CN103773351B - High salinity reservoir gas drive foam compositions and preparation method and purposes - Google Patents
High salinity reservoir gas drive foam compositions and preparation method and purposes Download PDFInfo
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- CN103773351B CN103773351B CN201210412617.5A CN201210412617A CN103773351B CN 103773351 B CN103773351 B CN 103773351B CN 201210412617 A CN201210412617 A CN 201210412617A CN 103773351 B CN103773351 B CN 103773351B
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- foaming agent
- gas
- alkyl
- foam compositions
- glycine betaine
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- 239000006260 foam Substances 0.000 title claims abstract description 45
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000004088 foaming agent Substances 0.000 claims abstract description 77
- 239000007789 gas Substances 0.000 claims abstract description 62
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229960003237 betaine Drugs 0.000 claims abstract description 31
- -1 polyoxy Polymers 0.000 claims abstract description 29
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000001294 propane Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 241001122767 Theaceae Species 0.000 claims 1
- 125000005257 alkyl acyl group Chemical group 0.000 claims 1
- 235000009508 confectionery Nutrition 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 9
- 125000000129 anionic group Chemical group 0.000 abstract description 5
- 125000003368 amide group Chemical group 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract description 3
- 230000005465 channeling Effects 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 12
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000013517 stratification Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 208000027418 Wounds and injury Diseases 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 208000014674 injury Diseases 0.000 description 4
- 150000007529 inorganic bases Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000003129 oil well Substances 0.000 description 3
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 description 2
- 229940073507 cocamidopropyl betaine Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- HLERILKGMXJNBU-UHFFFAOYSA-N norvaline betaine Chemical compound CCCC(C([O-])=O)[N+](C)(C)C HLERILKGMXJNBU-UHFFFAOYSA-N 0.000 description 2
- 238000005325 percolation Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 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
- 229910003202 NH4 Inorganic materials 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- SQBJBZVNGGZASY-UHFFFAOYSA-N [Na].ClS(=O)(=O)O Chemical compound [Na].ClS(=O)(=O)O SQBJBZVNGGZASY-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- 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
- C09K8/594—Compositions used in combination with injected gas, e.g. CO2 orcarbonated gas
-
- 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
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
- E21B43/166—Injecting a gaseous medium; Injecting a gaseous medium and a liquid medium
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Geology (AREA)
- Mining & Mineral Resources (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Fluid Mechanics (AREA)
- Geochemistry & Mineralogy (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Lubricants (AREA)
- Excavating Of Shafts Or Tunnels (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The present invention relates to a kind of high salinity reservoir gas drive foam compositions and preparation method and purposes, the problem of foaming agent present in existing high salinity reservoir gas drive oil recovery process meets divalent ion precipitation, causes has channeling is mainly solved.The present invention is by using a kind of foam compositions, including glycine betaine foaming agent, anionic and nonionic foaming agent and gas, glycine betaine foaming agent, anionic and nonionic foaming agent and gas phase are mixed to form foam, wherein glycine betaine foaming agent is alkyl amido betaine, anionic and nonionic foaming agent is any one in alkyl polyoxy second/propylene ether carboxylate or alkyl polyoxy second/propylene ether sulfonate, gas be with foaming agent into the gas of inertia relation any one, the mol ratio of described glycine betaine foaming agent and anionic and nonionic foaming agent is 1:0.01~1:100, gas is 0.1~10 with liquid volume ratio:1 technical scheme preferably solves the problem, available in gas drive enhanced oil recovery process.
Description
Technical field
The present invention relates to a kind of high salinity reservoir gas drive foam compositions and its production and use.
Background technology
China's main oilfield comes into high water-cut stage after primary and secondary exploitation, how to improve oil recovery factor,
Remaining reserves are developed to greatest extent, it has also become a vital task of petroleum industry.Gas drive is to be applied to Complex Reservoir, especially
It is that difficult exploitation oil reservoir improves one of most efficient method of recovery ratio.But in gas displacement process, there is serious skill
Art problem, i.e., because the viscosity contrast of underground crude oil and injection gas is big, so as to cause unfavorable mobility ratio, cause early stage gas
Body is broken through, and reduces reservoir coverage；And due to the anisotropism of oil reservoir, when being especially in the presence of crack or macropore, meeting
Produce serious has channeling, oil production reduction.
In order to improve the ability of closure high permeability zone, people have found by substantial amounts of research, foam have than polymer or
Glue preferably enters and reduces the infiltrative ability of high permeability zone.By adding foaming agent and gas mixing, with aerated fluid
Form carries out displacement, can selectively block high permeability zone, adjusts fluid entry profile, increases sweep efficiency.Gas drive foam blocking
The greatest difficulty run into application process is to be difficult to form foam steady in a long-term.
Current foaming agent used for tertiary oil recovery uses Recompounded multielement system mostly, at the same comprising nonionic surface active agent and
The auxiliary agents such as alkali, alcohol, polymer are additionally added in ionic surfactant, part formulation.As patent CN101619210A is provided
One kind is used for low-permeability oil deposit carbon dioxide foam stabilizer, and the agent is foaming agent, foam stabilizer from neopelex
It is made up of modified guanidine glue, hydroxyethyl cellulose, lauryl alcohol, neopelex is anion surfactant, using this
Agent make it that the salt resistant character of system is limited as foaming host, works as Ca2+、Mg2+Foaming agent just Precipitation during more than 300 μ g/g,
Influence its foaming properties.For another example patent CN1093589C discloses a kind of foam compsoite oil drive method, wherein using 0.5%-1.5%
Alkali, 0.05%-0.5% surfactant and 0.05%-0.5% polymer composition foaming agent combination, because system contains nothing
Machine alkali, injury is brought to stratum and oil well, the problems such as causing etching apparatus and pipeline, and inorganic base can seriously reduce polymer
Viscosity, have to greatly improve the concentration of polymer for the viscosity needed for reaching, make oil recovery integrated cost improve.
The content of the invention
One of technical problems to be solved by the invention are that existing gas drive foaming agent meets high salinity precipitation, gas drive process
Middle plugging effect is poor, simultaneously because foam system contains inorganic base, alcohol etc., brings injury to stratum and oil well, etching apparatus and
The problem of pipeline, there is provided a kind of new high salinity reservoir gas drive foam compositions.Said composition has in salinity 300000mg/
Foam is formed under L, calcium ions and magnesium ions concentration 8000mg/L stratum water condition have that resistance factor is high, that envelope alters effect is good, will not be right
Stratum and oil well bring injury, will not etching apparatus and pipeline advantage.The two of the technical problems to be solved by the invention are to carry
For a kind of preparation method of the foam compositions corresponding with solving technical problem one.The technical problems to be solved by the invention it
Three are to provide a kind of purposes of high salinity reservoir gas drive foam compositions.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of high salinity reservoir gas drive bubble
Foam composition, including glycine betaine foaming agent, anion-nonionic foaming agent and gas, glycine betaine foaming agent, anion-nonionic foaming agent
Foam is mixed to form with gas phase, wherein glycine betaine foaming agent is alkyl amido betaine, and anion-nonionic foaming agent is poly- for alkyl
Any one in oxygen second/propylene ether carboxylate or alkyl polyoxy second/propylene ether sulfonate, gas is and foaming agent is inert closes
Any one of the gas of system, described glycine betaine foaming agent and the mol ratio of anion-nonionic foaming agent are 1:0.01~1:
100, gas and liquid are that the volume ratio of glycine betaine foaming agent and anion-nonionic foaming agent sum is 0.1~10:1；
Alkyl polyoxyethylene/propylene ether carboxylate general molecular formula is：
Alkyl polyoxyethylene/propylene ether sulfonate general molecular formula is：
Wherein R is C8~C30Alkyl, any one in alkenyl, R ' is C1~C10Alkyl, substitution alkyl in appoint
Meaning is a kind of, and M is any one in alkali metal, alkaline-earth metal, ammonium ion, and n, m are any one integer or small in 0~30
Number, n+m >=1.
In above-mentioned technical proposal, carbon atom number is preferably square in the glycine betaine foaming agent alkyl amido betaine alkyl chain
Case is 10~20.The anion-nonionic foaming agent cationic M preferred schemes are selected from Na, K, Mg, Ca, NH4 +In it is any one
Kind, substituent R preferred scheme is C10~C24Alkyl, any one in alkenyl, interval base R ' preferred schemes are C1~C5's
Alkyl, substitution alkyl in any one, ethyoxyl polymerization degree n preferred scheme be 0~20 in any one integer or decimal,
Propoxyl group degree of polymerization m preferred schemes are any one integer or decimal in 0~10, n+m >=1.The gas preferred scheme choosing
From any one in air, nitrogen, carbon dioxide；The mol ratio of glycine betaine foaming agent and anion-nonionic foaming agent is preferably square
Case is 1:0.1~1:10, gas is 0.5~5 than preferred scheme with liquid volume:1.
To solve the two of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of high salinity reservoir gas drive bubble
The preparation method of foam composition, comprises the following steps：
A) by fatty alcohol, catalyst according to mol ratio 1:0.002~0.03 adds reactor, adds the desired amount of epoxy
Ethane, expoxy propane, react 1~10 hour in 100~200 DEG C；Described catalyst is at least one in CaO, KOH
Kind；
B) step a product is added into sulfonated reagent or carboxylating reagent, fatty alcohol:Sulfonated reagent or carboxylating reagent rub
You are than being 1:1~4, continue to react 1~20 hour in 50~200 DEG C, then add hydrochloric acid and be neutralized to pH<3, and carry out profit point
From, oil phase alkaline solution is added to be neutralized, finally obtain alkyl polyoxyethylene/propylene ether carboxylate or alkyl polyoxyethylene/
Propylene ether sulfonate, described sulfonated reagent is hydroxyl sulfoacid and its salt, halogenosulfonic acid and its salt；Carboxylating reagent is halogenated carboxylic acid
And its salt；
C) the obtained anion-nonionic foaming agent of glycine betaine foaming agent and step b is dissolved in water, then according to
Mol ratio 1:0.1~1:10 are well mixed, and finally, gas-liquid mixed are realized with the gas of gas drive, that is, form required foam group
Compound.
To solve the three of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：High salinity reservoir gas drive foam group
Compound is used in the oil displacement process of 0~300000mg/L of salinity oil reservoir.
The present invention foam compositions in glycine betaine foaming agent due in molecule simultaneously containing anionic group and sun from
Subbase group, makes whole molecule not show electrical externally, thus with the very strong bivalent ions ability of resistance, anion-nonionic surface
Activating agent greatly enhances the salt resistant character of the surfactant due to containing nonionic fragment in molecule.Not only such as
This, the presence of inorganic salts can also increase adsorption density of two kinds of surfactants at interface, both is occurred compounding collaboration and make
With.
Using the foam compositions of the present invention during high salinity reservoir gas drive, system is free of inorganic base, it is to avoid scene should
The problem of injury that used time inorganic base is caused to stratum, corrosion caused to equipment, and effectively macropore plugging, experiment hair
Existing, under conditions of salinity 300000mg/L, 60 DEG C, foam envelope, which alters composition, is used for CO2Resistance factor reaches 50 in drive,
High hypotonic percolation flow velocity ratio is from independent CO2Drive 125:1 is down to 2:1, effective envelope is realized to macropore and is altered, than independent gas injection
Drive and improve recovery ratio 9%, achieve preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
By C10H21OH and its 0.8% KOH of weight is added in reactor, then adds the desired amount of oxirane, in
200 DEG C are reacted 1 hour；Then according to C10H21OH and carboxylating reagent mol ratio 1:1 adds sodium chloroacetate, continues to react in 50 DEG C
20 hours, it is eventually adding hydrochloric acid and is neutralized to pH<3, stratification, oil phase adds the 30% weight NaOH aqueous solution and neutralized, and obtains
Anion-nonionic foaming agent.
Anion-nonionic foaming agent prepared by laurylamide base CAB and the present invention is dissolved separately in water
In, stir 30 minutes, 0.5% weightaqueous solution is configured to, then by above-mentioned foaming agent according to glycine betaine:Anion-nonionic foaming agent
Mol ratio 1:After 8 is well mixed, gas-liquid mixed is realized with the gas of gas drive, that is, forms required foam compositions, its composition,
Structure is shown in Table 1.
【Embodiment 2】
By C20H41OH and its 0.5% KOH of weight is added in reactor, then adds the desired amount of oxirane, ring
Ethylene Oxide, reacts 10 hours in 100 DEG C；Then according to C20H41OH and carboxylating reagent mol ratio 1:1.5 add sodium chloroacetate, in
80 DEG C are continued to react 8 hours, are eventually adding hydrochloric acid and are neutralized to pH<3, stratification, oil phase adds 10% w/w aqueous KOH and entered
Row is neutralized, and obtains anion-nonionic foaming agent.
Anion-nonionic foaming agent prepared by cocamidopropyl betaine and the present invention is dissolved in water, and is stirred
Mix 30 minutes, be configured to 0.5% weightaqueous solution, then by above-mentioned foaming agent according to glycine betaine:Anion-nonionic foaming agent mole
Than 1:10 are well mixed, after, gas-liquid mixed is realized with the gas of gas drive, that is, forms required foam compositions, it is constituted, knot
Structure is shown in Table 1.
【Embodiment 3】
By C14H29OH and its 3.0% CaO of weight is added in reactor, then adds the desired amount of oxirane, ring
Ethylene Oxide, reacts 10 hours in 150 DEG C；Then according to C14H29OH and carboxylating reagent mol ratio 1:2 add Br (CH2)5COOH, in
100 DEG C are continued to react 1 hour, are eventually adding hydrochloric acid and are neutralized to pH<3, stratification, oil phase adds 10% weight Mg (HCO3)2Water
Solution is neutralized, and obtains anion-nonionic foaming agent.
Anion-nonionic foaming agent prepared by stearyl amido-propyl CAB and the present invention is dissolved in water, and is stirred
Mix 30 minutes, be configured to 0.5% weightaqueous solution, then by above-mentioned foaming agent according to glycine betaine:Anion-nonionic foaming agent mole
Than 1:1.4 are well mixed, after, gas-liquid mixed is realized with the gas of gas drive, that is, forms required foam compositions, its composition,
Structure is shown in Table 1.
【Embodiment 4】
By C24H49OH and its 1.0% CaO of weight is added in reactor, then adds the desired amount of oxirane, ring
Ethylene Oxide, reacts 10 hours in 140 DEG C；Then according to C24H49OH and carboxylating reagent mol ratio 1:3 add sodium chloroacetate, in 60
DEG C continue react 16 hours, be eventually adding hydrochloric acid and be neutralized to pH<3, stratification, oil phase add ammoniacal liquor neutralized, obtain the moon-
Nonionic foaming agent.
Anion-nonionic foaming agent prepared by cocamidopropyl betaine and the present invention is dissolved in water, and is stirred
Mix 30 minutes, be configured to 0.5% weightaqueous solution, then by above-mentioned foaming agent according to glycine betaine:Anion-nonionic foaming agent mole
Than 1:0.5 is well mixed, after, gas-liquid mixed is realized with the gas of gas drive, that is, forms required foam compositions, its composition,
Structure is shown in Table 1.
【Embodiment 5】
By C18H37OH and its 1.5% KOH of weight is added in reactor, oxirane, epoxy needed for then adding
Propane, reacts 4 hours in 180 DEG C；Then according to C18H37OH and sulfonated reagent mol ratio 1:3 add chlorosulfonic acid sodium, in 120 DEG C
Continue to react 12 hours, be eventually adding hydrochloric acid and be neutralized to pH<3, stratification, oil phase adds 10% weight Ca (HCO3)2The aqueous solution
Neutralized, obtain anion-nonionic foaming agent.
Anion-nonionic foaming agent prepared by octadecyl amide base CAB and the present invention is dissolved separately in water
In, stir 30 minutes, 0.5% weightaqueous solution is configured to, then by above-mentioned foaming agent according to glycine betaine:Anion-nonionic foaming agent
Mol ratio 1:1.8 are well mixed, after, gas-liquid mixed is realized with the gas of gas drive, that is, forms required foam compositions, its group
1 is shown in Table into, structure.
【Embodiment 6】
By C18H35OH and its 0.8% KOH of weight is added in reactor, oxirane, epoxy needed for then adding
Propane, reacts 6 hours in 160 DEG C；Then according to C18H35OH and sulfonated reagent mol ratio 1:4 add chlorine amyl group sodium sulfonate, in
120 DEG C are continued to react 20 hours, are eventually adding hydrochloric acid and are neutralized to pH<3, stratification, oil phase adds the 30% weight NaOH aqueous solution
Neutralized, obtain anion-nonionic foaming agent.
Anion-nonionic foaming agent prepared by decyl amido propyl betaine and the present invention is dissolved in water,
Stirring 30 minutes, is configured to 0.5% weightaqueous solution, then by above-mentioned foaming agent according to glycine betaine:Anion-nonionic foaming agent rubs
You compare 1:0.1 is well mixed, after, gas-liquid mixed is realized with the gas of gas drive, that is, forms required foam compositions, its group
1 is shown in Table into, structure.
【Embodiment 7】
By C18H33OH and its 0.6% KOH of weight is added in reactor, oxirane, epoxy needed for then adding
Propane, reacts 6 hours in 160 DEG C；Then according to C18H33OH and sulfonated reagent mol ratio 1:4 add 3- chlorine-2-hydroxyl propane sulfonic acid
Sodium, continues to react 8 hours in 180 DEG C, is eventually adding hydrochloric acid and is neutralized to pH<3, stratification, oil phase adds 30% weight NaOH water
Solution is neutralized, and obtains anion-nonionic foaming agent.
Anion-nonionic foaming agent prepared by eicosyl amido propyl betaine and the present invention is dissolved separately in water
In, stir 30 minutes, 0.5% weightaqueous solution is configured to, then by above-mentioned foaming agent according to glycine betaine:Anion-nonionic foaming agent
Mol ratio 1:1.3 are well mixed, after, gas-liquid mixed is realized with the gas of gas drive, that is, forms required foam compositions, its group
1 is shown in Table into, structure.
The foam compositions of table 1 are constituted and structure
【Embodiment 8】Surface activator composition sealing characteristics is determined
Take【Embodiment 1-7】In surface activator composition in salinity 300000mg/L, calcium ions and magnesium ions concentration
8000mg/L, sealing characteristics evaluation experimental and two-tube experiment, hypertonic pipe permeability 1D, hypotonic pipe permeability are carried out under the conditions of 60 DEG C
0.2D, gas uses CO2、N2, air, determine pressure difference of blocking, calculate resistance factor and percolation flow velocity ratio, the results are shown in Table 2.
Composition closure experimental result in the embodiment of table 2
【Embodiment 9】Foam compositions Oil Displacing Capacity is studied
It it is 30 centimetres in length, a diameter of 2.5 centimetres, permeability is to carry out oil displacement test on 1D rock core.Gas drive is to gas
Body uses foam compositions instead after breaking through, improve oil recovery factor and the results are shown in Table 3.
The foam compositions oil displacement test result of table 3
| Composition sequence number | Improve recovery ratio % |
| 1 | 11.0 |
| 2 | 10.0 |
| 3 | 11.5 |
| 4 | 12.5 |
| 5 | 12.5 |
| 6 | 9.0 |
| 7 | 10.1 |
【Comparative example 1】
Using the experiment condition in embodiment 9, CO is individually noted2Gas flow velocity ratio Q is high:Q low is 125:1.
Claims (7)
1. a kind of high salinity reservoir gas drive foam compositions, including glycine betaine foaming agent, anion-nonionic foaming agent and gas, sweet tea
Dish alkali foaming agent, the aqueous solution of anion-nonionic foaming agent and gas phase are mixed to form foam, and wherein glycine betaine foaming agent is alkyl acyl
Amido glycine betaine, anion-nonionic foaming agent is alkyl polyoxy second/propylene ether carboxylate or alkyl polyoxy second/propylene ether sulfonate
In any one, gas be with the gas of the inert relation of foaming agent any one, described glycine betaine foaming agent with it is cloudy-
The mol ratio 1 of nonionic foaming agent:0.1~1:10, gas and liquid are glycine betaine foaming agent and anion-nonionic foaming agent sum
The aqueous solution volume ratio be 0.1~10:1；
Alkyl polyoxyethylene/propylene ether carboxylate general molecular formula is：
Alkyl polyoxyethylene/propylene ether sulfonate general molecular formula is：
Wherein R is C10~C24Alkyl, any one in alkenyl, R ' is C1~C5Alkyl, substitution alkyl in it is any one
Kind, M is any one in alkali metal, alkaline-earth metal, ammonium ion, and n is any one integer or decimal in 8.2~20,
Propoxyl group degree of polymerization m is any one integer or decimal in 0~10.
2. high salinity reservoir gas drive foam compositions according to claim 1, it is characterised in that the glycine betaine foaming agent alkane
Carbon atom number is 10~20 in base amide betaine alkyl chain.
3. high salinity reservoir gas drive foam compositions according to claim 1, it is characterised in that the anion-nonionic foaming agent
Cationic M is selected from Na+、K+、Mg2+、Ca2+、NH4 +In any one.
4. high salinity reservoir gas drive foam compositions according to claim 1, it is characterised in that the gas is selected from air, nitrogen
Any one in gas, carbon dioxide.
5. high salinity reservoir gas drive foam compositions according to claim 1, it is characterised in that gas is with liquid volume ratio
0.5~5:1.
6. the preparation method of high salinity reservoir gas drive foam compositions, comprises the following steps described in claim 1：
A) by fatty alcohol, catalyst according to mol ratio 1:0.002~0.03 addition reactor, the desired amount of oxirane of addition,
Expoxy propane, reacts 1~10 hour in 100~200 DEG C；Described catalyst is selected from least one of CaO, KOH；
B) step a product is added into sulfonated reagent or carboxylating reagent, fatty alcohol:The mol ratio of sulfonated reagent or carboxylating reagent is
1:1~4, continue to react 1~20 hour in 50~200 DEG C, then add hydrochloric acid and be neutralized to pH<3, and water-oil separating is carried out, oil
It is added to alkaline solution to be neutralized, finally obtains alkyl polyoxyethylene/propylene ether carboxylate or alkyl polyoxyethylene/propylene ether
Sulfonate, described sulfonated reagent is hydroxyl sulfoacid and its salt, halogenosulfonic acid and its salt；Carboxylating reagent be halogenated carboxylic acid and its
Salt；
C) the obtained anion-nonionic foaming agent of glycine betaine foaming agent and step b is dissolved in water, then according to mole
Than 1:0.1~1:10 are well mixed, and finally, gas-liquid mixed are realized with the gas of gas drive, that is, form required foam compositions.
7. high salinity reservoir gas drive described in claim 1 is used for the drive of 0~300000mg/L of salinity oil reservoir with foam compositions
During oil.
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| CN104120999B (en) * | 2014-07-03 | 2017-02-15 | 中国石油大学(北京) | Oil recovery method restraining channeling in CO2 flooding process in low-permeability fractured reservoir through two-stage channeling blocking |
| CN104152128A (en) * | 2014-08-18 | 2014-11-19 | 中国科学院理化技术研究所 | Foam oil displacement agent with oil resistance and application thereof |
| CN105368427B (en) * | 2014-08-27 | 2018-08-17 | 中国石油化工股份有限公司 | Anion surfactant and preparation method thereof |
| CN106590607B (en) * | 2015-10-20 | 2019-07-09 | 中国石油化工股份有限公司 | Temperature-resistant anti-salt low-tension foaming agent combination and preparation method thereof |
| CN106590567A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Low tension foaming agent for high-salinity strata, and preparation method and applications thereof |
| CN106590564B (en) * | 2015-10-20 | 2019-12-10 | 中国石油化工股份有限公司 | Temperature-resistant salt-resistant low-tension foam flooding composition and preparation method and application thereof |
| CN106634931A (en) * | 2017-01-19 | 2017-05-10 | 中国科学院理化技术研究所 | Foam oil displacement agent with anti-adsorption performance and application thereof |
| CN106883833B (en) * | 2017-02-20 | 2019-10-25 | 西安石油大学 | Oil displacement system for ultrahigh-temperature high rigidity oil reservoir with high salt |
| CN107880865B (en) * | 2017-11-01 | 2020-03-10 | 中国石油天然气股份有限公司 | Low-interfacial-tension foam oil displacement agent and preparation method thereof |
| CN109135713A (en) * | 2018-09-05 | 2019-01-04 | 安徽炎胜新材料科技有限公司 | A kind of clean fracturing fluid and preparation method thereof for high salinity recovered water |
| CN111088025B (en) * | 2018-10-23 | 2022-05-24 | 中国石油化工股份有限公司 | Efficient oil washing agent for improving carbon dioxide oil displacement efficiency and preparation method and application thereof |
| CN109777393B (en) * | 2019-03-19 | 2020-04-14 | 中国石油化工股份有限公司 | Foam oil displacement agent |
| CN114479812B (en) * | 2020-10-26 | 2023-05-02 | 中国石油化工股份有限公司 | Surfactant composition with ultralow oil-water interfacial tension and preparation method and application thereof |
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| CN101580705B (en) * | 2009-06-12 | 2012-03-21 | 中国石油大学(华东) | Foaming agent with low gas liquid ratio foam for common heavy oil reservoir and injection method thereof |
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