RU2568637C2 - Emulsifier for inverted water-oil emulsions - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: emulsifier for inverted water-oil emulsions contains an active substance and a solvent, where the active substance is in the form of (12-40) wt % of a product of reaction of oxidised fatty acid triglycerides (30-70) wt % and fatty acid glycerophosphatides (30-70) wt % with higher ethyleneamines (5-20) wt %, amino alcohols in wt % MEA:DEA:TEA = (5-15):(55-80):(15-30); the solvent is (60-88) wt % in pure form of oil distillates, absorbent A-2, C2-C3 alcohols or mixtures thereof in the ratio (1-99):(1-99):(1-99) wt %.

EFFECT: low emulsifier consumption, obtaining an emulsifier which enables to obtain inverted water-oil emulsions which are highly stable at high temperature.

1 tbl, 1 ex

Description

The invention relates to the oil and gas industry and is recommended for use in the preparation of oil-water emulsions used as process fluids in the secondary opening of reservoirs, hydraulic fracturing, killing wells, limiting water inflows in production wells and selective waterproofing with alignment of the injectivity profile of injection wells.

The invention relates to the oil industry and is proposed for use in the preparation of reverse water-oil emulsions used as process fluids in the secondary opening of reservoirs, hydraulic fracturing, killing wells, limiting water inflows in producing wells and selective waterproofing with equalization of the injectivity profile of injection wells.

In most hydrocarbon-based inverse emulsion emulsifiers, the basic active ingredient is the products of the interaction of tallow oils or fatty acids of vegetable oils with ethanolamines.

A known emulsifier of inverse emulsions (1) (US Pat. RF No. 2166988), containing in its composition surface-active substances in the form of a product of the interaction of acids of melt oil with triethanolamine and carbamide, chlorosulfonated polyethylene and aromatic hydrocarbon solvent. Its disadvantage is its low efficiency, which is manifested in the low aggregative stability of reverse water-oil emulsions formed with its participation.

Known emulsifier of oil-water emulsions (2) (US Pat. RF No. 2200056), which contains an oil-soluble surfactant based on tall oil acid esters of triethanolamine, additionally calcium chloride and organobentonite based on a compound of bentonite clay and a quaternary ammonium base; hydrocarbon solvent. The disadvantage of this emulsifier is the relatively low stability of inverse emulsions prepared on its basis at high reservoir temperatures, as well as the possibility of accumulation of bentonite as a decomposition product of the emulsion injected into the formation in the perforation zone in the production well.

Closest to the proposed emulsifier in technical properties is an emulsifier of inverse oil emulsions (3) (US Pat. RF No. 2414290) containing a surfactant in the form of a product of the interaction of unsaturated fatty acids and complex ethyleneamines, amino alcohols and mixtures thereof; as a solvent, hydrocarbon fractions containing alcohols, ethers, C ₁ -C ₁₂ aldehydes, petroleum distillates, hydroxyethylated alkyl phenols or a polyvinyl acetate depressant as functional additives.

The objective of the invention is to obtain an emulsifier that allows the production of reverse oil-water emulsions, highly stable at reservoir temperatures of more than 95 ° C. Such properties of the emulsion allow it to be used for waterproofing producing oil and gas wells. It should be noted that the average water cut of oil produced in Russia is 80-95% and the development of a product capable of long-term elimination of water inflow in the wells of high-temperature formations is an important research task.

The technical result is achieved in that the emulsifier of the inverse oil-water emulsions contains an active substance and a solvent, contains (12-40)% wt. As an active substance. in the form of a reaction product of oxidized triglycerides of fatty acids (30-70)% wt. and glycerophosphatyl vegetable oils (30-70)% wt. with complex ethyleneamyls (5-20)% wt., amino alcohols in% wt. MEA: DEA: TEA = (5-15) :( 55-80) :( 15-30); as a solvent (60-88)% wt. pure oil distillates, absorbent A-2, alcohols C2-C3, or mixtures in the ratios of% wt. (1-99) :( 1-99) :( 1-99).

The active substance is a mixture of amido amines, imidazoles of oxidized glycerophosphamides and glycerides of fatty acids synthesized at a temperature range of 90-180 ° C from the reaction mass of the composition,% wt .:

Oxidized Vegetable Oils 30-70 Vegetable Oil Glycerophosphatides 30-70 A mixture of amino alcohols MEA: DEA: TEA = (5-15) :( 55-80) :( 15-30) 5-20 A mixture of complex ethyleneamines 5-20

The raw materials of the claimed composition are:

1. Vegetable oils, TU oxidized at a temperature of T = 250-350 ° C with kinematic viscosity at T = 50 ° C from ν _5o = 20-25 cSt to ν _5o = 30-40 cSt.

2. Glycerophosphatides of fatty acids, representing the liquid mobile part of the tank sludge (hydrofuse) in the production of vegetable oils or phosphatide concentrate according to TU 9146-203-00334534-97.

3. Amino alcohols:

- monoethanolamine TU 2423-159-00203335-2004 - diethanolamine TU 2423-178-00203335-2007 - triethanolamine TU 2423-168-00203335-2007

4. A mixture of complex ethyleneamines manufactured by BASF under the trade name Amix-1000.

5. Solvents:

- winter diesel TU 38.101889-81 - kerosene TU 38.401-58-8-90 - absorbent A-2 TU 2411-019-73776139-2009 - technical ethyl alcohol TU 84-1203-89 - technical isopropyl alcohol GOST 9805-84

An example of a manufacturing technology of the proposed oil emulsifier

In a 500 ml three-necked flask equipped with a stirrer and a thermometer, it is loaded, g:

- oxidized vegetable oil 161 - tank sludge for the production of vegetable oils 105 - monoethanolamine 7 - diethanolamine 42 - triethanolamine 17.5 - "Amix-1000" 17.5

The reaction mass is stirred at a temperature of T = 160 - 170 ° C for 6-7 hours and cooled to a temperature of T = 35-45 ° C. From the obtained mixture of amido amines, imidazoles of oxidized glycerophosphamides and glycerides of fatty acids, the formulation of the inventive oil emulsifier for oil-water emulsions is prepared, wt.%:

- reaction mixture 35 - absorbent A-2 25 - kerosene thirty - ethanol 10

The resulting solution is mixed and emulsion samples are prepared from it, are shown in Table 1

The effectiveness of the inventive emulsifier was tested at 95 ° C by comparatively measuring the aggregate stability of reverse emulsions prepared in saline water with the addition of a saturated solution of calcium chloride and an additional hydrocarbon solvent of diesel fuel or oil from the Kumertau field of the Republic of Bashkortostan. Oil-water emulsions were prepared at Т = 20-25 ° С in a metal glass with stirring with a laboratory blade-type mixer at a speed of n = 1000-1200 rpm. Mineralized water with a density of 1005, 1015 and 1025 g / cm ^{3 was} prepared by dissolving NaCl (GOST 4233-77) and CaCl ₂ (GOST 450-77) in distilled water.

The density of mineralized water, g / DM ³ Weighed NaCl, g A portion of CaCl ₂ , g 1005 13 2 1015 eighteen 2 1025 37 3

A saturated solution of calcium chloride, density ρ = 1.29 g / cm ³ , is prepared by dissolving 33 g of anhydrous CaCl ₂ (GOST 450-77) in distilled water in a 100 ml volumetric flask.

Exposure of prepared samples of reverse emulsions was carried out in a thermal cabinet at a temperature of T = 95 ± 3 ° C until an aqueous phase separated from the emulsion appeared in a volume of up to 3-4% of the total emulsion volume.

The test results are shown in Table 1.

According to the test results shown in Table 1, the inventive composition has a lower flow rate (1.3-2 times) with a longer thermal stability (2-4 times) at high reservoir temperature.

Information sources

1. RF patent No. 2166998 IPC ⁷ B01F 17/34.

2. RF patent No. 2200056 IPC ⁷ B01F 17/34, B01F 17/42.

3. RF patent No. 2414290 IPC ⁷ B01F 17/34 (Prototype).

Claims (1)

An emulsifier of reverse oil-water emulsions containing an active substance and a solvent, characterized in that it contains (12-40)% wt. in the form of a reaction product of oxidized triglycerides of fatty acids (30-70)% wt. and glycerophosphatides of fatty acids (30-70)% wt. with complex ethyleneamines (5-20)% wt., amino alcohols in% wt. MEA: DEA: TEA = (5-15) :( 55-80) :( 15-30); as a solvent (60-88)% wt. in its pure form, petroleum distillates, absorbent A-2, alcohols C2-C3 or mixtures thereof in ratios of% wt. (1-99) :( 1-99) :( 1-99).