Emulsifier-stabilizer invert emulsions and method thereof

The invention relates to the production of invert emulsions used in drilling and overhaul of oil and gas wells as process fluids. Emulsifier-stabilizer invert emulsions contains the product of the interaction of VAT residue production of synthetic fatty acids (COSGC) and triethanolamine in wt. ratio (4-5):1, ether, obtained by blending oxypropylated glycerol with a degree of oxypropylation 5-8 and the number propylenoxide circuits 1-3 with the product of the interaction KOSIK and triethanolamine in a weight ratio of oxypropylene glycerin : a product of the interaction of 1:(4,56 - 12,18), and preferably diesel fuel or kerosene as a solvent in the following ratio, wt.%: the product of the interaction KOSIK and triethanolamine in wt. ratio (4-5):1 31,4-35,4; ether, obtained by blending oxopropylidene of glycerol by-product interaction KOSIK and triethanolamine 14,6-18,6; a hydrocarbon solvent else. The method of obtaining the emulsifier-stabilizer invert emulsions involves the following steps: heating and stirring KOSIK with triethanolamine in wt. the ratio of 4-5:1, the subsequent receipt of ether smashin OSGC and triethanolamine) with oxypropylated glycerin, the characteristics of which are described above. The result is a mixture of the product of the interaction KOSIK with triethanolamine and ether, taken respectively in the ratio(31,4-35,4):(18,6-14,6) wt.%, which type of hydrocarbon solvent (the rest up to 100%). The technical result consists in a comprehensive improvement of emulsifying ability of the emulsifier due to increase heat-resistance, thermal stability, bearing capacity, effective viscosity and reduce filtrated invert emulsions. 2 AD. and 1 C.p. f-crystals, 1 table.

The invention relates to the field of chemicals used during drilling and overhaul of oil and gas wells, specifically to obtain invert emulsions used as process fluids during drilling, development, opening, perforation and killing of oil and gas wells.

Known emulsifier invert emulsions, comprising the product of the interaction of the acids of tall oil and triethanolamine at a mass ratio of acid:amine is 2:1, the product of the interaction of the acids of tall oil and butter and VAT residue production alkylamidoamines containing 85-95% ethoxylated alkylamines followed, where Alki the attachment acid:VAT residue of 1.5:1, and a hydrocarbon solvent containing 20-50 wt.% aromatic hydrocarbons, the remainder (to 100%) - isoparaffin and naphthenic hydrocarbon fraction 170-320With the following ratio of components, wt.%: the product of the interaction of the acids of tall oil and triethanolamine 40-50; the product of the interaction of the acids of tall oil and VAT residue production alkylamidoamines 1-5; a hydrocarbon solvent containing 20-50 wt.% aromatic hydrocarbons, the remainder (to 100%) - isoparaffin and naphthenic hydrocarbon fraction 170-320With up to 100.

A method of obtaining emulsifier invert emulsions by the method of mixing the components at a temperature of 40-60(Patent RF №2062142, B 01 F 17/34, 17/40, 17/42, From 09 To 7/06).

The disadvantages of the known emulsifier and method of its production are:

1) low temperature resistance obtained on the basis of invert emulsions, limiting their applicability wells with bottomhole temperatures below 70;

2) weak stabilizing ability, expressed in high filtrationthe, low effective viscosity, metric bearing capacity and structural strength of invert emulsions to him about ayvacik liquids;

3) low thermal stability of invert emulsions based on it, expressed in a significant temperature liquefaction, which requires in their composition costly thermally activated thickeners.

These drawbacks limit the scope of the emulsifier low-temperature wells, and the purpose of invert emulsions based treatment of injection wells for the purpose of alignment of injectivity profile, acid treatment, perforation, dissection and launder layers.

Known emulsifier-stabilizer hydrophobic emulsion drilling fluids and method thereof (Patent RF №2201950, bull. No. 10, 2003, B 01 F 17/34, 17/40, 17/42, From 09 To 7/06) containing the product of the interaction of VAT residue production of synthetic fatty acids and triethanolamine in a ratio of 4-5:1 and the solvent in the following ratio, wt.%:

Product interaction

VAT residue

production of synthetic

fatty acids and

triethanolamine 57,9-85,0

The solvent 15,0-42,1

As a solvent it contains diesel fuel or kerosene.

A method of obtaining emulsifier-stabilizer hydrophobic-emulsion drilling fluid is carried out by heating, paramasivan is a rate of 4-5:1, moreover, the heating is carried out at a temperature of 120-150C for 4-8 hours in the environment of the solvent is diesel fuel or kerosene.

The disadvantages of the known emulsifier and method of its production are:

1) low emulsifying ability, leading to increased operating costs emulsifier;

2) insufficient high temperature resistance obtained on the basis of invert emulsions, limiting their applicability wells with bottomhole temperatures below 140;

3) the presence in the composition of the emulsifier-stabilizer unreacted VAT residue production of synthetic fatty acids, which forms with triethanolamine esters salt, impair the stabilizing ability of the emulsifier-stabilizer in the region of low (up to 50C) temperatures, resulting in high filtrationthe and low index of carrying capacity invert emulsion based, and requires their composition further reagents stabilizers.

The present invention solves the complex task of improving emulsifying ability, heat resistance, thermal stability, bearing capacity, the performance is top-stabilizer invert emulsions, contains the product of the interaction of VAT residue production of synthetic fatty acids (COSGC) with triethanolamine in the ratio of 4-5:1 and the solvent according to the invention optionally contains ether, obtained by blending oxypropylated glycerol with a degree of oxypropylation - 5-8 and the number polypropyleneoxide chains - 1-3 product interaction KOSIK and triethanolamine in a weight ratio of oxypropylene glycerin : a product of the interaction of 1:(4,56-12,18), in the following ratio, wt.%:

Product interaction

acid VAT residue

production of synthetic

fatty acids

the triethanolamine in

the ratio of 4-5:1 31,4-35,4

Ether, obtained by blending

oxopropylidene

glycerin with degree

oxypropylation 5-8 and

number polypropyleneoxide

circuits 1-3 with the product

the interaction of the cubic

residue production

synthetic fatty acids

and triethanolamine in mass

a ratio of

oxopropylidene

glycerin : product

interaction is equal to

1:(4,56-12,18) 14,6-18,6

The solvent (diesel

fuel or kerosene) Else

This task is solved in that in the method of producing emulsifier-stabilizer invert emoism, according to the invention is obtained the product of the interaction of VAT residue production of synthetic fatty acids with triethanolamine stirred at a temperature of 115-120With oxypropylated glycerine, having a degree oxypropylation - 5-8, the number polypropyleneoxide circuits 1-3, when the mass ratio oxypropylated glycerin : a product of the interaction of 1:(4,56-12,18), with a mixture of the product of the interaction of VAT residue production of synthetic fatty acids with triethanolamine, ether, the resulting mixing product of the interaction of VAT residue production of synthetic fatty acids and oxypropylated glycerol, in a ratio, respectively,(31,4-35,4):(18,6-14,6) wt.%, and then adding to the resulting mixture of solvent (diesel fuel or kerosene).

To obtain emulsifier stabilizer used:

- VAT residue synthetic fatty acids (TU 38.1071231 - 89);

- kerosene (TU 38.601-22-70-97);

- diesel oil GOST 305 - 82);

- triethanolamine (TU 6-02-916-79);

- oxypropylated glycerin, the General formula₃H₅(HE)(_3-y)[O(C₃H₆O)_xN]_ywhere I=1, 2, or 3 is the number of polypropylene oxypropylation.

Getting emulsifier-stabilizer illustrated by the following examples.

Example 1. Obtaining a solution of the product of the interaction of VAT residue production of synthetic fatty acids with triethanolamine in the hydrocarbon solvent. In a three-neck reactor equipped with a mixer nozzle Dean-stark and thermometer, was loaded 208,5 g VAT residue production of synthetic fatty acids (COSGC) having acid value of 120 mg KOH/g, and 46.4 g of triethanolamine. The mixture was heated to a temperature of 140-150With and kept at this temperature for 5 h under stirring. For the reaction time was autogyros 4.8 ml of water. Formed 250 g of the product containing complex triethanolamine esters KOSIK and unreacted excess KOSIK. The resulting product is a paste dark brown color with a density of 1.03 g/cm³the acid number of 29 mg KOH/g and interfacial tension of 0.5% solution in octane on the border with distilled water to 12.7 mn/m From the obtained product was separated 50g and mixed in a separate flask with 50 g of kerosene by stirring on a magnetic stirrer for 5-15 min before the formation of a homogeneous product. Received 100 g of the solution density of 0.92 g/cm³the acid number of 15 mg KOH/ distilled water to 21.2 mn/m, containing 50% of the product of the interaction KOSIK with triethanolamine and 50% kerosene.

Example 2. In a three-neck reactor equipped with a mixer nozzle Dean-stark and thermometer, was placed 50 g of the remaining 200 g of the product obtained in example 1 (before mixing with the solvent), and added 4.1 g of oxypropylated glycerin. The ratio oxypropylated glycerin : a product of the interaction KOSIK with triethanolamine was 1:12,18. The mixture was heated to a temperature of 120With and kept at this temperature for 3 h under stirring. For the reaction time was autogyros 0.9 ml of water. When mixing unreacted excess KOSIK contained in the product of the interaction KOSIK with triethanolamine, obtained in example 1, interacts with oxypropylated glycerin. The result was a 53.2 g of the product, which is a paste dark brown color with a density of 1.04 g/cm³the acid number of 10 mg KOH/g and interfacial tension of 0.5% solution in octane on the border with distilled water to 2.8 mn/m Obtained product was mixed with 50 g of kerosene by stirring for 5-15 min before the formation of a homogeneous product. Got to 106.5 g of a solution with a density of 0.92 g/cm³the acid number of 5,using distilled water to 3.5 mn/m, containing 35.4% of product interaction KOSIK with triethanolamine, 14.6% of the product of the interaction of oxopropylidene of glycerol COSIC, the rest of the kerosene.

Example 3. In a three-neck reactor equipped with a mixer nozzle Dean-stark and thermometer, was placed 50 g of the remaining 150 g of the product obtained in example 1 (before mixing with the solvent), and added 6.2 g of oxypropylated glycerin. The ratio oxypropylated glycerin : a product of the interaction KOSIK with triethanolamine was 1:8,12. The mixture was heated to a temperature of 120°C and kept at this temperature for 2.5 h with stirring. For the reaction time was autogyros 0.9 ml of water. The result was of 55.3 g of the product, which is a paste dark brown color with a density of 1.05 g/cm³the acid number of 7 mg KOH/g and interfacial tension of 0.5% solution in octane on the border with distilled water to 1.3 mn/m Obtained product was mixed with 50 g of kerosene by stirring for 5-15 min before the formation of a homogeneous product. Received by 110.6 g of a solution with a density of 0.93 g/cm³the acid number of 3.8 mg KOH/g pour point -19With, the interfacial tension of 0.5% solution in octane on the border with distilled into profilirovannogo of glycerol KOSIK, the rest of the kerosene.

Example 4. Analogously to examples 2 and 3 in a three-neck reactor equipped with a mixer nozzle Dean-stark and thermometer, was placed 50 g of the remaining 100 g of the product obtained in example 1 (before mixing with the solvent), and added 11 g of oxypropylated glycerin. The ratio oxypropylated glycerin : a product of the interaction KOSIK with triethanolamine was 1:4,56. The mixture was heated to a temperature of 120With and kept at this temperature for 2 h under stirring. For the reaction time was autogyros 1 ml of water. The result was 60 g of product, which is a paste dark brown color with a density of 1.06 g/cm³the acid number of 2 mg KOH/g and interfacial tension of 0.5% solution in octane on the border with distilled water to 1.1 mn/m Obtained product was mixed with 50 g of kerosene by stirring for 5-15 min before the formation of a homogeneous product. Received 120 g of a solution with a density of 0.93 g/cm³the acid number of 1.7 mg KOH/g, a pour point of -21°C, the interfacial tension of 0.5% solution in octane on the border with distilled water to 1.6 mn/m, containing 31.4% of the product of interaction KOSIK with triethanolamine, 18.6% of the product of the interaction of oxypropyl Dean-stark and thermometer, put the remaining 50 g of the product obtained in example 1 (before mixing with the solvent), and added 12.5 g of oxypropylated glycerin. The ratio oxypropylated glycerin : a product of the interaction KOSIK with triethanolamine was 1:4. The mixture was heated to a temperature of 120°C and kept at this temperature for 1.5 h with stirring. For the reaction time was autogyros 1 ml of water. The result was a 61.5 g of product, which is a paste dark brown color with a density of 1.06 g/cm³, acid value of 1 mg KOH/g and interfacial tension of 0.5% solution in octane on the border with distilled water to 1.0 mn/m Obtained product was mixed with 50 g of kerosene by stirring for 5-15 min before the formation of a homogeneous product. Received 123 g of a solution with a density of 0.93 g/cm³the acid number of 0.5 mg KOH/g pour point -26With, the interfacial tension of 0.5% solution in octane on the border with distilled water to 1.2 mn/m, containing 30.7% of the product of the interaction KOSIK with triethanolamine, and 19.3% of the product of the interaction of oxopropylidene of glycerol COSIC, the rest of the kerosene.

Example 6. Getting invert emulsion-based emulsifier-stabilizer. Took 12 g re mixing on the mixer at 3000 rpm portions 2 cm³added 192 g of an aqueous solution of calcium chloride density of 1.2 g/cm³. After adding the last portion of calcium chloride stirring was continued for 20 minutes resulted In 333 cm³invert emulsion which after settling within 12 hours had the following parameters: density of 1.02 g/cm³electrocapillary 280, filtrated 13 cm³/30 min, the resistance 147With effective viscosity 386,4 MPawith, the coefficient of thermal liquefaction of 0.57, a measure of the carrying capacity at 30And 90With respectively 557^-1and 863^-1. Similarly were prepared invert emulsion based formulations emulsifier-stabilizer, whose properties are presented in the table.

Electrocapillary invert emulsion was evaluated by measuring the breakdown voltage, detected device “IGER-1 (TU-39-156-79) with a measurement range electrical stability 0-600 V, manufactured by Bugulma plant Nefteavtomatika”, which corresponds to the moment of destruction of the emulsion enclosed between the electrodes of the measuring cell of the device in normal conditions.

Thermolabel the activity of the sample, measured after opening the autoclave was 100±10 Century.

Effective viscosity invert emulsion was determined by device Rheotest RV-2 at the shear rate of 3 c^-1and the coefficient of thermal dilution was calculated as the ratio of the effective viscosity, measured at 90With its value when 30C.

Indicator bearing capacity was calculated by the formulawhere₀dynamic shear stress (PA)_PLplastic viscosity invert emulsion (PAC) determined by the standard method on the points rheological profile obtained on the instrument Rheotest RV-2, for speed shift 1312^-1and 437^-1.

Filtrated invert emulsion was determined on the device VM-6. Interfacial tension was determined stalagmometer method. The pour point was determined according to GOST 6258. Acid number was determined according to GOST 22386.

The table shows that the proposed emulsifier-stabilizer can improve the quality of the invert emulsion in comparison with the prototype by emulsifying ability to 83-92%, heat resistance on 10-31%, filtrationthe 62-ability at 30And 90With respectively 17-130% and 46-739%. In addition, if the composition of the emulsifier-stabilizer free oxypropylated glycerin (example 5) its emulsifying power increases relative to the prototype at 94%. However, as can be seen from the table, the high reactivity of oxypropylated glycerin has a negative impact on the stability properties of the invert emulsion when the temperature rises, which limits the lower limit of the ratio of the product of the interaction KOSIK and triethanolamine : oxypropylated glycerin value 4,56:1, which is implemented in example 4 and is equimolar to the formation of monoamino acids VAT residue and oxypropylated glycerin. To change the ratio between the product of the interaction KOSIK and triethanolamine : oxypropylated glycerin to 12.18:1 (example 2) interfacial tension, effective viscosity and record the bearing capacity increases, the coefficient of thermal liquefaction and filtrated invert emulsion decreases and its temperature passes through a maximum, which is associated with an increase in the degree of substitution and molecular weight of the resulting esters of VAT residue production of synthetic enolimine : oxypropylated glycerin over 12,18 impractical because it reduces the output of the above esters and remains a large amount of unreacted VAT residue, forming with esters of salt, which degrades the properties of the emulsifier-stabilizer. Thus, the highest efficiency shows the composition of the emulsifier stabilizer 2, 3 and 4, in which the ratio of VAT residue : oxypropylated glycerol, respectively 4,56, 8,12 and 12,18.

These advantages of the present invention allow, as can be seen from the table, get termouplotnyayuscheysya invert emulsion, which increases its viscosity with increasing temperature and therefore preferred for use as a drill drilling fluids, killing fluids and fracturing fluids used in wells with high downhole temperatures.

Claims

1. Emulsifier-stabilizer invert emulsions containing the product of the interaction of VAT residue production of synthetic fatty acids and triethanolamine in wt. the ratio of 4-5:1 and a hydrocarbon solvent, characterized in that it additionally contains ether, obtained by blending oxypropylated glycerol with a degree of oxypropylene the definition of fatty acids and triethanolamine in a weight ratio of oxypropylene glycerin : product interaction equal to 1:(4,56-12,18) in the following ratio, wt.%:

The product of the interaction of the acid VAT residue production

synthetic fatty acids with triethanolamine wt.

ratio (4-5):1 31,4-35,4

Ether, obtained by blending oxypropylated glycerol with a degree of oxypropylation 5-8 and the number propylenoxide circuits 1-3 with the product of the interaction of VAT residue production of synthetic fatty acids and triethanolamine in a weight ratio of oxypropylene glycerin : product interaction,

equal 1:(4,56 -12,18) 14,6-18,6

Hydrocarbon solvent Else

2. Emulsifier-stabilizer under item 1, characterized in that the solvent it contains diesel fuel or kerosene.

3. The method of obtaining the emulsifier-stabilizer invert emulsions, comprising heating and mixing VAT residue production of synthetic fatty acids with triethanolamine in wt. the ratio of 4-5:1, mixing with the solvent, wherein the resulting product of the interaction of VAT residue production of synthetic fatty acids with triethanolamine stirred at a temperature of 115-120With oxypropylated glycerine, having a degree oksipropil the interaction, equal to 1:(4,56 -12,18), with a mixture of the product of the interaction of VAT residue production of synthetic fatty acids with triethanolamine, ether, the resulting mixing product of the interaction of VAT residue production of synthetic fatty acids with triethanolamine and oxypropylated glycerol, respectively sootnoshenii(31,4-35,4):(18,6-14,6) wt.%, and then adding to the mixture of kerosene (the rest).