CN113698259A - Rapid sensitization chemosensitizer for emulsion matrix explosives and rapid sensitization method - Google Patents
Rapid sensitization chemosensitizer for emulsion matrix explosives and rapid sensitization method Download PDFInfo
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- CN113698259A CN113698259A CN202111184848.0A CN202111184848A CN113698259A CN 113698259 A CN113698259 A CN 113698259A CN 202111184848 A CN202111184848 A CN 202111184848A CN 113698259 A CN113698259 A CN 113698259A
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- emulsion
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- sodium borohydride
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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
- C06B31/285—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with fuel oil, e.g. ANFO-compositions
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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
- C06B23/004—Chemical sensitisers
Abstract
The invention discloses a quick sensitizing chemical sensitizer and a quick sensitizing method for preparing an emulsion explosive with excellent foaming performance, and relates to the field of industrial explosive production, and the method specifically comprises a quick sensitizing method for quickly sensitizing sodium borohydride and adding a sodium borohydride solution to an emulsion matrix, wherein the quick sensitizing agent sodium borohydride is in a form of powder or blocky crystals, the quick sensitizing method is to dissolve sodium borohydride in water and an alkaline solution to prepare a quick sensitizing agent solution, the quick sensitizing agent solution is added to the emulsion matrix in a titration mode to be stirred and sensitized, and the mass ratio of the added amount of the sodium borohydride to the emulsion matrix is 0.01-5 wt%. The sensitizer has the advantages of high sensitizing speed, high efficiency and low price, and the explosive performance of the sensitized emulsion explosive reaches the standard. The rapid sensitization method has simple process, ensures that the sensitization rate and the sensitization effect of the emulsion matrix are not influenced under the condition of (0-25 ℃), reduces the strict requirements of chemical sensitization reaction on the temperature of medium and high temperature environment, and solves the problem of unsatisfactory sensitization effect of the emulsion explosive in northern severe cold climate areas.
Description
Technical Field
The invention relates to the field of industrial explosive production, in particular to a quick sensitization chemical sensitizer and a quick sensitization method for preparing emulsion explosive with excellent foaming performance.
Background
The W/O type emulsion in the production process of the emulsion explosive is called emulsion matrix (also called emulsion matrix), which is a basic body forming the emulsion explosive and has better stability and potential detonation performance. Ammonium nitrate aqueous phase solution (oxidant) in an emulsified matrix is dispersed into tiny particles in oil phase solution (combustible agent), the core of the ammonium nitrate aqueous phase solution is supersaturated inorganic salt solution, and a layer of extremely thin oil film with high strength is coated outside the ammonium nitrate aqueous phase solution, so that the ammonium nitrate aqueous phase solution presents high viscosity. The emulsion matrix is an unsensitized emulsion explosive which is relatively dense, requires significant initiation energy, and is very difficult to propagate. Therefore, in the process of preparing the emulsion explosive, the emulsion explosive can be prepared only by sensitizing through a physical or chemical or composite sensitizing method, namely, introducing a large number of uniformly distributed micro-bubbles into an emulsion matrix and generating detonator detonation sensitivity by utilizing the adiabatic compression and 'hot spot' characteristics of air in the bubbles. When the emulsion explosive is acted by external energy, the 'hot point' generated by sensitization is adiabatically compressed, so that the explosive can explode and propagate. It should be noted that chemical sensitization is the most common sensitization method in China at present, and the disadvantages of the early chemical foaming technology are that: the foaming agent is added into the latex matrix, and the foaming sensitization is qualified only by keeping the temperature for at least 4 hours in a foaming room (temperature control room) at 50-55 ℃, so that the process is interrupted and is not easy to manage, and the heat preservation needs to continuously supply steam, coal, water and electricity, particularly in the north, so that the temperature control cost is higher. Once the temperature of the drug is lowered, it is difficult to achieve foam sensitization by heating. In the prior art, sodium nitrite is mostly adopted as a chemical sensitization foaming agent, and sodium nitrite solution with a certain proportion is added into an emulsion matrix to carry out sensitization under the conditions of proper PH value and temperature control. The chemical sensitization method has strict requirements on the pH value and the sensitization temperature of sensitization reaction, the pH value of a matrix is required to be about 3 to 5 in the factory production process, the sensitization temperature is generally controlled to be 47 ℃ to 53 ℃, the high-temperature sensitization temperature is required to be higher, the sensitization at least needs 3 hours of foaming time, and the post-effect is achieved. The physical sensitizer is added at a certain temperature, so that the viscosity and the fluidity of the matrix are good, the uniform stirring is facilitated, but the physical sensitizer is high in price, and the cost of the explosive is increased. For emulsion explosives, good chemical foaming generally satisfies the following conditions: firstly, the method is not influenced by the sensitization temperature, and the sensitization process can be smoothly completed within the range of 0-75 ℃; secondly, the rapid foaming is carried out within 5-20min, and the sensitization work is completed; thirdly, the bubbles have proper size, uniform distribution and stable existence.
According to Chinese patent search, the name is 'new process for rapid foaming and sensitizing of emulsion explosive', application number: 92104016.4, publication number: CN 1072404A. The method is to select sodium nitrite as foaming agent, phosphoric acid as accelerant and urea as auxiliary foaming material. Patent application entitled "emulsion explosive and chemical foaming technology", application number: 92107069.1, publication No. CN 1070902A. The method is to add thiourea or sodium thiocyanate which are chemical foaming promoters into the emulsified foaming glue, and to adjust the foaming speed and the foaming degree by utilizing the temperature change. The name of the patent application is 'method for rapidly chemically foaming and sensitizing emulsion explosive', and the application number is as follows: 95110404.7, publication No. CN 1127239A. The method is that organic matter with amido is added into the emulsified base as foaming agent, inorganic acid is added as promoter, and at least three minutes after the inorganic acid is added as foaming promoter, single solution of alkali or alkali metal salt or mixed solution of alkali or alkali metal salt is added as terminating stabilizer to complete sensitization. Patent application entitled "emulsion explosive fast sensitizers", application number: 201010207666.6, publication No. CN 101870626A. The method comprises the steps of adding the component A (aqueous solution of sodium nitrite and ammonium nitrate) and the component B (mixed of oxalic acid and thiourea), and improving the reaction speed by controlling the proportion of the component A and the component B and carrying out sensitization reaction under a proper temperature control environment. Patent application entitled "a rapid sensitizer for emulsion explosives", application number: 201210225218.8, publication No. CN 102731228A. The method comprises adding agent A (expanded microsphere with thermoplastic polyacrylonitrile as shell and containing liquid low boiling point hydrocarbon) into agent B (mixture of ethanol, ethylene glycol and glycerol and water solution at a certain ratio), stirring at room temperature for 5-10min in a stirring tank to obtain sensitizer, and sensitizing. Patent application entitled "a method for low temperature sensitization of emulsion explosives", application number: CN201711245517.7, publication No. CN 107759426A. The method is that a foaming agent (comprising a sodium nitrite solution and an ammonium nitrate solution) and an accelerant citric acid are added to an emulsion matrix at the temperature of 45-55 ℃ for sensitization. Patent application entitled "a rapid foaming agent for emulsion explosive and emulsion explosive", application number: cn201810918085.x, publication No. CN 108997070A. The method provides a rapid foaming agent which is prepared by zinc nitrate and water in proportion, and the foaming speed is increased by the catalytic action of the zinc nitrate.
It can be seen from the above patents that the mechanism in the rapid sensitization method is not changed, sodium nitrite is used as the main component of the foaming agent, the acidic accelerant is added to increase the foaming rate, the sensitization reaction occurs under a certain heating temperature, and the sodium nitrite and the acidic accelerant chemically react in the emulsified matrix to generate nitrogen microbubbles. The foaming rate is accelerated along with the rising rate of the temperature, the foaming rate becomes slow at lower temperature, when the temperature is reduced to 25 ℃ at normal temperature or even low temperature (0-5 ℃), most methods cannot foam normally, and the sensitization effect cannot be well guaranteed under the northern severe cold climate condition. The traditional chemical sensitization method has complicated procedures and redundant steps, and the sensitization reaction has strict requirements on temperature and acid conditions, so that the method has more procedures, is difficult to manage and cannot better ensure the sensitization quality in actual production. Therefore, in order to reduce the sensitization time, save the process cost, improve the sensitization quality and ensure the sensitization effect in northern severe cold climate areas, it is important to research a sensitizer and a sensitization method which can be simply and rapidly foamed under the conditions of higher temperature (25-75 ℃) and normal temperature and low temperature (0-25 ℃).
Disclosure of Invention
The invention aims to provide a novel rapid sensitization chemical sensitizer and a rapid sensitization method, the sensitizer and the rapid sensitization method enable an emulsion matrix produced in industry to simply realize a rapid sensitization process under the conditions of (0-25 ℃) and (25-70 ℃), the sensitization time is reduced, the process cost is saved, the sensitization quality is improved, the emulsion matrix is ensured to have a better sensitization effect in a low-temperature environment and in northern severe cold climatic regions, and the emulsion explosive with excellent explosion performance and good storage stability is provided.
The invention adopts the following technical scheme for realizing the purpose:
a quick sensitizing chemical sensitizer and a quick sensitizing method for preparing an emulsion explosive with excellent foaming performance concretely comprise a quick sensitizing agent sodium borohydride and a quick sensitizing method for adding a sodium borohydride solution to an emulsion matrix, wherein the quick sensitizing agent sodium borohydride is in a powder or block crystallization form, the quick sensitizing method is to dissolve the sodium borohydride in water and an alkaline solution to prepare a quick sensitizing agent solution, the quick sensitizing agent solution is added to the emulsion matrix in a titration mode to be stirred and sensitized, and the mass ratio of the added amount of the sodium borohydride to the emulsion matrix is 0.01-5 wt%.
Further, the rapid sensitizer is sodium borohydride powder or slightly crystallized, the sodium borohydride is ground into fine particle powder and is used as a rapid foaming chemical sensitizer to be added into an emulsifying matrix at the temperature of 0-25 ℃ and at the temperature of 25-70 ℃, the emulsifying matrix is stirred and sensitized according to a conventional stirring mode, and foaming can be completed within 10-30 minutes.
Further, the sodium borohydride solution is prepared by uniformly dissolving sodium borohydride in an aqueous solution or an alkaline solution, wherein the dissolving amount is 1-1000g/L, and the density of the prepared emulsion explosive can be adjusted according to the requirement; the pH value of the alkaline solution is 7-14, and the alkaline solution is prepared by dissolving sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, potassium carbonate, silver diammine hydroxide, ammonia water (monohydrate ammonia), lithium hydroxide, barium hydroxide, calcium hydroxide, sodium hydroxide, potassium hydroxide and the like in distilled water or purified water according to a certain proportion.
Furthermore, the formula of the emulsion matrix is the same as that of the emulsion matrix commonly used in the existing emulsion explosive, and the emulsion matrix is generally composed of ammonium nitrate, sodium nitrate, calcium nitrate, sodium sulfate, urea, water, wax, rosin, sorbitol monooleate, an emulsifier and the like.
Further, the rapid sensitization method is that the prepared sodium borohydride solution is added into the emulsifying matrix at a certain titration speed under the condition of (0-25 ℃) or (25-70 ℃) and the titration speed is controlled by the mass of the added sodium borohydride, the mass ratio of the sodium borohydride sensitizer to the emulsifying matrix is 0.01-5 wt%, and the emulsifying matrix is stirred and sensitized according to a conventional stirring mode. The time from the beginning of titration to the completion of stirring sensitization is controlled within 10-30 minutes, the density of the stirred and sensitized explosive reaches the application requirement of the industrial explosive, and the method is controllablePrepared at 0.4-1.3 g/cm3In the meantime.
Further, the sensitization mechanism of the rapid sensitization method is specifically as follows, sodium borohydride and a small amount of bound water in the emulsified matrix are subjected to hydrolysis reaction to generate H2And the micro-bubbles are formed by diffusion in the emulsion matrix, so that a 'hot spot' of detonation and booster is formed, the sensitization process of the emulsion explosive is completed, and the emulsion explosive with detonator sensitivity is prepared. As the emulsified matrix presents subacidity, the reaction can be quickly completed in a short time and is irreversible, the reaction rate is not influenced under the normal temperature condition (25 ℃) or even under the low temperature condition (0-5 ℃), and the reaction rate is stable and efficient when the temperature is higher.
The chemical equation for the sensitization mechanism is as follows: NaBH4+2H2O→NaBO2+4H2
The invention has the beneficial effects that:
1. the quick sensitizing chemical sensitizer sodium borohydride is different from the traditional emulsion explosive chemical sensitizer (mainly sodium nitrite), is a novel sensitizing material, has low price and stable components, and can be used for the industrial production of emulsion explosives;
2. the rapid sensitization method has simple process, the sodium borohydride solution is added into the emulsion matrix to be stirred and sensitized, the acid accelerant is not needed to be added to increase the reaction rate like the traditional chemical sensitizer, the sensitization reaction rate is rapid, the efficiency is high, the reaction can be completed within 10-30 minutes, and the density and the explosion performance required by the finished explosive are achieved;
3. the sensitization reaction has low requirement on the temperature environment, the sensitization rate and the effect of the emulsion matrix are not influenced under the normal temperature condition (25 ℃) or even under the low temperature condition (0-5 ℃), the strict requirement on the medium and high temperature environment temperature of the chemical sensitization reaction is reduced, and the problem that the sensitization effect of the emulsion explosive is not ideal in northern severe cold climate areas is solved;
4. the emulsion explosive can be prepared by a field mixing truck, the emulsion matrix and the sensitizer solution are separated in the transportation process, the safe transportation of explosive materials is fundamentally ensured, the rapid sensitization process is carried out when the emulsion explosive is used on site, the sensitization requirement of industrial explosives can be met by filling and using the emulsion explosive, the time is short, the efficiency is high, and the technical problems of high sensitization temperature requirement and low sensitization speed of the emulsion explosive prepared by the field mixing truck are solved.
Drawings
FIG. 1 is a process flow chart of the rapid sensitization method of emulsion explosive in the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
adding a rapid sensitizer into the emulsified substrate at the temperature of 40 ℃ according to the following requirements, and mixing and stirring.
The mass ratio of the fast sensitizer (namely sodium borohydride powder) to the emulsion matrix is 1:100, 10g of sodium borohydride powder (massive and large sodium borohydride particles are changed into powder by grinding, the particle size is within 100 microns, the grinding is used for increasing the contact area of the sensitizer and the emulsion matrix and further increasing the sensitization efficiency) is uniformly added into 1000g of emulsion matrix within 3 minutes, the emulsion matrix is stirred while the sensitizer is added, after the sodium borohydride is added, the emulsion matrix is continuously stirred for 20 minutes and then stands for 10 minutes, the fast sensitization of the emulsion matrix is completed, and the emulsion explosive with detonator sensitivity is obtained and can be normally used.
Example 2:
1. adding a rapid sensitizer solution into the emulsified substrate at the normal temperature of 25 ℃ according to the following requirements, and carrying out titration, mixing and stirring;
proportioning of a rapid sensitizer solution: the mass ratio of sodium borohydride to alkaline solution (PH 13) was 1: 4.
250g of pure sodium borohydride substance is weighed and dissolved in 1L of the alkaline solution, and the rapid sensitizer solution is obtained after the pure sodium borohydride substance is completely dissolved.
The proportion of alkaline solution is as follows: the mass ratio of sodium hydroxide to distilled water was 4: 1000.
An alkaline solution having a PH of 13 was prepared by dissolving 4g of purified sodium hydroxide in 1L of distilled water solution.
The mass ratio of the sensitizer solution to the emulsion base was 0.5: 100.
2. And (3) adopting an emulsified base material which is cooled to normal temperature in a stirring channel of a factory, titrating the solution of the rapid sensitizer at a titration rate of 8ml/min, stirring the emulsified base material simultaneously in the process of adding the rapid sensitizer, and charging after stirring for 20 minutes. The sensitization stirring device and the mode are the same as the stirring mode and the mode of the emulsion explosive which are generally applied in the prior art, and the device and the method are suitable for any mature emulsion explosive formula.
Example 3:
1. adding a rapid sensitizer solution into the emulsified substrate at a low temperature of 5 ℃, and carrying out titration mixing and stirring;
proportioning of a rapid sensitizer solution: the mass ratio of sodium borohydride to alkaline solution (PH 14) is 1:2
And weighing 500g of pure sodium borohydride substance, dissolving the pure sodium borohydride substance in 1L of the alkaline solution, and obtaining the rapid sensitizer solution after the pure sodium borohydride substance is completely dissolved.
The proportion of alkaline solution is as follows: the mass of sodium hydroxide and distilled water was 40: 1000.
40g of purified sodium hydroxide was dissolved in 1L of distilled water to prepare an alkaline solution having a pH of 14.
The mass ratio of the sensitizer solution to the emulsion base was 1: 100.
2. And (3) adopting an emulsified base material which is cooled to normal temperature in a stirring channel of a factory, titrating the solution of the rapid sensitizer at a titration rate of 12ml/min, stirring the emulsified base material simultaneously in the process of adding the rapid sensitizer, and charging the powder after stirring for 15 minutes. The sensitization stirring device and the mode are the same as the stirring mode and the mode of the emulsion explosive which are generally applied in the prior art, and the device and the method are suitable for any mature emulsion explosive formula.
It is obvious to a person skilled in the art that the invention/utility model is not restricted to details of the above-described exemplary embodiments, but that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (6)
1. A rapid sensitization chemical sensitizer and a rapid sensitization method for preparing emulsion explosive with excellent foaming performance are characterized in that: the method specifically comprises a rapid sensitizing agent sodium borohydride and a rapid sensitizing method for adding a sodium borohydride solution to an emulsion matrix, wherein the rapid sensitizing agent sodium borohydride is in a powder or block crystal form, the rapid sensitizing agent sodium borohydride is dissolved in water and an alkaline solution to prepare a rapid sensitizing agent solution, the rapid sensitizing agent solution is added to the emulsion matrix in a titration mode to be stirred and sensitized, and the mass ratio of the added amount of the sodium borohydride to the emulsion matrix is 0.01-5 wt%.
2. A fast sensitizer according to claim 1, which is sodium borohydride powder or crystals, characterized in that: grinding sodium borohydride into fine particle powder, adding the fine particle powder serving as a quick foaming chemical sensitizer into an emulsified matrix at the temperature of 0-25 ℃ and at the temperature of 25-70 ℃, stirring and sensitizing the emulsified matrix according to a conventional stirring mode, and completing foaming within 10-30 minutes.
3. The sodium borohydride solution in the rapid sensitization method according to claim 1, wherein: the sodium borohydride is uniformly dissolved in the aqueous solution or the alkaline solution, the dissolving amount is between 1 and 1000g/L, and the density of the emulsion explosive prepared according to the requirement can be adjusted; the pH value of the alkaline solution is 7-14, and the alkaline solution is prepared by dissolving sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, potassium carbonate, silver diammine hydroxide, ammonia water (monohydrate ammonia), lithium hydroxide, barium hydroxide, calcium hydroxide, sodium hydroxide, potassium hydroxide and the like in distilled water or purified water according to a certain proportion.
4. The emulsion base of claim 1, wherein the formulation of the emulsion base is the same as the formulation of the emulsion base commonly used in the existing emulsion explosives, and the emulsion base is generally composed of ammonium nitrate, sodium nitrate, calcium nitrate, sodium sulfate, urea, water, wax, rosin, sorbitol monooleate, emulsifier, and the like.
5. A method of rapid sensitization according to claim 1 characterized in that: adding the prepared sodium borohydride solution into an emulsion matrix at a certain titration speed under the condition of (0-25 ℃) or (25-70 ℃) at a certain titration speed, wherein the titration speed is controlled by the mass of the added sodium borohydride, the mass ratio of a sensitizer sodium borohydride to the emulsion matrix is 0.01-5 wt%, and the emulsion matrix is stirred and sensitized according to a conventional stirring mode. The time from the beginning of titration to the completion of stirring sensitization is controlled within 10-30 minutes, and the density of the stirred and sensitized explosive reaches the application requirement of the industrial explosive and can be controlled within 0.4-1.3 g/cm3In the meantime.
6. The rapid sensitization process sensitization mechanism according to claim 1 wherein: sodium borohydride and a small amount of bound water in the emulsified base material are subjected to hydrolysis reaction to generate H2And the micro-bubbles are formed by diffusion in the emulsion matrix, so that a 'hot spot' of detonation and booster is formed, the sensitization process of the emulsion explosive is completed, and the emulsion explosive with detonator sensitivity is prepared. Because the emulsified matrix presents subacidity, the reaction can be quickly completed in a short time and is irreversible, and the reaction rate is very high under the condition of normal temperature (25 ℃)The reaction is not affected under the condition of low temperature (0-5 ℃), and the reaction rate is stable and efficient when the temperature is higher.
The chemical equation for the sensitization mechanism is as follows: NaBH4+2H2O→NaBO2+4H2。
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Cited By (4)
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| CN113754507A (en) * | 2021-10-19 | 2021-12-07 | 安徽理工大学 | Potassium borohydride sensitized emulsion explosive |
| CN113831204A (en) * | 2021-10-19 | 2021-12-24 | 安徽理工大学 | Lithium borohydride sensitized emulsion explosive |
| CN113912466A (en) * | 2021-10-12 | 2022-01-11 | 安徽理工大学 | Sodium borohydride sensitized emulsion explosive |
| CN114699985A (en) * | 2022-03-31 | 2022-07-05 | 神华准格尔能源有限责任公司 | Aqueous solution preparation method, apparatus and computer readable storage medium |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113912466A (en) * | 2021-10-12 | 2022-01-11 | 安徽理工大学 | Sodium borohydride sensitized emulsion explosive |
| CN113754507A (en) * | 2021-10-19 | 2021-12-07 | 安徽理工大学 | Potassium borohydride sensitized emulsion explosive |
| CN113831204A (en) * | 2021-10-19 | 2021-12-24 | 安徽理工大学 | Lithium borohydride sensitized emulsion explosive |
| CN114699985A (en) * | 2022-03-31 | 2022-07-05 | 神华准格尔能源有限责任公司 | Aqueous solution preparation method, apparatus and computer readable storage medium |
| CN114699985B (en) * | 2022-03-31 | 2023-06-13 | 神华准格尔能源有限责任公司 | Aqueous solution configuration method, apparatus, and computer-readable storage medium |
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Application publication date: 20211126 |