Composite functional additive as well as preparation method and application thereof

Abstract

The invention relates to a composite functional additive which comprises the following components in parts by weight: 5-15 parts of heavy calcium carbonate, 5-40 parts of porous granular ammonium nitrate, 5-10 parts of silicon dioxide, 10-20 parts of titanium dioxide and 6-8 parts of ammonium perchlorate. The invention also relates to a preparation method of the compound functional additive and application of the compound functional additive in preparation of a liquid-mixed expanded ammonium nitrate explosive, and compared with a common liquid-mixed expanded ammonium nitrate explosive, the bulk density of the liquid-mixed expanded ammonium nitrate explosive added with the compound functional additive is increased by 13%-29%; the free-running property is improved by 50%-68%, and the detonation performance still meets the requirements of GB28286-2012.

Description

Technical Field

[0001] The invention relates to the technical field of explosives, and in particular to a composite functional additive and a preparation method and application thereof. Background Art

[0002] In recent years, with the large-scale promotion and application of civil explosives, the performance and safety development of civil explosives have attracted great attention, and the advanced production processes and equipment in the civil explosives industry are being vigorously promoted and used. At present, the production process technology of expanded ammonium nitrate explosive production line adopts the "liquid mixing" expanded ammonium nitrate explosive continuous expansion production process technology and complete sets of pharmaceutical equipment. The product gradually shows some shortcomings: the product has high viscosity, poor fluidity, and low bulk density, resulting in low production efficiency and affecting production capacity; the product is easy to agglomerate. Guizhou Province is in a season with high humidity all year round, and expanded ammonium nitrate explosive products are easy to agglomerate, resulting in product performance attenuation and failure; Guizhou has different regional topography and rock hardness. Different densities of expanded ammonium nitrate explosives are required for blasting construction to form a reasonable charge amount, stabilize and improve blasting efficiency. Liquid-mixed expanded ammonium nitrate explosives have excellent detonation performance. When used in some blasting projects with higher requirements, the demand for fluidity and bulk density is high, but the current production process conditions cannot meet the market demand for expanded ammonium nitrate explosives with different bulk densities.

[0003] Ammonium nitrate, with the chemical formula NH4NO3, is a common inorganic compound. It is composed of ammonium ions (NH 4+ ) and nitrate ions (NO 3- ). Ammonium nitrate has many uses and can be used as a raw material for explosives. Porous ammonium nitrate is a modified ammonium nitrate that is prepared by a special treatment method to have a larger specific surface area and higher porosity. Porous ammonium nitrate can be used to prepare high-performance fuels and propellants. Due to its large specific surface area and pore structure, porous ammonium nitrate can provide more oxygen and a larger reaction interface, thereby increasing the combustion rate and energy release of the fuel, which makes porous ammonium nitrate an indispensable and important material in aerospace and rocket propulsion technology.

[0004] In order to meet the needs of blasting end users in Guizhou and even the whole country, the research team has developed composite functional additives to improve the physical and chemical properties, explosion properties, fluidity, anti-caking properties and charging density of expanded ammonium nitrate explosives, and to improve the production safety and suitability of expanded ammonium nitrate explosives. Summary of the invention

[0005] In order to solve the above-mentioned defects existing in the prior art, the purpose of the present invention is to provide a composite functional additive, and also provide the application of the composite functional additive to adjust the fluidity and bulk density of liquid mixed expanded ammonium nitrate explosive, prevent the expanded ammonium nitrate explosive from agglomerating, and improve the application of the series of expanded ammonium nitrate explosive products.

[0006] The part described in the present invention is a conventional weight unit in the art, which may be mg, g, kg, t, etc.

[0007] A composite functional additive consists of 5-15 parts of heavy calcium carbonate, 5-40 parts of porous granular ammonium nitrate, 5-10 parts of silicon dioxide, 10-20 parts of titanium dioxide and 6-8 parts of ammonium perchlorate in proportion by weight.

[0008] Preferably, the composite functional additive is composed of 8 to 13 parts of heavy calcium carbonate, 10 to 30 parts of porous granular ammonium nitrate, 7 to 10 parts of silicon dioxide, 12 to 18 parts of titanium dioxide, and 6 to 8 parts of ammonium perchlorate in parts by weight.

[0009] Further preferably, the composite functional additive is composed of 10 parts of heavy calcium carbonate, 20 parts of porous granular ammonium nitrate, 8 parts of silicon dioxide, 12 parts of titanium dioxide, and 6 parts of ammonium perchlorate in a weight ratio.

[0010] Another object of the present invention is to provide a method for preparing the composite functional additive.

[0011] The preparation method of the composite functional additive comprises the following steps: firstly, respectively passing heavy calcium carbonate, porous granular ammonium nitrate, silicon dioxide, titanium dioxide and ammonium perchlorate through a 120-140 mesh sieve, then weighing them according to weight percentage, and finally mixing them evenly to obtain the composite functional additive.

[0012] Furthermore, the preparation method of the composite functional additive comprises firstly passing heavy calcium carbonate, porous granular ammonium nitrate, silicon dioxide, titanium dioxide and ammonium perchlorate through a 130-mesh sieve respectively, then weighing them according to weight percentage, and finally mixing them evenly to obtain the composite functional additive.

[0013] Furthermore, the preparation method of the composite functional additive is as follows: first, heavy calcium carbonate, porous granular ammonium nitrate, silicon dioxide, titanium dioxide and ammonium perchlorate are respectively sieved through a 130-mesh sieve, those that do not meet the particle size requirements are ground and refined by a ball mill and then sieved, and then weighed according to weight percentage, first adding the weighed porous granular ammonium nitrate into a double-cone mixer, and then gradually adding heavy calcium carbonate, titanium dioxide, silicon dioxide and ammonium perchlorate, mixing evenly, to obtain the composite functional additive.

[0014] Another object of the present invention is to provide an application of the composite functional additive.

[0015] The composite functional additive is used for preparing ammonium nitrate explosive.

[0016] Furthermore, the composite functional additive is used in the preparation of liquid-mixed expanded ammonium nitrate explosives. Specifically, in order to achieve zero oxygen balance of the new formula, the expanded ammonium nitrate explosive changes the classic zero oxygen balance formula of ammonium nitrate: wood powder: oil phase = 92:4:4 to 91:4.5:4.5. The oil phase is an integrated composite oil phase, which is compounded by composite wax and composite emulsifier technology and adding various additives. The additive is one or more of paraffin, microcrystalline wax, fuel oil, engine oil, gelatin, vaseline, asphalt and mineral oil. The composite oil phase is added according to the formula ratio, heated to 90±5°C and kept warm until completely melted, and kept warm at no less than 65°C for standby use.

[0017] The beneficial effects of the present invention are:

[0018] 1. Heavy calcium carbonate, porous granular ammonium nitrate, silicon dioxide and titanium dioxide have the characteristics of not easy to agglomerate, good dispersibility and strong oil absorption capacity. Ammonium perchlorate has the basic characteristics of high oxygen content, thermal stability and chemical stability. The material sources are wide and the material price is moderate. It can be used to manufacture composite functional additives.

[0019] 2. Composite functional additives are used in the formulation of liquid-mixed expanded ammonium nitrate explosives to achieve the regulation of the flowability, bulk density and explosion performance of expanded ammonium nitrate explosives. The flowability is 5-9s, and the bulk density is from 0.38g / cm 3 Increased to 0.49g / cm 3 , prevent the agglomeration of expanded ammonium nitrate explosives, and the explosion performance meets the requirements of GB 28286-2012. DETAILED DESCRIPTION

[0020] The present invention will be described in detail below in conjunction with specific embodiments. The illustrative embodiments and descriptions of the present invention are used to explain the present invention but are not intended to limit the present invention.

[0021] Example 1

[0022] 10kg of heavy calcium carbonate, 20kg of porous granular ammonium nitrate, 8kg of silicon dioxide, 12kg of titanium dioxide and 6kg of ammonium perchlorate are mixed evenly to obtain a composite functional additive.

[0023] Example 2

[0024] 8g of heavy calcium carbonate, 10g of porous granular ammonium nitrate, 7g of silicon dioxide, 12g of titanium dioxide and 6g of ammonium perchlorate are mixed evenly to obtain a composite functional additive.

[0025] Example 3

[0026] 13g of heavy calcium carbonate, 30g of porous granular ammonium nitrate, 10g of silicon dioxide, 18g of titanium dioxide, and 8g of ammonium perchlorate are mixed evenly to obtain a composite functional additive.

[0027] Example 4

[0028] 5kg of heavy calcium carbonate, 5kg of porous granular ammonium nitrate, 5kg of silicon dioxide, 10kg of titanium dioxide and 6kg of ammonium perchlorate are mixed evenly to obtain a composite functional additive.

[0029] Example 5

[0030] Composite functional additive: 15kg of heavy calcium carbonate, 40kg of porous granular ammonium nitrate, 10kg of silicon dioxide, 20kg of titanium dioxide, 8kg of ammonium perchlorate, mix well to obtain the composite functional additive.

[0031] Example 6

[0032] 9g of heavy calcium carbonate, 13g of porous granular ammonium nitrate, 9g of silicon dioxide, 14g of titanium dioxide and 7g of ammonium perchlorate are mixed evenly to obtain a composite functional additive.

[0033] Example 7

[0034] 14kg of heavy calcium carbonate, 27kg of porous granular ammonium nitrate, 7kg of silicon dioxide, 11kg of titanium dioxide and 8kg of ammonium perchlorate are mixed evenly to obtain a composite functional additive.

[0035] Example 8

[0036] 8g of heavy calcium carbonate, 10g of porous granular ammonium nitrate, 7g of silicon dioxide, 12g of titanium dioxide and 6g of ammonium perchlorate are mixed evenly to obtain a composite functional additive.

[0037] Example 9

[0038] The preparation method of the composite functional additive comprises the following steps: firstly, respectively passing heavy calcium carbonate, porous granular ammonium nitrate, silicon dioxide, titanium dioxide and ammonium perchlorate through a 130-mesh sieve, grinding and refining the particles that do not meet the particle size requirements with a ball mill and then sieving them; then, weighing 10 kg of heavy calcium carbonate, 20 kg of porous granular ammonium nitrate, 8 kg of silicon dioxide, 12 kg of titanium dioxide and 6 kg of ammonium perchlorate according to weight percentage; firstly adding the weighed porous granular ammonium nitrate into a double cone mixer; then gradually adding heavy calcium carbonate, titanium dioxide, silicon dioxide and ammonium perchlorate; mixing them evenly to obtain the composite functional additive.

[0039] Example 10

[0040] The preparation method of the composite functional additive comprises the following steps: firstly, respectively passing heavy calcium carbonate, porous granular ammonium nitrate, silicon dioxide, titanium dioxide and ammonium perchlorate through a 120-mesh sieve, grinding and refining the particles that do not meet the particle size requirements with a ball mill and then sieving them; then, weighing 5 kg of heavy calcium carbonate, 5 kg of porous granular ammonium nitrate, 5 kg of silicon dioxide, 10 kg of titanium dioxide and 6 kg of ammonium perchlorate according to weight percentage; firstly adding the weighed porous granular ammonium nitrate into a double cone mixer; then gradually adding heavy calcium carbonate, titanium dioxide, silicon dioxide and ammonium perchlorate; mixing them evenly to obtain the composite functional additive.

[0041] Embodiment 11

[0042] The preparation method of the composite functional additive comprises the following steps: firstly, respectively passing heavy calcium carbonate, porous granular ammonium nitrate, silicon dioxide, titanium dioxide and ammonium perchlorate through a 140-mesh sieve, grinding and refining the particles that do not meet the particle size requirements with a ball mill and then sieving them; then, 14 kg of heavy calcium carbonate, 27 kg of porous granular ammonium nitrate, 7 kg of silicon dioxide, 11 kg of titanium dioxide and 8 kg of ammonium perchlorate are weighed according to weight percentage; first, the weighed porous granular ammonium nitrate is added into a double cone mixer; then, heavy calcium carbonate, titanium dioxide, silicon dioxide and ammonium perchlorate are gradually added and mixed evenly to obtain the composite functional additive.

[0043] In order to further verify the effectiveness of the present invention, the inventors conducted a series of verification experiments, the excerpts of which are as follows.

[0044] 1. Sample preparation

[0045] First, respectively pass heavy calcium carbonate, porous granular ammonium nitrate, silicon dioxide, titanium dioxide and ammonium perchlorate through a 130-mesh sieve, then weigh 10 g of heavy calcium carbonate, 20 g of porous granular ammonium nitrate, 8 g of silicon dioxide, 12 g of titanium dioxide and 6 g of ammonium perchlorate according to weight percentage, and finally mix them evenly to obtain a composite functional additive.

[0046] 92g of ammonium nitrate and 10g of water are stirred and dissolved in a melter at 125°C and kept warm for use; 4g of composite wax and 0.13g of expander are melted at 90°C and kept warm for use; the melted oil phase is added to the ammonium nitrate solution, stirred evenly, and then vacuum crystallization and expansion are immediately carried out for 15 minutes; after the expansion and crystallization is completed and the material is discharged, 4g of wood powder and 20g of composite functional additives in different proportions are added and mixed evenly to obtain improved expanded ammonium nitrate explosive samples, which are then bagged and placed in a desiccator.

[0047] 2 Performance Study

[0048] In order to verify the effectiveness of the present invention, a basic formula general scheme of the classic zero oxygen balance formula of expanded ammonium nitrate explosive, ammonium nitrate: wood powder: oil phase = 92:4:4, was set up. On this basis, the ratio of the composite functional additives in schemes 1-8 was the same as in embodiment 1-8, and expanded ammonium nitrate explosives containing composite functional additives were prepared. The detonation velocity and sympathetic detonation distance were tested according to the test conditions specified in GB28286, and the fluidity and bulk density were tested using a shock-type standard pendulum instrument. The samples tested were samples from the same batch as the detonation performance test to ensure the consistency of performance. The test results are shown in Table 1.

[0049] Table 1 Comparison of performance tests of liquid mixed expanded ammonium nitrate explosives

[0050]

[0051] As shown in Table 1, compared with the common expanded ammonium nitrate explosive, the detonation distance of the experimental group with the addition of composite functional additives remained basically unchanged, while the detonation velocity and intensity performance were partially improved. The comprehensive performance of Scheme 1 was the best. The bulk density of the liquid-mixed expanded ammonium nitrate explosive prepared with the composite functional additive was significantly improved and improved compared with the flowability and bulk density of the common expanded ammonium nitrate explosive. Overall, the bulk density with the addition of the composite functional additive was increased by 13%-29%; the flowability was increased by 50%-68%. This shows that the composite functional additive can significantly improve and enhance the charge density and flowability, and also verifies the rationality of the formula design, which has a significant effect on improving the performance of the explosive and the charge efficiency.

[0052] 3. Adjust the scale

[0053] Considering that the added composite functional additive contains porous granular nitric acid, and heavy calcium carbonate is a kind of material with high chemical purity, high inertness and not easy to react chemically, it is necessary to fine-tune the wood powder content and the oil phase content in order to minimize the influence of the oil phase viscosity on the fluidity. In this test, the composite functional additive porous granular ammonium nitrate is 20g, and the detonation performance test, fluidity and bulk density test are carried out. The test results are shown in Table 2.

[0054] Table 2 Adjustment of the proportion of liquid-mixed expanded ammonium nitrate explosives with composite functional additives

[0055]

[0056] Adding wood powder and oil phase can make the formula close to zero oxygen balance, which can increase the detonation reaction speed to a certain extent, increase the bulk density of the explosive, and greatly improve the fluidity. According to the actual production capacity and the test results of detonation performance, fluidity and bulk density, a new ratio of liquid-mixed expanded ammonium nitrate explosive with composite functional additives can be formed.

[0057] 4. Put into production

[0058] In order to verify the effectiveness of the present invention in actual production, the preferred ratio verified by the experiment is verified on the production line. The test results of the moisture density of the raw materials on the production line are shown in Table 3. The small package samples of the Keda workshop contain small packages of various components of the composite functional additives. The test results are shown in Table 4.

[0059] Table 3 Production line raw material moisture density test

[0060]

[0061] Table 4 Performance test of production line adding composite functional additives

[0062]

[0063]

[0064] It can be seen from Table 4 that the production line verification results are the same as the test verification results. The addition amount of 20 parts by weight is the optimal addition amount of the composite functional additive, which can ensure that the detonation performance meets the requirements of GB28286-2012, and can improve the product's fluidity and bulk density, and avoid the explosive absorbing water and agglomerating, which leads to performance degradation and failure.

[0065] Although the present invention has been described in detail above by means of general description, specific implementation methods and experiments, it is obvious to those skilled in the art that some modifications or improvements can be made to the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection claimed by the present invention.

Claims

1. A composite functional additive, characterized in that: The invention is composed of 5 to 15 parts of heavy calcium carbonate, 5 to 40 parts of porous granular ammonium nitrate, 5 to 10 parts of silicon dioxide, 10 to 20 parts of titanium dioxide and 6 to 8 parts of ammonium perchlorate in proportion by weight.

2. The composite functional additive according to claim 1, characterized in that: The invention is composed of 8 to 13 parts of heavy calcium carbonate, 10 to 30 parts of porous granular ammonium nitrate, 7 to 10 parts of silicon dioxide, 12 to 18 parts of titanium dioxide and 6 to 8 parts of ammonium perchlorate in proportion by weight.

3. The composite functional additive according to claim 1, characterized in that: The composition is composed of 10 parts of heavy calcium carbonate, 20 parts of porous granular ammonium nitrate, 8 parts of silicon dioxide, 12 parts of titanium dioxide and 6 parts of ammonium perchlorate in proportion by weight.

4. The method for preparing the composite functional additive according to any one of claims 1 to 3, characterized in that: Heavy calcium carbonate, porous granular ammonium nitrate, silicon dioxide, titanium dioxide and ammonium perchlorate are respectively passed through a 120-140 mesh sieve, then weighed according to weight percentage, and finally mixed evenly to obtain a composite functional additive.

5. The method for preparing the composite functional additive according to claim 4, characterized in that: Heavy calcium carbonate, porous granular ammonium nitrate, silicon dioxide, titanium dioxide and ammonium perchlorate are respectively passed through a 130-mesh sieve, then weighed according to weight percentage, and finally mixed evenly to obtain a composite functional additive.

6. The method for preparing the composite functional additive according to claim 5, characterized in that: Heavy calcium carbonate, porous granular ammonium nitrate, silicon dioxide, titanium dioxide and ammonium perchlorate are respectively passed through a 130-mesh sieve, those that do not meet the particle size requirements are ground and refined by a ball mill and then sieved, and then weighed according to weight percentage, first adding the weighed porous granular ammonium nitrate into a double-cone mixer, and then gradually adding heavy calcium carbonate, titanium dioxide, silicon dioxide and ammonium perchlorate, mixing evenly, to obtain a composite functional additive.

7. The use of the composite functional additive according to any one of claims 1 to 3, characterized in that: Application of the composite functional additive in the preparation of ammonium nitrate explosive.

8. The use of the composite functional additive according to claim 7, characterized in that: The composite functional additive is used in preparing liquid-mixed expanded ammonium nitrate explosive.

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