CN114196388B - Surfactant system with high foam performance and ultralow oil/water interfacial tension and application thereof - Google Patents
Surfactant system with high foam performance and ultralow oil/water interfacial tension and application thereof Download PDFInfo
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- CN114196388B CN114196388B CN202111533023.5A CN202111533023A CN114196388B CN 114196388 B CN114196388 B CN 114196388B CN 202111533023 A CN202111533023 A CN 202111533023A CN 114196388 B CN114196388 B CN 114196388B
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 85
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000006260 foam Substances 0.000 title abstract description 63
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 27
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 26
- 238000005187 foaming Methods 0.000 claims abstract description 22
- 125000000129 anionic group Chemical group 0.000 claims abstract description 17
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 16
- 125000002091 cationic group Chemical group 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- -1 alkyl glycoside Chemical class 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 7
- 125000005599 alkyl carboxylate group Chemical group 0.000 claims description 4
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 229930182470 glycoside Natural products 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 150000008051 alkyl sulfates Chemical class 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 49
- 239000010779 crude oil Substances 0.000 abstract description 25
- 238000006073 displacement reaction Methods 0.000 abstract description 5
- 230000002829 reductive effect Effects 0.000 abstract description 5
- 239000012530 fluid Substances 0.000 abstract description 4
- 239000000084 colloidal system Substances 0.000 abstract description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 46
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 44
- 239000000243 solution Substances 0.000 description 28
- 239000000203 mixture Substances 0.000 description 27
- 239000008398 formation water Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 7
- 230000003993 interaction Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 229910002056 binary alloy Inorganic materials 0.000 description 3
- 230000033558 biomineral tissue development Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 229930182478 glucoside Natural products 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- UGTHTQWIQKEDEH-BQBZGAKWSA-N L-alanyl-L-prolylglycine zwitterion Chemical compound C[C@H](N)C(=O)N1CCC[C@H]1C(=O)NCC(O)=O UGTHTQWIQKEDEH-BQBZGAKWSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000002099 adlayer Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- HUWNEIYHSQPEGW-UHFFFAOYSA-N azane;4,5-dihydro-1h-imidazole Chemical class N.C1CN=CN1 HUWNEIYHSQPEGW-UHFFFAOYSA-N 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical class N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- XCOHAFVJQZPUKF-UHFFFAOYSA-M octyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](C)(C)C XCOHAFVJQZPUKF-UHFFFAOYSA-M 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229940067741 sodium octyl sulfate Drugs 0.000 description 1
- XZTJQQLJJCXOLP-UHFFFAOYSA-M sodium;decyl sulfate Chemical compound [Na+].CCCCCCCCCCOS([O-])(=O)=O XZTJQQLJJCXOLP-UHFFFAOYSA-M 0.000 description 1
- WFRKJMRGXGWHBM-UHFFFAOYSA-M sodium;octyl sulfate Chemical compound [Na+].CCCCCCCCOS([O-])(=O)=O WFRKJMRGXGWHBM-UHFFFAOYSA-M 0.000 description 1
- JZVZOOVZQIIUGY-UHFFFAOYSA-M sodium;tridecanoate Chemical compound [Na+].CCCCCCCCCCCCC([O-])=O JZVZOOVZQIIUGY-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/204—Keeping clear the surface of open water from oil spills
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention discloses a surfactant system with high foam performance and ultralow oil/water interfacial tension and application thereof, belonging to the field of colloid and interfacial chemistry. The surfactant system is compounded by common anionic, cationic and nonionic surfactants, is dissolved in Daqing stratum water, and can reduce the interfacial tension of crude oil/stratum water to be ultra-low (10) within the concentration range of 2mM to 6mM ‑5 mN/m order), and the foaming properties are excellent, the foam produced has good oil resistance, the foam integrated index increases with the increase of the total concentration of the surfactant, and the foam integrated index can reach 1,340ls at the highest. The surfactant system is suitable for foam flooding, wherein the viscosity of the surfactant solution can be greatly improved by the existence of stable foam, so that the plugging efficiency and swept volume of the displacement fluid are improved, and the saturation of residual oil can be further reduced by the ultra-low oil/water interfacial tension.
Description
Technical Field
The invention particularly relates to a surfactant system with high foam performance and ultralow oil/water interfacial tension and application thereof, belonging to the technical field of colloid and interfacial chemistry.
Background
Petroleum is an indispensable important energy source for modern society, and is an important source of chemical industry, but is not renewable. With respect to oil recovery, primary (self-injection) and secondary (water flooding) oil recovery typically only produce 30-40% of the original reserves, with residual reserves up to 60-70%, referred to as residual oil, which is typically retained in porous media and difficult to produce at conventional water injection pressures. It is evident that this fraction of the residual oil is produced by using new techniques, which are of great importance.
In recent years, tertiary oil recovery (Enhanced Oil Recovery, EOR) technology has been widely studied, with the most studied tertiary oil displacement technologies based on surfactant action including surfactant flooding, polymer flooding, surfactant-polymer flooding, alkali-surfactant-polymer (ASP) ternary complex flooding, and the like. The ASP ternary composite flooding technology is particularly concerned, is suitable for most oil fields in China, and can further improve the recovery ratio by about 20% on the basis of water flooding.
The ASP ternary complex combines the actions of three chemical agents. Wherein the surfactant (S) is used to reduce the crude oil/water interfacial tension to ultra low (< 0.01 mN/m), the polymer (P) is used to increase the viscosity of the displacement fluid, and the base (a) is capable of reacting with the active ingredients in the crude oil, producing soap-like surfactants in situ, promoting the transition of rock from oil wetting to water wetting, and inhibiting adsorption of surfactants on the rock. However, in practical use, side effects such as fouling of pipes and equipment, clogging of capillary passages, etc. caused by the use of strong alkali are gradually developed. An alternative is to use alkali-free surfactant-polymer flooding or weak base ternary complex flooding, but with these alternatives, the original surfactant is mostly ineffective or inefficient, requiring the development of new surfactants.
On the other hand, foam flooding has been attracting attention in recent years, and the mechanism is to use foam to increase the viscosity of the displacement fluid (water) so as to achieve the aims of changing the gas/crude oil fluidity ratio, preventing fingering, blocking the hypertonic layer, expanding the sweep coefficient of the displacement fluid in the hypotonic layer, and the like. Foam flooding aims to obtain stable foam, and if surfactants are used to stabilize the foam, the surfactants can also reduce the crude oil/water interfacial tension. Obviously, if the ultra-low interfacial tension can be realized at the same time, the foam flooding can achieve the effect of surfactant-polymer composite flooding.
However, in practice, it has been found that conventional commercial surfactants, such as Sodium Dodecyl Sulfate (SDS), sodium Linear Alkylbenzene Sulfonate (LAS), alpha Olefin Sulfonate (AOS), alkyl sulfonates, alkyl carboxylates (soaps), fatty alcohol polyoxyethylene ether sulfate (AES) and like small molecular weight anionic surfactants are excellent foaming agents, but they generally have difficulty reducing crude oil/water interfacial tension to ultra low and their stable foams are generally not oil resistant, i.e., antifoaming, in the case of crude oils. On the other hand, surfactants that achieve ultra-low interfacial tension generally do not produce large amounts of stable foam. Thus, excellent foaming properties and ultra-low interfacial tension appear to be counter-current and non-compatible with surfactants.
Disclosure of Invention
The present invention aims to obtain surfactant systems having both excellent foaming properties and ultra low oil/water interfacial tension. Within a certain total concentration range, the surfactant system is dissolved in Daqing stratum water, and can reduce the interfacial tension of Daqing crude oil/stratum water to be ultra-low<10 -3 mN/m), and at the same time, can produce abundant foams, and these foams have good oil resistance, do not cause rapid defoaming when contacted with crude oil, and have a high foam comprehensive index.
The first object of the present invention is to provide a surfactant which has both foaming performance and reduced oil/water interfacial tension, and which is formulated from anionic, cationic and nonionic surfactants.
In one embodiment of the invention, the anionic surfactant is of mono-alkyl chain single-head structure, including alkyl sulphates, alkyl sulphonates and alkyl carboxylates, with an alkyl chain length of C 6 To C 18 。
The anionic surfactant according to the present invention may be selected from conventional commercial surfactants widely used as foaming agents in daily chemical products, such as sodium alkyl sulfate, sodium Linear Alkylbenzenesulfonate (LAS), alpha-olefin sulfonate (AOS), alkyl sulfonate, alkyl carboxylate (soap), and fatty alcohol polyoxyethylene ether sulfate (AES), etc. These anionic surfactants are commonly characterized by a mono-alkyl, mono-head structure with an alkyl chain length of C 6 -C 18 Polyoxyethylene (EO) numbers are 2-3.
In one embodiment of the invention, the cationic surfactant is of a mono-long alkyl mono-head structure, including alkyl trimethyl quaternary ammonium salt, alkyl pyridine ammonium salt, alkyl imidazoline ammonium salt, wherein the chain length of the long alkyl group is C 6 To C 18 。
In one embodiment of the present invention, the cationic surfactant may be selected from alkyl trimethyl quaternary ammonium salts, pyridine ammonium salts and imidazoline ammonium salts. They similarly have a mono-long alkyl single head structure in which the chain length of the long alkyl group is C 6 -C 18 。
In one embodiment of the inventionThe nonionic surfactant is selected from alkyl glucoside nonionic surfactants; wherein the fatty alcohol used to prepare the glycoside has an alkyl chain length of C 8 -C 12 The degree of polymerization of glucose is 1-3.
In one embodiment of the invention, the total alkyl chain length of the anionic and cationic surfactants is C 12 To C 32 Preferred total alkyl chain length is C 16 To C 28 。
In one embodiment of the present invention, one or more anionic surfactants may be used in the mixed surfactant system at a mole fraction of 0.1 to 0.9, preferably at a mole fraction of 0.2 to 0.6.
In one embodiment of the present invention, one or more cationic surfactants may be used in the mixed surfactant system at a mole fraction of 0.1 to 0.8, preferably at a mole fraction of 0.1 to 0.5.
In one embodiment of the invention, the mole fraction of nonionic surfactant in the mixed surfactant system is from 0.1 to 0.9, preferably from 0.2 to 0.7.
In one embodiment of the invention, to prevent precipitation of anionic and cationic surfactants, the total alkyl chain length of both surfactants should be controlled at C 12 -C 32 Wherein the preferred total alkyl chain length is C 16 -C 28 . In the mixed surfactant, the alkyl chain lengths of the anionic and cationic surfactants may be equal or unequal.
In one embodiment of the present invention, the molar ratio of the total amount of anionic surfactant and cationic surfactant to nonionic surfactant is (0.3-0.9): (0.1-0.7); preferably 0.6:0.4.
in one embodiment of the invention, the molar ratio of anionic surfactant to cationic surfactant is 3:2.
In one embodiment of the invention, the molar ratio of anionic surfactant, cationic surfactant, nonionic surfactant in the surfactant system is 0.36:0.24:0.4.
the invention selects surfactants with different properties to form a compound system, wherein the different surfactants respectively play different roles, and the surfactant system is comprehensively endowed with the properties which are not available originally.
Lowering the crude oil/water interfacial tension generally requires the surfactant to reach a hydrophilic-lipophilic balance, whereas surfactants meeting this requirement generally do not possess foaming properties. For this reason, the invention adopts the anionic surfactant and cationic surfactant of small molecular weight to compound. Due to the strong electrostatic attraction interactions, anionic and cationic surfactants form closely packed adsorbed monolayers at the oil/water interface and gas/liquid interface, which is advantageous for reducing crude oil/water interface tension to ultra low and obtaining very low aqueous surface tension. In order to prevent the anionic surfactant and the cationic surfactant from forming precipitates, the invention adopts asymmetric compounding on one hand, even if the mole fraction of the anions is larger than that of the cations, and on the other hand, a nonionic surfactant is added as a solubilizer to have foam stabilizing effect.
It is a second object of the present invention to provide the use of the above surfactant system in oil recovery.
In one embodiment of the invention, the surfactant system is used in an amount of 1 to 10mmol/L relative to the target. Preferably 5-8mmol/L.
The beneficial effects are that:
because the anionic/cationic surfactants with small molecular weight are mixed and the asymmetric mixing is adopted, the problem that the solubility of the surfactants is affected due to the formation of precipitation between the anionic/cationic surfactants is avoided. In addition, the surfactant system is dissolved in Daqing stratum water at 45 ℃ to obtain transparent solution.
The surfactant system constructed according to the present invention is capable of forming an intimately aligned mixed monolayer at the oil/water interface by means of a strong attractive interaction between anionic/cationic surfactants, wherein the anionic/cationic mixture is present in the mixed monolayerThe mole fraction in the layer reaches above 0.9. The interfacial tension of Daqing crude oil/formation water can be reduced to 10 within the total concentration range of 2-6mM at 45 DEG C -3 mN/m order of magnitude lower, the lowest interfacial tension can reach 3.0X10 -5 mN/m。
Similarly, by virtue of the strongly attractive interaction between anionic/cationic surfactants, the surfactant system constructed in accordance with the present invention is capable of forming closely aligned mixed monolayers at the air/water interface, thereby significantly reducing the surface tension of water and facilitating improved foaming properties. The mole fraction of the anionic/cationic mixture in the mixed monolayer reaches above 0.9 at 45 ℃ and the lowest possible water surface tension is reduced to 19.9mN/m.
By means of the synergistic effect between different surfactants, the surfactant system constructed according to the invention can obtain extremely low air/water interfacial tension, i.e. the surface tension of water, so that the initial foam volume (V i ). On the other hand, the presence of the nonionic solubilizer further improves the stability and oil resistance of the foam. At 45 ℃, the foam comprehensive index increases with the increase of the total concentration within the range of 2-8 mM, and reaches 1,340ls at maximum and oil resistance index reaches 0.75 at maximum.
Drawings
FIG. 1 (a) is a schematic view of SDS/DTAB binary mixed surfactant dissolved in Daqing formation water, total concentration of surfactant 5mM, wherein mole fraction (. Alpha.) of cationic surfactant c ) As shown in the upper part of the figure; (b) For the appearance diagram of SDS/DTAB/APG ternary mixed surfactant dissolved in Daqing formation water, the total concentration of the surfactant is 5mM, wherein the ratio of SDS/DTAB mole fraction is fixed to be 0.6/0.4, and the mole fraction (alpha) of the nonionic surfactant is fixed to be 0.6/0.4 n ) As shown in the upper part of the figure; the temperature is 45 ℃, and the total mineralization degree of the formation water is 6,778mg/L.
FIG. 2 (a) is an initial foam volume (V) i ) And solution/Daqing crude interfacial tension (IFT) as a function of the mole fraction of cations in the mixture; (b) 2.5mL of the solution was placed in a 15mL glass bottle and hand-foamed, and the mixture was shaken up and down for 20 times, photographed after 5 minutes, 5mM total surfactant concentration, DTAB mole fraction (. Alpha.) c ) As shown in the upper part of the graph, the temperature is 45 ℃.
FIG. 3 (a) is the initial foam volume (V) i ) And solution/Daqing crude interfacial tension (IFT) as a function of nonionic surfactant mole fraction (alpha) in the mixture n ) The ratio of SDS/DTAB mole fraction was fixed at 0.6/0.4; (b) 2.5mL of the solution was placed in a 15mL glass bottle and hand-foamed, and the mixture was shaken up and down for 20 times, photographed after 5 minutes, and the total concentration of the surfactant was 5mM, APG mole fraction (. Alpha. n ) As shown in the upper part of the graph, the temperature is 45 ℃.
FIG. 4 (a) is the initial foam volume (V) i ) And solution/Daqing crude interfacial tension (IFT) with total surfactant concentration (C t ) The ratio of SDS/DTABAPG mole fraction was 0.36/0.24/0.4; (b) 2.5mL of the solution is placed in a 15mL glass bottle for shaking and foaming, the solution is oscillated up and down for 20 times, photographed after 5min, and the temperature is 45 ℃.
FIG. 5 (a) is the initial foam volume (V) i ) Half-life (t) 1/2 ) With total surfactant concentration (C t ) Is a variation of (2); (b) Is SDS/DTAB/APG ternary mixture solution/Daqing crude oil interfacial tension (IFT) and the integrated foam index (f) of the SDS/DTAB/APG ternary mixture solution is determined according to the total concentration of the surfactant (C t ) Is a variation of (2); (c) For 10mL of different total concentration (C t ) The SDS/DTAB/APG ternary mixture solution and 0.25g of crude oil are placed in a 100mL measuring cylinder for hand shaking foaming, shaking up and down for 20 times, and shooting after 5 min. The ratio of SDS/DTAB/APG mole fraction was 0.36/0.24/0.4; the temperature was 45 ℃.
FIG. 6 (a) shows the foam combination index (f) of SDS/DTAB/APG ternary mixture solution under oil-free and oil-containing conditions as a function of total surfactant concentration (C t ) Is a variation of (2); (b) Oil resistance index (R) for foam of SDS/DTAB/APG ternary mixture solution o ) With total surfactant concentration (C t ) Is a variation of (2); the ratio of SDS/DTAB/APG mole fraction was 0.36/0.24/0.4; the temperature was 45 ℃.10mL of solution or 10mL of solution plus 0.25g of crude oil are placed in a 100mL cylinder with a stopper for hand shaking and foaming, and the mixture is oscillated up and down for 20 times.
FIG. 7 shows the change of the surface tension of an aqueous solution with concentration at 45℃in Daqing formation water with SDS/DTAB/APG complex systems and related single systems. The mole fraction ratio of the SDS/DTAB binary mixture was 0.6/0.4, and the mole fraction ratio of the SDS/DTAB/APG ternary mixture was 0.36/0.24/0.4.
Fig. 8 shows the dynamic interfacial tension between SDS/DTAB/APG (molar fraction ratio = 0.36/0.24/0.06) ternary complex surfactants dissolved in Daqing formation water, aqueous solution and Daqing crude oil at 45 ℃.
Detailed Description
The present invention relates to reagents: sodium Dodecyl Sulfate (SDS), 99.5%; sodium decyl sulfate, 98%; sodium octyl sulfate, 98%; purchased from Ara Ding Shiji Co., ltd (Aladdin Chemical Reagent Co. Ltd.) sodium dodecyl carboxylate, 99%, purchased from Adamas-beta reagent Co., shanghai. Sodium dodecyl sulfate, 98%, commercially available from Macleans biotechnology, inc. Dodecyl Trimethyl Ammonium Bromide (DTAB), 99%); decyl trimethyl ammonium bromide, 95%; octyl trimethyl ammonium bromide, 98%; purchased from ala Ding Shiji limited. Alkyl glucosides (APG), technical grade, 50% active content, manufactured by Jiangsu-panqi biotechnology, inc. Daqing crude oil (ρ=0.845 at 45 ℃) Daqing formation water, total mineralization degree 6,778mg/L, pH=8-9, calcium ion 23mg/L and magnesium ion 31mg/L.
Example 1 construction of surfactant systems
The two surfactants are weighed according to the mole fraction ratio of SDS/DTAB of 0.6/0.4 to prepare binary mixture, and the binary mixture is mixed with nonionic surfactant APG to form ternary mixture (mole fraction alpha of APG in ternary mixture n 0.1 to 0.7). That is, the mole fraction ratio of SDS/DTAB/APG in the ternary mixture was (0.6X (0.3-0.9)): (0.4× (0.3-0.9)): (0.1-0.7).
Example 2 determination of Properties of different surfactant systems
The mixture was dissolved in Daqing formation water to prepare a solution, or the components were first prepared into an aqueous solution and then mixed in proportion (the mixing order was not affected), the total concentration was set to 5mM, and the interfacial tension and foaming properties of the solution and Daqing crude oil were measured at 45℃respectively, and the results are shown in FIG. 3 and Table 1. FIG. 3 (a) shows that ultra-low interfacial tension can be obtained when the mole fraction of APG is 0.1 to 0.7.
2.5mL of the solution was placed in a 15mL glass bottle, and the mixture was hand-foamed at 45℃and shaken up and down for 20 times, and the initial foam volume (V was recorded i ) And after 5min, a photograph of the foam appearance was taken, the results are shown in fig. 3 (a) and (b), table 1.
Visible as alpha n Increase in V i Increase, at alpha n Maximum (12 mL) was reached when =0.4, then followed by α n Is decreased to alpha by increasing n Drop to half of the maximum value (6 mL) when=0.9. Unlike SDS/DTAB binary complex system, ternary system is in wider alpha n In the range of 0.1 to 0.7, simultaneously ultra-low oil/water interfacial tension and high initial foam volume (V) i ). Obviously V i Shows the foamability (foamability) of the surfactant, and the anionic/cationic/nonionic ternary complex system has both ultra-low interfacial tension and high foamability, and the optimal composition is alpha n The optimal molar ratio of the ternary system is SDS/DTAB/apg=0.36/0.24/0.4.
TABLE 1 Performance of surfactant systems of different compounding ratios
| α n | Initial foam volume (V) i )/mL | solution/Daqing crude oil interfacial tension (IFT)/mN.m -1 |
| 0.1 | 7.85 | 0.0053 |
| 0.2 | 8.62 | 0.0014 |
| 0.4 | 12.0 | 0.000029 |
| 0.6 | 9.17 | 0.0087 |
| 0.8 | 8.59 | 0.064 |
| 0.9 | 6.2 | 0.074 |
Example 3 determination of Performance of surfactant systems at different concentrations
The surfactant system consists of the following components: 0.36 mole fraction of anionic surfactant SDS, 0.24 mole fraction of cationic surfactant DTAB, 0.4 mole fraction of nonionic surfactant APG.
The fixed composition was SDS/DTAB/apg=0.36/0.24/0.4, changing the total concentration (C t ) The interfacial tension and initial foaming volume (2.5 mL solution in a 15mL glass bottle for hand foaming) with Daqing crude oil were measured, respectively, and the results are shown in FIGS. 4 (a) and (b). It can be seen that in the total concentration range of 2-7 mM, the crude oil/formation water interfacial tension can be reduced to ultra low while the initial bubble volume increases with increasing total concentration, approaching a plateau (V) i >12mL)。
Example 4 foaming experiments were carried out under oleaginous conditions
Surfactant stabilized foams are generally intolerantAnd (3) defoaming when the oil is in contact with the oil. For this example, the foam properties of the ternary system under oily conditions were examined. The method comprises placing 10mL of solution in 100mL glass graduated cylinder with graduation, adding 0.25g Daqing crude oil, keeping constant temperature to 45deg.C in an incubator, taking out, shaking for 20 times, and recording initial foam volume (V) i ) The cylinder was then returned to the incubator and the change in foam volume over time was observed to give a decrease in foam volume to (1/2) V i The time required, noted as half-life (t 1/2 ). The foam synthesis index (f) was recalculated: f= (3/4) V i ×t 1/2 (L.s) wherein the units of the foam comprehensive index are in liters.sec.
The results obtained are shown in FIG. 5. FIG. 5 (a) shows the V of the SDS/DTAB/APG (0.36/0.24/0.4) ternary system in the presence of crude oil i As the total concentration of surfactant increases, t 1/2 Also increasing with increasing total surfactant concentration, but reaching a maximum at 8mM, further increasing total concentration results in t 1/2 And drops sharply. Trend of change in foam comprehensive index f and t 1/2 Similarly, the maximum is reached at 8mM, followed by a decrease. Whereas in the total concentration range of 2-6mM, the system achieved ultra-low interfacial tension, as shown in FIG. 5 (b). FIG. 5 (c) is a photograph of the appearance of the foam, taken 5min after foaming. The results of foaming experiments performed under oily conditions at different concentrations of surfactant are shown in Table 2.
TABLE 2 Performance of surfactant systems of different concentrations
Example 5 oil resistance index of foam
To obtain the oil resistance index of the ternary system foam obtained in example 5, the ternary system was similarly dissolved in Daqing formation water, and a foaming test was performed under oil-free conditions to obtain V at different total concentrations i And t 1/2 And calculating a foam comprehensive index f, and further calculating an oil resistance index of the foam: r is R o =f (oil)/f (no oil). FIG. 6 (a) shows three under refuelling and non-refuelling conditionsThe foam comprehensive index of the meta-system changes along with the total concentration, and the foam comprehensive index under the oiling condition is generally lower than that under the non-oiling condition, so that the crude oil has a certain defoaming effect on the foam. The ternary complex system used in this example has a high oil resistance index (shown in FIG. 6 (b)), R at a low total concentration (1-6 mM) o Reaching 0.4 to 0.5, R is increased with the increase of the total concentration o Significantly up to 0.69 at 8mM and a maximum of 0.74 at 9 mM. Whereas common single surfactants such as SDS, LAS and AES have oil resistance indexes of only about 0.1.
Example 6
Commercial surfactants Sodium Dodecyl Sulfate (SDS) and Dodecyl Trimethyl Ammonium Bromide (DTAB) were mixed in various molar ratios and dissolved in Daqing formation water (total degree of mineralization 6,778mg/L), the total concentration was set at 5mM, and the molar fraction (. Alpha.) of DTAB was observed c ) At 0.4 to 0.7, the solution becomes cloudy, as shown in FIG. 1 (a). The ratio of the mole fraction of locked SDS/DTAB was 0.6/0.4, and the binary mixture was used as a fictive component (pseudo component) and was mixed with the nonionic surfactant APG, when the mole fraction (. Alpha.) of APG n ) At 0.2 or more, the solution becomes transparent as shown in FIG. 1 (b). APG is clearly a good solubilizer.
Example 7 synergistic effect analysis
The experimental examples show that the ternary surfactant compound system constructed by the invention not only has excellent foaming performance, but also can obtain ultralow oil/water interfacial tension, and is far superior to a single surfactant system or a binary surfactant compound system. The reason for this is that the surfactant of different types is adopted for compounding, and the synergistic effect exists among the components.
In terms of foaming properties, lowering the surface tension of the solution can lower the interfacial energy of the foam system at the time of foaming, so that the lower the surface tension, the larger the initial foam volume is likely to be, which is advantageous for improving the foaming ability (foamability) of the surfactant. FIG. 7 shows three single surfactant systems of SDS, DTAB, APG and a binary system of SDS/DTAB (0.6/0.4) and ternary of SDS/DTAB/APG (0.36/0.24/0.4)The surface tension of the solution obtained by dissolving the system in Daqing stratum water changes along with the concentration or the total concentration. It can be seen that for three single surfactants, the lowest surface tension of the solution is 27.8-36.2 mN/m, the lowest surface tension of the SDS/DTAB (0.6/0.4) binary system can reach 22.3mN/m, and the lowest surface tension of the SDS/DTAB/APG (0.36/0.24/0.4) ternary system reaches 19.9mN/m. According to the theory of non-ideal mixed adsorption, strong attraction interaction exists between SDS/DTAB, and the interaction parameter beta exists in an adsorption monomolecular layer of an air/water interface s (-9.23+ -1.69). In the ternary system of SDS/DTAB/APG (0.36/0.24/0.4), the mole fraction of the imaginary component formed by SDS/DTAB (0.6/0.4) in the mixed adsorption single molecule reaches 0.94, and the APG only occupies 0.06.
Similarly, at the oil/water interface, the interaction parameter β between SDS/DTAB s In the ternary system of SDS/DTAB/APG (0.36/0.24/0.4), the mole fraction of the imaginary component composed of SDS/DTAB (0.6/0.4) in the mixed adsorption single molecule is 0.94, and the APG only occupies 0.06. Such a monolayer structure ensures that the density of alkyl chains in the monolayer is much higher than in a single surfactant adsorbed monolayer, and thus the system is prone to ultra-low interfacial tension over a wide concentration range, as shown in figure 8.
From the obtained oil/water interfacial tension and surface tension data, the E (engineering) parameter, S (tapping) parameter, and B (bridging) parameter, which affect foam stability, can be calculated as shown in Table 3. Wherein e=γ aw +γ ow –γ ao ，S＝γ aw –γ ow –γ ao ，B＝(γ aw ) 2 +(γ ow ) 2 –(γ ao ) 2 Wherein gamma is interfacial tension, and subscripts a, o, w respectively represent air, oil, and water. Thus gamma is aw Indicating the surface tension of water, gamma ao Indicating the surface tension of the oil, gamma ow Indicating the oil/water interfacial tension. When E is>When 0, oil drops easily enter a gas/liquid interface film formed by the surfactant to damage the stable structure of the bubble film, so that the bubble film is broken; and when S>When 0, the oil drops enter the gas/liquid interface film and then spread further on the gas/liquid interface,resulting in rapid defoaming; and when B>At 0, the oil droplets can penetrate the liquid film between two adjacent bubbles, causing the liquid film to break, resulting in defoaming.
The data in Table 3 shows that, for three single surfactant systems, except that the APG gave a negative S value (-0.27), the remaining parameters were positive, and that it was evident that none of the stable foams alone were oil resistant. For an SDS/DTAB binary system, three parameters are negative, and the foam is oil-resistant and has good stability in theory, but the foam comprehensive index is not high due to the small initial foam volume. For the SDS/DTAB/APG ternary system, three parameters are negative, the foam is oil-resistant in theory and good in stability, and the addition of APG ensures a higher initial foam volume and a larger foam comprehensive index.
Other examples select different anionic/cationic surfactants to mix with APG, and experimental screening is performed according to the procedure described above to obtain more formulation combinations. And will not be described in detail herein.
TABLE 3 Single and Mixed surfactant System E, S and B parameters surfactant concentration was 5mM,45℃
Comparative example 1 binary surfactant system
The anionic surfactant SDS and the cationic surfactant DTAB are mixed in binary mode according to different molar ratios, the mixture is dissolved in Daqing stratum water to prepare a solution, and the total concentration is set to be 5mM. The interfacial tension of these aqueous solutions with Daqing crude oil was measured at 45℃and the results are shown in FIG. 2 (a), and it can be seen that the interfacial tension IFT was determined as a function of the DTAB mole fraction (. Alpha. c ) Increasing and decreasing, at alpha c Ultra-low pressure is reached within the range of about 0.35 to 0.45, and alpha is reached c Reaches a minimum of about 2×10 when=0.4 -3 mN/m. 2.5mL of the solution was placed in a 15mL glass bottle, and the mixture was hand-foamed at 45℃and shaken up and down for 20 times, and the initial foam volume (V was recorded i ) And a photograph of the appearance of the foam was taken after 5 minutes, the results are shown in fig. 2 (a) and (b). Visible as alpha c Is added to the number of the components,V i monotonically decrease, while V in the interval where ultra-low oil/water interfacial tension is obtained i Relatively small. It can be seen that for an anionic/cationic binary complex system, the ultra-low interfacial tension and the high foaming performance cannot be combined, and the two are incompatible.
Claims (2)
1. A surfactant system with foaming performance and oil/water interfacial tension reduction is characterized by being compounded by anionic, cationic and nonionic surfactants; the molar ratio of anionic surfactant, cationic surfactant, nonionic surfactant in the surfactant system was 0.36:0.24:0.4; the nonionic surfactant is alkyl glycoside; alkyl chain length of C 8 To C 16 The polymerization degree of glucose is 1-3;
the anionic surfactant has a mono-alkyl chain single-head structure and comprises any one or more of alkyl sulfate, alkyl sulfonate and alkyl carboxylate; alkyl chain length of C 6 To C 18 ；
The cationic surfactant has a single-chain alkyl single-head structure and comprises any one or more of alkyl trimethyl quaternary ammonium salt, alkyl pyridine ammonium salt and alkyl imidazoline ammonium salt; wherein the chain length of the long chain alkyl is C 6 To C 18 ；
The total alkyl chain length of the anionic and cationic surfactants is C 12 To C 32 。
2. Use of the surfactant system of claim 1 for oil recovery.
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