Emulsion explosive recovery method

Abstract

The invention discloses an emulsion explosive recovery method. The method comprises the following steps: S1, adding an emulsion explosive and a demulsifier into a demulsification device for demulsification treatment; s2, an organic solvent is added into the demulsified mixture for extraction, separation and recovery of an oil-phase material and a water-phase material are achieved, and the demulsifier is composed of a hyperbranched demulsifier and a polyether ester type demulsifier. According to the method, safety risks such as explosion or fire disasters possibly caused by direct treatment of the expired emulsion explosives are avoided, safe treatment of the expired emulsion explosives is achieved in the mode of combining physical, chemical and biological means, recovery and reutilization of oil phase materials are achieved through demulsification treatment and organic solvent extraction, and the method is suitable for industrial production. In addition, ammonium nitrate in the water phase is treated through the sewage treatment equipment, harmful substances are removed, and it is ensured that the treated water solution meets the greening water standard.

Description

Technical Field

[0001] The present invention relates to the technical field of emulsion explosives, and particularly to a method for recycling emulsion explosives. Background Art

[0002] As an industrial explosive widely used in fields such as mines, construction, and roads, the stability, safety, and explosion effect of emulsion explosives have received extensive attention. However, due to factors such as storage conditions and time, emulsion explosives may become expired, resulting in a decline in their performance and inability to meet the normal use requirements. The treatment of expired emulsion explosives has become an urgent problem to be solved. Currently, the following methods are mainly used for the treatment of expired emulsion explosives: 1. Incineration method: Open-air incineration of expired emulsion explosives to eliminate their explosion risk. However, this method will generate a large amount of harmful gases and soot, causing serious pollution to the environment. Water dissolution method: Mixing expired emulsion explosives with water to dissolve the useful components therein, and then treating the solution. However, the treatment effect of this method is not good, and the treatment cost of the generated wastewater is relatively high. Although the above methods can solve the problem of treating expired emulsion explosives to a certain extent, there are problems such as potential safety hazards, environmental pollution, and resource waste.

[0003] Therefore, it is of great significance to develop a safe, environmentally friendly, and efficient treatment process for expired emulsion explosives and its resource recycling method. Summary of the Invention

[0004] Based on the technical problems existing in the background art, the present invention proposes a method for recycling emulsion explosives, realizing the safe treatment of expired emulsion explosives.

[0005] The method for recycling emulsion explosives proposed by the present invention is as follows:

[0006] S1: Adding emulsion explosives and a demulsifier into a demulsification device for demulsification treatment;

[0007] S2: Adding an organic solvent to the demulsified mixture for extraction to achieve the separation and recycling of the oil-phase material and the water-phase material.

[0008] Preferably, the demulsifying device includes an outer cylinder body. The lower end of the outer cylinder body is fixedly connected with annularly and equidistantly distributed support rods. The upper side inside the outer cylinder body is fixedly connected with an inner cylinder body. The upper end of the outer cylinder body is provided with a detachable upper cover. The upper cover is internally rotatably connected with a stirring shaft. A fixed seat is installed on the outer surface of the stirring shaft. The outer side of the stirring shaft is fixedly connected with first stirring sleeves and second stirring sleeves which are alternately distributed up and down. The outer sides of the first stirring sleeves and the second stirring sleeves are respectively fixedly connected with first blades and second blades with opposite directions. A telescopic rod moving horizontally is inserted into the fixed seat. A movable seat is fixedly connected to the end of the telescopic rod. A scraper is installed in the movable seat. Insertion rods which can be adjusted in lifting and are symmetrically distributed left and right are inserted into the upper cover. The lower ends of the two insertion rods are fixedly connected with a limiting ring. The upper ends of the insertion rods are fixedly connected with a baffle plate. A spring is fixedly connected between the baffle plate and the upper cover. A groove for placing the limiting ring is opened at the lower end of the upper cover. A magnet is fixedly connected in the groove. The lower end of the inner cylinder body is fixedly connected with annularly and equidistantly distributed transducers. A jacket is arranged on the outer side of the outer cylinder body. A discharge pipe passing through the outer cylinder body and extending outwards is installed at the lower end of the inner cylinder body. A motor mounting bracket is fixedly connected to the upper end of the upper cover. A servo motor for driving the stirring shaft is installed at the upper end of the motor mounting bracket. A heating medium inlet and outlet connected to the internal coil pipe is arranged on the outer side of the jacket. A feeding port is arranged at the upper end of the upper cover.

[0009] Preferably, the stirring speed of the demulsifying device is 100 - 300 rpm, and the ultrasonic power is 200 - 500 W / cm 2 。

[0010] Preferably, the demulsifier is composed of a hyperbranched demulsifier and a polyether ester demulsifier in a mass ratio of 2:1 - 4.

[0011] Preferably, the preparation method of the hyperbranched demulsifier is: mixing hyperbranched polyethyleneimine, a surfactant, a silane coupling agent and nano - silica for reaction to obtain the hyperbranched demulsifier.

[0012] Preferably, the surfactant is sodium N - stearoyl - L - glutamate;

[0013] The silane coupling agent is KH - 560;

[0014] The mass ratio of hyperbranched polyethyleneimine, the surfactant, the silane coupling agent and nano - silica is 1:0.05 - 0.15:0.1 - 1:0.1 - 0.5;

[0015] The reaction temperature is 20 - 30 °C, and the time is 16 - 24 h.

[0016] Preferably, the preparation method of the polyether ester demulsifier is: mixing aromatic polyether with xylene, then adding p - toluenesulfonic acid and acrylic acid for reaction to obtain an esterification intermediate, and then adding azobisisobutyronitrile for reaction to obtain the polyether ester demulsifier.

[0017] Preferably, the structural formula of the aromatic polyether is as follows:

[0018]

[0019] The molar ratio of the aromatic polyether to acrylic acid is 1:2 - 4, the addition amount of p-toluenesulfonic acid is 0.5 - 1% of the mass of the aromatic polyether, and the addition amount of azobisisobutyronitrile is 1 - 10% of the mass of acrylic acid;

[0020] The reaction temperature is 100 - 120 °C and the time is 5 - 10 h.

[0021] Preferably, the addition amount of the demulsifier is 0.1 - 0.5% of the mass of the emulsion explosive.

[0022] Preferably, the organic solvent is one or more of diesel, n-hexane and isopropanol; the volume ratio of the mixture to the organic solvent is 1:1 - 3.

[0023] Advantageous technical effects of the present invention:

[0024] (1) The present invention not only avoids the safety risks that may be caused by directly treating expired emulsion explosives, such as explosion or fire, but also realizes the safe treatment of expired emulsion explosives through a combination of physical, chemical and biological means. Through demulsification treatment and organic solvent extraction, the recovery and reuse of the oil-phase materials are achieved, the recycling utilization rate of resources is improved, and resource waste is reduced. In addition, ammonium nitrate in the aqueous phase is treated by sewage treatment equipment to remove harmful substances and ensure that the treated aqueous solution meets the greening water use standard.

[0025] (2) The demulsifier of the present invention is composed of a hyperbranched demulsifier and a polyether ester demulsifier, which has a synergistic promoting effect on improving the demulsification effect of expired emulsion explosives. Description of the Drawings

[0026] Figure 1 It is a schematic three-dimensional sectional structure diagram of the demulsification device proposed by the present invention;

[0027] Figure 2 It is a schematic three-dimensional structure diagram of the stirring shaft and the scraper in the demulsification device proposed by the present invention;

[0028] Figure 3 It is a schematic three-dimensional structure diagram of the stirring shaft and the scraper in the demulsification device proposed by the present invention;

[0029] Figure 4 It is a schematic three-dimensional structure diagram of the insertion rod and the limiting ring in the demulsification device proposed by the present invention.

[0030] In the figure: 1 - outer cylinder body, 2 - support rod, 3 - inner cylinder body, 4 - upper cover, 5 - stirring shaft, 6 - fixed seat, 7 - first stirring sleeve, 8 - second stirring sleeve, 9 - first blade, 10 - second blade, 11 - telescopic rod, 12 - movable seat, 13 - scraper, 14 - inserting rod, 15 - limiting ring, 16 - baffle plate, 17 - spring, 18 - groove, 19 - magnet, 20 - transducer, 21 - jacket, 22 - discharge pipe, 23 - motor mounting bracket, 24 - servo motor, 25 - heating medium inlet and outlet, 26 - feeding port. Detailed implementation mode

[0031] The present invention will be further explained below in conjunction with specific embodiments.

[0032] Refer to Figures 1-4 , the demulsification device proposed by the present invention includes an outer cylinder body 1, the lower end of the outer cylinder body 1 is fixedly connected with support rods 2 distributed annularly and equidistantly, the upper side inside the outer cylinder body 1 is fixedly connected with an inner cylinder body 3, the upper end of the outer cylinder body 1 is provided with a detachable upper cover 4, the upper cover 4 is rotatably connected with a stirring shaft 5 inside, a fixed seat 6 is installed on the outer surface of the stirring shaft 5, the outer side of the stirring shaft 5 is fixedly connected with a first stirring sleeve 7 and a second stirring sleeve 8 distributed alternately up and down, the outer sides of the first stirring sleeve 7 and the second stirring sleeve 8 are respectively fixedly connected with a first blade 9 and a second blade 10 with opposite directions, a telescopic rod 11 moving horizontally is inserted into the fixed seat 6, the end of the telescopic rod 11 is fixedly connected with a movable seat 12, a scraper 13 is installed inside the movable seat 12, inserting rods 14 which can be adjusted up and down and are symmetrically distributed left and right are inserted into the upper cover 4, the lower ends of the two inserting rods 14 are fixedly connected with a limiting ring 15, the upper ends of the inserting rods 14 are fixedly connected with a baffle plate 16, a spring 17 is fixedly connected between the baffle plate 16 and the upper cover 4, a groove 18 for placing the limiting ring 15 is opened at the lower end of the upper cover 4, a magnet 19 is fixedly connected inside the groove 18, the lower end of the inner cylinder body 3 is fixedly connected with transducers 20 distributed annularly and equidistantly, a jacket 21 is arranged outside the outer cylinder body 1, the lower end of the inner cylinder body 3 is installed with a discharge pipe 22 extending outwards through the outer cylinder body 1, the upper end of the upper cover 4 is fixedly connected with a motor mounting bracket 23, a servo motor 24 for driving the stirring shaft 5 is installed at the upper end of the motor mounting bracket 23, a heating medium inlet and outlet 25 connected with the internal coil is arranged outside the jacket 21, and a feeding port 26 is arranged at the upper end of the upper cover 4.

[0033] When treating expired emulsion explosives, first, the support rod 2 supports the outer cylinder 1 to ensure the stability of the demulsification device. Through the feeding port 26 at the upper end of the upper cover 4, expired emulsion explosives and demulsifiers are added into the inner cylinder 3. The servo motor 24 at the upper end of the motor mounting bracket 23 is turned on to drive the stirring shaft 5 to stir the mixture at a speed of 100 rpm. The stirring shaft 5 drives the fixed seat 6, the first stirring sleeve 7, and the second stirring sleeve 8 to rotate. The first blade 9, the second blade 10, and the scraper 13 fully stir the mixture. The heating medium is sent into the jacket 21 through the heating medium inlet and outlet 25 to achieve heating. At the same time, the ultrasonic frequency power supply converts electrical energy into a high-frequency alternating current signal matching the transducer 20. The transducer 20 converts the input electric power into mechanical power, that is, ultrasonic waves, and then transmits them to enhance the demulsification effect inside the inner cylinder 3. Finally, after the mixing is completed, the baffle 16 is pushed downward, the insertion rod 14 pushes the limit ring 15 downward, the spring 17 returns to the initial state, the magnet 19 in the groove 18 is separated from the limit ring 15, the limit ring 15 is clamped at the upper end of the telescopic rod 11 between the fixed seat 6 and the movable seat 12, the scraper 13 fits with the inner wall of the inner cylinder 3, and as the stirring shaft 5 rotates, the scraper 13 scrapes off the mixture sticking to the inner wall of the inner cylinder 3, and finally the mixture is discharged from the discharge pipe 22.

[0034] Example 1

[0035] The emulsion explosive and the demulsifier are added to the demulsification device for demulsification treatment; an organic solvent is added to the demulsified mixture for extraction to achieve the separation and recovery of the oil-phase material and the water-phase material.

[0036] The stirring speed of the demulsification device is 200 rpm, and the ultrasonic power is 350 W / cm 2 。

[0037] The demulsifier is composed of a hyperbranched demulsifier and a polyether ester demulsifier in a mass ratio of 1:1.

[0038] The preparation method of the hyperbranched demulsifier is: mixing hyperbranched polyethyleneimine, surfactant, silane coupling agent, and nano-silica for reaction to obtain the hyperbranched demulsifier.

[0039] The surfactant is sodium N-stearoyl-L-glutamate;

[0040] The silane coupling agent is KH-560;

[0041] The mass ratio of hyperbranched polyethyleneimine, surfactant, silane coupling agent, and nano-silica is 1:0.1:0.5:0.3;

[0042] The reaction temperature is 25 °C and the time is 20 h.

[0043] The preparation method of the polyether ester type demulsifier is as follows: Mix the aromatic polyether with xylene, then add p-toluenesulfonic acid and acrylic acid to react to obtain an esterification intermediate, and then add azobisisobutyronitrile to react to obtain the polyether ester type demulsifier.

[0044] The structural formula of the aromatic polyether is as follows:

[0045]

[0046] The molar ratio of the aromatic polyether to acrylic acid is 1:3, the addition amount of p-toluenesulfonic acid is 0.8% of the mass of the aromatic polyether, and the addition amount of azobisisobutyronitrile is 5% of the mass of acrylic acid;

[0047] The reaction temperature is 110 °C and the time is 8 h.

[0048] The addition amount of the demulsifier is 0.3% of the mass of the emulsion explosive.

[0049] The organic solvent is one or several of diesel, n-hexane and isopropanol; the volume ratio of the mixture to the organic solvent is 1:2.

[0050] Example 2

[0051] Add the emulsion explosive and the demulsifier into a demulsification device for demulsification treatment; add an organic solvent to the demulsified mixture for extraction to realize the separation and recovery of the oil phase material and the water phase material.

[0052] The stirring speed of the demulsification device is 100 rpm and the ultrasonic power is 200 W / cm 2 .

[0053] The demulsifier is composed of a hyperbranched demulsifier and a polyether ester type demulsifier in a mass ratio of 2:1.

[0054] The preparation method of the hyperbranched demulsifier is as follows: Mix hyperbranched polyethyleneimine, a surfactant, a silane coupling agent and nano-silica for reaction to obtain the hyperbranched demulsifier.

[0055] The surfactant is sodium N-stearoyl-L-glutamate;

[0056] The silane coupling agent is KH-560;

[0057] The mass ratio of hyperbranched polyethyleneimine, the surfactant, the silane coupling agent and nano-silica is 1:0.05:0.1:0.1;

[0058] The reaction temperature is 20 °C and the time is 16 h.

[0059] The preparation method of the polyether ester demulsifier is as follows: Mix the aromatic polyether with xylene, then add p-toluenesulfonic acid and acrylic acid to react to obtain an esterification intermediate, and then add azobisisobutyronitrile to react to obtain the polyether ester demulsifier.

[0060] The structural formula of the aromatic polyether is as follows:

[0061]

[0062] The molar ratio of the aromatic polyether to acrylic acid is 1:2, the addition amount of p-toluenesulfonic acid is 0.5% of the mass of the aromatic polyether, and the addition amount of azobisisobutyronitrile is 1% of the mass of acrylic acid;

[0063] The reaction temperature is 100 °C and the time is 5 h.

[0064] The addition amount of the demulsifier is 0.1% of the mass of the emulsion explosive.

[0065] The organic solvent is one or several of diesel, n-hexane and isopropanol; the volume ratio of the mixture to the organic solvent is 1:1 - 3.

[0066] Example 3

[0067] Add the emulsion explosive and the demulsifier into the demulsification device for demulsification treatment; add an organic solvent to the demulsified mixture for extraction to realize the separation and recovery of the oil-phase material and the water-phase material.

[0068] The stirring speed of the demulsification device is 300 rpm and the ultrasonic power is 500 W / cm 2 .

[0069] The demulsifier is composed of a hyperbranched demulsifier and a polyether ester demulsifier in a mass ratio of 1:2.

[0070] The preparation method of the hyperbranched demulsifier is as follows: Mix hyperbranched polyethyleneimine, a surfactant, a silane coupling agent and nano-silica for reaction to obtain the hyperbranched demulsifier.

[0071] The surfactant is sodium N-stearoyl-L-glutamate;

[0072] The silane coupling agent is KH-560;

[0073] The mass ratio of hyperbranched polyethyleneimine, the surfactant, the silane coupling agent and nano-silica is 1:0.15:1:0.5;

[0074] The reaction temperature is 30 °C and the time is 24 h.

[0075] The preparation method of the polyether ester demulsifier is as follows: Mix the aromatic polyether with xylene, then add p-toluenesulfonic acid and acrylic acid to react to obtain an esterification intermediate, and then add azobisisobutyronitrile to react to obtain the polyether ester demulsifier.

[0076] The structural formula of the aromatic polyether is as follows:

[0077]

[0078] The molar ratio of the aromatic polyether to acrylic acid is 1:4, the addition amount of p-toluenesulfonic acid is 1% of the mass of the aromatic polyether, and the addition amount of azobisisobutyronitrile is 10% of the mass of acrylic acid;

[0079] The reaction temperature is 120 °C and the time is 10 h.

[0080] The addition amount of the demulsifier is 0.5% of the mass of the emulsion explosive.

[0081] The organic solvent is one or more of diesel, n-hexane and isopropanol; the volume ratio of the mixture to the organic solvent is 1:3.

[0082] Comparative Example 1

[0083] Add the emulsion explosive and the demulsifier into a demulsification device for demulsification treatment; add an organic solvent to the demulsified mixture for extraction to achieve the separation and recovery of the oil-phase material and the water-phase material.

[0084] The demulsifier is a hyperbranched demulsifier, and the other conditions are the same as those in Example 1.

[0085] Comparative Example 2

[0086] Add the emulsion explosive and the demulsifier into a demulsification device for demulsification treatment; add an organic solvent to the demulsified mixture for extraction to achieve the separation and recovery of the oil-phase material and the water-phase material.

[0087] The demulsifier is a polyether ester demulsifier, and the other conditions are the same as those in Example 1.

[0088] Measure the demulsification effects of Examples 1-3 and Comparative Examples 1-2. The demulsification degree is characterized by measuring the conductivity of the aqueous solution and the precipitation rate of ammonium nitrate. The specific method refers to the records in "Study on the Demulsification Experiment and Demulsification Mechanism of Unqualified Emulsion Explosives, Yin Yating". The test results are shown in Table 1.

[0089] Table 1 Demulsification Effects of Expired Emulsion Explosives

[0090] Group <![CDATA[Conductivity / μs·cm -1 > AN precipitation rate / % Example 1 26.1 85.2 Example 2 25.5 83.6 Example 3 25.9 84.7 Comparative Example 1 19.8 67.4 Comparative Example 2 18.7 69.2

[0091] As can be seen from the test results in Table 1, the present invention improves the separation effect of the aqueous phase and the oil phase of the emulsion explosive, improves the recycling rate of resources, and reduces resource waste. From the test results of Example 1, Comparative Example 1 and Comparative Example 2, it can be seen that the demulsifier of the present invention is composed of a hyperbranched demulsifier and a polyether ester demulsifier, which has a synergistic promoting effect on improving the demulsification effect of expired emulsion explosives.

[0092] Although the embodiments of the present application have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present application. The scope of the present application is defined by the appended claims and their equivalents, and all of them should be included within the protection scope of the present application.

Claims

1. A method for recovering emulsion explosives, characterized in that: The steps are as follows: S1: adding emulsion explosive and demulsifier into demulsification device for demulsification treatment; S2: adding an organic solvent to the demulsified mixture for extraction to achieve separation and recovery of the oil phase material and the water phase material.

2. The method for recovering emulsion explosive according to claim 1, characterized in that: The demulsification device comprises an outer cylinder (1), the lower end of the outer cylinder (1) is fixedly connected to a supporting rod (2) distributed in an annular manner with equal spacing, the inner upper side of the outer cylinder (1) is fixedly connected to an inner cylinder (3), a detachable upper cover (4) is installed on the upper end of the outer cylinder (1), a stirring shaft (5) is rotatably connected inside the upper cover (4), a fixed seat (6) is installed on the outer surface of the stirring shaft (5), a first stirring sleeve (7) and a second stirring sleeve (8) which are alternately distributed up and down are fixedly connected to the outer side of the stirring shaft (5), a first blade (9) and a second blade (10) which are in opposite directions are fixedly connected to the outer side of the first stirring sleeve (7) and the second stirring sleeve (8), a telescopic rod (11) which moves in the transverse direction is inserted into the fixed seat (6), a movable seat (12) is fixedly connected to the end of the telescopic rod (11), a scraper (13) is installed in the movable seat (12), and a plug rod (14) which can be raised and lowered and is symmetrically distributed is inserted into the upper cover (4). The lower ends of the two plug rods (14) are fixedly connected to a limit ring (15), the upper ends of the plug rods (14) are fixedly connected to a baffle (16), a spring (17) is fixedly connected between the baffle (16) and the upper cover (4), a groove (18) for accommodating the limit ring (15) is provided at the lower end of the upper cover (4), a magnet (19) is fixedly connected in the groove (18), the lower end of the inner cylinder (3) is fixedly connected to an annular equidistantly distributed transducer (20), and the outer cylinder ( 1) is provided with a jacket (21) on the outside, a discharge pipe (22) is installed at the lower end of the inner cylinder (3) and passes through the outer cylinder (1) and extends outward, a motor mounting frame (23) is fixedly connected to the upper end of the upper cover (4), a servo motor (24) for driving the stirring shaft (5) is installed on the upper end of the motor mounting frame (23), a heating medium inlet and outlet (25) connected to the internal coil is provided on the outside of the jacket (21), and a feeding port (26) is provided at the upper end of the upper cover (4).

3. The method for recovering emulsion explosive according to claim 1, characterized in that: The stirring speed of the demulsifier is 100-300rpm, and the ultrasonic power is 200-500W / cm 2 .

4. The method for recovering emulsion explosive according to claim 1, characterized in that: The demulsifier is composed of a hyperbranched demulsifier and a polyether ester demulsifier in a mass ratio of 2:1-4.

5. The method for recovering emulsion explosive according to claim 4, characterized in that: The preparation method of the hyperbranched demulsifier comprises the following steps: mixing and reacting hyperbranched polyethyleneimine, a surfactant, a silane coupling agent and nano silicon dioxide to obtain the hyperbranched demulsifier.

6. The method for recovering emulsion explosive according to claim 5, characterized in that: The surfactant is disodium N-stearoyl-L-glutamate; The silane coupling agent is KH-560; The mass ratio of branched polyethyleneimine, surfactant, silane coupling agent and nano-silicon dioxide is 1:0.05-0.15:0.1-1:0.1-0.5; The reaction temperature is 20-30°C and the reaction time is 16-24h.

7. The method for recovering emulsion explosive according to claim 4, characterized in that: The preparation method of the polyether ester type demulsifier is as follows: aromatic polyether is mixed with xylene, p-toluenesulfonic acid and acrylic acid are added to react to obtain an esterification intermediate, and azobisisobutyronitrile is added to react to obtain the polyether ester type demulsifier.

8. The method for recovering emulsion explosive according to claim 7, characterized in that: The structural formula of the aromatic polyether is as follows: The molar ratio of the aromatic polyether to acrylic acid is 1:2-4, the amount of p-toluenesulfonic acid added is 0.5-1% of the mass of the aromatic polyether, and the amount of azobisisobutyronitrile added is 1-10% of the mass of acrylic acid; The reaction temperature is 100-120°C and the reaction time is 5-10h.

9. The method for recovering emulsion explosive according to claim 1, characterized in that: The added amount of the demulsifier is 0.1-0.5% of the mass of the emulsion explosive.

10. The method for recovering emulsion explosive according to claim 1, characterized in that: The organic solvent is one or more of diesel, n-hexane and isopropanol; the volume ratio of the mixture to the organic solvent is 1:1-3.

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