An integrated oil phase for emulsion explosive and preparation method thereof

Abstract

The invention discloses an integrated oil phase for emulsion explosive and a preparation method thereof. The integrated oil phase comprises an oil phase and an emulsifier, wherein the oil phase is white oil and cyclohexane oil, and the emulsifier is polyglycerol-3-diisostearate, stearyl alcohol phosphate and methyl vinyl ether-maleic anhydride copolymer. The preparation method comprises the following steps: (1) weighing white oil, cyclohexane oil, polyglycerol-3-diisostearate, stearyl alcohol phosphate and methyl vinyl ether-maleic anhydride copolymer; (2) first heating and melting the white oil, polyglycerol-3-diisostearate, stearyl alcohol phosphate and methyl vinyl ether-maleic anhydride copolymer, stirring, adding cyclohexane oil after the white oil, polyglycerol-3-diisostearate, stearyl alcohol phosphate and methyl vinyl ether-maleic anhydride copolymer are completely melted, continuing stirring and heat preservation, cooling after discharging, and obtaining the integrated oil phase; the integrated oil phase selects polyglycerol-3-diisostearate, stearyl alcohol phosphate and methyl vinyl ether-maleic anhydride copolymer as composite emulsifiers, thereby improving the stability and frost resistance of the emulsion explosive under low temperature conditions.

Description

Technical Field

[0001] The invention relates to oil, in particular to an integrated oil phase for emulsion explosive and a preparation method thereof. Background Art

[0002] Emulsion explosives are water-in-oil (W / O) latex-type water-resistant industrial explosives prepared by emulsification technology. They use fine droplets of oxidant ammonium nitrate aqueous solution as dispersed phase, and oil-like substances with dispersed bubbles or hollow glass microspheres or other porous materials as continuous phase, forming a special water-in-oil emulsion system. Since the invention of emulsion explosives and the realization of industrial production, its oil phase has been mainly paraffin, ozokerite, beeswax, microcrystalline wax, vaseline, motor oil, composite wax, etc., and the emulsifier is mainly lecithin, SPAN-80 and polyisobutylene succinimide and their compounds.

[0003] The study in the literature (Shen Xiaxia, Wu Hongbo, Huang Wenyao, et al. Effects of Span-80 and T-152 on the Low-Temperature Stability of Emulsion Explosives [J]. Engineering Blasting, 2015, 21(4): 20-23) shows that when composite wax is used as the oil phase material, the emulsifiers Span-80 and T-152 affect the low-temperature stability of emulsion explosives. The type of emulsifier has an effect on the low-temperature stability of emulsion explosives. After being stored in a low-temperature environment of -30°C for 10 days, both emulsion explosives have demulsified. The crystallization rate of the emulsion explosive using T-152 is 3.57 times that of the emulsion explosive using Span-80. The emulsion explosive prepared with T-152 has poorer low-temperature stability than the emulsion explosive prepared with Span-80.

[0004] Literature (Zhu Keke, Wu Hongbo, Xia Manman, et al. Effect of Oil Phase Materials on Low Temperature Resistance of Emulsion Explosives [J]. Explosives, 2018, (2): 48-51) shows that emulsion explosives were prepared with Span-80 as emulsifier and Inner Mongolia wax, Huayue wax, 2# wax, 5# wax and ozokerite wax as oil phases. The samples were frozen at -30℃ and the crystallization rate was measured every 5 days using the formaldehyde method. The microstructure of each sample before and after freezing at -30℃ for 30 days was observed using Nikon series microscopes. The results show that short-term low-temperature freezing has little effect on the stability of emulsion explosives prepared with different oil phases. Under long-term freezing, the emulsion explosives prepared with 5# wax and Huayue wax are relatively stable, and the emulsion explosives prepared with ozokerite wax have the worst low temperature resistance.

[0005] Emulsion explosives have poor stability and frost resistance under low temperature conditions, resulting in higher rates of emulsion explosive refusal, explosion interruption, blind shot and misfire than in low altitude areas, which seriously limits the use of emulsion explosives in high altitude and low pressure areas. Summary of the invention

[0006] Purpose of the invention: The first purpose of the present invention is to provide an integrated oil phase for emulsion explosives that improves the stability of emulsion explosives at low temperatures; the second purpose of the present invention is to provide a method for preparing the integrated oil phase for emulsion explosives.

[0007] Technical solution: The integrated oil phase for emulsion explosives of the present invention comprises an oil phase and an emulsifier, wherein the oil phase is white oil and cyclohexane oil, and the emulsifier is polyglycerol-3-diisostearate, stearyl alcohol phosphate and methyl vinyl ether-maleic anhydride copolymer.

[0008] White oil and cyclohexane oil are selected as the basic oil phase materials of the integrated oil phase. The characteristics of white oil, such as being odorless, non-toxic, and having excellent chemical stability and light resistance, are utilized to improve the stability of the oil phase materials under extreme conditions such as high altitudes, low pressure areas, and strong ultraviolet rays. Cyclohexane oil has the characteristics of a low pour point (-50 to -12°C) and excellent low-temperature resistance. At the same time, cyclohexane oil has a high viscosity, which can adjust the viscosity of the integrated oil phase materials and improve the stability of the latex matrix. Using cyclohexane oil and white oil as the basic materials of the composite integrated oil phase can improve the low-temperature resistance of the emulsion explosive under extreme conditions such as high altitudes, low pressure, low temperatures, and strong ultraviolet rays, thereby improving the stability of the performance of the emulsion explosive.

[0009] The composite emulsifier prepared by using stearyl alcohol phosphate, polyglycerol-3-diisostearate and methyl vinyl ether-maleic anhydride copolymer is mixed with white oil and cyclohexane oil to prepare an integrated oil phase. The non-ionic oil-in-water emulsifier polyglycerol-3-diisostearate has an HLB value of 4.5 and has strong emulsification ability. The ammonium nitrate in the water phase of emulsion explosives is a strong acid and weak base salt, and sodium nitrate is a strong acid and strong base salt. The oil-soluble emulsifier stearyl alcohol phosphate has the ability to resist acid, alkali, salt and static electricity; methyl vinyl ether-maleic anhydride copolymer plays the role of dispersing, emulsifying, thickening, film-forming and antistatic agent. At the same time, it has a higher average molecular weight, which improves the viscosity of the matrix and the toughness and strength of the oil film, and the coating effect is enhanced to prevent the crystallization of ammonium nitrate under low temperature conditions, and improve the stability of the emulsified matrix. The lipophilic groups of stearyl alcohol phosphate and polyglycerol-3-diisostearate penetrate deeply into the oil phase, which can significantly improve the strength and tightness of the emulsion interface film, effectively prevent ammonium nitrate and sodium nitrate aqueous solution from penetrating the oil film, and prevent ammonium nitrate from crystallizing, stratifying, and puncturing the oil film due to low temperature, which leads to the reduction of explosive performance. The excellent properties of stearyl alcohol phosphate, polyglycerol-3-diisostearate and methyl vinyl ether-maleic anhydride copolymer are comprehensively utilized to improve the stability of emulsion explosives under low temperature environmental conditions, ensuring that the explosives have reliable detonation ability and good explosion transmission performance under low temperature working conditions.

[0010] Preferably, the integrated oil comprises, by mass percentage, 15-45% white oil, 30-40% cycloparaffin oil, 5-10% polyglycerol-3-diisostearate, 10-20% stearyl alcohol phosphate and 10-15% methyl vinyl ether-maleic anhydride copolymer.

[0011] Preferably, the polyglycerol-3-diisostearate comprises 8-10%, stearyl alcohol phosphate comprises 15-20% and methyl vinyl ether-maleic anhydride copolymer comprises 10-15%.

[0012] Preferably, the purity of the methyl vinyl ether-maleic anhydride copolymer is MW 80,000-130,000.

[0013] Preferably, the purity of the naphthenic oil is 95-99%.

[0014] The method for preparing the integrated oil phase for emulsion explosives of the present invention comprises the following steps:

[0015] (1) Weighing white oil, naphthenic oil, polyglycerol-3-diisostearate, stearyl alcohol phosphate and methyl vinyl ether-maleic anhydride copolymer;

[0016] (2) First, heat and melt white oil, polyglycerol-3-diisostearate, stearyl alcohol phosphate and methyl vinyl ether-maleic anhydride copolymer, stir, and add cyclohexane oil after they are completely melted, continue stirring and heat preservation, and cool after discharging to obtain an integrated oil phase.

[0017] Preferably, in step (2), the heating and melting temperature is 92-96°C.

[0018] Preferably, in step (2), the heating and melting is performed using a wax melter, and the wax melter is heated in a water bath.

[0019] Preferably, in step (2), the stirring speed is 200 to 600 rpm.

[0020] Preferably, in step (2), the insulation time is 30 to 50 minutes.

[0021] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: (1) The integrated oil phase selects polyglycerol-3-diisostearate, stearyl alcohol phosphate and methyl vinyl ether-maleic anhydride copolymer as composite emulsifiers, which improves the stability and frost resistance of the emulsion explosive under low temperature conditions; (2) The oil phase does not use paraffin, ozokerite, beeswax, microcrystalline wax, vaseline, motor oil, composite wax, etc. commonly used in explosives as the main materials of the oil phase, but uses liquid white oil and cycloalkane oil, which makes the preparation process simpler and reduces the solid waste generated by solid wax packaging; (3) The preparation method of the integrated oil phase of the present invention is simple and does not require special equipment. It only needs to perform melting, stirring and heat preservation processes, which simplifies the preparation process, reduces the number of operators, has the advantages of low energy consumption, and reduces production costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a diagram of a latex matrix prepared using the integrated oil phase prepared in Example 3. DETAILED DESCRIPTION

[0023] The technical solution of the present invention is further described below in conjunction with embodiments.

[0024] Example 1

[0025] The integrated oil phase for emulsion explosives of the present invention comprises, by mass percentage, 30% white oil, 40% cyclohexane oil, 10% polyglycerol-3-diisostearate, 10% stearyl alcohol phosphate and 10% methyl vinyl ether-maleic anhydride copolymer.

[0026] The preparation method comprises the following steps:

[0027] (1) Weigh 600 g of white oil, 200 g of polyglycerol-3-diisostearate, 200 g of stearyl alcohol phosphate and 200 g of methyl vinyl ether-maleic anhydride copolymer;

[0028] (2) Heat the wax melter to 92-96° C. in a water bath and keep the heating temperature constant. Add the above raw materials into the wax melter and heat to melt at 92-96° C. with stirring at a speed of 200-300 rpm. After complete melting, add 800 g of cyclohexane oil and stir and keep warm for 30 minutes. Then stop stirring and cool the material after discharging to obtain an integrated oil phase.

[0029] Example 2

[0030] The integrated oil phase for emulsion explosives of the present invention comprises, by mass percentage, 35% white oil, 30% cyclohexane oil, 10% polyglycerol-3-diisostearate, 15% stearyl alcohol phosphate and 10% methyl vinyl ether-maleic anhydride copolymer.

[0031] The preparation method comprises the following steps:

[0032] (1) Weigh 700 g of white oil, 200 g of polyglycerol-3-diisostearate, 300 g of stearyl alcohol phosphate and 200 g of methyl vinyl ether-maleic anhydride copolymer;

[0033] (2) heating the wax melter to 92-96° C. in a water bath and keeping the heating temperature constant, adding the above raw materials into the wax melter, heating and melting at 92-96° C., stirring at a speed of 400-500 rpm, and after complete melting, adding 600 g of cyclohexane oil, stirring and keeping the temperature for 30 minutes, stopping stirring, cooling after discharging, and obtaining an integrated oil phase;

[0034] Example 3

[0035] The integrated oil phase for emulsion explosive of the present invention comprises, by mass percentage, 15% white oil, 40% cyclohexane oil, 10% polyglycerol-3-diisostearate, 20% stearyl alcohol phosphate and 15% methyl vinyl ether-maleic anhydride copolymer.

[0036] The preparation method comprises the following steps:

[0037] (1) Weigh 300 g of white oil, 200 g of polyglycerol-3-diisostearate, 400 g of stearyl alcohol phosphate and 300 g of methyl vinyl ether-maleic anhydride copolymer;

[0038] (2) Heat the wax melter to 92-96° C. in a water bath and keep the heating temperature constant. Add the above raw materials into the wax melter and heat to melt at 92-96° C. with stirring at a speed of 500-600 rpm. After complete melting, add 800 g of cyclohexane oil and stir and keep warm for 30 minutes. Then stop stirring, cool after discharging, and obtain an integrated oil phase.

[0039] Example 4

[0040] The integrated oil phase for emulsion explosive of the present invention comprises, by mass percentage, 45% white oil, 30% cyclohexane oil, 5% polyglycerol-3-diisostearate, 10% stearyl alcohol phosphate and 10% methyl vinyl ether-maleic anhydride copolymer.

[0041] The preparation method comprises the following steps:

[0042] (1) Weigh 900 g of white oil, 100 g of polyglycerol-3-diisostearate, 200 g of stearyl alcohol phosphate and 200 g of methyl vinyl ether-maleic anhydride copolymer;

[0043] (2) Heat the wax melter to 92-96° C. in a water bath and keep the heating temperature constant. Add the above raw materials into the wax melter and heat to melt at 92-96° C. with stirring at a speed of 200-300 rpm. After complete melting, add 600 g of cycloalkane oil and stir and keep warm for 30 min. Then stop stirring and cool the material after discharging to obtain an integrated oil phase.

[0044] Comparative Example 1

[0045] On the basis of Example 3, polyglycerol-3-diisostearate was not added, 516 g of stearyl alcohol phosphate and 387 g of methyl vinyl ether-maleic anhydride copolymer were added, and the other conditions remained unchanged.

[0046] Comparative Example 2

[0047] On the basis of Example 3, stearyl alcohol phosphate was not added, 360 g of polyglycerol-3-diisostearate and 540 g of methyl vinyl ether-maleic anhydride copolymer were added, and the other conditions remained unchanged.

[0048] Comparative Example 3

[0049] 200g polyglyceryl-3-diisostearate, 400g stearyl alcohol phosphate and 300g methyl vinyl ether-maleic anhydride copolymer

[0050] On the basis of Example 3, methyl vinyl ether-maleic anhydride copolymer was not added, 300 g of polyglycerol-3-diisostearate and 600 g of stearyl alcohol phosphate were added, and the other conditions remained unchanged.

[0051] Performance Testing

[0052] The latex matrix was prepared by using the integrated oil phase prepared in Examples 1 to 4 and Comparative Examples 1 to 3, and the formula was (mass percentage) water phase: oil phase = 93.5: 6.5; the water phase formula was (mass percentage) sodium nitrate: ammonium nitrate: water = 8: 81: 11.5. Then the detonation velocity, sympathetic detonation distance, intensity, working capacity, and high and low temperature cycle number of the latex matrix were tested, and the test standard was GB28286-2012 "General Technical Conditions for Industrial Explosives", and the test results are shown in Table 1.

[0053] Table 1 Explosion performance test results of samples

[0054]

[0055] It can be seen from the data in Table 1 that the explosive properties of the emulsion explosives prepared by the integrated oil phase prepared in Examples 1 to 3 all meet the requirements of GB28286-2012 "General Technical Conditions for Industrial Explosives". The integrated oil phase composed of polyglycerol-3-diisostearate, stearyl phosphate and methyl vinyl ether-maleic anhydride copolymer and white oil and cycloparaffin oil has a better emulsification effect, and the matrix viscosity and the toughness of the oil film are improved, so that the explosive has excellent explosive performance, can undergo 12 high and low temperature cycles, and the matrix stability and low temperature resistance are improved.

[0056] The integrated oil phase of comparative example 1 does not contain emulsifier polyglycerol-3-diisostearate, but only contains emulsifier stearyl alcohol phosphate and methyl vinyl ether-maleic anhydride copolymer; comparative example 2 does not contain stearyl alcohol phosphate, and the integrated oil phase contains polyglycerol-3-diisostearate and methyl vinyl ether-maleic anhydride copolymer. Performance tests show that under the condition that appropriate mass percentages of polyglycerol-3-diisostearate and stearyl alcohol phosphate are not added to the integrated oil phase at the same time, the emulsification effect and matrix stability are reduced to a certain extent, resulting in reduced explosion performance and high and low temperature cycle times.

[0057] In Comparative Example 3, without adding methyl vinyl ether-maleic anhydride copolymer, the matrix viscosity and the toughness of the oil film are reduced. In the high and low temperature cycle test, it is easy to demulsify, the matrix stability is reduced, and the low temperature resistance is reduced.

[0058] By making full use of the excellent properties of stearyl phosphate, polyglycerol-3-diisostearate and methyl vinyl ether-maleic anhydride copolymer, the emulsion explosive has excellent stability under low temperature conditions and is not easy to demulsify, meeting the requirements of blasting operations under low temperature conditions for explosives' explosive performance and stability.

Claims

1. An integrated oil phase for emulsion explosives, characterized in that: Calculated by mass percentage, the integrated oil phase includes: 15-45% white oil, 30-40% cycloparaffin oil, 5-10% polyglycerol-3-diisostearate, 10-20% stearyl alcohol phosphate and 10-15% methyl vinyl ether-maleic anhydride copolymer.

2. The integrated oil phase for emulsion explosive according to claim 1, characterized in that: By mass percentage, the polyglycerol-3-diisostearate comprises 8-10%, stearyl alcohol phosphate comprises 15-20% and methyl vinyl ether-maleic anhydride copolymer comprises 10-15%.

3. The integrated oil phase for emulsion explosive according to claim 1, characterized in that: The M of the methyl vinyl ether-maleic anhydride copolymer W It is 80,000~130,000.

4. The integrated oil phase for emulsion explosive according to claim 1, characterized in that: The purity of the naphthenic oil is 95-99%.

5. A method for preparing the integrated oil phase for emulsion explosive according to claim 1, characterized in that: The following steps are involved: (1) Weigh white oil, cyclohexane oil, polyglycerol-3-diisostearate, stearyl alcohol phosphate and methyl vinyl ether-maleic anhydride copolymer; (2) First, heat and melt white oil, polyglycerol-3-diisostearate, stearyl alcohol phosphate and methyl vinyl ether-maleic anhydride copolymer, stir, and add cyclohexane oil after they are completely melted. Continue stirring and heat preservation, and cool after discharging to obtain an integrated oil phase.

6. The method for preparing an integrated oil phase for emulsion explosive according to claim 5, characterized in that: In step (2), the heating melting temperature is 92-96°C.

7. The method for preparing an integrated oil phase for emulsion explosive according to claim 5, characterized in that: In step (2), the heating and melting is performed by using a wax melter, and the wax melter is heated in a water bath.

8. The method for preparing an integrated oil phase for emulsion explosive according to claim 5, characterized in that: In step (2), the stirring speed is 200-600 rpm.

9. The method for preparing an integrated oil phase for emulsion explosive according to claim 5, characterized in that: In step (2), the insulation time is 30 to 50 minutes.

Images