Composite oil phase and composite emulsion matrix for site-mixed emulsion explosive and preparation methods therefor

Abstract

A composite oil phase and composite emulsion matrix for site-mixed emulsion explosive and preparation methods therefor. The composite oil phase is divided into material A and material B, wherein in the material A, a high-viscosity polyisobutylene maleic anhydride amine esterification derivative is used as a primary emulsifier to increase the strength and thickness of an emulsification film of an emulsion matrix, thereby improving the stability of the emulsion matrix; in the material B, a low-viscosity polyisobutylene maleic anhydride amine esterification derivative and SP-80 are used as primary emulsifiers to regulate the ammonium nitrate dissolution rate of the emulsion matrix, thereby improving the sensitization characteristic of the emulsion matrix; and the emulsion matrix prepared from two composite oil phases can effectively improve the water resistance of the emulsion matrix while the problems of high-temperature over-sensitization and low-temperature insensitivity are solved, so that the explosion quality is guaranteed.

Description

Composite oil phase and composite emulsification matrix for on-site mixed emulsion explosive and preparation method thereof TECHNICAL FIELD

[0001] The present application belongs to the technical field of industrial explosive, and particularly relates to a composite oil phase and a composite emulsification matrix for on-site mixed emulsion explosive and a preparation method thereof. BACKGROUND

[0002] Emulsion explosive has been widely applied in the fields of mine exploitation, stone excavation and water conservancy and transportation due to its good explosive performance, water resistance and safety, simple production process, wide raw material sources and low cost.

[0003] The composite oil phase mainly constitutes the continuous phase of the emulsion explosive, and forms a stable emulsion with the water phase through the emulsifying effect of the emulsifier. The material composition and properties of the oil phase will directly affect the application of the emulsion explosive in actual production. Only by selecting appropriate substances as the oil phase components can the emulsion explosive with stable properties and good explosiveness be prepared.

[0004] According to the related literature, patent CN102675003B discloses a composite oil phase for bulk waterproof explosive emulsion matrix and a preparation method thereof. The composite oil phase is composed of base oil MVI, base oil HVI, liquid paraffin, lipid polar multifunctional polymer emulsifier, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether and fatty amine, and can quickly form emulsion with the water phase material under the condition of low shear rate ≤5.52 m / s (≤500 revolutions / min). A composite three-dimensional network interface film is formed during the emulsification process, which increases the strength and thickness of the emulsification film. Patent CN102675004B discloses a composite oil phase for bulk waterproof emulsion explosive and a preparation method thereof. The composite oil phase is composed of base oil MVI, liquid paraffin, lipid polar multifunctional polymer emulsifier, soybean lecithin, lauric acid monoglyceride and isomeric decanol polyoxyethylene ether, and can quickly form emulsion with the water phase material under the condition of low shear rate ≤5.52 m / s (≤500 revolutions / min) in the ground station emulsion preparation process. A composite three-dimensional network interface film is formed during the emulsification process, which increases the strength and thickness of the emulsification film and improves the stability of the emulsion matrix.

[0005] Although the above patents have better improved the stability of the emulsion matrix, they do not provide better solutions for effectively controlling the sensitization density under different temperature conditions to adapt to the operation conditions of the on-site mixed preparation truck.

[0006] However, the national standard puts forward more strict requirements for the performance of emulsion explosive, such as for the emulsion preparation process of primary low-speed mixing stirring + secondary static shearing emulsification, it is required to meet the rapid emulsification under low-speed condition (less than 650 rpm), and the prepared emulsion matrix has good stability and suitable sensitization density under different environmental temperatures, so as to ensure the blasting effect. However, there are still some difficult problems to be solved in actual production. For example, during the actual operation process of the emulsion matrix mixed explosive truck, the storage period of the emulsion matrix in the matrix tank and the explosive truck is usually 1-3 days, and the matrix temperature changes in the range of 35-65 DEG C, and the change amplitude reaches 30 DEG C. The environmental temperature has great influence on the sensitization density of the emulsion matrix, and the specific performance is that when the temperature is relatively low (about 40 DEG C), the sensitization is not obvious, which is easy to cause the sensitization density to be too high; when the temperature is relatively high (about 60 DEG C), the sensitization is too fast, which is easy to cause the sensitization density to be too low. The sensitization density being too low or too high will lead to the misfire phenomenon. There are few reports on how to solve the problem in the prior art.

[0007] SUMMARY

[0008] The purpose of the present application is to solve the problem that the existing emulsion explosive is greatly affected by the change of the storage environment temperature, and a composite oil phase and a composite emulsion matrix for on-site mixed emulsion explosive and a preparation method are provided. The present application develops a composite oil phase material taking a series of high-activity polyisobutylene maleic anhydride amine ester derivatives as emulsifiers for the emulsion preparation process of primary low-speed mixing stirring + secondary static shearing emulsification. The composite oil phase is divided into A material and B material. The A material takes high-viscosity polyisobutylene maleic anhydride amine ester derivatives as the main emulsifier to increase the strength and thickness of the emulsion film of the emulsion matrix and improve the stability of the emulsion matrix. The B material takes low-viscosity polyisobutylene maleic anhydride amine ester derivatives and SP-80 as the main emulsifiers to control the ammonium nitrate dissolution rate of the emulsion matrix and improve the sensitization characteristics of the emulsion matrix. The emulsion matrix prepared by mixing the two kinds of composite oil phases in a suitable proportion can effectively improve the water resistance of the emulsion matrix (storage period is greater than 6 months), solve the problems of over-sensitization at high temperature and non-sensitization at low temperature, and realize the controllable sensitization density (1.08-1.20 g / cm 3 ) in the temperature range of 35-65 DEG C, so as to ensure the blasting quality.

[0009] The technical scheme of the present application is a composite oil phase for on-site mixed emulsion explosive, and the composite oil phase includes A material and B material. The various raw materials and mass percentages in the A material and the B material are shown in Table 1:

[0010] Table 1, types and proportions of composite oil phase materials

[0011] Further, the mass percentage of LVI1#+LVI2# in the A material of the composite oil phase for the on-site mixed emulsion explosive is 67%-70%; the mass percentage of LVI1#+LVI2# in the B material is 74%-77%.

[0012] Further, the specifications of various raw materials in the A material and the B material of the composite oil phase for the on-site mixed emulsion explosive are shown in Table 2, wherein, the polyisobutylene maleic anhydride amine esterification derivatives 1#, 2# and 3# are a series of amine ester polymer emulsifiers generated by the reaction of polyisobutylene maleic anhydride and alcohol amine:

[0013] Table 2, specifications of various raw materials in the A material and the B material

[0014] Further, the preparation method of the composite oil phase for the on-site mixed emulsion explosive:

[0015] The preparation method of the A material: according to the proportioning of various raw materials of the A material, low-viscosity base oil LVI1# and LVI2# are selected and put into a reaction kettle, a stirrer is started to stir uniformly and heat, and the temperature is raised to 40-50 DEG C; then, the high-molecular emulsifier SP-80 is put into the reaction kettle, and the temperature is kept at 40-50 DEG C to stir uniformly; then, the high-molecular emulsifier polyisobutylene maleic anhydride amine esterification derivative 3# is put into the reaction kettle, and the temperature is raised to 65-70 DEG C to continue stirring for 45-60 minutes, so as to obtain the A material.

[0016] The preparation method of the B material: according to the proportioning of various raw materials of the B material, low-viscosity base oil LVI1# and LVI2# are selected and put into a reaction kettle, a stirrer is started to stir uniformly and heat, and the temperature is raised to 40-50 DEG C; then, the high-molecular emulsifier SP-80 is put into the reaction kettle, and the temperature is kept at 40-50 DEG C to stir uniformly; then, the high-molecular emulsifier polyisobutylene maleic anhydride amine esterification derivative 1# is put into the reaction kettle, and the temperature is kept at 40-50 DEG C to stir uniformly; then, the high-molecular emulsifier polyisobutylene maleic anhydride amine esterification derivative 2# is put into the reaction kettle, and the temperature is kept at 40-50 DEG C to stir uniformly; finally, the sensitizing aid oleic acid is put into the reaction kettle, and the temperature is raised to 65-70 DEG C to continue stirring for 45-60 minutes, so as to obtain the B material.

[0017] The application further provides a composite emulsion matrix for on-site mixed emulsion explosive, which is composed of emulsion matrix C and emulsion matrix D according to a mass ratio of 45%-55%:55%-45%, wherein, the emulsion matrix C is composed of water phase and the A material in the composite oil phase according to a mass ratio of 90-92:10-8, and the emulsion matrix D is composed of water phase and the B material in the composite oil phase according to a mass ratio of 90-92:10-8.

[0018] The water phase is the water phase in the prior art, preferably, the water phase is composed of water, ammonium nitrate and ammonium acetate with a mass percentage of 19.80%-19.95%:80%:0.05%-0.20%.

[0019] Further, the preparation method of the composite emulsification base for the on-site mixed emulsion explosive:

[0020] The water phase with a temperature of 75-80 DEG C is mixed with the composite oil phase A material with a temperature of 40-50 DEG C and the composite oil phase B material with a temperature of 40-50 DEG C according to the proportion, and then is subjected to primary stirring and mixing emulsification and secondary static shearing emulsification at 600-650 r / min to form emulsification base C and emulsification base D; then the emulsification base C and the emulsification base D are stirred uniformly according to the proportion to obtain the composite emulsification base, which is stored in a heat preservation bin and used for on-site charging blasting.

[0021] Compared with the prior art, the present application has the following beneficial effects:

[0022] (1) The composite oil phase material is divided into A and B, the A material takes the high-viscosity polyisobutylene maleic anhydride amine esterification derivative as the main emulsifier, can effectively increase the strength and thickness of the emulsification film of the emulsification base, and improve the stability of the emulsification base; the B material takes the low-viscosity polyisobutylene maleic anhydride amine esterification derivative and SP-80 as the main emulsifier, can effectively control the ammonium nitrate dissolution rate of the emulsification base, and improve the sensitization characteristics of the emulsification base.

[0023] (2) The emulsification base prepared by mixing the two kinds of composite oil phases in a suitable proportion is the composite emulsification base, through this kind of way, the water resistance of the emulsification base can be effectively improved (the storage period is greater than 6 months), the final viscosity (Brookfield viscosity) of the base can be stably controlled between 25-35, and the problems of high-temperature over-sensitization and low-temperature non-sensitization are solved, so that the sensitization density in the temperature range of 35-65 DEG C can be controlled (1.08-1.20 g / cm 3 ), and the blasting quality is ensured. DETAILED DESCRIPTION

[0024] The water phase in the following examples is composed of water, ammonium nitrate and acetic acid with a mass percentage of 19.95%:80%:0.05%.

[0025] The polyisobutylene maleic anhydride amine esterification derivatives 1#, 2# and 3# are a series of amine ester high molecular emulsifiers prepared by the reaction of polyisobutylene maleic anhydride and alcohol amine. The structure is composed of three parts, i.e. the lipophilic group (hydrocarbon group), the polar group and the connecting group. The specifications are divided according to the nitrogen content, the acid value and the kinematic viscosity value.

[0026] The base oil LVI1# in the following examples has the parameters of flash point 148 DEG C, open, kinematic viscosity 10.9 mm 2 / s, 40℃; density 0.84 g / cm 3 , Class III oil; base oil LVI2# parameters are flash point 192℃, open; kinematic viscosity 32.2 mm 2 / s, 40℃; density 0.86 g / cm 3 , Class III oil; emulsifier SP-80 parameters are acid value 6.8 mgKOH / g; hydroxyl value 207 mgKOH / g; saponification value 149 mgKOH / g; polyisobutylene maleic anhydride amine ester derivative 1# parameters are nitrogen content 0.9%; acid value 16.4 mgKOH / g; kinematic viscosity 56, 100℃; polyisobutylene maleic anhydride amine ester derivative 2# parameters are nitrogen content 1.1%; acid value 15.3 mgKOH / g; kinematic viscosity 92, 100℃; polyisobutylene maleic anhydride amine ester derivative 3# parameters are nitrogen content 1.2%; acid value 12.2 mgKOH / g; kinematic viscosity 152, 100℃.

[0027] Example 1

[0028] A composite emulsified matrix for on-site mixed emulsion explosive is composed of emulsified matrix C and emulsified matrix D, wherein the emulsified matrix C is composed of water phase and A material in composite oil phase, and the emulsified matrix D is composed of water phase and B material in composite oil phase. The preparation method is as follows:

[0029] 1. The indexes of each raw material in the composite oil phase A material and B material meet the requirements in Table 2, and the mass ratio of each raw material is shown in Table 3.

[0030] Table 3, types and proportions of composite oil phase materials

[0031] 2. Composite oil phase material preparation process

[0032] A material preparation method: according to the A material ratio, low viscosity base oil LVI1#, LVI2# is selected and sequentially put into the reaction kettle, the stirrer is started to stir uniformly and heated, the temperature is raised to 45℃; the high molecular emulsifier SP-80 is put into the reaction kettle, and the temperature is kept at 45℃ for uniform stirring; the high molecular emulsifier polyisobutylene maleic anhydride amine ester derivative 3# is put into the reaction kettle, stirred and heated to 68℃, and continues to stir for 60 minutes to obtain A material.

[0033] B material preparation method: according to the B material ratio, select low viscosity base oil LVI1#, LVI2# into the reaction kettle in turn, start the stirrer to stir evenly and heat, the temperature rises to 45 DEG C; the high molecular emulsifier SP-80 is put into the reaction kettle, and the temperature is kept at 45 DEG C and stirred evenly; the high molecular emulsifier polyisobutylene maleic anhydride amine ester derivative 1# is put into the reaction kettle, and the temperature is kept at 45 DEG C and stirred evenly; the high molecular emulsifier polyisobutylene maleic anhydride amine ester derivative 2# is put into the reaction kettle, and the temperature is kept at 45 DEG C and stirred evenly; the sensitizing aid oleic acid is put into the reaction kettle, stirred and heated to 68 DEG C, and stirred for 60 minutes, to obtain B material.

[0034] 3. Compound oil phase preparation emulsion base

[0035] The water phase (temperature 80 DEG C) and the A material (temperature 40 DEG C) and the B material (temperature 40 DEG C) of the compound oil phase are mixed and emulsified by one-stage stirring (650 r / min) and two-stage static shear emulsification according to the mass ratio of 92:8 to form emulsion base C and emulsion base D; the emulsion base C and the emulsion base D are stirred evenly according to the mass ratio of 1:1 to obtain a compound emulsion base, which is stored in a heat preservation bin and used for on-site charging and blasting.

[0036] Implementation effect:

[0037] The technical indexes of the prepared compound oil phase are shown in table 4, and the emulsion preparation effect of the compound oil phase is shown in table 5.

[0038] Table 4, technical indexes of compound oil phase

[0039] Table 5, emulsion preparation effect of compound oil phase

[0040] Example 2

[0041] A compound emulsion base for on-site mixed charging emulsion explosive is composed of emulsion base C and emulsion base D, wherein the emulsion base C is composed of water phase and A material in compound oil phase, and the emulsion base D is composed of water phase and B material in compound oil phase. Its preparation method is as follows:

[0042] 1. The indexes of each raw material in the compound oil phase A material and B material meet the requirements of table 2, and the mass ratio of each raw material is shown in table 6.

[0043] Table 6, types and mass ratio of compound oil phase materials

[0044] 2. Compound oil phase preparation process

[0045] A material preparation method: according to the A material ratio, select low viscosity base oil LVI1#, LVI2# into the reaction kettle in turn, open the stirrer to stir evenly and heat, the temperature is raised to 40 DEG C; the high molecular emulsifier SP-80 is put into the reaction kettle, and the temperature is kept at 40 DEG C and stirred evenly; the high molecular emulsifier polyisobutylene maleic anhydride amine ester derivative 3# is put into the reaction kettle, stirred and heated to 65 DEG C, and then stirred for 60 minutes to obtain A material.

[0046] B material preparation method: according to the B material ratio, select low viscosity base oil LVI1#, LVI2# into the reaction kettle in turn, open the stirrer to stir evenly and heat, the temperature is raised to 40 DEG C; the high molecular emulsifier SP-80 is put into the reaction kettle, and the temperature is kept at 40 DEG C and stirred evenly; the high molecular emulsifier polyisobutylene maleic anhydride amine ester derivative 1# is put into the reaction kettle, and the temperature is kept at 40 DEG C and stirred evenly; the high molecular emulsifier polyisobutylene maleic anhydride amine ester derivative 2# is put into the reaction kettle, and the temperature is kept at 40 DEG C and stirred evenly; the sensitizing aid oleic acid is put into the reaction kettle, stirred and heated to 65 DEG C, and then stirred for 60 minutes to obtain B material.

[0047] 3. Compound oil phase material preparation emulsion matrix

[0048] The water phase (temperature 80 DEG C) and the A material (temperature 40 DEG C) and the B material (temperature 40 DEG C) of the compound oil phase are mixed and emulsified by primary stirring (650 r / min) and secondary static shear emulsification to form emulsion matrix C and emulsion matrix D according to the mass ratio of 92:8; the emulsion matrix C and the emulsion matrix D are stirred evenly according to the mass ratio of 1:1 to obtain a compound emulsion matrix, which is stored in a heat preservation bin for on-site charging and blasting.

[0049] Implementation effect:

[0050] The technical indexes of the prepared compound oil phase are shown in table 7, and the emulsification effect of the compound oil phase is shown in table 8.

[0051] Table 7, technical indexes of compound oil phase

[0052] Table 8, emulsification effect of compound oil phase material

[0053] Example 3

[0054] A compound emulsion matrix for on-site mixed charging emulsion explosive is composed of emulsion matrix C and emulsion matrix D, wherein the emulsion matrix C is composed of water phase and A material in compound oil phase, and the emulsion matrix D is composed of water phase and B material in compound oil phase. The preparation method is as follows:

[0055] 1. The indexes of each raw material in the compound oil phase A material and B material meet the requirements of table 2, and the mass ratio of each raw material is shown in table 9.

[0056] Table 9, composite oil phase material type and proportion

[0057] 2. Preparation process of composite oil phase

[0058] A material preparation method: according to the A material ratio, select low viscosity base oil LVI1#, LVI2# into the reaction kettle in turn, open the stirrer to stir uniformly and heat, the temperature is raised to 50℃; the high molecular emulsifier SP-80 is put into the reaction kettle, and the temperature is kept at 50℃ and stirred uniformly; the high molecular emulsifier polyisobutylene maleic anhydride amine ester derivative 3# is put into the reaction kettle, stirred and heated to 70℃, continue to stir for 60 minutes, get A material.

[0059] B material preparation method: according to the B material ratio, select low viscosity base oil LVI1#, LVI2# into the reaction kettle in turn, open the stirrer to stir uniformly and heat, the temperature is raised to 50℃; the high molecular emulsifier SP-80 is put into the reaction kettle, and the temperature is kept at 50℃ and stirred uniformly; the high molecular emulsifier polyisobutylene maleic anhydride amine ester derivative 1# is put into the reaction kettle, and the temperature is kept at 50℃ and stirred uniformly; the high molecular emulsifier polyisobutylene maleic anhydride amine ester derivative 2# is put into the reaction kettle, and the temperature is kept at 50℃ and stirred uniformly; the sensitizing aid oleic acid is put into the reaction kettle, stirred and heated to 70℃, continue to stir for 60 minutes, get B material.

[0060] 3. Preparation of emulsion matrix of composite oil phase

[0061] The water phase (temperature 80℃) and the composite oil phase A material (temperature 50℃) and B material (temperature 50℃) are respectively mixed and emulsified by one-stage stirring (650r / min) and two-stage static shearing to form emulsion matrix C and emulsion matrix D according to the mass ratio of 92:8; the emulsion matrix C and the emulsion matrix D are stirred uniformly according to the mass ratio of 1:1 to obtain the composite emulsion matrix, which is stored in the heat preservation bin for on-site charging and blasting.

[0062] Implementation effect:

[0063] The technical indexes of the prepared composite oil phase are shown in table 10, and the emulsion preparation effect of the composite oil phase is shown in table 11.

[0064] Table 10, technical indexes of composite oil phase

[0065] Table 11, emulsion preparation effect of composite oil phase material

Claims

1. A composite oil phase for use in field mixed emulsion explosives, characterized in that, The composite oil phase comprises A material and B material, and the various raw materials and mass percentages in the A material and B material are shown in Table 1: Table 1, types and proportions of composite oil phase materials 2. The complex oil phase for use in a field-mix emulsion explosive according to claim 1, characterized by, The mass percentage of LVI1#+LVI2# in the A material is 67%-70%, and the mass percentage of LVI1#+LVI2# in the B material is 74%-77%.

3. The complex oil phase for use in a field-mix emulsion explosive according to claim 1, characterized by, The specifications of the various raw materials in the A material and B material are shown in Table 2: Table 2: Specifications of various raw materials in A and B materials 4. The preparation method of the composite oil phase for the field mixed emulsion explosive according to claim 1, characterized in that, The A material preparation method is as follows: according to the proportioning of the various raw materials of the A material, low-viscosity base oil LVI1# and LVI2# are selected and put into a reaction kettle, a stirrer is started to stir and heat, and the temperature is raised to 40-50 DEG C; then high-molecular emulsifier SP-80 is put into the reaction kettle, and the temperature is kept at 40-50 DEG C to stir uniformly; then high-molecular emulsifier polyisobutylene maleic anhydride amine ester derivative 3# is put into the reaction kettle, and the temperature is raised to 65-70 DEG C to continue stirring for 45-60 minutes to obtain the A material; The B material preparation method is as follows: according to the proportioning of the various raw materials of the B material, low-viscosity base oil LVI1# and LVI2# are selected and put into a reaction kettle, a stirrer is started to stir and heat, and the temperature is raised to 40-50 DEG C; then high-molecular emulsifier SP-80 is put into the reaction kettle, and the temperature is kept at 40-50 DEG C to stir uniformly; then high-molecular emulsifier polyisobutylene maleic anhydride amine ester derivative 1# is put into the reaction kettle, and the temperature is kept at 40-50 DEG C to stir uniformly; then high-molecular emulsifier polyisobutylene maleic anhydride amine ester derivative 2# is put into the reaction kettle, and the temperature is kept at 40-50 DEG C to stir uniformly; finally, sensitizing aid oleic acid is put into the reaction kettle, and the temperature is raised to 65-70 DEG C to continue stirring for 45-60 minutes to obtain the B material.

5. A composite emulsion base for use in field mixed emulsion explosive, characterized by comprising: The composite emulsification matrix for the field mixed emulsion explosive comprising the composite oil phase of claim 1.

6. The composite emulsion base for field mixed emulsion explosive according to claim 5, characterized in that, The composite emulsification matrix is composed of emulsification matrix C and emulsification matrix D according to a mass ratio of 45-55%:55-45%, wherein the emulsification matrix C is composed of a water phase and the A material in the composite oil phase according to a mass ratio of 90-92:10-8, and the emulsification matrix D is composed of a water phase and the B material in the composite oil phase according to a mass ratio of 90-92:10-8.

7. The method of claim 6, wherein the composite emulsion base for field mixed emulsion explosive is prepared by adding the water-soluble polymer to the water phase, and then adding the oil phase to the water phase. The water phase at a temperature of 75-80 DEG C is mixed with the composite oil phase A material at a temperature of 40-50 DEG C and the composite oil phase B material at a temperature of 40-50 DEG C according to the proportioning, and is subjected to primary stirring and mixing emulsification and secondary static shearing emulsification at 600-650 r / min to form emulsification matrix C and emulsification matrix D; then the emulsification matrix C and the emulsification matrix D are stirred uniformly according to the proportioning to obtain the composite emulsification matrix, which is stored in a heat preservation bin and used for field charging blasting.

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