CN117165275B - Brine gel-anionic-cationic surfactant oil displacement agent suitable for high-mineralization oil reservoir oil displacement and application - Google Patents
Brine gel-anionic-cationic surfactant oil displacement agent suitable for high-mineralization oil reservoir oil displacement and application Download PDFInfo
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- 239000003093 cationic surfactant Substances 0.000 title claims abstract description 106
- 238000006073 displacement reaction Methods 0.000 title claims abstract description 86
- 239000012267 brine Substances 0.000 title claims abstract description 61
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 61
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 57
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 112
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 79
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 64
- 125000000129 anionic group Chemical group 0.000 claims abstract description 44
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 7
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 5
- 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 claims abstract description 3
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 27
- -1 alkyl quaternary ammonium salt Chemical class 0.000 claims description 25
- 230000033558 biomineral tissue development Effects 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 13
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 9
- 239000000194 fatty acid Substances 0.000 claims description 9
- 229930195729 fatty acid Natural products 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- CAQWNKXTMBFBGI-UHFFFAOYSA-N C.[Na] Chemical compound C.[Na] CAQWNKXTMBFBGI-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 29
- 238000011084 recovery Methods 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 8
- 230000035699 permeability Effects 0.000 abstract description 7
- 238000005406 washing Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract description 2
- LJRGBERXYNQPJI-UHFFFAOYSA-M sodium;3-nitrobenzenesulfonate Chemical compound [Na+].[O-][N+](=O)C1=CC=CC(S([O-])(=O)=O)=C1 LJRGBERXYNQPJI-UHFFFAOYSA-M 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 127
- 239000004094 surface-active agent Substances 0.000 description 29
- 239000000499 gel Substances 0.000 description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- 239000002245 particle Substances 0.000 description 21
- 238000003756 stirring Methods 0.000 description 21
- 239000010779 crude oil Substances 0.000 description 19
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 19
- 150000003839 salts Chemical group 0.000 description 13
- PSHBPUXCVNHJAL-UHFFFAOYSA-N methyl dodecanoate;sodium Chemical compound [Na].CCCCCCCCCCCC(=O)OC PSHBPUXCVNHJAL-UHFFFAOYSA-N 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 9
- 239000012530 fluid Substances 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229940045870 sodium palmitate Drugs 0.000 description 7
- GGXKEBACDBNFAF-UHFFFAOYSA-M sodium;hexadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCC([O-])=O GGXKEBACDBNFAF-UHFFFAOYSA-M 0.000 description 7
- 230000006870 function Effects 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- SDXMBGGEEUQSEL-UHFFFAOYSA-N [Na].C(CCCCCCCCCCCCC)(=O)OC Chemical compound [Na].C(CCCCCCCCCCCCC)(=O)OC SDXMBGGEEUQSEL-UHFFFAOYSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 230000036571 hydration Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 150000007942 carboxylates Chemical class 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PYPCLUOPAQYZSY-UHFFFAOYSA-N [Na].C(CCCCCCCCCCCCCCC)(=O)OC Chemical compound [Na].C(CCCCCCCCCCCCCCC)(=O)OC PYPCLUOPAQYZSY-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 description 2
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- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- HEBRGEBJCIKEKX-UHFFFAOYSA-M sodium;2-hexadecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HEBRGEBJCIKEKX-UHFFFAOYSA-M 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 238000010795 Steam Flooding Methods 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- YGEVMZLRIOFHSG-UHFFFAOYSA-L disodium dodecanoate Chemical compound [Na+].[Na+].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O YGEVMZLRIOFHSG-UHFFFAOYSA-L 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
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- 229920002401 polyacrylamide Polymers 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
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- 239000011435 rock Substances 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- KKVTYAVXTDIPAP-UHFFFAOYSA-M sodium;methanesulfonate Chemical compound [Na+].CS([O-])(=O)=O KKVTYAVXTDIPAP-UHFFFAOYSA-M 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
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- Colloid Chemistry (AREA)
Abstract
A brine gel-anionic-cationic surfactant oil displacement agent suitable for high-mineralization oil reservoir oil displacement and application thereof comprise a brine gel and an anionic-cationic surfactant composition; the brine gel is silica sol; the silica sol is acidic silica sol, neutral silica sol or alkaline silica sol; the anionic surfactant in the anionic-cationic surfactant composition is fatty acid methyl ester sodium sulfonate; the cationic surfactant in the cationic surfactant composition is quaternary ammonium salt of C 8-C14 alkyl; the brine gel-anionic and cationic surfactant oil displacement agent can be applied to oil displacement in high-salinity oil reservoir areas. The advantages are that: the method has the advantages of high interfacial activity, strong oil washing capability, simple system, good selectivity and different permeability adjustment effects on an oil layer and a water layer, is particularly suitable for displacement of the anionic and cationic surfactants of the high-mineralization oil reservoir, can resist salt, has high sweep efficiency and can improve the recovery ratio of the high-mineralization oil reservoir.
Description
Technical Field
The invention relates to a brine gel-anionic surfactant oil-displacing agent, in particular to a brine gel-anionic surfactant oil-displacing agent suitable for oil displacement of a hypersalinity oil reservoir.
Background
Along with the continuous increase of energy demands and the realization of efficient exploitation of oil and gas resources, the requirements on the exploitation efficiency of crude oil are also higher and higher, and the improvement of the crude oil exploitation rate has not only realistic economic significance but also important strategic significance. Conventional primary and secondary oil recovery methods generally only produce about 30% of the crude oil in the geological reserves, and about 70% of the crude oil cannot be produced, so that the improvement of oil recovery efficiency has become an important problem to be solved in the case of extremely intense energy. The tertiary oil recovery technology is an effective method for improving oil recovery rate, and can be roughly divided into four categories: firstly, a thermal drive, including hot water, steam drive and the like; secondly, a mixed phase flooding comprising a carbon dioxide mixed phase, a hydrocarbon mixed phase and other inert gases is carried out; thirdly, chemical flooding of various chemical agents; and fourthly, microbial oil extraction comprising microorganisms, microbial polymers, microbial active agent flooding and the like. Chemical flooding is a very important and large-scale technology in enhanced oil recovery worldwide, including polymer flooding, surfactant flooding, aqueous alkaline flooding, and various combinations of polymer, alkali, and surfactant technologies. The effect of chemical flooding is the result of physical action, which refers to the sweep effect of the displacement fluid, and chemical action, which refers to the microscopic displacement effect of the displacement fluid. The core of the chemistry is to reduce the interfacial tension of the displacement fluid and crude oil. The surfactant has both oleophilic and hydrophilic properties, so that when the surfactant is dissolved in water, the molecules of the surfactant are mainly distributed on an oil-water interface, and the tension of the oil-water interface can be obviously reduced. The reduction in oil-water interfacial tension means that the surfactant system can overcome cohesive force, adhesive force and capillary force between crude oils, thereby reducing resistance of crude oil flowing through pore throats to be expelled. The oil displacement effect of the surfactant is also represented by the effects of reversing the wettability of the lipophilic rock surface, emulsifying crude oil, improving the surface charge density, coalescing oil drops and the like, which are the reasons why the surfactant plays a significant role in the chemical flooding technology.
At present, the largest oil displacement amount of the surfactant is an anionic surfactant such as petroleum sulfonate, petroleum carboxylate, alkylbenzenesulfonate and the like, and a single cationic surfactant is poor in oil-water interfacial tension reducing capability because the single cationic surfactant is easily adsorbed or precipitated by a stratum, and is generally not used in surfactant oil displacement. As the aqueous solution of the anionic and cationic surfactants is easy to form precipitation when being mixed in an approximately equal proportion, the anionic and cationic surfactant mixed system becomes a incompatibility in practical application, and the related theoretical research is also lagged. In recent years, research shows that the mixed system aqueous solution of the anionic and cationic surfactants has a plurality of abnormal properties, such as that the anionic and cationic surfactants have strong electrostatic action and interaction between hydrophobic carbon chains in the aqueous solution, so that association between two surfactants with different charges is promoted, micelles are easily formed in the solution, and the higher surface activity than that of a single surfactant is generated. In addition, the cationic surfactant mixed system can obviously reduce the adsorption loss of the cationic surfactant on the core, thereby obviously overcoming the inherent defects of the cationic surfactant. The addition of the cationic surfactant improves the interfacial activity of the alkyl sulfonate, petroleum carboxylate, alkylbenzenesulfonate, petroleum sulfonate.
CN 103422840B is an anionic surfactant-oil displacement agent system composed of sulfonate, carboxylate and quaternary salt; CN 1075739168B adopts anionic and cationic surfactant polymer binary oil displacement method of sodium dodecyl sulfate, N-dodecyl-N-methyl pyrrolidone bromide and partially hydrolyzed polyacrylamide; CN 112707945B, CN 111088013A and the like are also driven by anionic and cationic surfactants. Although some obvious progress is made on the anionic and cationic surfactant oil displacement agents, the anionic and cationic surfactant composite systems have a certain effect on reducing the oil-water interfacial tension and improving the oil displacement efficiency, but have obvious defects such as the improvement degree of the interfacial properties, the improvement range of the surface activity of the composite systems, the economy and the operation performance still need to be improved. Especially in a hypersalinity oil reservoir, the problems are more, and the most main problems are that the surface activity of the anionic and cationic surfactant complex is greatly reduced, the sweep efficiency is poor, the oil displacement efficiency is low, the economical efficiency is poor, the system is too complex and the like in a high-salinity environment of the hypersalinity oil reservoir, and the anionic and cationic surfactant complex needs to be continuously improved and improved. Therefore, there is a need to develop a surfactant flooding system that is both salt resistant and has high sweep efficiency to enhance the recovery of highly mineralized reservoirs.
Disclosure of Invention
The invention aims to solve the technical problem of providing the brine gel-anionic surfactant oil displacement agent for high-mineralization oil reservoir oil displacement, which has the advantages of high interfacial activity, strong oil washing capability, simple system, good selectivity and different permeability adjustment effects on an oil layer and a water layer, is particularly suitable for the anionic surfactant oil displacement of the high-mineralization oil reservoir, can resist salt, has high sweep efficiency and can improve the recovery ratio of the high-mineralization oil reservoir.
The technical scheme of the invention is as follows:
a brine gel-anionic-cationic surfactant oil displacement agent suitable for high-mineralization oil reservoir oil displacement comprises a brine gel and an anionic-cationic surfactant composition;
The brine gel has the functions of generating different functions with oil and water under the condition of a hypersalinity stratum, selectively adjusting different flow resistances of an oil phase and a water phase, improving the viscosity ratio of the oil phase to the water phase, and further reducing the permeability of the water phase so as to enlarge the volume sweep coefficient of the displacement fluid, wherein the brine gel is silica sol; the silica sol is acidic silica sol, neutral silica sol or alkaline silica sol; the anionic surfactant in the anionic-cationic surfactant composition is fatty acid methyl ester sodium sulfonate, and the molecular formula is as follows: R-CHSO 3Na-COO-CH3
Wherein R is C 12-C20 alkyl; the cationic surfactant in the cationic surfactant composition is an alkyl quaternary ammonium salt, preferably a quaternary ammonium salt of a C 8-C14 alkyl group, particularly preferably a quaternary ammonium salt of a C 12-C14 alkyl group;
The mass ratio of the anionic surfactant to the cationic surfactant in the anionic-cationic surfactant composition is 1 (0.05-1);
the brine gel-anionic and cationic surfactant oil displacement agent comprises the following components in percentage by weight:
0.05 to 15 percent of silica sol;
0.01 to 0.3 percent of anionic and cationic surfactant composition;
The balance of water.
In a further preferred scheme, the brine gel-anionic and cationic surfactant oil displacement agent comprises the following components in percentage by weight:
1% -4% of silica sol;
0.08% of an anionic/cationic surfactant composition;
The balance of water.
Further preferred embodiments, the anionic surfactant has the formula: R-CHSO 3Na-COO-CH3 and R are methyl ester sulfonates of C 12-C16 alkyl.
In a further preferred embodiment, the alkyl quaternary ammonium salt is a quaternary ammonium salt of a C 12-C14 alkyl group.
Further preferred is an anionic surfactant to cationic surfactant mass ratio of 1:0.4 in the cationic and anionic surfactant composition.
In a further preferred scheme, the silica sol is an alkaline silica sol, wherein SiO 2 of the alkaline silica sol is more than or equal to 35%, the pH value is=9-10, and Na 2 O is less than or equal to 0.3%.
According to a further preferred scheme, the preparation method of the brine gel-anionic-cationic surfactant oil displacement agent for high-salinity oil reservoir oil displacement comprises the following specific steps:
(1) Dissolving the fatty acid sodium methane sulfonate anionic surfactant in water to obtain a fatty acid sodium methane sulfonate solution; (2) Dissolving the alkyl quaternary ammonium salt cationic surfactant in water to obtain cationic alkyl quaternary ammonium salt solution;
(3) And uniformly mixing the silica sol with a fatty acid methyl sodium sulfonate solution, a cationic alkyl quaternary ammonium salt solution and water to obtain the brine gel-anionic surfactant oil displacement agent suitable for oil displacement of the hypersalinity oil reservoir.
On the other hand, the brine gel-anionic and cationic surfactant oil displacement agent suitable for the oil displacement of the high-salinity oil reservoir is applied to the oil displacement of the stratum of the high-salinity oil reservoir.
Further preferred is a hypersalinity stratum with a mineralization of 50000mg/L to 300000mg/L.
Further preferred embodiments, the hypersalinity formation has a mineralization of 50000mg/L to 250000mg/L.
The brine gel-anionic/cationic surfactant oil-displacing agent is particularly suitable for oil displacement of high-mineralized oil reservoirs, namely oil reservoir oil displacement with the mineralization degree of 50000-300000 mg/L, because under the mineralization degree condition, the silica sol can generate aqueous gel, the generated aqueous gel can increase the viscosity of water, the pressure of a water layer is increased, and the surfactant oil-displacing agent is favorable for steering to oil layer oil washing and oil displacement. And oil reservoirs with salt concentration below 50000mg/L form gel too weak or not at all, so that the sweep efficiency is not obviously improved. The brine gel-anionic and cationic surfactant oil displacement agent is not only suitable for high-mineralization oil reservoirs, but also suitable for oil displacement of any mineralization oil reservoir.
The construction process of the brine gel-anionic and cationic surfactant oil displacement agent comprises the following steps: a general injection process is selected, and an injection string in the well is utilized to inject the brine gel-anionic surfactant oil displacement agent. The process is simple in construction, the pipe column is not moved, and the injection pressure and the discharge capacity of the construction are controlled during construction. The brine gel-anionic surfactant oil displacement agent adopts a general injection mode, namely utilizes the heterogeneous permeability of the stratum. When the oil displacement agent is injected, the oil displacement agent mainly enters the high permeable layer because the flowing resistance of the high permeable layer is small, and the high permeable layer is usually a high water-bearing layer, after the oil displacement agent enters the high water-bearing layer, the aqueous gel is gradually formed under the action of high-concentration sodium chloride, so that the aqueous phase viscosity is greatly improved, the flowing resistance of water is increased, the oil displacement agent entering an oil layer is not generated due to the lack of sodium chloride, and the crude oil is gradually eluted by the anionic surfactant, so that the purpose of selectively displacing the oil is realized. The absorption capacity of the high-permeability water permeable layer is reduced, the absorption capacity of the low-permeability oil layer is started, and the oil displacement sweep degree and the oil extraction efficiency of the surfactant are improved.
Silica sols are capable of undergoing a range of chemical changes in high concentration brine to form aqueous gels without or with low salt conditions. The reason is that the silica sol is injected into the stratum and encounters saline water to generate aqueous gel, the viscosity of the saline water is increased, the pressure of the water layer is increased, and the displacement fluid is driven to be turned to low pressure. If it is driven into oil layer, because the salt content in oil layer is suddenly reduced, its salt concentration is very low, there is no condition for forming gel, it can not gel in oil layer, and its original property and state are still kept unchanged, and the pressure of oil layer also remains unchanged, so that between water-bearing layer and oil-bearing layer there is different pressure difference, the oil-displacing agent can naturally be pushed into the oil layer with low pressure, so that it can raise flushing efficiency of oil layer and raise oil-washing efficiency. Therefore, the brine gel has the functions of selectively tackifying, increasing resistance and pressurizing brine, can automatically adjust the pressure and permeability of an oil layer and a water layer and automatically adjust the displacement profile, and is very suitable for oil displacement operation of a high-salt oil reservoir.
Silica sol particles are spherical particles with diameters of 1-100nm, and are one of the most stable and most common and least expensive inorganic nanomaterials. The inside of spherical particles in the silica sol is an irregular three-dimensional network structure composed of amorphous silica, and the surfaces of the particles are covered by silanol groups (-Si-OH). The silica sol is dispersed in water in a stable state when no external influence exists, hydrogen bonds are formed between silica hydroxyl groups on the surfaces of the silica sol particles and surrounding water molecules, the water molecules form hydration films which are arranged in an oriented mode and have elasticity on the surfaces of the silica sol particles, when the silica sol particles approach to a certain distance range, the elasticity of the hydration film layer can prevent the silica sol particles from approaching further, and the particles are prevented from approaching to a distance which is enough for collision to generate chemical reaction; another reason for the stability of silica sol particles is that silica particles are very small, having a particle size in the range of 1-100nm, they have a large specific surface area, they have a strong adsorption effect on anions such as OH -、SiO3 2- in solution, so that basic silica sol particles are negatively charged and have a zeta potential of about 100mV, so that when silica sol particles approach a certain distance, a strong electrostatic repulsion prevents them from being further approached, and such electrostatic repulsion also prevents silica sol particles from colliding with each other, thereby maintaining the stability of silica sol.
However, when the silica sol solution is exposed to high concentrations of salt, silica sol particles gradually combine to form an aqueous gel. The reason for this phenomenon is that the compression of the electric double layer around the silica sol particles by the high concentration of salt ions promotes the reduction of the zeta potential of the silica sol particles, and the electrostatic repulsive effect between the silica sol particles is weakened to be mutually combined. Another reason for this is that the strong hydration of Na + in brine deprives the silica sol particles of water in the hydrated film, which is stripped to expose the silica particles, and the silica particles that are stripped from the hydrated film collide with each other to chemically react and bind together, resulting in the occurrence of macroscopic gels. The two factors lead to that the silica sol particles can be mutually close, when the silica sol particles are close to a small enough distance, dehydration reaction occurs between silicon hydroxyl groups with very high chemical activity on the surfaces of the silica sol particles on a microcosmic scale, and a net-shaped Si-O-Si-chemical bond with higher stability is generated, and the net-shaped chemical bond contains a large amount of water to form the aqueous gel. The aqueous gel, which retains a large amount of moisture therein, has a low density and can be suspended in a saline solution, and the gel can greatly increase the viscosity and flow resistance of the saline. If the silica sol solution is driven into the oil layer, the electrolyte effect which leads to the reduction of zeta potential does not occur in the oil layer due to the low salt concentration in the oil layer, and a large amount of Na + ions which do not have strong hydration function exist to destroy the hydration membrane layer of the silica sol particles, so that the silica sol does not gel in the oil layer, the silica sol still exists in a fluid state, flows along with the oil flow, and does not have an obstruction effect on the oil layer channel. Therefore, the brine gel blocking agent has the function of selectively tackifying and blocking water for high-concentration brine.
The fatty acid sodium methane sulfonate is selected as the anionic surfactant of the anionic surfactant composition, because the steric hindrance effect of the carboxyl ester group which is closely connected with the sulfonic acid group in the structure of the anionic surfactant is greatly improved, and the salt resistance and hard water resistance of the sulfonic acid group are not easy to precipitate, which is more excellent than that of common alkyl sulfonate or alkyl benzene sulfonate. Also, the presence of sulfonic acid groups greatly enhances the hydrolysis resistance of the adjacent carboxylate groups, which results in good surface activity in either brine or hard water, which is very different from conventional sulfonate surfactants.
The anionic and cationic surfactant composition of the invention has the advantages that the adsorption quantity of surfactant molecules on an oil-water interface is obviously increased due to the electrostatic action between opposite charge polar groups of the anionic and cationic surfactants, so that the anionic and cationic surfactant composition has high surface activity which is impossible to have by a single surfactant; meanwhile, due to the ultrahigh interfacial activity of the anionic surfactant and the cationic surfactant, the oil-water interface forms ultralow interfacial tension, so that cohesion, capillary force and adhesive force between crude oils are effectively overcome, and the extraction of the crude oils is facilitated. On the other hand, the cationic surfactant composition can also change the wettability of the oil layer surface, and the cationic surfactant in the composition can desorb the negatively charged groups of crude oil adsorbed on the stratum surface through the interaction of the cationic surfactant and the negatively charged groups of the crude oil, so that the oil wetting surface is changed into a water wetting surface, and the surfactant oil displacement agent easily enters the oil layer, thereby being beneficial to displacement and extraction of the crude oil. Meanwhile, the mixed solution of the anionic surfactant and the cationic surfactant has a solubilization effect on crude oil, and crude oil adhered to the stratum can be further eluted.
Among the many decisive factors affecting oil recovery, sweep efficiency and wash efficiency of the displacement agent are the most important parameters. The improvement of the oil washing efficiency is generally achieved by reducing the interfacial tension of oil and water. In the surfactant flooding process, whether the interfacial tension of the surfactant solution is lower than 10 -3 mN/m is a main index for evaluating the flooding effect of the surfactant. Surfactants with interfacial tension below 10 -3 mN/m have the potential to increase wash oil efficiency. The spreading efficiency is more important, and the surfactant with high activity cannot play a role of washing oil if the surfactant cannot contact an oil layer. The sweep efficiency is generally improved by increasing the viscosity of the water phase, reducing the permeability of the water phase and improving the oil-water viscosity ratio, so that the volume sweep coefficient is enlarged, and the recovery ratio of crude oil is improved.
The invention reduces the oil-water interfacial tension to the order of magnitude of 10 -3 mN/m by the high surface activity of the anionic and cationic surfactant composition, and increases the flow resistance and pressure of a water layer by the aqueous gel tackifying brine formed by silica sol at high salt concentration, thereby realizing the improvement of the sweep efficiency of the surfactant displacement fluid.
Compared with the prior art of the same kind, the invention has the following advantages and beneficial effects:
(1) The anionic fatty acid sodium methyl sulfonate and the cationic alkyl quaternary ammonium salt adopted by the invention form an anionic-cationic surfactant composition, the anionic-cationic surfactant composition has high oil-water interfacial activity, and the oil-water interface can form ultralow interfacial tension of 10 -3 m N/m under the condition that the dosage of the anionic-cationic surfactant composition is 0.03-0.05%;
(2) The salt resistance is good: the anionic and cationic surfactant composition can still reach ultra-low interfacial tension of 10 -3 m N/m under the condition of 50000-300000 mg/L NaCl hypersalinity oil reservoir;
(3) The brine gel of the invention generates a series of chemical reactions under the action of stratum brine to generate aqueous gel, so that the viscosity of the stratum brine is increased, the flowing resistance is increased, the permeability of the water phase is reduced and the injection pressure is increased. If the oil is driven into the oil layer, the oil layer is not subjected to similar chemical change, the original state of the oil layer is still maintained, gel in the oil layer is not generated, the injection pressure of the oil layer is not increased, thus the stratum pressure difference with different heights exists between the water-bearing layer and the oil-bearing layer, the oil displacement agent can turn to the oil layer with low pressure, the flushing of the oil layer is increased, and the oil washing efficiency is improved. Therefore, the brine gel has the functions of selectively tackifying, pressurizing and blocking water for the brine of the stratum, and can automatically adjust the oil displacement profile in the oil displacement process of the salt-containing oil reservoir, so that the volume wave and coefficient of displacement fluid are enlarged, and the oil displacement efficiency is improved.
Detailed Description
Example 1
According to the formula requirement, respectively adding sodium methyl laurate sulfonate and dodecyl trimethyl ammonium chloride into water with the mineralization degree of 50000mg/L, 100000mg/L, 150000mg/L and 250000mg/L, stirring and dissolving, then mixing the above anionic and cationic surfactant solutions, and uniformly stirring to respectively obtain four mixed solutions of anionic and cationic surfactants of different mineralization degrees, namely sodium methyl laurate sulfonate and dodecyl trimethyl ammonium chloride, wherein the mass ratio of the anionic surfactant to the cationic surfactant is 1:0.4, and the total mass concentration of the anionic and cationic surfactants is 0.08%.
Example 2
According to the formula requirement, respectively adding methyl laurate sodium sulfonate and tetradecyl trimethyl ammonium chloride into water with mineralization degree of 50000mg/L, 100000mg/L, 150000mg/L and 250000mg/L, stirring for dissolving, then mixing the above anionic and cationic surfactant solutions, and uniformly stirring to respectively obtain four mixed solutions of the anionic and cationic surfactants of different mineralization degrees, namely methyl laurate sodium sulfonate and tetradecyl trimethyl ammonium chloride, wherein the mass ratio of the anionic surfactant to the cationic surfactant is 1:0.4, and the total mass concentration of the anionic and cationic surfactants is 0.08%.
Example 3
According to the formula requirement, respectively adding sodium methyl myristate sulfonate and dodecyl trimethyl ammonium chloride into water with mineralization degree of 50000mg/L, 100000mg/L, 150000mg/L and 250000mg/L, stirring for dissolving, then mixing the above anionic and cationic surfactant solutions, and stirring uniformly to respectively obtain four mixed solutions of the anionic and cationic surfactants of sodium methyl myristate sulfonate and dodecyl trimethyl ammonium chloride with different mineralization degrees, wherein the mass ratio of the anionic surfactant to the cationic surfactant is 1:0.4, and the total mass concentration of the anionic and cationic surfactants is 0.08%.
Example 4
According to the formula requirement, respectively adding methyl palmitate sodium sulfonate and dodecyl trimethyl ammonium chloride with the mineralization degree of 50000mg/L, 100000mg/L, 150000mg/L and 250000mg/L into water, stirring and dissolving, then mixing the above anionic and cationic surfactant solutions, and uniformly stirring to respectively obtain four mixed solutions of the anionic and cationic surfactants sodium palmitate and dodecyl trimethyl ammonium chloride with different mineralization degrees, wherein the mass ratio of the anionic surfactant to the cationic surfactant is 1:0.4, and the total mass concentration of the anionic and cationic surfactants is 0.08%.
Example 5
According to the formula requirement, respectively adding sodium methyl palmitate sulfonate and tetradecyl trimethyl ammonium chloride into water with the mineralization degree of 50000mg/L, 100000mg/L, 150000mg/L and 250000mg/L, stirring for dissolving, then mixing the above anionic and cationic surfactant solutions, and uniformly stirring to respectively obtain four mixed solutions of the anionic and cationic surfactants of different mineralization degrees, wherein the mass ratio of the anionic surfactant to the cationic surfactant is 1:0.4, and the total mass concentration of the anionic and cationic surfactants is 0.08%.
Example 6
According to the formula requirement, respectively adding methyl laurate sodium sulfonate and dodecyl trimethyl ammonium chloride into water with the mineralization degree of 50000mg/L, 100000mg/L, 150000mg/L and 250000mg/L, stirring and dissolving, and then mixing the anionic and cationic surfactant solutions to respectively obtain four mixed solutions of the anionic and cationic surfactants of sodium laurate sodium sulfonate and dodecyl trimethyl ammonium chloride with different mineralization degrees, wherein the mass ratio of the anionic surfactant to the cationic surfactant is 1:0.4, and the total mass concentration of the anionic and cationic surfactants is 0.04%.
1. Determination of interfacial tension of brine gel-anionic-cationic surfactant combination liquid
The cationic and anionic surfactant solutions of examples 1-6 were measured for oil-water interfacial tension with a Qinghai oilfield oil extraction plant using a TX-500C rotary drop interfacial tensiometer. The measurement temperature was 70℃in which the crude oil density was 0.85g/cm 3 and the viscosity was 17.2 mm. The measurement results are shown in Table 1.
TABLE 1 interfacial tension of anionic and cationic surfactant solutions oil and water
As shown in Table 1, the mixed solutions of the anionic and cationic surfactants prepared in examples 1 to 6 have good oil-water interfacial activity in hypersalinity water and have good applicability to hypersalinity oil reservoirs.
The alkaline silica sol used in the invention examples 7-11 is commercial alkaline silica sol of Jinan first pass chemical technology Co., ltd, wherein the index of the alkaline silica sol is SiO 2 -35%, the pH value is=9-10, and Na 2 O is less than or equal to 0.3%.
Example 7
And respectively adding sodium methyl laurate sulfonate and dodecyl trimethyl ammonium chloride into water according to the formula requirement, stirring and dissolving, then mixing the anionic surfactant solution, adding alkaline silica sol with the formula amount, and uniformly stirring to obtain the silica sol-anionic surfactant oil displacement agent with the total mass concentration of 0.08% of sodium methyl laurate sulfonate and dodecyl trimethyl ammonium chloride, the mass ratio of the sodium methyl laurate sulfonate to the dodecyl trimethyl ammonium chloride being 1:0.4 and the mass concentration of the silica sol being 1%.
Example 8
And respectively adding sodium methyl laurate sulfonate and tetradecyl trimethyl ammonium chloride into water according to the formula requirement, stirring and dissolving, then mixing the anionic surfactant solution and the cationic surfactant solution, adding alkaline silica sol with the formula amount, and uniformly stirring to obtain the silica sol-anionic surfactant oil displacement agent with the total mass concentration of 0.08% of sodium methyl laurate sulfonate and tetradecyl trimethyl ammonium chloride, the mass ratio of the sodium methyl laurate sulfonate to the tetradecyl trimethyl ammonium chloride being 1:0.4 and the mass concentration of the silica sol being 2%.
Example 9
And respectively adding sodium methyl myristate sulfonate and dodecyl trimethyl ammonium chloride into water according to the formula requirement, stirring and dissolving, then mixing the anionic surfactant solution, adding alkaline silica sol with the formula amount, and stirring uniformly to obtain the silica sol-anionic surfactant oil displacement agent with the total mass concentration of 0.08% of sodium methyl myristate sulfonate and dodecyl trimethyl ammonium chloride, the mass ratio of sodium methyl myristate sulfonate to dodecyl trimethyl ammonium chloride being 1:0.4 and the mass concentration of 3% of silica sol.
Example 10
And respectively adding sodium palmitate sulfonate and dodecyl trimethyl ammonium chloride into water according to the formula requirement, stirring and dissolving, then mixing the anionic surfactant solution, adding alkaline silica sol with the formula amount, and stirring uniformly to obtain the silica sol-anionic surfactant oil displacement agent with the total mass concentration of 0.08% of sodium palmitate sulfonate and dodecyl trimethyl ammonium chloride, the mass ratio of sodium palmitate sulfonate to dodecyl trimethyl ammonium chloride being 1:0.4 and the mass concentration of 4% of silica sol.
Example 11
And respectively adding sodium palmitate sulfonate and tetradecyl trimethyl ammonium chloride into water according to the formula requirement, stirring and dissolving, then mixing the anionic surfactant solution, adding alkaline silica sol with the formula amount, and stirring uniformly to obtain the silica sol-anionic surfactant oil displacement agent with the total mass concentration of 0.08% of sodium palmitate sulfonate and tetradecyl trimethyl ammonium chloride, the mass ratio of sodium palmitate sulfonate to tetradecyl trimethyl ammonium chloride being 1:0.4 and the mass concentration of silica sol being 5%.
2. Viscosity measurement of brine gel-anionic/cationic surfactant-displacing agent mixed hypersalinity brine the viscosity of the silica sol-anionic/cationic surfactant-displacing agent of examples 7-11 was measured with a DV2TRVT viscometer, and four kinds of water of different mineralizations of 50000mg/L, 100000mg/L, 150000mg/L and 250000mg/L were mixed, and after standing for 30min, the viscosity was measured, and the measurement temperature was 60 ℃; the measurement results are shown in Table 2.
TABLE 2 viscosity of brine gel-anionic and cationic surfactant oil-displacing agent blended into hypersalinity water
As shown in Table 2, the silica sol-anionic/cationic surfactant oil displacement agent of the invention is obviously gelled in hypersalinity water, and has obvious plugging regulating effect on hypersalinity water layers.
Comparative example 1
The sodium dodecyl benzene sulfonate and the dodecyl trimethyl ammonium chloride surfactant are respectively dissolved in water according to the mass ratio of 1:0.4 to prepare a solution with the total concentration of 0.1 percent of the sodium dodecyl benzene sulfonate and the dodecyl trimethyl ammonium chloride cationic surfactant.
Comparative example 2
Sodium hexadecyl benzenesulfonate and tetradecyl trimethyl ammonium chloride surfactant are respectively dissolved in water according to the mass ratio of 1:0.4 to prepare a solution with the total concentration of 0.1 percent of the sodium hexadecyl benzenesulfonate and the tetradecyl trimethyl ammonium chloride anionic-cationic surfactant.
Comparative example 3
Sodium laurate methyl sulfonate is dissolved in water to prepare a solution with the concentration of 0.1 percent.
3. The surfactant solutions of comparative examples 1-3 and example 3 were tested for oil-water interfacial tension with a Qinghai oilfield oil recovery two-plant using a TX-500C rotary drop interfacial tensiometer. The salt content of the water is 200000mg/L, the measurement temperature is 70 ℃, the crude oil density is 0.85g/cm 3, and the viscosity is 17.2 mm. The measurement results are shown in Table 3.
TABLE 3 oil-water interfacial tension comparison results
| Project | Oil-water interfacial tension/(mN/m.times.10 -3) |
| Comparative example 1 | 16.6 |
| Comparative example 2 | 11.8 |
| Comparative example 3 | 19.2 |
| Example 3 | 2.7 |
As can be seen from table 3, neither the anionic or cationic surfactants alone nor the other sulfonates were paired with alkyl quaternary ammonium salts, nor the fatty acid sodium methanesulfonate and alkyl quaternary ammonium salts of the present invention were compounded to have a strong interfacial tension reducing ability, demonstrating that the anionic and cationic surfactant combinations of the present invention have excellent wash oil efficiency.
The above is only a specific embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A brine gel-anionic-cationic surfactant oil displacement agent suitable for high-mineralization oil reservoir oil displacement is characterized in that:
The brine gel-anionic surfactant oil displacement agent comprises a brine gel and an anionic surfactant composition;
The brine gel is silica sol; the silica sol is alkaline silica sol;
the anionic surfactant in the anionic-cationic surfactant composition is fatty acid methyl ester sodium sulfonate, and the molecular formula is as follows:
R-CHSO3Na-COO-CH3
wherein R is C 12-C20 alkyl;
The cationic surfactant in the cationic surfactant composition is alkyl quaternary ammonium salt, and the alkyl quaternary ammonium salt is quaternary ammonium salt of C 8-C14 alkyl;
the mass ratio of the anionic surfactant to the cationic surfactant in the anionic-cationic surfactant composition is 1 (0.05-1);
the brine gel-anionic and cationic surfactant oil displacement agent comprises the following components in percentage by weight:
0.05% -15% of silica sol;
0.01% -0.3% of an anionic and cationic surfactant composition;
The balance of water.
2. The brine gel-anionic surfactant oil-displacing agent for oil displacement of high-salinity oil reservoir according to claim 1, wherein the brine gel-anionic surfactant oil-displacing agent is characterized in that:
the brine gel-anionic and cationic surfactant oil displacement agent comprises the following components in percentage by weight:
1% -4% of silica sol;
0.08% of an anionic/cationic surfactant composition;
The balance of water.
3. The brine gel-anionic surfactant oil-displacing agent for oil displacement of high-salinity oil reservoir according to claim 1, wherein the brine gel-anionic surfactant oil-displacing agent is characterized in that: the molecular formula of the anionic surfactant is as follows: R-CHSO 3Na-COO-CH3 and R are methyl ester sulfonates of C 12-C16 alkyl.
4. The brine gel-anionic surfactant oil-displacing agent for oil displacement of high-salinity oil reservoir according to claim 1, wherein the brine gel-anionic surfactant oil-displacing agent is characterized in that: the alkyl quaternary ammonium salt is quaternary ammonium of C 12-C14 alkyl.
5. The brine gel-anionic surfactant oil-displacing agent for oil displacement of high-salinity oil reservoir according to claim 1, wherein the brine gel-anionic surfactant oil-displacing agent is characterized in that: the mass ratio of the anionic surfactant to the cationic surfactant in the anionic-cationic surfactant composition is 1:0.4.
6. The brine gel-anionic surfactant oil-displacing agent for oil displacement of high-salinity oil reservoirs according to claim 1, which is characterized in that: the alkaline silica sol SiO 2 is more than or equal to 35%, the pH value is=9-10, and Na 2 O is less than or equal to 0.3%.
7. The brine gel-anionic surfactant oil-displacing agent for oil displacement of high-salinity oil reservoirs according to claim 1, which is characterized in that: the preparation method of the brine gel-anionic-cationic surfactant oil displacement agent for high-salinity oil reservoir oil displacement comprises the following specific steps:
(1) Dissolving the fatty acid sodium methane sulfonate anionic surfactant in water to obtain a fatty acid sodium methane sulfonate solution;
(2) Dissolving the alkyl quaternary ammonium salt cationic surfactant in water to obtain cationic alkyl quaternary ammonium salt solution;
(3) And uniformly mixing the silica sol with a fatty acid methyl sodium sulfonate solution and a cationic alkyl quaternary ammonium salt solution to obtain the brine gel-anionic surfactant oil displacement agent suitable for oil displacement of the hypersalinity oil reservoir.
8. The use of a brine gel-anionic surfactant oil-displacing agent for displacing high-salinity reservoir according to claim 1 in displacing high-salinity reservoir stratum.
9. The application of the brine gel-anionic surfactant oil-displacing agent for oil displacement of high-salinity oil reservoirs in oil displacement of high-salinity stratum reservoirs, which is characterized in that: the mineralization degree of the stratum with high mineralization degree is 50000-300000 mg/L.
10. The application of the brine gel-anionic surfactant oil-displacing agent for oil displacement of high-salinity oil reservoirs according to claim 9 in oil displacement of high-salinity stratum oil reservoirs, which is characterized in that: the mineralization degree of the stratum with high mineralization degree is 50000-250000 mg/L.
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