CN115725288B - Surfactant composition, wettability regulator, and preparation method and application thereof - Google Patents
Surfactant composition, wettability regulator, and preparation method and application thereof Download PDFInfo
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 141
- 239000000203 mixture Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 69
- 229920000570 polyether Polymers 0.000 claims description 69
- 239000002736 nonionic surfactant Substances 0.000 claims description 60
- 125000000217 alkyl group Chemical group 0.000 claims description 49
- 239000003093 cationic surfactant Substances 0.000 claims description 37
- 239000007864 aqueous solution Substances 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 125000002947 alkylene group Chemical group 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000010779 crude oil Substances 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 14
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 101150065749 Churc1 gene Proteins 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- 102100038239 Protein Churchill Human genes 0.000 claims description 4
- 238000011161 development Methods 0.000 claims description 4
- -1 halogen ion Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 239000011435 rock Substances 0.000 abstract description 17
- 230000035699 permeability Effects 0.000 abstract description 13
- 238000005213 imbibition Methods 0.000 abstract description 10
- 238000011084 recovery Methods 0.000 abstract description 10
- 238000006073 displacement reaction Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 229920006395 saturated elastomer Polymers 0.000 abstract description 4
- 239000003921 oil Substances 0.000 description 20
- 230000033558 biomineral tissue development Effects 0.000 description 19
- 229910001425 magnesium ion Inorganic materials 0.000 description 19
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 17
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 17
- 239000011575 calcium Substances 0.000 description 17
- 229910001424 calcium ion Inorganic materials 0.000 description 17
- 239000008398 formation water Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- 238000000502 dialysis Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 125000001453 quaternary ammonium group Chemical group 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000009738 saturating Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 2
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000001450 anions Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
Abstract
The invention provides a surfactant composition, a wettability regulator, a preparation method and application thereof, and a surfactant composition, a preparation method and application thereof. The surfactant composition can regulate and control the oil-wet saturated rock core into weak water-wet, promote the imbibition and oil displacement effects, and greatly improve the recovery ratio of the ultralow permeability reservoir.
Description
Technical Field
The invention relates to the technical field of low-permeability oil reservoirs, in particular to a surfactant composition, a wettability regulator, a preparation method and application thereof.
Background
Low permeability reservoirs refer to crude oil reservoirs with lower porosity and poorer permeabilityA layer. The permeability of the hypotonic oil field is generally 10×10 according to international standards -3 μm 2 ～50×10 -3 μm 2 The permeability of ultra-low permeability oil fields is generally 1×10 -3 μm 2 ～10×10 -3 μm 2 The permeability of ultra-low permeability oil fields is generally less than 1X 10 -3 μm 2 . The pore throat radius of the ultralow permeability reservoir is very small, so that oil and water are difficult to enter pores, and the ultralow permeability reservoir belongs to the very compact low permeability reservoir. The water saturation is generally greater than 50%, the natural productivity is basically not generated, and large-scale fracturing measures and high-tech technologies are required to be economically beneficial. Development difficulties of ultra-low permeability fields and ultra-low permeability fields are relatively greater. The hypotonic oil reservoir has huge resource potential and great exploration and development difficulty, and is the focus of attention of the present domestic and foreign specialists. The wettability is an important characteristic of oil reservoir rock and controls the position, distribution state and flow characteristic of a fluid area. The reservoir, after fracturing, will be converted from a single pore medium system to a dual medium system. In a fracture system, the main power of oil displacement is driving pressure difference and gravity; in matrix systems, the primary motive force for displacement of oil is capillary force. When the rock wettability is hydrophilic-weakly hydrophilic, the capillary force is more pronounced for driving crude oil. Water enters the matrix rock mass containing oil from the fracture under the action of capillary force, and crude oil in the matrix rock mass is displaced through oil-water displacement, and the process is called imbibition displacement. The research on the effect of the imbibition phenomenon in the low-permeability oil reservoir has important significance for improving the crude oil recovery rate of the low-permeability oil reservoir, in particular to the ultra-low-permeability oil reservoir.
The surfactant has hydrophilic and lipophilic groups, and can obviously change the physicochemical properties of the surface (interface) when the addition amount is small, thereby generating a series of application functions. The wettability of the reservoir can be effectively regulated and controlled by utilizing a proper surfactant in the ultralow permeability reservoir, so that the imbibition effect is affected, and the crude oil recovery ratio is improved. BABADAGLI (SPE 84866, 2003) measured imbibition efficacy in spontaneous imbibition experiments of surfactants using harvest rate and final recovery. Experiments show that the nonionic surfactant can increase the recovery speed and the final recovery ratio of heavy oil in water-wet sandstone. Han Dong, pengjiang, etc. (university of petroleum: natural science edition, 2009, 33 (6): 142-147; oil and gas geology and recovery ratio, 2010, 17 (4): 48-51) have studied water wet sandstone and neutral sandstone, respectively, and the results show that the imbibition effect of anionic surfactants is better than other types of surfactants for water wet sandstone and neutral sandstone.
In summary, the surfactant for imbibition displacement in the prior art has the problems of high use concentration, low imbibition displacement efficiency and the like.
Disclosure of Invention
Aiming at the problems of high use concentration, low imbibition and oil displacement efficiency and the like of the surfactant in the prior art, the invention provides a surfactant composition, a wettability regulator, a preparation method and application thereof.
The first aspect of the present invention provides a surfactant composition comprising: cationic surfactants, nonionic surfactants, and anionic-nonionic surfactants;
the cationic surfactant satisfies formula (1):
wherein R is 1 Is C 1 ～C 30 At least one of the alkyl groups of (a);
R 2 、R 3 、R 4 each independently is substituted and unsubstituted C 1 ～C 4 Preferably, the substituent comprises a hydroxy group;
M 1 an anionic or anionic group to render the cationic surfactant molecule electrically neutral;
Poly 1 is- (RO) a -, wherein, R is C 2 ～C 6 Straight chain alkylene of C 3 ～C 6 At least one of branched alkylene groups of (a) is any number from 0 to 20;
y is any number from 1 to 3;
the nonionic surfactant satisfies formula (2):
R 5 O-(Poly 2 ) x -R 6 OH
(2)
Wherein R is 5 Is C 1 ～C 30 Alkyl, C of (2) 6 ～C 30 At least one of aryl groups of (a);
R 6 is substituted and unsubstituted C 2 ～C 4 Preferably, the substituent comprises a hydroxyl group;
Poly 2 is- (R' O) b -, wherein R' is C 2 ～C 6 Straight chain of C 3 ～C 6 At least one of branched alkylene groups, b is any number from 0 to 20;
x is any number from 1 to 3;
the anionic-nonionic surfactant satisfies formula (3):
R 7 O-(Poly 3 ) z -R 8 OOC(CH 2 ) p SO 3 M 2
(3)
Wherein R is 7 Is C 1 ～C 30 Alkyl, C of (2) 6 ～C 30 At least one of aryl groups of (a);
R 8 is substituted and unsubstituted C 2 ～C 4 Preferably, the substituent comprises a hydroxyl group;
Poly 3 is- (R' O) c -, wherein, R' is C 2 ～C 6 Straight chain alkylene of C 3 ～C 6 At least one of branched alkylene groups, c is any number from 0 to 20;
z is any number from 1 to 3;
p is any number from 1 to 5;
M 2 for making anionic-nonionic surfactants electrically neutral cations or cationsA child group.
According to the invention, the cationic surfactant (polyether quaternary ammonium surfactant) and the anionic-nonionic surfactant (polyether sulfonate surfactant) are compounded, and as the anionic head group has a strong electrostatic effect, the compound system has lower critical micelle concentration, limited occupied area and better interfacial activity, is favorable for stripping organic matters adsorbed on the rock surface at low concentration, reduces the water-wet surface and promotes dialysis. Nonionic surfactant helps promote interaction of hydrophobic chains of surfactant molecules with hydrophobic groups in crude oil to form a bilayer adsorption structure, so that wettability of the rock surface is reversed.
According to some embodiments of the surfactant composition of the present invention, R in the cationic surfactant represented by formula (1) 1 Is C 1 ～C 22 At least one of the alkyl groups of (a), preferably R 1 Is C 12 ～C 22 At least one of the alkyl groups of (a); and/or R 2 、R 3 Each independently is C 1 ～C 4 At least one of the alkyl groups of (a); r is R 4 Is hydroxy-substituted C 1 ～C 4 At least one of the alkyl groups of (a); and/or M 1 Is halogen ion, preferably-Cl - 、-Br - and-I - At least one of (a) and (b); and/or y is 2; and/or preferably, the cationic surfactant is a polyether quaternary ammonium surfactant, more preferably a long chain alkyl dimethyl polyether ammonium chloride surfactant.
Further, the cationic surfactant includes a polyether quaternary ammonium surfactant satisfying the formula (1A):
wherein R is 1 Is C 1 ～C 30 At least one of the alkyl groups of (a), preferably R 1 Is C 1 ～C 22 More preferably, R 1 Is C 12 ～C 22 At least one of the alkyl groups of (a); r is R 2 、R 3 、R 4 Each independently is C 1 ～C 4 Alkyl, C of (2) 1 ～C 4 At least one of the hydroxyl-substituted alkyl groups, preferably R 2 、R 3 Each independently is C 1 ～C 4 At least one of the alkyl groups, R 4 Is hydroxy-substituted C 1 ～C 4 At least one of the alkyl groups of (a); x is an anion or anionic group that renders the cationic surfactant molecule electrically neutral, j is the reciprocal of the absolute value of the valence of X, preferably X is a halide, more preferably-Cl - 、-Br - and-I - At least one of them.
Further, X may be-Cl - J is 1; a1 is any number from 0 to 10, and a2 is any number from 0 to 10.
According to some embodiments of the surfactant composition of the present invention, R in the nonionic surfactant represented by formula (2) 5 Is C 1 ～C 20 Alkyl, C of (2) 6 ～C 20 At least one of the aryl groups of (a), preferably R 5 Is C 8 ～C 20 Alkyl, C of (2) 8 ～C 20 At least one of aryl groups of (a); and/or R 6 Is C 2 ～C 4 At least one of alkylene groups of (a); and/or b is 6 to 12; and/or x is 2; and/or preferably, the nonionic surfactant is an alkyl polyether surfactant.
Further, the nonionic surfactant satisfies formula (2A):
R 5 O(CHCH 3 CH 2 O) m (CH 2 CH 2 O) n R 6 OH
(2A)
Wherein R is 5 Is C 1 ～C 30 Alkyl, C of (2) 1 ～C 30 At least one of the aryl groups of (a), preferably R 5 Is C 1 ～C 20 Alkyl, C of (2) 1 ～C 20 At least one of the aryl groups of (a), more preferably, R 5 Is C 8 ～C 20 Alkyl, C of (2) 8 ～C 20 At least one of aryl groups of (a); r is R 6 Is C 2 ～C 4 Alkylene group, C 2 ～C 4 At least one of the hydroxyl-substituted alkylene groups, preferably R 6 Is C 2 ～C 4 At least one of alkylene groups of (a); m is any number from 0 to 20, preferably m is any number from 0 to 10, in particular m is the sum of the propoxy groups; n is any number from 0 to 20, preferably n is any number from 2 to 10, in particular n is the sum of the ethoxy groups.
According to some embodiments of the surfactant composition of the present invention, R in the anionic-nonionic surfactant represented by formula (3) 7 Is C 1 ～C 20 Alkyl, C of (2) 6 ～C 20 At least one of the aryl groups of (a), preferably R 7 Is C 8 ～C 20 Alkyl, C of (2) 8 ～C 20 At least one of aryl groups of (a); and/or R 8 Is C 2 ～C 4 At least one of alkylene groups of (a); and/or z is 2 and/or p is 2 to 5; and/or M 2 Is at least one of ammonium ion and alkali metal ion.
Further, the anionic-nonionic surfactant is a polyether sulfonate surfactant satisfying formula (3A):
R 7 O(CHCH 3 CH 2 O) m’ (CH 2 CH 2 O) n’ R 8 OOC(CH 2 ) p SO 3 M 2
(3A)
Wherein R is 7 Is C 1 ～C 30 Alkyl, C of (2) 1 ～C 30 At least one of the aryl groups of (a), preferably R 7 Is C 1 ～C 20 Alkyl, C of (2) 1 ～C 20 At least one of the aryl groups of (a), more preferably, R 7 Is C 8 ～C 20 Alkyl, C of (2) 8 ～C 20 At least one of aryl groups of (a); r is R 8 Is C 2 ～C 4 Alkylene group, C 2 ～C 4 In alkylene radicals containing hydroxy substituentsAt least one of R, preferably 8 Is C 2 ～C 4 At least one of alkylene groups of (a); m ' is any number from 0 to 20, preferably m ' is any number from 0 to 10, in particular m ' is the sum of the propoxy groups; n ' is any number from 0 to 20, preferably n ' is any number from 2 to 10, in particular n ' is the sum of the ethoxy groups; p is any number from 1 to 5, preferably p is 2 to 5; m is M 2 For the anionic-nonionic surfactant to be electrically neutral cationic or cationic groups, preferably M 2 Is at least one of ammonium ion and alkali metal ion.
According to some embodiments of the surfactant composition of the present invention, in the formula (2) and formula (2A), the R 5 、R 6 Each independently is C 2 ～C 3 Straight chain alkylene of C 3 At least one of branched alkylene groups; and/or in the formula (3) and formula (3A), the R 7 、R 8 Each independently is C 2 ～C 3 Straight chain alkylene of C 3 At least one of branched alkylene groups; and/or preferably, the anionic-nonionic surfactant is a polyether sulfonate surfactant.
According to some embodiments of the surfactant composition of the present invention, the molar ratio of the anionic-nonionic surfactant, the nonionic surfactant and the cationic surfactant is 1: (0.01-1): (0.01 to 100), preferably 1: (0.02-0.5): (1 to 10), more preferably 1: (0.03-0.1): (1-5).
According to some embodiments of the surfactant composition of the present invention, the surfactant composition further comprises who the water content is 98wt% to 99.98wt% based on the total mass of the surfactant composition.
In a second aspect, the present invention provides a process for preparing a surfactant composition comprising the steps of:
the cationic surfactant, nonionic surfactant and anionic-nonionic surfactant are mixed to form surfactant composition I. Preferably, the surfactant composition I is injected into water to be mixed, and the pH is adjusted to 7.0 to 10.0, preferably 8.0 to 9.5; wherein the mass ratio of the cationic surfactant, the nonionic surfactant and the anionic-nonionic surfactant is 1: (0.01-10): (0.01-100).
Further, the total mineralization degree of the injected water is 10000-50000 mg/L, ca 2+ +Mg 2+ The total amount is 0-1000 mg/L.
According to some embodiments of the method for preparing a surfactant composition of the present invention, the nonionic surfactant is a polyether surfactant, preferably polyoxyethylene polyoxypropylene ether.
Further, the method for preparing the polyoxyethylene polyoxypropylene ether comprises the following steps:
c is C 1 ～C 30 Mixing alkylphenol or alkyl alcohol with propylene oxide and/or ethylene oxide, and carrying out reaction I in the presence of an alkaline catalyst to obtain polyoxyethylene polyoxypropylene ether;
preferably, the alkaline catalyst is used in an amount of C in parts by weight 1 ～C 30 1 to 3wt% of alkylphenol or alkyl alcohol;
more preferably, the temperature of reaction I is 100-180deg.C and the pressure of reaction I is less than 0.60MPa gauge.
Still further, the basic catalyst may be various types of basic catalysts commonly used in the art for alkoxylation reactions, such as, but not limited to, alkali metal hydroxides.
According to some embodiments of the method for preparing a surfactant composition of the present invention, the anionic-nonionic surfactant is a polyether sulfonate surfactant, the method for preparing the polyether sulfonate surfactant comprising the steps of:
step I) selecting a polyether surfactant, preferably a polyether surfactant as described above;
step II) mixing the polyether surfactant selected in step I) with C 3 ～C 6 Is mixed with unsaturated acid and reacted II in the presence of a strongly acidic catalyst to give a catalyst having terminal double bondsPolyether, mixing the polyether with terminal double bond with sulfonating agent;
preferably, the polyether, C 3 ～C 6 The molar ratio of unsaturated acid to strongly acidic catalyst is 1: (1-3): (0.05-0.5), wherein the mol ratio of the polyether with terminal double bond to the sulfonating agent is 1: (1-2);
more preferably, the sulfonating agent is at least one of sulfurous acid, sulfite, and bisulfite.
Further, the strong acid catalyst may be various types of strong acid catalysts commonly used in the art for esterification reactions, such as, but not limited to, concentrated sulfuric acid.
Further, the reaction in step II) is carried out in the presence of a strongly acidic catalyst to give a polyether having terminal double bonds, the temperature of reaction II being from 30 to 90 ℃, preferably from 60 to 90 ℃, more preferably from 80 to 90 ℃.
Still further, the sulfonating agent is at least one of sulfurous acid, sulfite and bisulfite, preferably, the sulfonating agent is at least one of sulfite and bisulfite, more preferably, the sulfonating agent is at least one of ammonium sulfite, sodium sulfite and potassium sulfite; and mixing the polyether with terminal double bonds with a sulfonating agent, and then carrying out a reaction III to obtain the polyoxyethylene polyoxypropylene ether sulfonate, wherein the temperature of the reaction III is 30-60 ℃, and preferably 30-50 ℃.
Specifically, in the step II), the polyether with terminal double bonds is mixed with a sulfonating agent, stirred at a certain temperature for reaction, solvent water is distilled off, the crude product is extracted by an ethanol/water mixed solvent, and the solvent is removed, so as to obtain the polyoxyethylene polyoxypropylene ether sulfonate.
A third aspect of the present invention provides a wettability modulator comprising a surfactant composition as defined in any one of the preceding claims or a surfactant composition prepared by a method of preparation as defined in any one of the preceding claims;
preferably, in the surfactant composition, the anionic-nonionic surfactant is used in an amount of 0.1 to 0.3wt% of the wettability regulator, and the cationic surfactant is used in an amount of 0.02 to 0.15wt% of the wettability regulator.
In a fourth aspect the present invention provides the use of a surfactant composition or a process for preparing a surfactant composition as described above in the development of a hypotonic, ultra hypotonic reservoir; preferably, the surfactant composition is injected into the reservoir formation in the form of an aqueous solution by fracturing, and after a period of time, the subsurface crude oil is drained from the matrix pores to enhance the yield of the hypotonic, ultra hypotonic reservoir.
The surfactant can be used for being distributed with other oil extraction agents.
The invention has the beneficial effects that:
after the anionic-nonionic, nonionic and cationic surfactant (polyether quaternary ammonium surfactant) composition is adopted, and the anionic-nonionic and polyether quaternary ammonium surfactant is compounded, the problem that the interfacial film is loose in arrangement and the like due to electrostatic repulsion between the same charges of the traditional surfactant can be avoided due to the fact that nonionic fragments exist in the anionic surfactant and the cationic surfactant, so that the interfacial activity of a compound system is enhanced, crude oil is effectively stripped, and the wettability of an oil reservoir is improved. The added small amount of nonionic surfactant can promote the interaction of the anionic surfactant and crude oil to form a bilayer, and a hydrophilic surface is constructed to realize wettability reversal. The anionic and cationic surfactant compound system also enhances the calcium and magnesium ion resistance of the surfactant composition, so that the surfactant composition has the possibility of being applied to high-mineralization oil reservoirs.
The surfactant composition capable of improving the recovery ratio can be used for stratum with the temperature of 40 ℃ and the mineralization degree of 3 multiplied by 10 4 The water drop contact angle of the northwest-cutting rock core soaked in the wettability regulator after the crude oil aging is measured by using 0.1-0.3 wt% of polyether sulfonate, 0.01-0.03wt% of nonionic surfactant and 0.02-0.15 wt% of alkyl polyether quaternary ammonium salt to form the wettability regulator of the surfactant composition in mg/L and 600mg/L of calcium-magnesium ions and crude oil. Through wettability regulatorThe saturated rock core has weak wettability, the dialysis recovery ratio can reach 10-20%, and a better technical effect is obtained.
Detailed Description
In order that the invention may be more readily understood, the invention will be described in detail below with reference to the following examples, which are given by way of illustration only and are not limiting of the scope of application of the invention.
[ preparation of surfactant composition ]
The surfactant compositions/surfactants of the examples and comparative examples of the present invention were prepared by a method comprising or similar to the following steps, and the compositions of the examples each satisfy the above general formula.
It should be noted that the raw materials selected in the examples of the present invention are commercially available conventional products, and the purity is chemically pure/analytically pure, and the present invention is not limited thereto.
The method comprises the following specific steps:
step 1) adding a certain amount of alkyl alcohol or alkylphenol and 1% KOH by weight into a polymerization reaction kettle, heating the system to 80-90 ℃ under stirring, starting a vacuum system, dehydrating under high vacuum for 1 hour, then purging with nitrogen for 3-4 times to remove air in the system, then slowly introducing calculated amount of propylene oxide to control the reaction pressure to be less than 0.40MPa after the reaction temperature of the system is adjusted to 130 ℃ for propoxylation and alkylation, continuously slowly introducing calculated amount of ethylene oxide after the reaction is finished, purging with nitrogen to remove unreacted ethylene oxide, and neutralizing, decolorizing, filtering and dehydrating after cooling to obtain polyoxypropylene polyoxyethylene ether with different polymerization degrees.
Step 2) polyether synthesized in the step 1), acrylic acid and concentrated sulfuric acid are mixed according to a mole ratio of 1:1.2:0.1, adding the polyether into a reaction device, heating the system to 80-90 ℃ under stirring, and reacting to obtain polyether with terminal double bonds; polyether with terminal double bond and ammonium sulfite are mixed according to a mol ratio of 1:1.1, stirring and reacting at 40 ℃, evaporating solvent water, extracting a crude product by using an ethanol/water mixed solvent, and removing the solvent to obtain the polyoxyethylene polyoxypropylene ether sulfonic acid.
Step 3) uniformly mixing the polyether sulfonate surfactant and the polyether quaternary ammonium salt surfactant synthesized in the step 2) with the calculated amount of alkali liquor and water at 50-60 ℃ to obtain the surfactant product with the required content.
[ Performance test of surfactant composition ]
1. Wettability Change Capacity test
Cutting the rock core into slices with the thickness of 3-4mm, and soaking with petroleum ether to remove residual oil in the rock core. And taking out the core slice, drying, pumping the saturated crude oil by using a vacuum pump, immersing the saturated crude oil in the Weibei crude oil for 40 hours, taking out, and wiping the crude oil on the surface. The core after saturating the crude oil was immersed in the 0.1% strength surfactant composition solution of each example, immersed for 24 hours, taken out, and the contact angle was measured after wiping off the surface liquid.
2. Static dialysis experiments
(i) And cutting, measuring, drying and weighing the rock core taken by the stratum, and carrying out a rock core saturation experiment by using a rock core saturator. The cores after saturating the crude oil were immersed in 0.5% strength surfactant composition solutions of the examples for static dialysis tests.
(ii) And cutting, measuring, drying and weighing the rock core taken by the stratum, and carrying out a rock core saturation experiment by using a rock core saturator. The cores after saturating the crude oil were immersed in a 0.5% strength solution of the surfactant composition of each comparative example for static dialysis testing.
[ example 1 ]
Alkyl alcohol polyether sulfonate, nonionic surfactant (R) 5 ＝C 8 H 17 ，R 6 ＝CH 2 CH 2 ，m＝9，n＝4，R 7 ＝R 5 ，R 8 ＝R 6 M=m ', n=n'), and alkyl polyether quaternary ammonium salt (R) 1 ＝C 22 H 45 ，R 2 ＝CH 3 ，R 3 ＝CH 3 ，R 4 ＝CH(OH)CH 3 A1=3, a2=6) surfactant was dissolved in mineralization degree 3×10, respectively 4 mg/L, 600mg/L of calcium-magnesium ion formation water, stirring for 30 minutes,is prepared into 0.1 to 0.5 percent by weight of aqueous solution, and then is prepared according to the anion-nonionic: nonionic: cationic surfactant molar ratio 1:0.05:0.6 mixing the above surfactants uniformly to obtain a surfactant composition product solution 1a having a pH of 8.0.
[ example 2 ]
Alkyl alcohol polyether sulfonate, nonionic surfactant (R) 5 ＝C 14 H 29 ，R 6 ＝CH 2 CH 2 ，m＝6，n＝2，R 7 ＝R 5 ，R 8 ＝R 6 M=m ', n=n'), and alkyl polyether quaternary ammonium salt (R) 1 ＝C 16 H 33 ，R 2 ＝CH 3 ，R 3 ＝CH 3 ，R 4 ＝CH(OH)CH 3 A1=0, a2=5) surfactant was dissolved in mineralization degree 3×10, respectively 4 Formation water of 600mg/L calcium and magnesium ions is stirred for 30 minutes to prepare 0.1 to 0.5 percent by weight of aqueous solution, and then the aqueous solution is prepared according to anion-nonionic: nonionic: cationic surfactant molar ratio 1:0.05:0.4 mixing the above surfactants uniformly to obtain a surfactant composition product solution 2a having a pH of 8.0.
[ example 3 ]
Alkyl alcohol polyether sulfonate, nonionic surfactant (R) 5 ＝C 18 H 37 ，R 6 ＝CH 2 CH 2 ，m＝0，n＝10，R 7 ＝R 5 ，R 8 ＝R 6 M=m ', n=n'), and alkyl polyether quaternary ammonium salt (R) 1 ＝C 16 H 33 ，R 2 ＝CH 3 ，R 3 ＝CH 3 ，R 4 ＝CH(OH)CH 3 A1=3, a2=5) surfactant was dissolved in mineralization degree 3×10, respectively 4 Formation water of 600mg/L calcium and magnesium ions is stirred for 30 minutes to prepare 0.1 to 0.5 percent by weight of aqueous solution, and then the aqueous solution is prepared according to anion-nonionic: nonionic: cationic surfactant molar ratio 1:0.05:0.5 mixing the above surfactants uniformly to obtain a surfactant composition product solution 3a having a pH of 9.0.
[ example 4 ]
Alkyl alcohol polyether sulfonate, notIonic surfactant (R) 5 ＝C 18 H 37 ，R 6 ＝CH 2 CH 2 CH 2 ，m＝5，n＝10，R 7 ＝R 5 ，R 8 ＝R 6 M=m ', n=n'), and alkyl polyether quaternary ammonium salt (R) 1 ＝C 16 H 33 ，R 2 ＝CH 3 ，R 3 ＝CH 3 ，R 4 ＝CH(OH)CH 3 A1=0, a2=5) surfactant was dissolved in mineralization degree 3×10, respectively 4 Formation water of 600mg/L calcium and magnesium ions is stirred for 30 minutes to prepare 0.1 to 0.5 percent by weight of aqueous solution, and then the aqueous solution is prepared according to anion-nonionic: nonionic: cationic surfactant molar ratio 1:0.1:0.8 mixing the above surfactants uniformly to obtain a surfactant composition product solution 4a with a pH of 8.5.
[ example 5 ]
Alkyl alcohol polyether sulfonate, nonionic surfactant (R) 5 ＝C 18 H 37 ，R 6 ＝CH 2 CH 2 ，m＝10，n＝6，R 7 ＝R 5 ，R 8 ＝R 6 M=m ', n=n'), and alkyl polyether quaternary ammonium salt (R) 1 ＝C 12 H 25 ，R 2 ＝CH 3 ，R 3 ＝CH 3 ，R 4 ＝CH(OH)CH 3 A1=0, a2=7) surfactant was dissolved in mineralization degree 3×10, respectively 4 Formation water of 600mg/L calcium and magnesium ions is stirred for 30 minutes to prepare 0.1 to 0.5 percent by weight of aqueous solution, and then the aqueous solution is prepared according to anion-nonionic: nonionic: cationic surfactant molar ratio 1:0.04:0.4 mixing the above surfactants uniformly to obtain a surfactant composition product solution 5a with a pH of 7.5.
[ example 6 ]
The nonylphenol polyether sulfonate and nonionic surfactant are treatedR 6 ＝CH 2 CH 2 ，m＝0，n＝6，R 7 ＝R 5 ，R 8 ＝R 6 M=m ', n=n') and alkyl polyether quaternaryAmmonium salt (R) 1 ＝C 18 H 37 ，R 2 ＝CH 3 ，R 3 ＝CH 3 ，R 4 ＝CH(OH)CH 3 A1=2, a2=9) surfactant was dissolved in mineralization degree 3×10, respectively 4 Formation water of 600mg/L calcium and magnesium ions is stirred for 30 minutes to prepare 0.1 to 0.5 percent by weight of aqueous solution, and then the aqueous solution is prepared according to anion-nonionic: nonionic: cationic surfactant molar ratio 1:0.05:0.5 mixing the above surfactants uniformly to obtain a surfactant composition product solution 6a having a pH of 8.0.
[ example 7 ]
Dodecyl phenyl polyether sulfonate, nonionic surfactant (R) 5 ＝C 18 H 29 ，R 6 ＝CH 2 CH 2 ，m＝5，n＝6，R 7 ＝R 5 ，R 8 ＝R 6 M=m ', n=n'), and alkyl polyether quaternary ammonium salt (R) 1 ＝C 14 H 29 ，R 2 ＝CH 3 ，R 3 ＝CH 3 ，R 4 ＝CH(OH)CH 3 A1=2, a2=6) surfactant was dissolved in mineralization degree 3×10, respectively 4 Formation water of 600mg/L calcium and magnesium ions is stirred for 30 minutes to prepare 0.1 to 0.5 percent by weight of aqueous solution, and then the aqueous solution is prepared according to anion-nonionic: nonionic: cationic surfactant molar ratio 1:0.05:0.7 mixing the above surfactants uniformly to obtain a surfactant composition product solution 7a having a pH of 8.0.
[ example 8 ]
Dodecyl phenol polyether sulfonate, nonionic surfactant (R) 5 ＝C 18 H 29 ，R 6 ＝CH 2 CH 2 ，m＝0，n＝6，R 7 ＝R 5 ，R 8 ＝R 6 M=m ', n=n'), and alkyl polyether quaternary ammonium salt (R) 1 ＝C 16 H 33 ，R 2 ＝CH 3 ，R 3 ＝CH 3 ，R 4 ＝CH(OH)CH 3 A1=0, a2=5) surfactant was dissolved in mineralization degree 3×10, respectively 4 The water is stirred for 30 minutes to prepare 0.1 to 0.5 percent of water soluble by weightLiquid, then according to anionic-nonionic: nonionic: cationic surfactant molar ratio 1:0.04:1.2 mixing the above surfactants uniformly to obtain a surfactant composition product solution 8a having a pH of 8.0.
[ example 9 ]
Dodecyl phenol polyether sulfonate, nonionic surfactant (R) 5 ＝C 18 H 29 ，R 6 ＝CH 2 CH 2 ，m＝0，n＝6，R 7 ＝R 5 ，R 8 ＝R 6 M=m ', n=n'), and alkyl polyether quaternary ammonium salt (R) 1 ＝C 16 H 33 ，R 2 ＝CH 3 ，R 3 ＝CH 3 ，R 4 ＝CH(OH)CH 3 A1=0, a2=5) surfactant was dissolved in mineralization degree 3×10, respectively 4 Formation water of 600mg/L calcium and magnesium ions is stirred for 30 minutes to prepare 0.1 to 0.5 percent by weight of aqueous solution, and then the aqueous solution is prepared according to anion-nonionic: nonionic: cationic surfactant molar ratio 1:0.04:1.2 mixing the above surfactants uniformly to obtain a surfactant composition product solution 9a having a pH of 8.0.
[ example 10 ]
Alkyl alcohol polyether sulfonate, nonionic surfactant (R) 5 ＝C 14 H 29 ，R 6 ＝CH 2 CH 2 ，m＝6，n＝2，R 7 ＝C 18 H 37 ，R 8 ＝CH 2 CH 2 M '=0, n' =10) and alkyl polyether quaternary ammonium salt (R 1 ＝C 16 H 33 ，R 2 ＝CH 3 ，R 3 ＝CH 3 ，R 4 ＝CH(OH)CH 3 A1=0, a2=5) surfactant was dissolved in mineralization degree 3×10, respectively 4 Formation water of 600mg/L calcium and magnesium ions is stirred for 30 minutes to prepare 0.1 to 0.5 percent by weight of aqueous solution, and then the aqueous solution is prepared according to anion-nonionic: nonionic: cationic surfactant molar ratio 1:0.05:0.4 mixing the above surfactants uniformly to obtain a surfactant composition product solution 10a having a pH of 8.0.
Comparative example 1
According to patent CN105884255A method of dissolving nonionic surfactant OP-10 in a mineralizer having a degree of mineralization of 3X 10 4 In the formation water of mg/L and 600mg/L of calcium and magnesium ions, 0.5 wt% of aqueous solution is prepared. Stirring for 30 min, and mixing to obtain reference surfactant composition 1b.
Comparative example 2
Alkyl alcohol polyether sulfonate (R) 5 ＝C 14 H 29 ，R 6 ＝CH 2 CH 2 M=6, n=2) surfactant and alkyl polyether quaternary ammonium salt (R 1 ＝C 16 H 33 ，R 2 ＝CH 3 ，R 3 ＝CH 3 ，R 4 ＝CH(OH)CH 3 A1=0, a2=5) surfactant was dissolved in mineralization degree 3×10, respectively 4 Formation water of 600mg/L calcium and magnesium ions is stirred for 30 minutes to prepare 0.5 wt% of aqueous solution, and then anions are used as follows: cationic surfactant molar ratio 1: and 0.4, uniformly mixing the surfactant to obtain a surfactant composition product solution 2b.
[ comparative example 3 ]
Alkyl alcohol polyether sulfonate, nonionic surfactant (R) 5 ＝C 14 H 29 ，R 6 ＝CH 2 CH 2 ，m＝6，n＝2，R 7 ＝R 5 ，R 8 ＝R 6 M=m ', n=n'), and alkyl polyether quaternary ammonium salt (R) 1 ＝C 16 H 33 ，R 2 ＝CH 3 ，R 3 ＝CH 3 ，R 4 ＝CH(OH)CH 3 A1=0, a2=5) surfactant was dissolved in mineralization degree 3×10, respectively 4 Formation water of 600mg/L calcium and magnesium ions is stirred for 30 minutes to prepare 0.1 to 0.5 percent by weight of aqueous solution, and then the aqueous solution is prepared according to anion-nonionic: nonionic: cationic surfactant molar ratio 1:0.05:0.4 mixing the above surfactants uniformly to obtain a surfactant composition product solution 3b having a pH of 11.0.
[ comparative example 4 ]
Alkyl alcohol polyether sulfonate, nonionic surfactant (R) 5 ＝C 14 H 29 ，R 6 ＝CH 2 CH 2 ，m＝6，n＝2，R 7 ＝R 5 ，R 8 ＝R 6 M=m ', n=n'), and alkyl polyether quaternary ammonium salt (R) 1 ＝C 16 H 33 ，R 2 ＝CH 3 ，R 3 ＝CH 3 ，R 4 ＝CH(OH)CH 3 A1=0, a2=5) surfactant was dissolved in mineralization degree 3×10, respectively 4 Formation water of 600mg/L calcium and magnesium ions is stirred for 30 minutes to prepare 0.1 to 0.5 percent by weight of aqueous solution, and then the aqueous solution is prepared according to anion-nonionic: nonionic: cationic surfactant molar ratio 1:0.05:0.4 mixing the above surfactants uniformly to obtain a surfactant composition product solution 4b having a pH of 6.0.
As in the wettability changing ability test above, the water drop contact angle test results are shown in table 1:
TABLE 1
Wherein, test temperature: 40 ℃; formation water mineralization degree 3 x 10 4 mg/L, calcium and magnesium ions 600mg/L.
Static dialysis tests as above for each example, test results are shown in table 2:
TABLE 2
Test conditions: test temperature: 40 ℃; formation water mineralization degree 3 x 10 4 mg/L, calcium and magnesium ions 600mg/L.
The static dialysis tests as above for example 2 and each comparative example 2 are shown in table 3:
TABLE 3 Table 3
| Component (A) | Before soaking | 2a | 1b | 2b | 3b | 4b |
| Replacement efficiency | 5％ | 18％ | 8％ | 10％ | 9％ | 7％ |
Wherein, test temperature: 40 ℃; formation water mineralization degree 3 x 10 4 mg/L, calcium and magnesium ions 600mg/L.
The surfactant compositions of the invention are adopted in tables 1, 2 and 3, and the contact angle becomes smaller after soaking in the wettability test of the compound system, so that the calcium and magnesium ion resistance is enhanced, and the compound system has the possibility of being applied to high-mineralization oil reservoirs. Through static dialysis experiments, the dialysis recovery ratio can reach 10-20%.
What has been described above is merely a preferred example of the present invention. And do not constitute any limitation of the invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. It should be noted that other equivalent modifications and improvements will occur to those skilled in the art, and are intended to be within the scope of the present invention, as a matter of common general knowledge in the art, in light of the technical teaching provided by the present invention.
Claims (29)
1. A surfactant composition comprising: cationic surfactants, nonionic surfactants, and anionic-nonionic surfactants;
the cationic surfactant satisfies formula (1A):
(1A)
Wherein R is 1 Is C 1 ~C 30 At least one of the alkyl groups of (a);
R 2 、R 3 、R 4 each independently is C 1 ～C 4 Alkyl, C of (2) 1 ～C 4 At least one of the hydroxyl substituent-containing alkyl groups;
x is a halogen ion;
a1 is any number of 0 to 10, and a2 is any number of 5 to 10;
j is the reciprocal of the absolute value of the X valence;
the nonionic surfactant satisfies formula (2A):
R 5 O(CHCH 3 CH 2 O) m (CH 2 CH 2 O) n R 6 OH
(2A)
Wherein R is 5 Is C 1 ~C 30 Alkyl, C of (2) 6 ~C 30 At least one of aryl groups of (a);
R 6 is unsubstituted C 2 ~C 4 At least one of alkylene groups of (a);
m is any number from 0 to 20;
n is any number from 2 to 10;
the anionic-nonionic surfactant satisfies formula (3A):
R 7 O(CHCH 3 CH 2 O) m’ (CH 2 CH 2 O) n’ R 8 OOC(CH 2 ) p SO 3 M 2
(3A)
Wherein R is 7 Is C 1 ~C 30 Alkyl, C of (2) 6 ~C 30 At least one of aryl groups of (a);
R 8 is unsubstituted C 2 ~C 4 At least one of alkylene groups of (a);
m' is any number from 0 to 20;
n' is any number from 2 to 10; p is any number from 1 to 5;
M 2 is at least one of ammonium ion and alkali metal ion;
R 6 =R 8 ；
the molar ratio of the anionic-nonionic surfactant, the nonionic surfactant and the cationic surfactant is 1: (0.03 to 0.1): (0.01 to 5).
2. The surfactant composition according to claim 1, wherein R is a cationic surfactant represented by the formula (1A) 1 Is C 1 ~C 22 At least one of the alkyl groups of (a); and/or
R 2 、R 3 Each independently is C 1 ~C 4 At least one of the alkyl groups of (a); and/or
R 4 Is hydroxy-substituted C 1 ~C 4 At least one of the alkyl groups of (a); and/or
The cationic surfactant is a long-chain alkyl dimethyl polyether ammonium chloride surfactant.
3. The surfactant composition according to claim 2, wherein R1 is at least one of C12 to C22 alkyl groups.
4. The surfactant composition according to claim 1, wherein X is-Cl - 、-Br - and-I - At least one of them.
5. The surfactant composition according to any one of claims 1 to 4, wherein R in the nonionic surfactant represented by the formula (2A) 5 Is C 1 ~C 20 Alkyl, C of (2) 6 ~C 20 At least one of aryl groups of (a); and/or
The nonionic surfactant is an alkyl polyether surfactant.
6. The surfactant composition according to claim 5, wherein said R 5 Is C 8 ~C 20 Alkyl, C of (2) 8 ~C 20 At least one of the aryl groups of (a).
7. The surfactant composition according to any one of claims 1 to 4, wherein R in the anionic-nonionic surfactant represented by the formula (3A) 7 Is C 1 ~C 20 Alkyl, C of (2) 6 ~C 20 At least one of aryl groups of (a); and/or
R 8 Is C 2 ~C 4 At least one of alkylene groups of (a); and/or
p is 2 to 5.
8. The surfactant composition according to claim 7, wherein said R 7 Is C 8 ~C 20 Alkyl, C of (2) 8 ~C 20 At least one of the aryl groups of (a).
9. The surfactant composition of any of claims 1-4, further comprising:
in the formula (2A), the R 5 、R 6 Each independently is C 2 ~C 3 Straight chain alkylene of C 3 At least one of branched alkylene groups;
in the formula (3A), the R 7 、R 8 Each independently is C 2 ~C 3 Is a straight chain of (2)Alkylene, C 3 At least one of branched alkylene groups.
10. The surfactant composition of any of claims 1-4, wherein the anionic-nonionic surfactant is an alkyl polyether sulfonate surfactant.
11. The surfactant composition according to any one of claims 1 to 4, wherein the molar ratio of the anionic-nonionic surfactant, the nonionic surfactant and the cationic surfactant is 1: (0.03 to 0.1): (1-5).
12. The surfactant composition according to any of the claims 1-4, wherein the surfactant composition further comprises water,
the content of water is 98-99.98 wt% based on the total mass of the surfactant composition.
13. A process for preparing a surfactant composition according to any one of claims 1 to 12, comprising the steps of:
mixing a cationic surfactant, a nonionic surfactant, and an anionic-nonionic surfactant to form a surfactant composition I;
wherein the molar ratio of the anionic-nonionic surfactant, the nonionic surfactant and the cationic surfactant is 1: (0.03 to 0.1): (0.01 to 5).
14. The method according to claim 13, wherein the surfactant composition I is mixed with water, and the pH is adjusted to 7.0 to 10.0.
15. The method according to claim 14, wherein the pH is adjusted to 8.0 to 9.5.
16. The method of any one of claims 13-15, wherein the nonionic surfactant is a polyether surfactant.
17. The method of claim 16, wherein the nonionic surfactant is polyoxyethylene polyoxypropylene ether;
the method for preparing the polyoxyethylene polyoxypropylene ether comprises the following steps:
c is C 1 ~C 30 Mixing the alkylphenol or alkyl alcohol with propylene oxide and/or ethylene oxide, and carrying out reaction I in the presence of an alkaline catalyst to obtain the polyoxyethylene polyoxypropylene ether.
18. The preparation method according to claim 17, wherein the basic catalyst is used in an amount of C in parts by mass 1 ~C 30 1 to 3wt% of alkylphenol or alkyl alcohol.
19. The method according to claim 17 or 18, wherein the temperature of reaction I is 100-180 ℃, and the pressure of reaction I is less than 0.60MPa gauge.
20. The method of any one of claims 13-15, wherein the anionic-nonionic surfactant is a polyether sulfonate surfactant, the method of preparing the polyether sulfonate surfactant comprising the steps of:
step I) selecting polyether surfactant;
step II) mixing the polyether surfactant selected in step I) with C 3 ~C 6 And (2) carrying out reaction II in the presence of a strongly acidic catalyst to obtain polyether with terminal double bonds, and mixing the polyether with terminal double bonds with a sulfonating agent.
21. The method of claim 20, wherein the polyether surfactant is polyoxyethylene polyoxypropylene ether; preparation of the polyoxyethylene polyoxypropylene etherThe method of (1) comprises the following steps: c is C 1 ~C 30 Mixing the alkylphenol or alkyl alcohol with propylene oxide and/or ethylene oxide, and carrying out reaction I in the presence of an alkaline catalyst to obtain the polyoxyethylene polyoxypropylene ether.
22. The method according to claim 21, wherein the polyether, C 3 ~C 6 The molar ratio of unsaturated acid to strongly acidic catalyst is 1: (1-3): (0.05-0.5), wherein the mol ratio of the polyether with terminal double bond to the sulfonating agent is 1: (1-2).
23. The method of claim 21, wherein the sulfonating agent is at least one of sulfurous acid, sulfite, and bisulfite.
24. The preparation method according to claim 21, wherein the basic catalyst is used in an amount of C in parts by mass 1 ~C 30 1 to 3wt% of alkylphenol or alkyl alcohol.
25. The method of claim 24, wherein the temperature of reaction I is 100-180 ℃ and the pressure of reaction I is less than 0.60MPa gauge.
26. A wettability controlling agent comprising the surfactant composition according to any one of claims 1 to 12 or the surfactant composition produced by the production method according to any one of claims 13 to 25.
27. The wettability control agent of claim 26 wherein said surfactant composition comprises 0.1 to 0.3 wt.% of said wettability control agent per mass fraction of anionic-nonionic surfactant and 0.02 to 0.15 wt.% of said wettability control agent per mass fraction of cationic surfactant.
28. Use of a surfactant composition according to any one of claims 1-12 or a surfactant composition prepared according to the method of preparation of any one of claims 13-25 or a wettability modulator according to claim 26 or 27 in the development of hypotonic, ultra hypotonic reservoirs.
29. The use of claim 28, wherein the surfactant composition is injected into the reservoir formation as an aqueous solution by fracturing to remove subsurface crude oil from the pores of the matrix and to increase the yield of the hypotonic, ultra hypotonic reservoir.
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