RU2381204C2 - Emulsifying composition for preparation of water-in-oil emulsions - Google Patents

Abstract

FIELD: technological processes.

SUBSTANCE: invention is related to emulsifying compositions for making of water-in-oil emulsions used to produce emulsive explosives. Emulsifying composition for preparation of water-in-oil emulsions contains mixture of reaction product of polyisobutylene succinic or polyisobutylene bissuccinic anhydride with organic mono- or polyamine, ethers of acids and polyatomic alcohols and industrial oil. Ether of acids and polyatomic alcohols is represented by mixture of sorbitan ethers of fatty and tar acids. Ratio of ingredients in emulsifying composition makes as follows, %: reaction product of polyisobutylene succinic or polyisobutylene bissuccinic anhydride with organic mono- or polyamine 20-70; mixture of sorbitan ethers of fatty and tar acids 5-35; industrial oil 3-75.

EFFECT: invention provides for improvement of technological parameters of emulsifying composition production used to manufacture emulsive explosives, and makes it possible to control viscous-temperature properties of composition and expansion of raw materials assortment for its production.

3 cl, 1 tbl

Description

The invention relates to the field of emulsifying compositions used in the manufacture of emulsion industrial explosives (PVV).

Currently, the most developed is a new class of industrial explosives based on water-in-oil emulsions.

Emulsion industrial explosives have taken a leading position in the extraction of minerals in Russia and abroad. The excellent explosive characteristics of emulsion formulations are largely determined by the surfactant used (emulsifying composition) for the manufacture of high-quality and stable emulsions. The most stable reverse emulsions are formed from aqueous solutions of salts - oxidizing agents in the carbon phase (matrix emulsions of industrial explosives), which contain an emulsifier based on condensation products of alkenyl (polyisobutylene) succinic anhydrides and amino derivatives from among alkanolamines, polyamines of various molecular weights or bottoms from the production of ethylene di or polyamine, or a mixture of alkenyl (polyisobutylene) succinic anhydrides and their amino derivatives (patents Ri No. 2277965, No. 2155094 and No. 204888).

Abroad, these emulsifiers are produced under the brand name Lubrizol and Pibsa, and in Russia - REM. To improve the technological or operational properties of matrix emulsions, co-emulsifiers are often added to these emulsifiers, since the use of only one emulsifier in the composition of emulsion PVV is not enough to obtain an emulsion of the required quality. In the industrial use of emulsifying compositions containing only one emulsifier based on succinic anhydride, there are significant technological disadvantages, such as the significant circulation time of the emulsion. This leads to increased energy consumption and reduces the productivity of the manufacturing process. However, with the introduction of a co-emulsifier, it is possible to control the physicochemical properties of matrix emulsions and the entire emulsion explosive composition.

As one of the analogues known emulsifying composition according to US Pat. RF №2048881, which contains the condensation product of alkenyl succinic (polyisobutylene succinic) anhydride with alkanolamine. The emulsifying composition further comprises an ester of an acid selected from the group: tall oil fatty acids, acids of the fractions C ₁₇ -C ₂₁ or C ₂₁ -C ₂₅ , and an alcohol selected from the group: pentaerythritol, glycerol or polyglycerol. Products that meet the formula of this patent, provide emulsion explosives that are quite stable during storage.

Closest to the claimed emulsifier by type of feedstock and production technology, the products described in US Pat. RF №2263096. According to the patent, an emulsifier is synthesized by mixing polyisobutylene succinic or polyisobutylene bis succinic anhydride with the product of its interaction with an organic mono- or polyamine, moreover, fatty acid esters with polyhydric alcohols are introduced into the resulting mixture at a temperature of 70-150 ° C with constant stirring. Then, at a temperature of 20-150 ° C, add alkyl benzosulfonates Ca, K, Mg, Mo, or mixtures thereof in the form of a 20-70% solution in industrial oil. The mixture is stirred at 100-150 ° C and filtered at 100-150 ° C. The emulsifier contains the above components in the following ratio (wt.%): Polyisobutylene succinic or polyisobutylene bis succinic anhydride 1-10; the reaction product of polyisobutylene succinic or polyisobutylene bis succinic anhydride with an organic mono- or polyamine 40-90; fatty acid esters with polyols 2-30; alkylbenzosulfonates Ca, K, Mg, Mo, or mixtures thereof 6-30. The emulsifier described in the patent, obtained in a protected manner, has a sufficient life time at a reduced cost of the emulsion explosive composition by reducing the content of the emulsifier in the emulsion explosive composition. However, the composition of the emulsifier does not allow to control its viscous-temperature properties.

An object of the invention is the creation of an emulsifying composition for the manufacture of emulsion PVV, which improves the technological parameters of the production of emulsion substances and regulates the viscous-temperature properties, as well as expand the raw material base of its production.

The problem is solved due to the fact that in the emulsifying composition for the manufacture of water-in-oil emulsions containing a mixture of the reaction product of polyisobutylene succinic or polyisobutylene bis succinic anhydride with organic mono- or polyamine, esters of acids and polyhydric alcohols and industrial oil, as an ester of acids and polyhydric alcohols use a mixture of sorbitan esters of fatty and resin acids in the following ratio of ingredients by weight,%:

interaction product polyisobutylene amber or polyisobutylene bisuccinic anhydride with organic mono- or polyamine 20-70 mixture of sorbitan esters of fatty and resin acids 5-35 industrial oil 3-75

It is advisable that the mixture of sorbitan esters of fatty and resin acids was taken in the ratio, respectively, by weight,%: 20-80 / 20-80.

It is possible to include in the emulsifying composition up to 2-10% sodium salt of fatty acids of tall oil in excess of 100% of the mixture.

Obtaining a mixed emulsifying composition is carried out as follows in several stages:

1. The synthesis of condensation products of polyisobutylene succinic anhydride with amino derivatives is carried out by one of the known methods. For example, a reaction vessel with a stirrer, a direct refrigerator, a thermometer and an adapter for supplying nitrogen is placed in a thermostatic device. 100 g of polyisobutylene succinic anhydride with a molecular weight of at least 1098 and a concentration of 80-84% in a solution of polyisobutene and 11.1 g of triethanolamine or 22.4 g of polyethylene polyamine with an average molecular weight of 300.

The reaction mass is kept under stirring with a nitrogen purge at a temperature of 150-200 ° C for 0.5-3.0 hours until the end of the distillation of water.

2. Obtaining sorbitan esters of fatty and resin acids is carried out by the esterification reaction of 100 g of a mixture of fatty and resin acids (R-COOH), in an approximate ratio of 2: 1 with an average molecular weight of 965 and 18.9 g of sorbitol (C ₆ H ₁₄ O ₆ ) with stirring and distillation of the released water by an inert gas flow or under vacuum in a similar reaction vessel (1 stage) at temperatures of 160-230 ° C for 2-6 hours.

3. Obtaining a mixed emulsifying composition is carried out by mixing the product from the first stage (20-70%) and a mixture of sorbitan esters of fatty and resin acids (5-35%) (mixing is carried out in amounts corresponding to those indicated in the formula) at temperatures obtained after unloading from reactors through a filtering device for separating impurities, and the mass is cooled by mixing with the addition of industrial oil (3-75%) with ambient temperature.

4. If it is necessary to increase the viscosity of emulsion PVV, up to 2-10% sodium salt of tallow oil fatty acids (R-COONa) is introduced into the resulting mixed emulsifying composition.

Samples of the mixed emulsifying composition was used to obtain a reference emulsion in comparison with the prototype. The composition of the reference emulsion,%:

sodium nitrate - 14;

water - 12;

industrial oil - 5;

emulsifying composition - 2;

ammonium nitrate - the rest is up to 100.

Samples of emulsion PVV were prepared according to the following procedure: weighed portions of ammonia and sodium nitrate and water were placed in a heat-resistant vessel.

The vessel with the contents was heated until the components were completely dissolved and kept to a saturated solution at a temperature of 85 ± 5 ° C. Samples of industrial oil with an emulsifying composition were placed in a reactor heated with a thermostat, equipped with a stirrer. The combustible phase was heated to 75 ± 5 ° C and, with the stirrer switched on, an oxidizer solution was poured for one minute. Next, the emulsification process was continued for 3 minutes and after that, studies on the resulting emulsion were carried out.

To assess the technological parameters and the quality of the emulsions of the emulsifying composition obtained, the methods described in the literature for determining the technological characteristics of emulsifiers were used:

The phase reversal time, one of the most important technological characteristics, represents the period of time during which, at the beginning of mixing, the resulting oil-in-water emulsion turns into a water-in-oil emulsion. The smaller it is, the more effective is the emulsifying composition. The moment of transition of one type of emulsion into another is recorded by an abrupt decrease in the strength of the current passing through the inverse emulsion formed.

Express quality control of an emulsion consists in measuring the electric capacitance of a sensor immersed in an emulsion: the lower the measured capacitance value, the higher the quality of the emulsion.

X-ray structural analysis of the mass fraction of crystals of oxidizing salts in the emulsion is the most reliable way to assess changes as a result of long-term storage of the emulsion.

According to the rheological characteristics in the measuring assembly of the device "Reotest-2" dynamic viscosity was measured for 30 minutes.

The results of the experiments are summarized in the table, the data of which indicate an improvement in the technological efficiency of the proposed variants of the mixed polymer emulsifying composition, which resulted in a significant reduction in the phase rotation time, a certain decrease in the electric capacitance of the sensor immersed in the emulsion, and the practical identity of the data for the prototype and new emulsion samples by the number of crystals after storage at low temperatures. With the introduction of sodium salt of tallow oil fatty acids, an increase in the viscosity of the composition is observed, which increases the stability of the emulsion and reduces the loss of explosive when charging fractured rocks.

The components of the emulsifying composition and the composition of the receiving Prototype Pat. No. 2263096 According to the invention one 2 3 one 2 3 four 5 6 7 one 2 3 four 5 6 7 8 9 10 eleven Condensation Products of Polyisobutylene Amber amine anhydride 40 60 90 twenty 40 70 twenty 45 60 70 Esters of sorbitan and acids from among: - fatty thirty fifteen 2 - - - - - - - - a mixture of fatty and tar - - - 35 fifteen 5 35 fifteen 5 22 Industrial oil 10 fifteen 6 45 45 25 35 35 33 3 Alkylbenzenesulfonates Ca, K, Mg twenty 10 2 - - - - - - - Tall oil fatty acid sodium salt - - - - - - 10 5 2 5 Technological characteristic by time of circulation phases, min 12-22 14-26 16-37 6-10 6-12 14-18 5-10 10-14 6-8 4-5

Table continuation one one 2 3 one 2 3 four 5 6 7 Emulsion quality: - electric capacity of the sensor at 85 ± 5 ° С, pF 25-122 38-45 20-34 34-36 19-22 16-22 36-40 32-38 20-24 15-19 The number of crystals after storage at minus 35 ° C,% 16 ÷ 33 10 ÷ 12 8-10 12 ÷ 24 8 ÷ 12 7 ÷ 11 30 ÷ 34 6-7 18 ÷ 20 28 ÷ 31 Viscosity, cP 60,000 65,000 70,000 5800 64500 72000 180,000 155,000 98000 167000

Claims (3)

1. An emulsifying composition for the manufacture of water-in-oil emulsions containing a mixture of the product of the interaction of polyisobutylene succinic or polyisobutylene bis succinic anhydride with an organic mono- or polyamine, esters of acids and polyhydric alcohols and industrial oil, characterized in that a mixture is used as esters of acids and polyhydric alcohols sorbitan esters of fatty and resin acids in the following ratio of ingredients, wt.%:
the product of the interaction of polyisobutylene or polyisobutylene bisuccinic anhydride with organic mono- or polyamine 20-70 mixture of sorbitan esters of fatty and resin acids 5-35 industrial oil 3-75 2. The emulsifying composition for the manufacture of emulsions "water in oil" according to claim 1, characterized in that the mixture of sorbitan esters of fatty and resin acids is taken in the ratio, respectively, wt.%: 20-80 / 20-80. 3. The emulsifying composition for the manufacture of water-in-oil emulsions according to claim 1, characterized in that it additionally contains up to 2-10% sodium salt of tallow oil fatty acids in excess of 100% of the mixture.