, the development of a sensitizer with excellent sensitization effect, which can improve the detonation performance index of emulsion explosives and has high safety performance is of great significance to the technological progress of emulsion explosives. Summary of the invention
[0006] One object of the present invention is to provide a composite sensitizer for mixed emulsion explosives, comprising the following components by mass fraction: 20-25% sodium nitrite, 10-12% graphite fluoride microspheres, 2-5% foaming agent, and the remainder water.
[0007] Preferably, the foaming agent comprises the following components in mass fractions: 20-30% zinc sulfate and 70-80% sodium thiocyanate.
[0008] Preferably, the fluorine-to-carbon ratio of the fluorinated graphite microspheres is greater than 1.
[0009] A method for preparing a composite sensitizer for mixed emulsion explosives is provided, comprising the following steps: S1. Heat water to 30-50°C, add sodium nitrite and dissolve it under continuous stirring at a speed of 50-100 r / min to form a mixed solution A; S2, maintaining the temperature at 30-50°C, soaking the fluorinated graphite microspheres in the mixed solution A for 24-48 hours to obtain a mixed solution B; S3. After the mixed solution B is cooled to room temperature, a foaming agent is added and stirred at a speed of 20-50 r / min for 10-20 min to obtain a composite sensitizer.
[0010] A method for preparing a mixed emulsion explosive is provided, comprising the following steps: Step 1: Heat water to 50-65°C, add ammonium nitrate and calcium nitrate, stir and dissolve, and then heat to 65°C to obtain an aqueous phase; Step 2: Mix the engine oil, emulsifier and diesel evenly and heat to 65°C to obtain an oil phase. Step 3, mixing the oil phase and the water phase and emulsifying them to obtain an emulsified base; Step 4: When the emulsified matrix is cooled to 15°C-35°C, a composite sensitizer is added and stirred evenly to obtain a mixed emulsion explosive, wherein the composite sensitizer includes 20-25% sodium nitrite, 10-12% graphite fluoride microspheres, 2-5% foaming agent, and the remainder is water.
[0011] Preferably, the emulsified matrix comprises the following components in mass fractions: 55-65% ammonium nitrate, 10-25% calcium nitrate, 17-19% water, 1-2% emulsifier, 0.5-1% engine oil, and 3.5-5% diesel.
[0012] Preferably, the emulsifier is any one of polyisobutylene succinic anhydride, polysorbate 80 and Span 80.
[0013] Preferably, in step 3, the emulsification of the oil phase and the water phase is carried out by static emulsification, the emulsification pressure is 0.6-0.8 MPa, and the emulsification time is 8-12 min.
[0014] Preferably, in step 4, the mass ratio of the composite sensitizer to the emulsified matrix is 1-2:5.
[0015] Preferably, the density of the mixed emulsion explosive is 1.22-1.25 g / cm 3 .
[0016] The present invention has at least the following beneficial effects: First, the present invention helps to improve the detonation performance of mixed emulsion explosives by utilizing a composite sensitizer formed by combining fluorinated graphite microspheres with sodium nitrite and a foaming agent.
[0017] Second, the composite sensitizer prepared by the present invention through fluorinated graphite microspheres with a high fluorine-carbon ratio, sodium nitrite, a foaming agent, etc., helps to improve the long-term storage stability of mixed emulsion explosives.
[0018] Other advantages, objectives and features of the present invention will be embodied in part through the following description, and in part will be understood by those skilled in the art through study and practice of the present invention. DETAILED DESCRIPTION
[0019] The present invention is further described in detail below in conjunction with embodiments so that those skilled in the art can implement the invention with reference to the description.
[0020] It should be noted that the experimental methods described in the following embodiments are conventional methods unless otherwise specified, and the reagents and materials can be obtained from commercial channels unless otherwise specified.
[0021] Graphite fluoride microspheres, also known as graphite fluoride (microspheres), were purchased from Hubei Zhuoxi Fluorination Co., Ltd. with a particle size of 250 mesh. The fluorine-carbon ratio of graphite fluoride microspheres refers to the ratio of fluorine atoms to carbon atoms.
[0022] <Example 1> The preparation method of the mixed emulsion explosive comprises the following steps: Step 1: Heat 45 g of water to 50°C, add 165 g of ammonium nitrate and 75 g of calcium nitrate in sequence, stir until fully dissolved, and then heat to 65°C to obtain an aqueous phase; Step 2: 1.5 g of engine oil, 3 g of isobutylene succinic anhydride and 10.5 g of diesel were mixed evenly and heated to 65° C. to obtain an oil phase; Step 3: Use static emulsification to mix the oil phase and the water phase, control the emulsification pressure to 0.6 MPa, and the emulsification time to 12 min, so that the two are fully mixed and emulsified to obtain an emulsified matrix; Step 4: When the emulsified matrix is cooled to 15°C, 60 g of the composite sensitizer is added according to the mass ratio of the composite sensitizer to the emulsified matrix of 1:5, and stirred evenly to obtain a mixed emulsion explosive; Wherein, the preparation method of the composite sensitizer comprises the following steps: S1: Heat 68 g of water to 30°C, slowly add 20 g of sodium nitrite while stirring at 50 r / min, and continue stirring until the sodium nitrite is completely dissolved to form a mixed solution A; S2: maintaining 30°C, adding 10 g of fluorinated graphite microspheres into the mixed solution A and soaking for 24 h to obtain a mixed solution B, wherein the fluorine-carbon ratio of the fluorinated graphite microspheres is 1.01; S3: After the mixed solution B is naturally cooled to room temperature, a foaming agent consisting of 0.4 g zinc sulfate and 1.6 g sodium thiocyanate is added, and the mixture is stirred at a speed of 20 r / min for 20 min to obtain a composite sensitizer.
[0023] <Example 2> The preparation method of the mixed emulsion explosive comprises the following steps: Step 1: Heat 47.1 g of water to 60°C, add 180 g of ammonium nitrate and 54 g of calcium nitrate in sequence, stir until fully dissolved, and then heat to 65°C to obtain an aqueous phase; Step 2: 2.4 g of engine oil, 4.5 g of isobutylene succinic anhydride and 12 g of diesel were mixed evenly and heated to 65° C. to obtain an oil phase; Step 3: Use static emulsification to mix the oil phase and the water phase, control the emulsification pressure to 0.7 MPa, and the emulsification time to 8 min, so that the two are fully mixed and emulsified to obtain an emulsified matrix; Step 4: When the emulsified matrix is cooled to 25°C, 90 g of the composite sensitizer is added according to the mass ratio of the composite sensitizer to the emulsified matrix of 1.5:5, and stirred evenly to obtain a mixed emulsion explosive; Wherein, the preparation method of the composite sensitizer comprises the following steps: S1: Heat 64 g of water to 30°C, slowly add 22 g of sodium nitrite while stirring at 70 r / min, and continue stirring until the sodium nitrite is completely dissolved to form a mixed solution A; S2: maintaining 40°C, adding 11 g of fluorinated graphite microspheres into the mixed solution A, and soaking for 36 h to obtain a mixed solution B, wherein the fluorine-carbon ratio of the fluorinated graphite microspheres is 1.06; S3: After the mixed solution B is naturally cooled to room temperature, a foaming agent consisting of 0.75 g zinc sulfate and 2.25 g sodium thiocyanate is added, and the mixture is stirred at a speed of 30 r / min for 15 min to obtain a composite sensitizer.
[0024] <Example 3> The preparation method of the mixed emulsion explosive comprises the following steps: Step 1: Heat 51 g of water to 60°C, add 195 g of ammonium nitrate and 30 g of calcium nitrate in sequence, stir until fully dissolved, and then heat to 65°C to obtain an aqueous phase; Step 2: 3 g of engine oil, 6 g of isobutylene succinic anhydride and 15 g of diesel are mixed evenly and heated to 65° C. to obtain an oil phase; Step 3: Use static emulsification to mix the oil phase and the water phase, control the emulsification pressure to 0.8 MPa, and the emulsification time to 12 min, so that the two are fully mixed and emulsified to obtain an emulsified matrix; Step 4: When the emulsified matrix is cooled to 35°C, 120 g of the composite sensitizer is added according to the mass ratio of the composite sensitizer to the emulsified matrix of 2:5, and stirred evenly to obtain a mixed emulsion explosive; Wherein, the preparation method of the composite sensitizer comprises the following steps: S1: Heat 58 g of water to 50°C, slowly add 25 g of sodium nitrite while stirring at 100 r / min, and continue stirring until the sodium nitrite is completely dissolved to form a mixed solution A; S2: maintaining 50°C, adding 12 g of fluorinated graphite microspheres into the mixed solution A, and soaking for 48 h to obtain a mixed solution B, wherein the fluorine-carbon ratio of the fluorinated graphite microspheres is 1.1; S3: After the mixed solution B is naturally cooled to room temperature, a foaming agent consisting of 1.5 g zinc sulfate and 3.5 g sodium thiocyanate is added, and the mixture is stirred at a speed of 50 r / min for 10 min to obtain a composite sensitizer.
[0025] <Blank Group> The preparation method of the mixed emulsion explosive comprises the following steps: Step 1: Heat 51 g of water to 60°C, add 195 g of ammonium nitrate and 30 g of calcium nitrate in sequence, stir until fully dissolved, and then heat to 65°C to obtain an aqueous phase; Step 2: 3 g of engine oil, 6 g of isobutylene succinic anhydride and 15 g of diesel are mixed evenly and heated to 65° C. to obtain an oil phase; Step 3: Use static emulsification to mix the oil phase and the water phase, control the emulsification pressure to 0.8 MPa, and the emulsification time to 12 min, so that the two are fully mixed and emulsified to obtain an emulsified matrix; Step 4: When the emulsified matrix is cooled to 15°C, 120 g of the composite sensitizer is added according to the mass ratio of the composite sensitizer to the emulsified matrix of 2:5, and stirred evenly to obtain a mixed emulsion explosive; Wherein, the preparation method of the composite sensitizer comprises the following steps: S1: Heat 60 g of water to 50°C, slowly add 25 g of sodium nitrite while stirring at 100 r / min, and continue stirring until the sodium nitrite is completely dissolved to form a mixed solution A; S3: After the mixed solution A is naturally cooled to room temperature, a foaming agent consisting of 1.5 g zinc sulfate and 3.5 g sodium thiocyanate is added, and the mixture is stirred at a speed of 50 r / min for 10 min to obtain a composite sensitizer.
[0026] The mixed emulsion explosives prepared in Examples 1 to 3 have a stable density after foaming at 15 to 35° C. for 30 to 40 minutes, without any foaming aftereffect.
[0027] <Performance Test 1> The density of the mixed emulsion explosives prepared in Examples 1 to 3 and the blank group was measured three times, and the average value was taken. The density results are shown in Table 1 below; The detonation velocity, intensity and detonation distance of the mixed emulsion explosives prepared in Examples 1 to 3 and the blank group were tested with reference to GB / T13228-2015, GB / T12440-1990 and GB / T12438-1990 respectively. The results are shown in Table 1 below: Table 1 Performance test results of each group of mixed emulsion explosives According to the data in Table 1, the mixed emulsion explosives of Examples 1 to 3 with the addition of graphite fluoride microspheres are superior to the blank group without the addition of graphite fluoride microspheres in key properties such as density, detonation velocity, intensity and sympathetic detonation distance, indicating that graphite fluoride microspheres can effectively improve the performance of mixed emulsion explosives.
[0028] <Comparative Example 1> The preparation method of the mixed emulsion explosive comprises the following steps: Step 1: Heat 51 g of water to 60°C, add 195 g of ammonium nitrate and 30 g of calcium nitrate in sequence, stir until fully dissolved, and then heat to 65°C to obtain an aqueous phase; Step 2: 3 g of engine oil, 6 g of isobutylene succinic anhydride and 15 g of diesel are mixed evenly and heated to 65° C. to obtain an oil phase; Step 3: Use static emulsification to mix the oil phase and the water phase, control the emulsification pressure to 0.8 MPa, and the emulsification time to 12 min, so that the two are fully mixed and emulsified to obtain an emulsified matrix; Step 4: When the emulsified matrix is cooled to 15°C, 120 g of the composite sensitizer is added according to the mass ratio of the composite sensitizer to the emulsified matrix of 2:5, and stirred evenly to obtain a mixed emulsion explosive; Wherein, the preparation method of the composite sensitizer comprises the following steps: S1: Heat 58 g of water to 50°C, slowly add 25 g of sodium nitrite while stirring at 100 r / min, and continue stirring until the sodium nitrite is completely dissolved to form a mixed solution A; S2: maintaining 50°C, adding 12 g of expanded perlite into the mixed solution A, and soaking for 48 h to obtain a mixed solution B, wherein the particle size of the expanded perlite is 80 mesh; S3: After the mixed solution B is naturally cooled to room temperature, a foaming agent consisting of 1.5 g zinc sulfate and 3.5 g sodium thiocyanate is added, and the mixture is stirred at a speed of 50 r / min for 10 min to obtain a composite sensitizer.
[0029] <Comparative Example 2> The preparation method of the mixed emulsion explosive comprises the following steps: Step 1: Heat 51 g of water to 60°C, add 195 g of ammonium nitrate and 30 g of calcium nitrate in sequence, stir until fully dissolved, and then heat to 65°C to obtain an aqueous phase; Step 2: 3 g of engine oil, 6 g of isobutylene succinic anhydride and 15 g of diesel are mixed evenly and heated to 65° C. to obtain an oil phase; Step 3: Use static emulsification to mix the oil phase and the water phase, control the emulsification pressure to 0.8 MPa, and the emulsification time to 12 min, so that the two are fully mixed and emulsified to obtain an emulsified matrix; Step 4: When the emulsified matrix is cooled to 35°C, 120 g of the composite sensitizer is added according to the mass ratio of the composite sensitizer to the emulsified matrix of 2:5, and stirred evenly to obtain a mixed emulsion explosive; Wherein, the preparation method of the composite sensitizer comprises the following steps: S1: Heat 58 g of water to 50°C, slowly add 25 g of sodium nitrite while stirring at 100 r / min, and continue stirring until the sodium nitrite is completely dissolved to form a mixed solution A; S2: maintaining 50°C, adding 12 g of fluorinated graphite microspheres into the mixed solution A, and soaking for 48 h to obtain a mixed solution B, wherein the fluorine-carbon ratio of the fluorinated graphite microspheres is 0.88; S3: After the mixed solution B is naturally cooled to room temperature, a foaming agent consisting of 1.5 g zinc sulfate and 3.5 g sodium thiocyanate is added, and the mixture is stirred at a speed of 50 r / min for 10 min to obtain a composite sensitizer.
[0030] <Comparative Example 3> The preparation method of the mixed emulsion explosive comprises the following steps: Step 1: Heat 51 g of water to 60°C, add 195 g of ammonium nitrate and 30 g of calcium nitrate in sequence, stir until fully dissolved, and then heat to 65°C to obtain an aqueous phase; Step 2: 3 g of engine oil, 6 g of isobutylene succinic anhydride and 15 g of diesel are mixed evenly and heated to 65° C. to obtain an oil phase; Step 3: Use static emulsification to mix the oil phase and the water phase, control the emulsification pressure to 0.8 MPa, and the emulsification time to 12 min, so that the two are fully mixed and emulsified to obtain an emulsified matrix; Step 4: When the emulsified matrix is cooled to 35°C, 120 g of the composite sensitizer is added according to the mass ratio of the composite sensitizer to the emulsified matrix of 2:5, and stirred evenly to obtain a mixed emulsion explosive; Wherein, the preparation method of the composite sensitizer comprises the following steps: S1: Heat 58 g of water to 50°C, slowly add 25 g of sodium nitrite while stirring at 100 r / min, and continue stirring until the sodium nitrite is completely dissolved to form a mixed solution A; S2: Maintaining 50°C, 12 g of fluorinated graphite microspheres, a foaming agent consisting of 1.5 g of zinc sulfate and 3.5 g of sodium thiocyanate were added to the mixed solution A, and stirred at 50 r / min for 10 min to obtain a composite sensitizer, wherein the fluorine-carbon ratio of the fluorinated graphite microspheres was 1.1.
[0031] <Performance Test 2> The density, detonation velocity, intensity, detonation distance and storage stability of the mixed emulsion explosives prepared in Example 3, the blank group and comparative examples 1 to 3 were respectively tested, and the results are shown in 2 and Table 3 below; Among them, the storage stability test is as follows: Usually, the storage stability of emulsion explosives is characterized by the number of high and low temperature cycle tests: 10 high and low cycles are equivalent to a natural period of 180 days. High and low temperature cycle tests are used to detect the changes in emulsion explosives over time and the storage stability of emulsion explosives. A high number of cycles means that the emulsion explosive has good stability.
[0032] Specific operation steps: first place each group of mixed emulsion explosives in a constant temperature box at 50℃ for 8 hours, and then put them in a -15℃ refrigerator to freeze for 14 hours. Repeat this cycle many times until the mixed emulsion explosives refuse to explode.
[0033] Table 2 Performance test results of mixed emulsion explosives Table 3 Storage stability test results of each group of mixed emulsion explosives According to the data in Table 2, the detonation performance of the mixed emulsion explosive prepared in Comparative Example 1 is better than that of the blank group, but worse than that of Example 3 and Comparative Example 2, indicating that the sensitization effect of the composite sensitizer composed of expanded perlite, sodium nitrite and foaming agent on the emulsified matrix is not as good as that of the composite sensitizer including fluorinated graphite microspheres; the detonation performance of Comparative Example 2 is not much different from that of Example 3, indicating that the fluorinated graphite microspheres with different fluorine-carbon ratios have no obvious effect on the detonation performance of the mixed emulsion explosive; the detonation performance of Comparative Example 3 is obviously inferior to that of Example 3, indicating that the way in which the fluorinated graphite microspheres are mixed with sodium nitrite and foaming agent can significantly affect the detonation performance of the mixed emulsion explosive.
[0034] According to the data in Table 3, after 20 high and low temperature cycles (equivalent to a natural storage period of 360 days), the detonation velocity of the mixed emulsion explosive prepared in Example 3 is 5739 m / s, and the detonation velocity can still be maintained at more than 90%. After 20 high and low temperature cycles, the detonation velocities of the mixed emulsion explosives in the blank group and comparative examples 1 to 3 are greatly reduced, which are reduced to 69.7%, 73.4%, 71.9% and 83.6% of the initial detonation velocities, respectively. It can be seen that the mixed emulsion explosive prepared by the present invention has long-term storage stability, and the storage stability of comparative example 2 is significantly lower than that of example 3, indicating that the fluorinated graphite microspheres with a high fluorine-carbon ratio can effectively improve the stability of the mixed emulsion explosive.
[0035] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and the implementation modes. They can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to the specific details and the embodiments shown and described herein.
Claims
1. A composite sensitizer for mixed emulsion explosives, characterized in that: The invention comprises the following components in mass fractions: 20-25% sodium nitrite, 10-12% graphite fluoride microspheres, 2-5% foaming agent, and the rest is water.
2. The composite sensitizer for mixed emulsion explosive according to claim 1, characterized in that: The foaming agent comprises the following components in mass fractions: 20-30% zinc sulfate and 70-80% sodium thiocyanate.
3. The composite sensitizer for mixed emulsion explosive according to claim 1, characterized in that: The fluorine-carbon ratio of the fluorinated graphite microspheres is greater than 1.
4. The method for preparing a composite sensitizer for mixed emulsion explosives according to any one of claims 1 to 3, characterized in that: The following steps are involved: S1. Heat water to 30-50°C, add sodium nitrite and dissolve it under continuous stirring at a speed of 50-100 r / min to form a mixed solution A; S2, maintaining the temperature at 30-50°C, soaking the fluorinated graphite microspheres in the mixed solution A for 24-48 hours to obtain a mixed solution B; S3. After the mixed solution B is cooled to room temperature, a foaming agent is added and stirred at a speed of 20-50 r / min for 10-20 min to obtain a composite sensitizer.
5. A method for preparing a mixed emulsion explosive, characterized in that: The following steps are involved: Step 1: Heat water to 50-65°C, add ammonium nitrate and calcium nitrate, stir and dissolve, and then heat to 65°C to obtain an aqueous phase; Step 2: Mix the engine oil, emulsifier and diesel evenly and heat to 65°C to obtain an oil phase. Step 3, mixing the oil phase and the water phase and emulsifying them to obtain an emulsified base; Step 4: When the emulsified matrix is cooled to 15° C. to 35° C., a composite sensitizer is added and stirred evenly to obtain a mixed emulsion explosive, wherein the composite sensitizer is the composite sensitizer according to any one of claims 1 to 4.
6. The method for preparing the mixed emulsion explosive according to claim 5, characterized in that: The emulsified matrix comprises the following components in mass fractions: 55-65% ammonium nitrate, 10-25% calcium nitrate, 17-19% water, 1-2% emulsifier, 0.5-1% engine oil, and 3.5-5% diesel.
7. The method for preparing the mixed emulsion explosive according to claim 6, characterized in that: The emulsifier is any one of polyisobutylene succinic anhydride, polysorbate 80 and Span 80.
8. The method for preparing the mixed emulsion explosive according to claim 5, characterized in that: In step 3, the emulsification of the oil phase and the water phase is carried out by static emulsification, the emulsification pressure is 0.6-0.8 MPa, and the emulsification time is 8-12 min.
9. The method for preparing the mixed emulsion explosive according to claim 5, characterized in that: The mass ratio of the composite sensitizer to the emulsified matrix in step 4 is 1-2:
5.
10. The method for preparing the mixed emulsion explosive according to claim 5, characterized in that: The density of mixed emulsion explosive is 1.22~1.25 g / cm 3 .