RU2336292C1 - Composition to stimulate process flows of oil recovery, improve oil recovery of pay beds and reduce flow frictions of oil transportation - Google Patents

Abstract

FIELD: oil and gas production industry.

SUBSTANCE: invention is related to the area of oil production and pipeline transportation of oil and petroleum products. Composition to stimulate process flows of oil recovery, improve oil recovery of pay beds and reduce flow frictions of oil transportation contains, wt %: nonionic surfactant 2-20, polyelectrolyte - demulsifier 1-17, nitrogenated block copolymer of ethylene oxide and propylene oxide on the basis of ethylenediamine 5-25, alkyl phosphate 1-5, chelating agent 0.5-2.0, trialkylammoniomethan-sulfonate 0.5-5.0, natrium alkylbenzenesulfonate 10-20, ammonium salts of low-molecular carboxylic acids C₂-C₅ 1-5.0, natrium alkane sulfonate - other. At that is can additionally contain, wt %: aliphatic alcohol of the C₁-C₃ group 10-30 and ethyleneglycol or propylene-glycol 10-20.

EFFECT: enhanced efficiency of combined effect of the composition in process operations of oil recovery with application of physical fields, enhanced functions under reservoir conditions, improved reservoir properties, enhanced coverage of formation by effect.

2 cl, 2 tbl

Description

The invention relates to the field of oil production and pipeline transport of oil and oil products and can be used to increase oil recovery of productive formations, secondary oil production by displacing water in a wide range of reservoir temperatures, treatment of the bottom-hole formation zone, to prevent formation on hard surfaces (pipe walls, pumps, downhole equipment, etc.) of asphalt-resin-paraffin deposits (AFS) and deposits of mineral salts, to reduce hydraulic resistance during transportation high-viscosity oil and water-oil emulsions of the pipes, cleaning of tanks and pipelines from oil slops and for downhole and demulsification of oil field treatment.

Known composition to prevent the formation of paraffin [USSR Patent No. 1706204, class. E 21 B 37/00, published. 1994.11.15], containing sodium alkanesulfonate, sodium alkylbenzenesulfonate, a nonionic surfactant with 6-13 hydroxyethyl groups, an ethoxylated alkyl ester of phosphoric acid or its potassium or ethanolamine salt, a hydrocarbon solvent, as well as an aliphatic alcohol, ethylene glycol or propylene components, wt.%:

Sodium alkylbenzenesulfonate 0-30 Nonionic surfactant, with 6-13 hydroxyethyl groups 4-10 Oxyethylated alkyl ester of phosphoric acid or potassium or ethanolamine salt thereof 1-5 Hydrocarbon solvent 7.5-15 Aliphatic alcohol 10-20 Ethylene glycol or propylene glycol 5-15 Sodium alkanesulfonate rest

The disadvantage of this composition is the ability of its aqueous solutions to partially mix with the transported oil, which reduces the period of effective protection of surfaces from paraffin deposits, the level and duration of the reduction of hydraulic resistance when oil moves through pipes, and at the same time increases the residual oil content in the solution.

Closest to the proposed invention in technical essence and the achieved result is a composition for increasing oil recovery of productive formations, intensifying oil production processes and reducing hydraulic resistance during oil transportation [RF Patent No. 2205198, published. 2003.05.27 - prototype], including a non-ionic surfactant, sodium alkanesulfonate, polyelectrolyte demulsifier, nitrogen-containing block copolymer of ethylene oxide and propylene oxide based on ethylene diamine, alkyl phosphate, complexone and triethanolamine in the following ratio of components (wt.%):

Fatty Based Polyethylene Glycol Monoalkyl Esters alcohols of fraction C ₁₀ -C ₁₃ or fraction C ₁₀ -C ₂₀ , either mono- and dialkyl ethers of polyethylene glycol or polyethylene glycol ethers monoethanolamides of fatty acids of fraction C ₁₀ -C ₁₆ , or ethoxylated alkyl phenols based on propylene trimers 2-20 Polyelectrolyte demulsifier 1-7 Block copolymer of ethylene oxide and propylene oxide 5-25 Triethanolamine 1-10 Oxyethylated Phosphoric Alkyl Ether acid or potassium salt 1-5 Complexon 0.5-2 Sodium alkyl sulfonate containing 11-18 atoms carbon rest

The disadvantage of this composition is the limited kinetics of wetting it with solutions of highly active oil, rock, and metal, especially when combined with synthetic surfactants and physical (electrical, magnetic, ultrasonic) fields and a change in alkalinity (pH) of the aqueous phase.

The objective of the invention is to increase the effectiveness of the complex action of the composition in oilfield production operations using physical fields, as well as expanding its functions (improving oil displacement ability in reservoir conditions, improving reservoir properties and increasing coverage by the bottom-hole formation zone in an acidic and alkaline environment).

The problem is solved in that the composition for the intensification of technological processes of oil production, increase oil recovery in productive formations and reduce hydraulic resistance during oil transport, including non-ionic surfactant, sodium alkanesulfonate, polyelectrolyte demulsifier, nitrogen-containing block copolymer of ethylene oxide and propylene oxide, alkylene phosphate according to the invention additionally contains trialkylammoniomethanesulfonate, sodium alkylbenzenesulfonate and low molecular weight ammonium salts (C ₂ - C ₅ ) carboxylic acids, in the following ratio of components (wt.%):

Nonionic Surfactant 2-20 Polyelectrolyte demulsifier 1-7 Specified block copolymer 5-25 Alkyl Phosphate 1-5 Complexon 0.5-2.0 Trialkylammonomethanesulfonate 0.5-5.0 Sodium alkylbenzenesulfonate 10-20 The specified ammonium salts 1.0-5.0 Sodium alkanesulfonate rest

To reduce the pour point and improve the commodity form (lower viscosity and reduce pricing), the composition may also contain an aliphatic alcohol of the group C ₁ -C ₃ 20-30 wt.% And ethylene glycol or propylene glycol 10-20 wt.%.

As a non-ionic surfactant, the composition contains ethoxylated alkyl phenols based on propylene trimers (Neonol 9-12, Neonol 9-10, TU 38-1036-25-87), monoalkyl ethers of polyethylene glycol based on fatty alcohols of fraction C ₁₀ -C ₁₃ (Syntanol DT -7, TU 6-14-1037-79) or fractions C ₁₀ -C ₂₀ (Sintanol DS-10, TU 6-14-577-77), mono- and dialkyl ethers of polyethylene glycol (Wetting agent DB, MRTU 6-02- 530-80), polyethylene glycol esters of monoethanolamides of fatty acids of the C ₁₀ -C ₁₆ fraction (Sintamide 5, Sintamide 10, TU 6-02-640-80).

As sodium alkanesulfonate, an alkyl sulfonate containing 12-18 carbon atoms (TU 6-01-5763450-102-90) or a volgonate containing 11-17 carbon atoms (OST 6-01-32-77) is used.

As the polyelectrolyte, sodium carboxymethyl cellulose is used with an esterification degree from 0.4 to 1.2 (Na-CMC), sodium polyacrylate or polymethacrylate (PAA or PMAA), polyacrylamide (PAA), poly N, N-dialkyl, N, N- diallylammonium chloride (VPK-402, TU 6-05-231-238-83), a copolymer of N, N-dialkyl, N, N-diallylammonium chloride with acrylic acid (copolymer AT-2, STP 01-22-81), polyethyleneimine (PEI ) or polymers of the pyridine salt (PPS).

As complexones, 2 hydroxy-1,3 diaminepropane tetramethylene phosphonic acid (DPF-1, TU-09-4915-80) or its sodium salt (DPF-1H, TU 6-09-20-36-80), 1- hydroxyethylene diphosphonic acid or its salt (OEDP, OEDP-k) or nitrilotrimethylene phosphonic acid (NTP).

The alkyl phosphate used is the ethoxylated alkyl ester of phosphoric acid (Oxyphos KD-6) or its potassium salt (Oxyphos A, Oxyphos B - TU 6-02-1177-79).

Diproxamine-57, Diproxamine-157 (TU 6-14-614-76), Proxamine HP-71, Tetronic serie (BASF) or Genapol PF (Hoechst, Germany) are used as a nitrogen-containing block copolymer of ethylene oxide and propylene oxide based on ethylene diamine) .

Trialkylammonomethanesulfonate (Sulfobetaine) [(C _n H _{2n + 1} ) ₃ NCH ₂ SO ₂ ], where n = 10-18, is used as an ampholytic surfactant.

Ammonium salts of low molecular weight (C ₂ -C ₅ ) carboxylic acids are used as a demulsifier AK NMK.

Sulfonol (TU 6-14-30-69), Sulfonol 40% or Sulfonol SP (TU 07510508.135-98) are used as sodium alkylbenzenesulfonate.

As aliphatic alcohols of group C ₁ -C ₂ , technical ethyl alcohol (GOST 17299-78), propyl alcohol (GOST 69-95-77) or isopropyl alcohol (GOST 9805-84) are used.

The composition options are shown in table 1, and their performance characteristics are shown in table 2. When introduced into oil, the composition is dissolved in fresh, sea or formation water to a content of 0.001-100%.

The effectiveness of the composition was determined in laboratory and field conditions by the following indicators.

1. Decrease in hydraulic resistance of high-viscosity oils during their movement through pipes (increase in useful productivity of the pipeline).

2. Hydrodynamic stability of the peripheral annular flow.

3. The effectiveness of preventing the formation of paraffin.

4. Stabilizing ability (residual oil content in solution).

5. Oil displacement ability and oil displacement coefficient at different reservoir temperatures.

6. Kinetics of wetting ability.

7. Detergency in neutral, alkaline and acidic environments.

Examples of specific use.

When mixing the components, the ampholytic surfactant 0.5-5%, sodium alkylbenzenesulfonate 10-20% and the ammonium salts of low molecular weight (C ₂ -C ₅ ) carboxylic acids 1-5% are first mixed. The mixture is maintained until complete homogenization. Thus, a complex modifier is obtained, and then it is mixed in an amount of 11.5-30% with the remaining components. The ratio of components is shown in table 1.

In table 1, examples 1 and 2 are known, examples 3-11 are according to the proposed invention.

The oil displacement coefficient and oil displacement ability were determined on the model of a porous medium using the express method of SibNIPI.

The compositions at a fixed pressure were passed through a thermostatically controlled bulk core, previously saturated with water and high viscosity Uzen oil with a known viscosity and density. Oil displacement coefficient KB was calculated by the formula

KB = Vn2 / Vn1,

where Vн2 - the volume of oil displaced by the test composition from the core, ml,

Vн1 - oil volume taken for preliminary saturation of the core, ml.

The oil-displacing ability of the composition of the NSA was calculated by the formula

НВС = Vн2 / Vпор,

where Vpor is the pre-determined pore volume of the core, ml.

Hydraulic resistance when moving through pipes of high viscosity oils was determined on an open-type tubular rheometer with two operated parallel tubes. The test composition was injected into one of the tubes directly into the volume of the squeezed oil. Oil consumption was determined at an equal pressure drop using liquid flow meters.

The hydrodynamic stability of the peripheral annular flow of the test composition was determined on the same device by the duration of the periods of relaxation and aftereffect, determined from the moment of termination of the introduction of the reagent into the tube.

The effectiveness of surface protection from sediment deposits was determined by the "cold cylinder" method and was calculated using

E = (m0-mi) 100% / m0,

where m0 is the ARPD mass deposited on the walls of the “cold cylinder” from the control sample (without introducing the composition into the oil), mi is the ARPD mass deposited on the walls of the “cold cylinder” in the presence of the test composition.

The stabilizing ability of the composition was characterized by a residual oil content in its aqueous 0.1% solution after 100 g of oil was added to 1 liter of this solution, dosed mechanical dispersion and seven-day sediment.

The oil content in the solution was determined by infrared spectroscopy after removal of the floating oil from the surface of the solution.

As can be seen from the data in table 2, the additional introduction of low molecular weight (C ₂ -C ₅ ) carboxylic acids into the composition of the trialkylammoniomethanesulfonate, alkylbenzenesulfonate and ammonium salt provides, in contrast to the prototype, an increase in the efficiency of the complex action of the composition in oil production technological operations, as well as the expansion of its functions (improvement of oil-displacing ability in reservoir conditions, improvement of reservoir properties and increase in coverage by the impact of the bottom-hole formation zone in acid and alkaline environments e), gives a more significant and long-lasting in comparison with the prototype, a decrease in hydraulic resistance when high-viscosity oil moves through pipes. The low stabilizing ability of the composition allows it to be used repeatedly, which helps to prevent environmental pollution during technological operations to intensify the work of production and injection wells, pipelines and tanks.

Table 1 Reagent Compositions №№ pp Component Name The content of components, wt.% one 2 3 four 5 6 7 8 9 10 eleven Famous [one] [2] one Nonionic surfactant: Sintanol DT7 7 - - - - - 2 10 - - - NeonolAF9-12 - 10 9 6 2 10 - - 6 6 5 2 Polyelectrolyte: AT2 - - - - one 7 - - - - - VPK402 - 1,5 3,5 1,5 - - 7 one 1,5 1,5 one 3 Na-alkanesulfonate: 35 65 50,5 48.5 42.5 42 42 55 23.5 20.5 24.5 four Alkyl Phosphate: Oxyfos B 3 3 3,5 one 3,5 5 - - 3,5 3,5 - Oksifos KD6 - - - - - - 3,5 3,5 - - 3 5 Block copolymer of ethylene oxide and propylene: Diproxamine 157 - fifteen 8 25 fifteen fifteen 25 5 fifteen 10 5 6 Triethanolamine - 5 - - - - - - - - - 7 Complexon - 0.5 0.5 2 0.5 one 0.5 0.5 2 0.5 one 8 White Spirit 10 - - - - - - - - - - 9 Ampholytic surfactant: Sulfobetaine - - 2 5 0.5 2 2 2 0.5 5 0.5 10 Ammonium salts of carboxylic acids: demulsifier AK NMK - - 3 one 5 3 3 3 3 3 5 eleven Na-alkylbenzenesulfonate twenty - twenty 10 thirty fifteen fifteen twenty fifteen 10 thirty 12 Isopropyl alcohol fifteen - - - - - - - 10 thirty fifteen 13 Ethylene glycol 10 - - - - - - - twenty 10 10

table 2 Technological properties of aqueous reagent solutions Composition Properties No. of composition according to table 1 one 2 3 four 5 6 7 8 9 10 eleven The decrease in hydraulic resistance,% 34.6 40.1 50.3 49.8 49.6 51.3 49.9 50.1 52.6 52.6 53.8 Hydrodynamic stability of the peripheral annular flow, min twenty 130 > 300 > 300 > 300 > 300 > 300 > 300 > 300 > 300 > 300 The effectiveness of surface protection from paraffin,% Uzen oil 89 88 91.8 92.5 92 92.6 92.6 93.6 91.9 89.3 92.3 model oil 45 53 57.6 57.6 57.8 59 58.8 59 59 59.1 58.9 Stabilizing ability, mg / l 38 17,2 11.1 11.6 11.8 12.9 13 13.5 11.5 11.6 eleven Washing ability: AFS on metal, alkaline medium, GOSNITI points 8 8.5 9.5 9 9 9 9 9.5 10 10 10 AFS on metal, acidic medium, GOSNITI points 6 6.5 9 8.5 9 9 9 9 9.5 9.5 9.5 AFS in a porous medium, wt.% 93 98 99 99 99 99 99 99 99 99 99 The effectiveness of inhibition of deposits of mineral salts,%: calcium sulfate and barium sulfate - one hundred one hundred one hundred one hundred one hundred one hundred one hundred one hundred one hundred one hundred calcium carbonate - 98 one hundred one hundred one hundred one hundred one hundred one hundred one hundred one hundred one hundred Oil displacement ratio: Ostashkinsky oil - 0.81 0.86 - 0.86 0.83 0.85 - 0.84 0.88 0.88 Uzen oil 0.33 0.52 0.74 0.78 - 0.76 0.76 0.79 0.8 0.8 0.81 Oil displacing ability: at a temperature of 20 ° C 0.32 0.35 0.37 0.39 0.4 0.39 0.38 0.39 0.39 0.39 0.4 at a temperature of 90 ° C 0.17 0.3 0.39 0.42 0.43 0.43 0.4 0.42 0.43 0.43 0.43

Claims (2)

1. Composition for intensifying oil production technological processes, increasing oil recovery in productive formations and reducing hydraulic resistance during oil transportation, including non-ionic surfactant, sodium alkanesulfonate, polyelectrolyte demulsifier, nitrogen-containing block copolymer of ethylene oxide and propylene oxide based on ethylene diamine, alkylene phosphate characterized in that it further comprises trialkylammonomethanesulfonate, sodium alkylbenzenesulfonate and low molecular weight ammonium salts carboxylic x C ₂ -C ₅ acids with the following ratio of components, wt.%: nonionic surfactant 2-20 polyelectrolyte demulsifier 1-17 specified block copolymer 5-25 alkyl phosphate 1-5 complex 0.5-2.0 trialkylammonomethanesulfonate 0.5-5.0 sodium alkylbenzenesulfonate 10-20 specified ammonium salts 1-5.0 sodium alkanesulfonate rest 2. The composition according to claim 1, characterized in that it further comprises an aliphatic alcohol of the group C ₁ -C ₃ 10-30 wt.% And ethylene glycol or propylene glycol 10-20 wt.%.