CN104312567A - Alkali-free composite flooding composition suitable for middle-low permeability oil reservoir and use thereof - Google Patents
Alkali-free composite flooding composition suitable for middle-low permeability oil reservoir and use thereof Download PDFInfo
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Abstract
The invention relates to an alkali-free composite flooding composition suitable for middle-low permeability oil reservoir. The alkali-free composite flooding composition comprises, by weight, 0.03-0.5% of a betaine surfactant, 0.01-0.3% of a functional polymeric surfactant, 0.01-0.3% of a nonionic surfactant and the balance water. The alkali-free composite flooding composition realizes a plurality of chemical flooding mechanisms without alkali and polymer, is used for middle-low permeability oil reservoir, improves a crude oil recovery ratio, and utilizes conventional components which are obtained easily and have a low cost and a certain economic benefit.
Description
Technical field
The present invention relates to a kind of alkali-free compound flooding composition and the application thereof that are applicable to middle and low permeable reservoir, belong to technical field of petroleum extraction.
Background technology
Low Permeability Oil/gas resource portion in proven reserve reaches more than 40%, and Prospective resources may more than 60%.Coming 10 years, the oil and gas production possibility more than 50% of China comes from low-permeability oil deposit.Current, low-permeability oil deposit mainly still adopts waterflooding behavior mode, and after water breakthrough, production rate decline is very fast, and ultimate recovery factor is at about 20-40%.
Gas drive (air drives, N2 gas drive, CO2 gas drive etc.) is the main raising recovery ratio tackling key problem technology of current low-permeability oil deposit, but the uncertain factor of gas drive is too many.The oil property of China determines and is difficult to realize mixed phase with CO2, and mixed phase drives in the application difficulty of China larger.
Surfactant flooding can improve displacement efficiency, but there is mobility control problem equally at low-permeability oil deposit, simple surfactant flooding due to " water breakthrough " serious, improve recovery ratio limited extent.
Because middle and low permeable reservoir pore throat radius is little, the polymkeric substance of macromolecule is difficult to enter in porous medium, and the polymer viscosified limited efficiency of small-molecular-weight, polymer flooding is difficult to use in middle and low permeable reservoir and improves oil recovery factor.
The alkali added in ternary composite driving often reacts with the mineral substance in stratum, produces precipitation, can block duct, therefore, can not use alkali in middle and low permeable reservoir chemical flooding formula for middle and low permeable reservoir.
Employing can reduce oil water interfacial tension and improve displacement efficiency, can control again the flooding system that mobility improves microcosmic swept volume on microcosmic, is that low-permeability oil deposit improves one of important development direction of oil recovery factor.
Summary of the invention
For improving the recovery ratio of crude oil, especially for the exploitation of middle and low permeable reservoir, the invention provides a kind of alkali-free compound flooding composition, can oil recovery factor be improved, obtaining better effect than flooding system of the prior art.
Technical scheme of the present invention is as follows:
Be applicable to an alkali-free compound flooding composition for middle and low permeable reservoir, it is characterized in that: by weight percentage, described alkali-free compound flooding composition comprises the composition of following composition:
Beet alkali surface activator 0.03-0.5%
Functional polymer tensio-active agent 0.01-0.3%
Nonionogenic tenside 0.01-0.3%
Surplus is water;
Described functional polymer tensio-active agent, is selected from the one in the multipolymer of acrylamide monomer and/or hydrophilic monomer and/or functional monomer;
Described beet alkali surface activator, has the structure of formula I or II:
Wherein: R1 is selected from alkyl, thiazolinyl, alkyl polyoxyethylene base, arylalkyl and arylalkyl polyoxyethylene groups;
X is selected from ethyl sulfonic acid root, propanesulfonic acid root, hydroxypropyl sulfonate radical, acetate moiety or propionate.
Further, by weight percentage, described alkali-free compound flooding composition comprises the composition of following composition:
Beet alkali surface activator 0.15-0.3%
Functional polymer tensio-active agent 0.03-0.15%
Nonionogenic tenside 0.03-0.15%
Surplus is water.
Further, described hydrophilic monomer is selected from one or more in vinylformic acid, acrylate, methacrylic acid, methacrylate, 2-methacrylic acid, 2-methacrylate, methylene-succinic acid, itaconate, toxilic acid, maleate, vinyl sulfonic acid, vinylsulfonate, 2-alkenyl benzene sulfonic acid, 2-alkenyl benzene sulfonic acid salt, styrene sulfonic acid, styrene sulfonate, allyl sulphonic acid and allylsulfonate.
Further, one or more preferably in vinylformic acid, acrylate, allyl sulphonic acid, allylsulfonate, allyl benzene sulfonic acid and allyl benzene sulfonate of described hydrophilic monomer.
Further, described functional monomer is selected from 2-acrylamide-2-methyl propane sulfonic, 2-acrylamide-2-methyl propane sulfonic salt, N-allyl benzene ethanamide, N, N-dimethyl-N-allyl group cetyl chloride ammonium, N, N-diallyl para toluene sulfonamide, allyl group para toluene sulfonamide, phenylacetamide, allyl group cetyl chloride ammonium, 3-acrylamide imido grpup-3 Methylbutanoic acid, 3-acrylamide imido grpup-3 Methylbutanoic acid salt, 2-acryloxy-2-methyl propane sulfonic acid, 2-acryloxy-2-methyl propane sulfonic acid salt, 1-allyloxy-2-hydroxypropanesulfonic acid, 1-allyloxy-2-hydroxypropanesulfonic acid salt, NVP, dialkyl aminoalkyl (methyl) acrylate, the quaternary amine of dialkyl aminoalkyl (methyl) acrylate, the acid salt of dialkyl aminoalkyl (methyl) acrylate, dialkyl aminoalkyl (methyl) acrylamide, the quaternary amine of dialkyl aminoalkyl (methyl) acrylamide, the acid salt of dialkyl aminoalkyl (methyl) acrylamide, diallyldialkylammonium halide, vinylbenzene, Hydroxyethyl acrylate, C1-30 alkyl (methyl) acrylate, polyvinyl alcohol and one or more in the polyxyethylated ester of (methyl) vinylformic acid.
As further preferred, described functional monomer is selected from one or more of 2-acrylamide-2-methyl propane sulfonic, 2-acrylamide-2-methyl propane sulfonic salt, N, N-dimethyl-N-allyl group cetyl chloride ammonium, allyl group cetyl chloride ammonium and the polyxyethylated ester of (methyl) vinylformic acid.
Described functional polymer tensio-active agent normally causes copolyreaction by two or three monomer by free radical and obtains.The first monomer is acrylamide monomer, the second monomer is hydrophilic monomer, different hydrophilic monomers can be selected according to the characteristic difference for oil reservoir, such as the optional vinylformic acid of conventional oil reservoir, for the optional allyl group of high temperature and high salt oil deposit (benzene) sulfonic acid, also can with other anionic monomers with alkenyl group; The third monomer is functional monomer, different oil reservoir, different application target, different primary surfactant, and functional monomer uses also different.
Further, in formula I or II, R1 is preferably the alkyl of C14-C28, the thiazolinyl of C16, the thiazolinyl of C20 or C16-C28 arylalkyl, and X is preferably hydroxypropyl sulfonate radical.
Described beet alkali surface activator is alkyl and/or thiazolinyl and/or arylalkyl hydroxypropyl sultaine, one of ordinary skill in the art can adopt Measures compare of the prior art easily to prepare, such as: alkyl tertiary amine and/or alkenyl amide propyl group tertiary amine and/or arylalkyl tertiary amine and 3-chlorine-2-hydroxyl propanesulfonate carry out quaternary ammonium reaction, obtain final product alkyl and/or alkenyl amide propyl group and/or arylalkyl hydroxypropyl sultaine, the trimethyl-glycine of arylalkyl structure or other structures has same synthetic method.Its reaction formula is as follows:
And/or
Wherein: R1 is alkyl and/or thiazolinyl and/or arylalkyl structure.
When R1 is alkyl structure, its molecular formula is: C
nh
2n+1, wherein: n is the positive integer of 14-28;
When R1 is alkenyl structures, its molecular formula is: CH
3(CH
2)
7cH=CH (CH
2)
6or CH
3(CH
2)
7cH=CH (CH
2)
10;
When R1 is arylalkyl structure, the skeleton symbol that aromatic base is positioned on main chain is:
CH
3(CH
2)m-R-（CH2)p
Wherein: m, p are zero or positive integer, and R is phenyl ring or naphthalene nucleus, and total carbon number of aryl and alkyl structure is 16-28.
When R1 is arylalkyl structure, the skeleton symbol that aromatic base is positioned on side chain is:
Wherein: q, s are zero or positive integer, and R ＇ is benzene, alkylbenzene, naphthalene, alkylnaphthalene etc., and total carbon number of aryl and alkyl structure is 16-28.
Further, nonionogenic tenside has the structure of general formula III or IV:
Wherein: R2 is selected from the one in alkyl, thiazolinyl, arylalkyl and alkylaryl alkyl, and p is selected from 0,1,2 ... the positive integer of 50, q is selected from 5,6,7 ... the positive integer of 50.
Further, in general structure III or IV, R2 is preferably the alkyl of C13-C29 or the arylalkyl of C13-C29, and p is preferably 5,6,7 ... the positive integer of 15, q is preferably 10,11,12 ... the positive integer of 30.
As preferably, described nonionogenic tenside is selected from aliphatic alcohol polyethenoxy (10-25) ether, fatty alcohol polyoxypropylene (5-15) polyoxyethylene (10-30) ether, isomery alcohol polyoxyethylene (10-25) ether, isomery alcohol polyoxypropylene (5-15) polyoxyethylene (10-30) ether, m-xylene base octodecyl alcohol polyoxyethylene (10-25) ether, m-xylene base stearyl alcohol polyoxypropylene (5-15) polyoxyethylene (10-30) ether, alkylaryl alkyl polyoxyethylene (10-25) ether and alkylaryl alkyl polyoxypropylene (5-15) polyoxyethylene (10-30) ether, m-xylene base octadecane carboxylic acid polyoxyethylene (10-25)) one in ester and m-xylene base octadecane carboxylic acid polyoxypropylene (5-15) polyoxyethylene (10-30) ester, the polymerization degree scope of each polymkeric substance of the numeric representation in its bracket, lower same.
The described nonionogenic tenside ring-opening reaction that to be fatty alcohol and/or arylalkyl alcohol and/or arylalkyl carboxylic acids and propylene oxide and/or oxyethane carry out under acid or basic catalyst, is easier to realize in ethoxylation device.
Further, described wet concentration injects the one of sewage from surface water, underground water or oil field.
In above all technical schemes, by weight percentage, described combination flooding composition also comprises short carbon chain alcohol and/or the short carbon chain alcohol Soxylat A 25-7 of 0.01-0.2%.
Further, described short carbon chain alcohol and/or short carbon chain alcohol Soxylat A 25-7 are selected from one or more in n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, primary isoamyl alcohol, propylene glycol, glycerol, ethylene glycol, propyl carbinol Soxylat A 25-7 and n-hexyl alcohol Soxylat A 25-7.
Described propyl carbinol Soxylat A 25-7 is propyl carbinol polyoxyethylene (2) ether, and described n-hexyl alcohol Soxylat A 25-7 is n-hexyl alcohol polyoxyethylene (6) ether.
Another technical purpose of the present invention is to provide described alkali-free compound flooding composition improving the application in oil recovery factor for middle and low permeable reservoir.Be inject mineral oil reservoir by least a bite Injection Well, and from described oil reservoir, extract crude oil by least a bite recovery well out.
Beneficial effect of the present invention:
The first, alkali-free compound flooding composition of the present invention utilizes functional polymer surfactant molecule and beet alkali surface activator molecule to form orderly aggregate, increases system viscosity, controls mobility, improves swept volume; Beet alkali surface activator reduces interfacial tension, starts irreducible oil; The strong electrostatic repulsion of polar functionalities group and the sterically hindered of non-ionic surfactant polyoxyethylene chain strong aquation adsorption layer in functional polymer tensio-active agent simultaneously, self-assembly forms macromolecule micelle, increases substantially displacement efficiency.Nonionogenic tenside plays the effect of solubilising beet alkali surface activator, can play reinforced effects again to emulsification, wetting etc. simultaneously.Said composition achieves the multiple mechanism of chemical flooding when alkali-free and non-polymer, improve oil recovery factor for middle and low permeable reservoir.
The second, alkali-free compound flooding composition composition of the present invention is conventional, and be easy to get, cost is low, has certain economic benefit.
Embodiment
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
Embodiment 1
(1) beet alkali surface activator: octadecyl hydroxypropyl sultaine: the mixture of m-xylene base octadecyl hydroxypropyl sultaine=50:50 (w/w).
Octadecyl hydroxypropyl sultaine: octadecyl tertiary amine and 3-chlorine-2-hydroxyl propanesulfonate proportioning are 1:1.1 (mol ratio), and 125 DEG C of methyl alcohol make solvent, and carry out quaternary ammonium reaction 8 hours, separating methanol obtains;
M-xylene base octadecyl hydroxypropyl sultaine: oil recovery National Key Laboratory provides by raising.
(2) functional polymer tensio-active agent: cause copolyreaction by acrylamide monomer, Acrylic Acid Monomer and vinylformic acid polyoxyethylene (9) alkyl ester three kinds of monomers by free radical and obtain: add acrylamide monomer, hydrophilic monomer vinylformic acid, functional monomer vinylformic acid polyoxyethylene (9) alkyl fat and sodium carbonate in there-necked flask, be dissolved in deionized water, add sodium formiate and ammoniacal liquor, total mass is 30% of there-necked flask volume; Adding Diisopropyl azodicarboxylate, sodium pyrosulfate and Sodium Persulfate under nitrogen protection, is 0.05% of total mass; Sealed reaction 3h after deoxidation 10min, dries the gel of synthesis and pulverizes, obtain product.
(3) nonionogenic tenside: m-xylene base octadecane carboxylic acid polyoxypropylene (9) polyoxyethylene (18) ester (from synthesis): m-xylene and oleic acid carry out Friedel-Crafts alkylation and obtains m-xylene base octadecane carboxylic acid under an acidic catalyst effect, under basic catalyst effect, carry out addition reaction with propylene oxide and oxyethane again, obtain product.
The composition of alkali-free compound flooding composition of the present invention:
Beet alkali surface activator (from synthesis) 0.215%
Functional polymer tensio-active agent (from synthesis) 0.085%
Nonionogenic tenside (from synthesis) 0.085%
All the other are water.
Application examples 1
The alkali-free compound flooding composition of Application Example 1 carries out Berea core oil displacement experiment:
Berea core oil displacement experiment carries out according to People's Republic of China (PRC) oil and gas industry standard SY/T6424-2000.Experiment oil is grand celebration one factory simulated oil, and experimental water is grand celebration one factory Simulated Water, experimental temperature 45 DEG C.When water drive to moisture 100% time inject the alkali-free compound flooding composition of the embodiment 1 of 0.7 times of volume of voids (PV), then carry out water drive to moisture 100% time terminate.
Berea core parameter is as shown in table 1:
The Berea core parameter of table 1. application examples 1
The alkali-free compound flooding composition of embodiment 1 is utilized to carry out Berea core oil displacement experiment result as shown in table 2:
The oil displacement experiment result of the alkali-free compound flooding composition of table 2. embodiment 1
Embodiment 2
(1) beet alkali surface activator: octadecyl hydroxypropyl sultaine: the mixture of docosene base amidopropyl hydroxypropyl sultaine=30:70 (w/w).
The preparation of octadecyl hydroxypropyl sultaine is with embodiment 1.
Docosene base amidopropyl hydroxypropyl sultaine: erucicamide propyl group tertiary amine and 3-chlorine-2-hydroxyl propanesulfonate proportioning are 1:1.1 (mol ratio), and 125 DEG C of methyl alcohol make solvent, and carry out quaternary ammonium reaction 8 hours, separating methanol obtains.
(2) functional polymer tensio-active agent: with embodiment 1.
(3) nonionogenic tenside: m-xylene base stearyl alcohol polyoxypropylene (9) polyoxyethylene (18) ether, its preparation process is: m-xylene and Witconol 2301 carry out Friedel-Crafts alkylation under an acidic catalyst effect, obtain m-xylene base octadecane carboxylate methyl ester, under hydrogenation catalyst effect, carry out reduction reaction again generate m-xylene base Stearyl alcohol, under basic catalyst, carry out addition reaction with propylene oxide and oxyethane again, obtain product.
The composition of alkali-free compound flooding composition of the present invention:
Beet alkali surface activator (from synthesis) 0.215%
Functional polymer tensio-active agent (from synthesis, with embodiment 1) 0.085%
Nonionogenic tenside (from synthesis) 0.085%
All the other are water.
Application examples 2
The alkali-free compound flooding composition of Application Example 2 carries out Berea core oil displacement experiment:
Berea core oil displacement experiment carries out according to People's Republic of China (PRC) oil and gas industry standard SY/T6424-2000.Experiment oil is grand celebration one factory simulated oil, and experimental water is grand celebration one factory Simulated Water, experimental temperature 45 DEG C.When water drive to moisture 100% time inject the alkali-free compound flooding composition of the embodiment 2 of 0.7 times of volume of voids (PV), then carry out water drive to moisture 100% time terminate.
Berea core parameter is as shown in table 3:
The Berea core parameter of table 3. application examples 2
The alkali-free compound flooding composition of embodiment 2 is utilized to carry out Berea core oil displacement experiment result as shown in table 4:
The oil displacement experiment result of the alkali-free compound flooding composition of table 4. embodiment 2
Embodiment 3
(1) beet alkali surface activator: octadecyl hydroxypropyl sultaine: the mixture of m-xylene base stearylamide propyl group hydroxypropyl sultaine=40:60 (w/w).
The preparation of octadecyl hydroxypropyl sultaine is with embodiment 1.
M-xylene base stearylamide propyl group hydroxypropyl sultaine: m-xylene and oleic acid carry out Friedel-Crafts alkylation under an acidic catalyst effect, obtain m-xylene base octadecane carboxylic acid, again with N, N-dimethyl propylamine carries out amidate action, obtain m-xylene base stearylamide propyl group tertiary amine, then be 1:1.1 (mol ratio) with 3-chlorine-2-hydroxyl propanesulfonate proportioning, 125 DEG C of methyl alcohol make solvent, carry out quaternary ammonium reaction 8 hours, separating methanol obtains product.
(2) functional polymer tensio-active agent: with embodiment 1.
(3) nonionogenic tenside: octadecyl polyoxypropylene (5) polyoxyethylene (20) ether, is provided by Tianjin University of Technology.
The composition of alkali-free compound flooding composition of the present invention:
Beet alkali surface activator (from synthesis) 0.215%
Functional polymer tensio-active agent (from synthesis, with embodiment 1) 0.085%
Nonionogenic tenside 0.085%
All the other are water.
Application examples 3
The alkali-free compound flooding composition of Application Example 3 carries out Berea core oil displacement experiment:
Berea core oil displacement experiment carries out according to People's Republic of China (PRC) oil and gas industry standard SY/T6424-2000.Experiment oil is grand celebration one factory simulated oil, and experimental water is grand celebration one factory Simulated Water.When water drive to moisture 100% time inject the alkali-free compound flooding composition of the embodiment 3 of 0.7 times of volume of voids (PV), then carry out water drive to moisture 100% time terminate.
Berea core parameter is as shown in table 5:
The Berea core parameter of table 5. application examples 3
The alkali-free compound flooding composition of embodiment 3 is utilized to carry out Berea core oil displacement experiment result as shown in table 6:
The oil displacement experiment result of the alkali-free compound flooding composition of table 6. embodiment 3
Claims (8)
1. be applicable to an alkali-free compound flooding composition for middle and low permeable reservoir, it is characterized in that: by weight percentage, described alkali-free compound flooding composition comprises the composition of following composition:
Beet alkali surface activator 0.03-0.5%
Functional polymer tensio-active agent 0.01-0.3%
Nonionogenic tenside 0.01-0.3%
Surplus is water;
Described functional polymer tensio-active agent, is selected from the one in the multipolymer of acrylamide monomer and/or hydrophilic monomer and/or functional monomer;
Described beet alkali surface activator, has the structure of formula I or II:
Wherein: R1 is selected from alkyl, thiazolinyl, alkyl polyoxyethylene base, arylalkyl and arylalkyl polyoxyethylene groups;
X is selected from ethyl sulfonic acid root, propanesulfonic acid root, hydroxypropyl sulfonate radical, acetate moiety or propionate.
2. alkali-free compound flooding composition according to claim 1, is characterized in that: described hydrophilic monomer is selected from one or more in vinylformic acid, acrylate, methacrylic acid, methacrylate, 2-methacrylic acid, 2-methacrylate, methylene-succinic acid, itaconate, toxilic acid, maleate, vinyl sulfonic acid, vinylsulfonate, 2-alkenyl benzene sulfonic acid, 2-alkenyl benzene sulfonic acid salt, styrene sulfonic acid, styrene sulfonate, allyl sulphonic acid and allylsulfonate.
3. alkali-free compound flooding composition according to claim 1, is characterized in that: described functional monomer is selected from 2-acrylamide-2-methyl propane sulfonic, 2-acrylamide-2-methyl propane sulfonic salt, N-allyl benzene ethanamide, N, N-dimethyl-N-allyl group cetyl chloride ammonium, N, N-diallyl para toluene sulfonamide, allyl group para toluene sulfonamide, phenylacetamide, allyl group cetyl chloride ammonium, 3-acrylamide imido grpup-3 Methylbutanoic acid, 3-acrylamide imido grpup-3 Methylbutanoic acid salt, 2-acryloxy-2-methyl propane sulfonic acid, 2-acryloxy-2-methyl propane sulfonic acid salt, 1-allyloxy-2-hydroxypropanesulfonic acid, 1-allyloxy-2-hydroxypropanesulfonic acid salt, NVP, dialkyl aminoalkyl (methyl) acrylate, the quaternary amine of dialkyl aminoalkyl (methyl) acrylate, the acid salt of dialkyl aminoalkyl (methyl) acrylate, dialkyl aminoalkyl (methyl) acrylamide, the quaternary amine of dialkyl aminoalkyl (methyl) acrylamide, the acid salt of dialkyl aminoalkyl (methyl) acrylamide, diallyldialkylammonium halide, vinylbenzene, Hydroxyethyl acrylate, C1-30 alkyl (methyl) acrylate, polyvinyl alcohol and one or more in the polyxyethylated ester of (methyl) vinylformic acid.
4. alkali-free compound flooding composition according to claim 1, is characterized in that: described nonionogenic tenside has the structure of general formula III or IV:
Wherein: R2 is selected from the one in alkyl, thiazolinyl, arylalkyl and alkylaryl alkyl, and p is selected from 0,1,2 ... the positive integer of 50, q is selected from 5,6,7 ... the positive integer of 50.
5. alkali-free compound flooding composition according to claim 1, is characterized in that: described wet concentration injects the one of sewage from surface water, underground water or oil field.
6. the alkali-free compound flooding composition according to claim 1 any one, is characterized in that: by weight percentage, also comprises short carbon chain alcohol and/or the short carbon chain alcohol Soxylat A 25-7 of 0.01-0.2%.
7. alkali-free compound flooding composition according to claim 6, is characterized in that: described short carbon chain alcohol and/or short carbon chain alcohol Soxylat A 25-7 are selected from one or more in n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, primary isoamyl alcohol, propylene glycol, glycerol, ethylene glycol, propyl carbinol Soxylat A 25-7 and n-hexyl alcohol Soxylat A 25-7.
8. the alkali-free compound flooding composition described in claim 1 ~ 7 any one is used for middle and low permeable reservoir and is improving the application in oil recovery factor.
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Application publication date: 20150128 |