CN113416112A - Preparation method of high-temperature rapid chemical sensitization emulsion explosive with high storage stability - Google Patents
Preparation method of high-temperature rapid chemical sensitization emulsion explosive with high storage stability Download PDFInfo
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- CN113416112A CN113416112A CN202110825486.2A CN202110825486A CN113416112A CN 113416112 A CN113416112 A CN 113416112A CN 202110825486 A CN202110825486 A CN 202110825486A CN 113416112 A CN113416112 A CN 113416112A
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
- C06B31/28—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
- C06B31/30—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with vegetable matter; with resin; with rubber
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/002—Sensitisers or density reducing agents, foam stabilisers, crystal habit modifiers
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/006—Stabilisers (e.g. thermal stabilisers)
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Abstract
The invention discloses a preparation method of a high-temperature rapid chemical sensitization emulsion explosive with high storage stability, belonging to the technical field of emulsion explosive manufacture. The emulsion explosive comprises the following raw materials in parts by weight: 100 parts of water phase, 7-8 parts of composite oil phase, 2-3 parts of foaming agent and 0.5-2 parts of sensitization promoter. According to the invention, the proportion of the aqueous phase solution is optimized, the pH of the aqueous phase solution is adjusted, and the polymethyl methacrylate is added into the oil phase, so that the trend from small bubbles to large bubbles to breakage in the subsequent foaming sensitization process is effectively delayed, and the storage performance of the emulsion explosive is greatly improved. The emulsion explosive prepared by the method has the advantages of simple preparation process, good detonation performance, long storage period, good stability and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of emulsion explosive manufacturing, and particularly relates to a preparation method of a high-storage-stability high-temperature rapid chemical sensitization emulsion explosive.
Background
The emulsion explosive is a new water-based ammonium nitrate industrial explosive. The basic composition of the explosive is different from other ammonium nitrate explosives, and particularly has no essential difference compared with slurry explosives and water gel explosives. However, due to different manufacturing processes, the emulsion explosive adopts an emulsion pharmaceutical process, and the functions of the components in the system are quite different. Therefore, the explosive of the variety has unique internal structure (W/O) and appearance form, and even the physical and chemical properties, the explosion performance and the like of the explosive are greatly different.
At present, the production process of the emulsion explosive is mainly a medium-low temperature sensitization production process. The medium-low temperature sensitization production process is that the emulsified base material is cooled to about 50 ℃ and then is subjected to physical sensitization, chemical sensitization or composite sensitization to produce the emulsified explosive with detonator sensitivity; the method has the advantages of simple equipment, good sensitization quality, open conveying of a belt or a steel belt in the whole production process, low automation degree of the production line, more personnel operation, low chemical sensitization foaming speed, certain aftereffect, soft medicine state, high viscosity, difficulty in control and potential safety hazard due to the fact that the production capacity of the production line is limited by a cooling facility, sensitization equipment and charging equipment.
Aiming at the defects of the medium-low temperature sensitization production process of the emulsion explosive, the high-temperature sensitization production technology of the emulsion explosive is introduced in recent years. The high-temperature sensitization production technology means that a chemical sensitizer is directly added at a high temperature without cooling an emulsified substrate to quickly complete foaming so as to achieve sensitization; the method has the advantages that the sensitization process is carried out at a higher temperature, the reaction and decomposition speed of the chemical sensitization medicament is high, the foaming can be completed in a shorter time, the medicament has no after-effect and is beneficial to packaging, the high-temperature sensitization charging viscosity is low and easy to control, but the diameter uniformity and stability of high-temperature sensitization bubbles are poorer than those of medium-and-low-temperature chemical sensitization, and particularly the subsequent storage time is short, so that the production process needs to be further improved.
Disclosure of Invention
Aiming at the problem that the storage period of the emulsion explosive prepared by the conventional high-temperature rapid chemical sensitization is short, the invention provides a preparation method of the high-temperature rapid chemical sensitization emulsion explosive with high storage stability. The emulsion explosive with good storage performance is obtained by optimizing the proportion of the aqueous phase solution, adjusting the pH of the aqueous phase solution, selecting proper oil phase components to prepare the composite oil phase, mixing the aqueous phase and the composite oil phase to form emulsion to obtain an emulsion matrix, and finally adding the foaming sensitizer containing the graphene nanosheets to sensitize the emulsion matrix.
The invention is realized by the following technical scheme:
a preparation method of a high-temperature rapid chemical sensitization emulsion explosive with high storage stability is characterized by comprising the following steps:
preparing water phase solution, oil phase and composite oil phase, mixing the water phase solution and the composite oil phase to form emulsion to obtain an emulsion matrix, mixing a foaming agent and a sensitization promoter, directly adding the emulsion matrix for sensitization, and packaging.
Further, the emulsion explosive comprises the following raw materials in parts by weight: 100 parts of water phase, 7-8 parts of composite oil phase, 2-3 parts of foaming agent and 0.5-2 parts of sensitization promoter.
Further, the preparation method of the aqueous phase solution comprises the following steps: adding 14.5 percent of water, 68.8 percent of ammonium nitrate, 13.2 percent of industrial sodium nitrate and 3.5 percent of flame retardant into a water phase dissolving tank according to the mass percent, and heating to 85-110 ℃ to dissolve to obtain a water phase solution.
Furthermore, a small amount of citric acid monohydrate is added after the aqueous phase solution is prepared until the pH value of the solution is 3.5-4.2.
The high and low crystallization point of the water phase of the emulsion explosive is very important for the emulsification link of the emulsion explosive, and ammonium nitrate can be separated out when the crystallization point is too high for emulsification, so that the emulsion breaking of an emulsion matrix is caused, and the emulsification effect is seriously influenced. The invention optimizes the proportion of the water phase, properly reduces the content of ammonium nitrate in the water phase, increases the content of industrial sodium nitrate in the water phase, effectively reduces the crystallization point of the water phase, and adds a small amount of citric acid monohydrate into the water phase to adjust the pH value of the water phase to 3.5-4.2 in order to ensure that the detonation velocity, the brisance and the storage period of the emulsion explosive can not be obviously reduced.
Further, the oil phase is paraffin, composite wax, vaseline and polymethyl methacrylate according to a mass ratio of 1: 2: 1.6: 0.2 mixing; the melting point of the composite wax is 65-80 ℃, and the kinematic viscosity of the composite wax is 12-24mm at 100 DEG C2/s。
According to the invention, a proper amount of polymethyl methacrylate is added into the oil phase, so that the external phase strength of a bubble liquid film in the subsequent foaming process can be increased, the external pressure of bubbles can be increased by matching with other components in the oil phase, and the internal and external pressure difference of the bubbles is reduced, so that the trend of the bubbles from small to large to being broken is effectively delayed, and the storage performance of the emulsion explosive is greatly improved.
Further, adding an emulsifier into the oil phase, heating to 75-90 ℃ and melting to obtain a composite oil phase, wherein the adding amount of the emulsifier is 2/3 of the mass of the oil phase.
Further, the emulsifier is polyisobutylene succinimide.
Further, the foaming agent is sodium nitrite aqueous solution with the mass fraction of 36% -42%.
Further, the sensitization promoter is prepared from the following components in percentage by mass: ammonium dihydrogen phosphate 18-22%, ammonium nitrate 22-30%, graphene nano-sheets 5-7% and the balance of water.
Further, the thickness of the graphene nanosheet is 8-20nm, and the width of the graphene nanosheet is 4-6 μm.
The added graphene nano-sheet can be adsorbed on the surface of bubbles formed in the foaming process, so that gas diffusion is reduced, the stability of the bubbles is obviously improved, and the trend of reducing the free energy of the bubbles is prolonged, thereby further prolonging the storage period of the prepared emulsion explosive.
Further, the specific operations of sensitization are as follows: heating the emulsified substrate to 80-90 ℃, then directly adding the evenly mixed foaming agent and the sensitization promoter, and reacting for 2-5 minutes.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the storage period of the emulsion explosive is effectively prolonged by optimizing the proportion of the aqueous phase solution, adjusting the contents of ammonium nitrate and sodium nitrate, and adding citric acid monohydrate to reduce the pH of the aqueous phase solution. In addition, the proper amount of polymethyl methacrylate is added into the oil phase, and the external pressure of the bubbles can be increased by matching with other components in the oil phase, so that the trend from small to large to breakage of the bubbles is effectively delayed, and the storage performance of the emulsion explosive is greatly improved. According to the invention, the sensitization promoter containing the graphene nanosheets is adopted, the graphene nanosheets can be adsorbed on the surfaces of bubbles formed in the foaming process, so that gas diffusion is reduced, and the trend of reducing the free energy of the bubbles is prolonged, so that the storage period of the prepared emulsion explosive is further prolonged. The emulsion explosive prepared by the method has the advantages of simple preparation process, good detonation performance, long storage period, good stability and wide application prospect.
Detailed Description
The present invention will be further described with reference to specific examples, but the present invention is not limited to the following examples. The process is conventional unless otherwise specified, and the starting materials are commercially available from the open literature.
Example 1
A high-temperature rapid chemical sensitization emulsion explosive with high storage stability comprises:
1. adding 14.5 percent of water, 68.8 percent of ammonium nitrate, 13.2 percent of industrial sodium nitrate and 3.5 percent of flame retardant into a water phase dissolving tank according to the mass percent, and heating to 100 ℃ to dissolve to obtain a water phase solution; a small amount of citric acid monohydrate was then added to bring the aqueous solution to pH 3.9.
2. According to the mass ratio of 1: 2: 1.6: 0.2 mixing paraffin, composite wax, vaseline and polymethyl methacrylate to prepare an oil phase, adding polyisobutylene succinimide with the mass of the oil phase of 2/3 into the prepared oil phase, and heating to 85 ℃ to melt the polyisobutylene succinimide to obtain the composite oil phase.
3. Preparing a sodium nitrite aqueous solution with the mass fraction of 40% as a foaming agent; and uniformly mixing 21% of ammonium dihydrogen phosphate, 27% of ammonium nitrate and 6% of graphene nano-sheets by mass percent, and the balance of water to prepare the sensitization promoter.
4. Taking the following components in parts by weight: 100 parts of water phase solution, 8 parts of composite oil phase, 3 parts of foaming agent and 1.5 parts of sensitization promoter; mixing the water phase solution and the composite oil phase to form emulsion to obtain an emulsion matrix, heating the emulsion matrix to 85 ℃, then directly adding the uniformly mixed foaming agent and the uniformly mixed sensitization promoter, reacting for 4 minutes, and packaging to obtain the emulsion explosive.
Example 2
A high-temperature rapid chemical sensitization emulsion explosive with high storage stability comprises:
1. adding 14.5 percent of water, 68.8 percent of ammonium nitrate, 13.2 percent of industrial sodium nitrate and 3.5 percent of flame retardant into a water phase dissolving tank according to the mass percent, and heating to 100 ℃ to dissolve to obtain a water phase solution; a small amount of citric acid monohydrate was then added to bring the aqueous solution to pH 3.6.
2. According to the mass ratio of 1: 2: 1.6: 0.2 mixing paraffin, composite wax, vaseline and polymethyl methacrylate to prepare an oil phase, adding polyisobutylene succinimide with the mass of the oil phase of 2/3 into the prepared oil phase, and heating to 85 ℃ to melt the polyisobutylene succinimide to obtain the composite oil phase.
3. Preparing a sodium nitrite aqueous solution with the mass fraction of 40% as a foaming agent; and uniformly mixing 19% of ammonium dihydrogen phosphate, 28% of ammonium nitrate, 7% of graphene nano-sheets and the balance of water according to mass percentage to obtain the sensitization accelerator.
4. Taking the following components in parts by weight: 100 parts of water phase solution, 8 parts of composite oil phase, 3 parts of foaming agent and 1.2 parts of sensitization promoter; mixing the water phase solution and the composite oil phase to form emulsion to obtain an emulsion matrix, heating the emulsion matrix to 85 ℃, then directly adding the uniformly mixed foaming agent and the uniformly mixed sensitization promoter, reacting for 3 minutes, and packaging to obtain the emulsion explosive.
Example 3
A high-temperature rapid chemical sensitization emulsion explosive with high storage stability comprises:
1. adding 14.5 percent of water, 68.8 percent of ammonium nitrate, 13.2 percent of industrial sodium nitrate and 3.5 percent of flame retardant into a water phase dissolving tank according to the mass percent, and heating to 95 ℃ to dissolve to obtain a water phase solution; a small amount of citric acid monohydrate was then added to bring the aqueous solution to pH 4.2.
2. According to the mass ratio of 1: 2: 1.6: 0.2 mixing paraffin, composite wax, vaseline and polymethyl methacrylate to prepare an oil phase, adding polyisobutylene succinimide with the mass of the oil phase of 2/3 into the prepared oil phase, and heating to 90 ℃ to melt the polyisobutylene succinimide to obtain the composite oil phase.
3. Preparing a sodium nitrite aqueous solution with the mass fraction of 42 percent as a foaming agent; and uniformly mixing 22% of ammonium dihydrogen phosphate, 24% of ammonium nitrate and 6% of graphene nano-sheets by mass percent, and the balance of water to prepare the sensitization promoter.
4. Taking the following components in parts by weight: 100 parts of water phase solution, 7 parts of composite oil phase, 2 parts of foaming agent and 1.8 parts of sensitization promoter; mixing the water phase solution and the composite oil phase to form emulsion to obtain an emulsion matrix, heating the emulsion matrix to 80 ℃, then directly adding the uniformly mixed foaming agent and the uniformly mixed sensitization promoter, reacting for 4 minutes, and packaging to obtain the emulsion explosive.
The emulsion explosive samples prepared in examples 1 to 3 were subjected to quality inspection: the initial explosion speed is 4430-4570m/s, the explosion speed is 4410-4550m/s after storage for 7 months, the explosion speed is 4280-4390m/s after storage for 12 months, and the explosion speed is 4040-4160m/s after storage for 16 months. It can be seen that the preparation method of the invention can greatly improve the storage stability of the emulsion explosive and greatly prolong the storage period of the emulsion explosive.
Comparative example 1
A high-temperature rapid chemical sensitization emulsion explosive:
1. adding 14.5 percent of water, 68.8 percent of ammonium nitrate, 13.2 percent of industrial sodium nitrate and 3.5 percent of flame retardant into a water phase dissolving tank according to the mass percent, and heating to 100 ℃ to dissolve to obtain a water phase solution; a small amount of citric acid monohydrate was then added to bring the aqueous solution to pH 3.9.
2. According to the mass ratio of 1: 2: 1.6 mixing paraffin, composite wax and vaseline to prepare an oil phase, adding polyisobutylene succinimide with the mass of 2/3 of the oil phase into the prepared oil phase, and heating to 85 ℃ to melt the polyisobutylene succinimide to obtain the composite oil phase.
3. Preparing a sodium nitrite aqueous solution with the mass fraction of 40% as a foaming agent; and uniformly mixing 21% of ammonium dihydrogen phosphate, 27% of ammonium nitrate and 6% of graphene nano-sheets by mass percent, and the balance of water to prepare the sensitization promoter.
4. Taking the following components in parts by weight: 100 parts of water phase solution, 8 parts of composite oil phase, 3 parts of foaming agent and 1.5 parts of sensitization promoter; mixing the water phase solution and the composite oil phase to form emulsion to obtain an emulsion matrix, heating the emulsion matrix to 85 ℃, then directly adding the uniformly mixed foaming agent and the uniformly mixed sensitization promoter, reacting for 4 minutes, and packaging to obtain the emulsion explosive.
Comparative example 2
A high-temperature rapid chemical sensitization emulsion explosive:
1. adding 14.5 percent of water, 68.8 percent of ammonium nitrate, 13.2 percent of industrial sodium nitrate and 3.5 percent of flame retardant into a water phase dissolving tank according to the mass percent, and heating to 100 ℃ to dissolve to obtain a water phase solution; a small amount of citric acid monohydrate was then added to bring the aqueous solution to pH 3.9.
2. According to the mass ratio of 1: 2: 1.6: 0.2 mixing paraffin, composite wax, vaseline and polymethyl methacrylate to prepare an oil phase, adding polyisobutylene succinimide with the mass of the oil phase of 2/3 into the prepared oil phase, and heating to 85 ℃ to melt the polyisobutylene succinimide to obtain the composite oil phase.
3. Preparing a sodium nitrite aqueous solution with the mass fraction of 40% as a foaming agent; and uniformly mixing 21% of ammonium dihydrogen phosphate, 27% of ammonium nitrate and the balance of water according to mass percentage to prepare the sensitization promoter.
4. Taking the following components in parts by weight: 100 parts of water phase solution, 8 parts of composite oil phase, 3 parts of foaming agent and 1.5 parts of sensitization promoter; mixing the water phase solution and the composite oil phase to form emulsion to obtain an emulsion matrix, heating the emulsion matrix to 85 ℃, then directly adding the uniformly mixed foaming agent and the uniformly mixed sensitization promoter, reacting for 4 minutes, and packaging to obtain the emulsion explosive.
And (3) carrying out quality inspection on the emulsion explosives prepared in the comparative examples 1 and 2: the initial explosion speed is 4420-4540m/s, the explosion speed is 4100-4150m/s after storage for 7 months, and the explosion speed is 3820-3880m/s after storage for 10 months.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solutions of the present application and not to limit them; although the present application has been described in detail with reference to preferred embodiments, those of ordinary skill in the art will understand that: modifications to the embodiments of the present application or equivalent replacements of some technical features may still be made, which should all be covered by the scope of the technical solution claimed in the present application.
Claims (10)
1. A preparation method of a high-temperature rapid chemical sensitization emulsion explosive with high storage stability is characterized by comprising the following steps:
preparing an aqueous phase solution, an oil phase and a composite oil phase, mixing the aqueous phase solution and the composite oil phase into emulsion to obtain an emulsified matrix, mixing a foaming agent and a sensitization promoter, directly adding the emulsified matrix into the mixture for sensitization, and packaging the mixture;
wherein the sensitization promoter comprises graphene nanoplatelets;
the emulsion explosive comprises the following raw materials in parts by weight: 100 parts of water phase, 7-8 parts of composite oil phase, 2-3 parts of foaming agent and 0.5-2 parts of sensitization promoter.
2. The preparation method of the high-storage-stability high-temperature rapid chemical sensitization emulsion explosive according to claim 1, wherein the preparation method of the aqueous phase solution comprises the following steps: adding 14.5 percent of water, 68.8 percent of ammonium nitrate, 13.2 percent of industrial sodium nitrate and 3.5 percent of flame retardant into a water phase dissolving tank according to the mass percent, and heating to 85-110 ℃ to dissolve to obtain a water phase solution.
3. The method for preparing the high-temperature rapid chemical sensitization emulsion explosive with high storage stability according to claim 2, wherein a small amount of citric acid monohydrate is added after the aqueous phase solution is prepared until the pH value of the solution is 3.5-4.2.
4. The preparation method of the high-storage-stability high-temperature rapid chemical sensitization emulsion explosive according to claim 1, wherein the oil phase is paraffin, composite wax, vaseline, polymethyl methacrylate in a mass ratio of 1: 2: 1.6: 0.2 mixing; the melting point of the composite wax is 65-80 ℃, and the kinematic viscosity of the composite wax is 12-24mm at 100 DEG C2/s。
5. The preparation method of the high-temperature fast chemical sensitization emulsion explosive with high storage stability according to claim 4, wherein an emulsifier is added into the oil phase and is heated to 75-90 ℃ to be melted to obtain a composite oil phase, and the addition amount of the emulsifier is 2/3 of the mass of the oil phase.
6. The method for preparing the high-temperature fast chemical sensitization emulsion explosive with high storage stability according to claim 5, wherein the emulsifier is polyisobutylene succinimide.
7. The preparation method of the high-storage-stability high-temperature rapid chemical sensitization emulsion explosive according to claim 1, wherein the foaming agent is a sodium nitrite aqueous solution with the mass fraction of 36% -42%.
8. The preparation method of the high-storage-stability high-temperature rapid chemical sensitization emulsion explosive according to claim 1, wherein the sensitization promoter is prepared from the following components in percentage by mass: ammonium dihydrogen phosphate 18-22%, ammonium nitrate 22-30%, graphene nano-sheets 5-7% and the balance of water.
9. The preparation method of the high-storage-stability high-temperature rapid chemical-sensitized emulsion explosive according to claim 8, wherein the graphene nanosheet is 8-20nm thick and 4-6 μm wide.
10. The preparation method of the high-storage-stability high-temperature rapid chemical sensitization emulsion explosive according to claim 1, characterized in that the specific operations of sensitization are as follows: heating the emulsified substrate to 80-90 ℃, then directly adding the evenly mixed foaming agent and the sensitization promoter, and reacting for 2-5 minutes.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114380655A (en) * | 2021-12-13 | 2022-04-22 | 河南华通化工有限公司 | Foaming agent for rapidly and stably foaming emulsion explosive, preparation method and emulsion explosive |
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