CN102834170A - Method for producing crude oil using cationic surfactants comprising a hydrophobic block having a chain length of 6 - 10 carbon atoms - Google Patents
Method for producing crude oil using cationic surfactants comprising a hydrophobic block having a chain length of 6 - 10 carbon atoms Download PDFInfo
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- CN102834170A CN102834170A CN2011800182983A CN201180018298A CN102834170A CN 102834170 A CN102834170 A CN 102834170A CN 2011800182983 A CN2011800182983 A CN 2011800182983A CN 201180018298 A CN201180018298 A CN 201180018298A CN 102834170 A CN102834170 A CN 102834170A
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- 239000010779 crude oil Substances 0.000 title claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 title claims description 17
- 239000003093 cationic surfactant Substances 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title abstract 3
- 230000002209 hydrophobic effect Effects 0.000 title description 5
- 239000004094 surface-active agent Substances 0.000 claims abstract description 109
- 239000002480 mineral oil Substances 0.000 claims abstract description 41
- 235000010446 mineral oil Nutrition 0.000 claims abstract description 41
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 27
- 239000002563 ionic surfactant Substances 0.000 claims abstract description 6
- 239000003921 oil Substances 0.000 claims description 55
- -1 ethoxyl Chemical group 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 29
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 238000011084 recovery Methods 0.000 claims description 21
- 239000003945 anionic surfactant Substances 0.000 claims description 13
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 13
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 150000001450 anions Chemical group 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 125000005055 alkyl alkoxy group Chemical group 0.000 claims description 2
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 15
- 238000002347 injection Methods 0.000 abstract description 13
- 239000007924 injection Substances 0.000 abstract description 13
- 238000009472 formulation Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 17
- 150000001412 amines Chemical class 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- 239000011435 rock Substances 0.000 description 6
- 230000008719 thickening Effects 0.000 description 6
- 150000001447 alkali salts Chemical class 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000005702 oxyalkylene group Chemical group 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000013011 aqueous formulation Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 230000005591 charge neutralization Effects 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 239000004064 cosurfactant Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007046 ethoxylation reaction Methods 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SBGFNHWKIOFPRM-UHFFFAOYSA-N 1-[2-(2-hydroxyethoxy)ethoxy]hexan-2-ol Chemical compound CCCCC(O)COCCOCCO SBGFNHWKIOFPRM-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229920000469 amphiphilic block copolymer Polymers 0.000 description 1
- XIWFQDBQMCDYJT-UHFFFAOYSA-M benzyl-dimethyl-tridecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 XIWFQDBQMCDYJT-UHFFFAOYSA-M 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 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
- SCXCDVTWABNWLW-UHFFFAOYSA-M decyl-dimethyl-octylazanium;chloride Chemical group [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCC SCXCDVTWABNWLW-UHFFFAOYSA-M 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008398 formation water Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000004899 motility Effects 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940117359 quaternium-24 Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229940032912 zephiran Drugs 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 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
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
- C07C217/08—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to an acyclic carbon atom
-
- 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
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- 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
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/18—Quaternary ammonium compounds
Abstract
The invention relates to a method for producing crude oil by means of Winsor type III microemulsion flooding, wherein an aqueous surfactant formulation which comprises at least one ionic surfactant of general formula R1 N+ (R2)m (R3)n (R4) X- is forced through injection wells into a mineral oil deposit and crude oil is withdrawn from the deposit through production wells.
Description
The present invention relates to a kind of method, wherein will comprise at least a general formula R through Winsor III type microemulsion flooding exploitation mineral oil
1N
+(R
2)
m(R
3)
n(R
4) X
-The aqueous surfactant preparaton of ionic surfactant inject the mineral oil reservoir via injecting well, and from said oil reservoir, extract crude oil out via the extraction well.
The invention further relates to ionic surfactant of said general formula and preparation method thereof.
In the natural minerals oil reservoir, mineral oil is present in the hole of porous reservoir rock, its towards ground one side by not thoroughly the layer seal.Said hole can be superfine hole, capillary, hole etc.The pore neck for example can only have the diameter of about 1 μ m.Except mineral oil (comprising gas component), oil reservoir also comprises and has or the water of high or low salt content.
In the mineral oil exploitation, be divided into primary recovery, secondary recovery and tertiary recovery usually.In primary recovery, mineral oil is because the self-generated pressure of oil reservoir is drilled beginning after flow to the surface automatically by boring at oil reservoir.
Therefore after primary recovery, use secondary recovery.In secondary recovery, except the boring (so-called extraction well) that is used to exploit mineral oil, also in containing the stratum of mineral oil, pierce other boring.Inject water to keep pressure or it is raise once more via these so-called injection wells to oil reservoir.Because inject the event of water, mineral oil slowly is pressed into the stratum by the direction of injecting well extraction well via hole.Yet this only just works under the situation that hole is filled by oil fully and more the oil of thickness is promoted to advance by water.In case the penetration by water hole of motion, it is along the minimum path flow of resistance this moment, the passage of promptly flowing through and forming, and no longer promote oil and advance.
Primary recovery and secondary recovery only can be exploited about 30-35% of existing mineral oil mass in the said oil reservoir usually.
Known mineral oil output can further improve through the tertiary oil recovery measure.The summary that adopts for three times can be referring to for example " Journal of Petroleum Science of Engineering 19 (1998) ", 265-280 page or leaf.Tertiary oil recovery comprises for example by the use of thermal means, wherein hot water or steam is injected oil reservoir.This reduces oil viscosity.Used flow media can be gas such as CO equally
2Or nitrogen.
Three mineral oil exploitations also comprise wherein uses the method for suitable chemicals as the oil recovery auxiliary agent.These can be used for influencing the terminal situation of water flows, and therefore also are used for exploiting the mineral oil that firmly remains in the rock stratum.
In contiguous secondary recovery latter stage, viscous force and capillary force act on and are captured on the mineral oil that preserves in the petrosal foramen, and wherein these two kinds of power ratios respect to one another depend on the separation of microcosmic oil.These power are by dimensionless group, and promptly so-called capillary number is described.Viscous force (viscosity of speed * driving phase) is to the ratio of capillary force (interfacial tension * rock between the profit wetting):
In this formula; μ is the viscosity of ordering about the fluid of mineral oil motion, and ν is Darcy velocity (flow of unit are), and σ orders about the liquid of mineral oil motion and the interfacial tension between the mineral oil; And θ is the contact angle (C.Melrose between mineral oil and the rock; C.F.Brandner, J.Canadian Petr.Techn.58, the 10-12 month in 1974).Capillary number is high more, and the motility of oil is just high more, and therefore oily removal degree is also just big more.
The capillary number that known contiguous secondary mineral oil is exploited latter stage is about 10
-6, must make capillary number be increased to about 10
-3-10
-2Thereby, can make extra mineral oil motion.
For this reason, can implement the flooding method of particular form-be called Winsor III type microemulsion flooding.In microemulsion flooding, the surfactant of injection should form Winsor III type microemulsion with existing water of oil reservoir and oil phase.Winsor III type microemulsion is not the emulsion with droplet, but the thermodynamically stable liquid mixture of water, oil and surfactant.Its three advantages are:
-obtain the utmost point low interfacial tension σ between mineral oil and the water thus;
-therefore it has extremely low viscosity usually and is not captured by porous matrix;
-itself in addition form down and can keep stable (high shear force that conventional emulsions need common not occur, and only be dynamic stabilizationization in contrast) in the time at endless in oil reservoir in the input of minimum energy.
Winsor III type microemulsion is the equilibrium system of excessive water and excessive oil.Under these conditions that form microemulsion, surfactant covers oil-water interface, and interfacial tension σ is low more, and is then right<10
-2The value of mN/m (ultralow interfacial tension) is favourable more.In order to obtain optimum, under the surfactant of confirming amount, the microemulsion ratio in said water-microemulsion-oil body system should be maximum naturally, because can correspondingly obtain lower interfacial tension.
Can change oil droplet shape (to such an extent as to the interfacial tension between the profit reduce to the minimum interface state of degree like this no longer favourable and spherical no longer favourable) in this way, and they can be owing to displacement of reservoir oil water-driven is passed through capillary pipe opening.
In the presence of excess surface active agent, when oil-water interface is covered by surfactant, form Winsor III type microemulsion.Therefore it constitute the surfactant reservoir that causes the utmost point low interfacial tension between oil phase and the water.Because Winsor III type microemulsion has low viscosity, it also moves through porous reservoir rock (in contrast, emulsion can capture in porous matrix and stop up oil reservoir) in oil displacement process.When Winsor III type microemulsion when not met as yet by the oil-water interface that surfactant covered, the surfactant of said microemulsion can significantly reduce the interfacial tension at this new interface, and causes oil motion (for example because the oil droplet distortion).
Said oil droplet can merge with continuous oily reservoir subsequently.This has two advantages:
At first, because said continuous oily reservoir is pushed ahead through new porous rock, the oil droplet that is present in wherein can merge with said reservoir.
In addition, oil droplet merges the oily reservoir of formation significantly reduces oil-water interface, and the surfactant that therefore will no longer need discharges once more.Thereafter, the surfactant that discharges as stated can order about oil droplet motion residual in the stratum.
Therefore, microemulsion flooding is a kind of special effective method, and compares the surfactant that needs much less with the emulsion flooding method.In microemulsion flooding, usually that surfactant is optional with cosolvent and/or basic salt (optional with chelating agent) injection.Subsequently, the polymer solution that injects thickening is to control flowability.Another program is the mixture that injects thickening polymer, surfactant, cosolvent and/or basic salt (optional with chelating agent), and the solution that injects thickening polymer then is to control flowability.These solution should be clarification usually, to prevent to stop up oil reservoir.
There is significant difference in the exploitation of three mineral oil with the requirement of surfactant and to the requirement of the surfactant that is used for other application scenario: the suitable surfactant that is used for tertiary oil recovery answers the interfacial tension (being generally about 20mN/m) between Jiang Shui and the oil to reduce to less than 10
-2The low especially value of mN/m, thus can make mineral oil fully mobile.This must realize in the presence of reservoir temperature that is generally about 15-130 ° C and the water at high content of salt, is more particularly also realizing in the presence of calcium and/or the magnesium ion at high proportion; Therefore said surfactant also must dissolve in the oil reservoir water of high content of salt.
In order to satisfy these requirements, surfactant mixtures is proposed often, especially the mixture of anion and non-ionic surface active agent.
US4,374,734 disclose cationic surfactant is used for breakdown of emulsion in the mineral oil exploitation as demulsifier purposes.A mentioned embodiment is a Quaternium 24.
US4,596,662 disclose the combination of ethylene glycol diester, 30-50% propoxylation alkylamine and the 0.1-4% alkylphenol ether sulfate of 30-70% sulfosuccinic acid.Said propoxylation alkylamine can comprise 2-20 PO unit and have 1-6 alkyl that is positioned at the carbon atom on the nitrogen.
DD260713A1 discloses and has used C at the same time
12-C
18Mersolates and C
12-C
18Form microemulsion under the situation of zephiran.
WO93/04265A1 discloses the mixture of a kind of anion surfactant and a kind of cationic surfactant, it is said that it does not form deposition and demonstrates good frothing capacity with combinations-of surfactants the time.Said cationic surfactant is dodecyl (dihydroxymethyl) ammonio methacrylate.
Therefore, those skilled in the art regulate application parameter, for example surfactant types, concentration and mixing ratio respect to one another according to the condition that exists in the given oil reservoir (for example temperature and salt content).
As stated, the mineral oil exploitation is proportional with capillary number.Interfacial tension between the profit is low more, and then capillary number is high more.Usually be difficult to enough dissolubilities of obtaining low interfacial tension and obtaining surfactant simultaneously.Existing carboxylic acid is not converted under the situation of basic salt of hydrophobic surfactant (at this moment, the hydrophilic surfactant active who only must injection has good aqueous solubility thus) in adding crude oil, and is especially true.The combination of long chain cation surfactant and long-chain anion surfactant can be used as non-charged complex compound sediment and goes out or under the situation of unfavorable combination, loses through being dissolved in the oil.Because high salinity is used the impossible success of cation counterbalancing ion (like etamon) and anion surfactant, this is because there is high excessive sodium ion.During flooding method, counter ion counterionsl gegenions exchange.
Therefore, the purpose of this invention is to provide a kind of surfactant flooding or the specially suitable surfactant of preferred microemulsion flooding and modification method of tertiary recovery mineral oil of being used for.
Therefore; A kind of method through Winsor III type microemulsion flooding tertiary recovery mineral oil is provided; The aqueous surfactant preparaton that wherein will comprise at least a ionic surfactant injects well via at least one and injects the mineral oil reservoir so that the interfacial tension between the profit is reduced to < 0.1mN/>m; Preferred < 0.05mN/>m; More preferably 0.01mN/m, and from said oil reservoir, extract crude oil out via at least one extraction well, wherein said surfactant preparaton comprises the surfactant of at least a following general formula:
R
1N
+(R
2)
m(R
3)
n(R
4)X
-
Wherein
R
1Be the straight or branched with 6-10 carbon atom, saturated or undersaturated aliphatic series and/or aromatic hydrocarbyl,
R
2And R
3Be inferior ethoxyl, inferior propoxyl group and/or inferior butoxy and/or inferior amoxy independently of one another, preferred inferior ethoxyl and/or inferior propoxyl group, more preferably inferior ethoxyl,
R
4Be alkyl or hydroxyalkyl, benzyl or phenyl-CH with 1-4 carbon atom
2-CH
2-or phenyl-CH (CH
3)-,
M is 1-8,
N is 1-8, and wherein the m+n sum is 2-8, and
X is an anion.
In other preferred embodiments of said method, said surfactant preparaton comprises the surfactant of at least a following general formula:
R
1N
+(R
2)
m(R
3)
n(R
4)X
-
Wherein
R
1Be the straight or branched with 6-10 carbon atom, saturated or undersaturated aliphatic series and/or aromatic hydrocarbyl,
R
2And R
3Be methyl, ethyl and/or benzyl independently of one another,
R
4Be alkyl or hydroxyalkyl, benzyl or phenyl-CH with 1-4 carbon atom
2-CH
2-or phenyl-CH (CH
3)-,
N=m=1, and
X is an anion.
A kind of surfactant mixture that is used to exploit mineral oil also is provided, its comprise at least a such as preceding text the ionic surfactant of definition general formula.
The hereinafter reply the present invention specify.
Through in the inventive method of Winsor III type microemulsion flooding tertiary recovery mineral oil, use surfactant of the present invention interfacial tension between the profit to be reduced to < 0.1mN/>m, preferred < 0.05mN/>m, the more preferably < value of 0.01mN/>m.Therefore, the interfacial tension between the profit is reduced to 0.1-0.0001mN/m, preferred 0.05-0.0001mN/m, the more preferably value of 0.01-0.0001mN/m.
In the method for above-mentioned exploitation mineral oil of the present invention, use the aqueous surfactant preparaton of the surfactant that comprises at least a said general formula.In addition, it can comprise other surfactants and/or other components.
Said at least a surfactant can be by the defined general formula R of preceding text
1N
+(R
2)
m(R
3)
n(R
4) X
-Summarize.Because preparation is, said general formula also can be contained the multiple different surface active agents that is present in the said surfactant preparaton.
R
1Be the straight or branched with 6-10 carbon atom, saturated or undersaturated aliphatic series and/or aromatic hydrocarbyl.In a preferred embodiment of the invention, R
1Group is hexyl, octyl group, 2-ethylhexyl, different nonyl, decyl or 2-propylheptyl.
In above-mentioned general formula, R
2And R
3Be defined as methyl, ethyl or benzyl independently of one another or respectively do for oneself inferior ethoxyl, inferior propoxyl group, inferior butoxy and/or inferior amoxy.Said inferior ethoxyl, inferior propoxyl group, inferior butoxy and inferior amoxy be random, alternately distribute or be two, three, four or more a plurality of block form of any desired sequence.
In the defined general formula of preceding text, m and the n integer of respectively doing for oneself.Yet as far as the technical staff in poly-alkoxylation thing field, clearly in each case, this is defined as the definition of single surfactant.Comprise in existence under the situation of surfactant mixture or surfactant preparaton of surfactant of several said general formulas; Number m and n are the mean value of all surface active agent molecule, and this is because the alkoxylate of amine and ethylene oxide or propylene oxide or butylene oxide or oxidation amylene always obtains to have the chain length of certain distributed.This distribution can be described by polydispersity D with known in principle mode.D=Mw/Mn is the merchant of weight-average molar mass and mumber average molar mass.Polydispersity can known by one of skill in the art method, for example passes through gel permeation chromatography.
In above-mentioned general formula, m is 1-8, preferred 1-4.
In above-mentioned general formula, n is 1-8, preferred 1-4.
According to the present invention, the m+n sum is 2-8, is preferably the number of 2-5.
In above-mentioned general formula, R
4Be alkyl or hydroxyalkyl with 1-4 carbon atom.In another embodiment of the present invention, R
4Be benzyl or phenyl-CH
2-CH
2-or phenyl-CH (CH
3)-.In a preferred embodiment of the invention, R
4Be selected from methyl, ethyl, propyl group and butyl.
" hydroxyalkyl " means by a substituted alkyl of hydroxyl.Preferred hydroxyl low-grade alkyl.The instance of preferred group comprises: methylol, 2-ethoxy, 2-hydroxypropyl, 3-hydroxypropyl and 2-hydroxyl butyl.
In following formula, X
-Be anion, be preferably and be selected from chlorion, bromide ion, iodide ion, sulfate radical, pyrovinic acid root, methylsulfate, carbonate and phosphate radical.
The surfactant of said general formula can be with known in principle mode, through the alkoxylate preparation of corresponding primary amine.Be that those skilled in the art are known on this oxyalkylated implementation principle.The same known reaction conditions of those skilled in the art (especially selection of catalysts) can influence the molecular weight distribution of alcoxylates.
Other surfactants
Except the surfactant of above-mentioned general formula, said preparaton can be chosen extra other surfactants that comprises wantonly.Should mention the anion surfactant that does not for example have alkoxyl here, like alkylbenzenesulfonate, alkene sulfonate, alkane sulfonate, alkyl carboxylate, alkyl sulfate and/or alkylphosphonic; Anion surfactant with alkoxyl is like ether sulfate (more preferably alkyl propoxyl group sulfate), ether sulfonate, ether carboxylate and ether phosphate; Alkyl alkoxylates such as alkyl ethoxylate, alkyl propoxyl group ethoxylate; Perhaps betaine or zwitterionic surfactant such as alkyl dimethyl amine oxide.These other surfactants especially also can be oligomer or polymeric surfactant.Advantageously use this type cosurfactant to reduce the amount that forms the required surfactant of microemulsion.
Therefore, this class in polymer type surfactant is also referred to as " microemulsion auxiliary agent ".The instance of this class in polymer type surfactant comprises amphiphilic block copolymer, and it comprises at least one hydrophilic block and at least one hydrophobic block.The example comprises PPOX-polyethylene oxide block copolymer; Polyisobutene-polyethylene oxide block copolymer; And the comb copolymer with ethylene oxide side chain and hydrophobic main chain, wherein said main chain preferably comprises alkene or (methyl) acrylic acid ester basically as monomer.Here, term " polyethylene glycol oxide " should comprise like the defined polyethylene glycol oxide block that comprises propylene oxide unit of preceding text in each case.The further details of this type surfactant is disclosed among the WO2006/131541A1.
The mineral oil recovery method
In mineral oil recovery method of the present invention by WinsorIII type microemulsion flooding; The suitable aqueous formulation of said general formula surfactant is injected well injection mineral oil reservoir via at least one, and from said oil reservoir, extract crude oil out via at least one extraction well.In context of the present invention, term " crude oil " does not mean single phase certainly, and is meant common crude oil-aqueous emulsion.Generally speaking, oil reservoir has several injection wells and several extraction wells usually.The interfacial tension that mainly the acting as of surfactant reduced between the water oil-desirable is to reduce to significantly＜value of 0.1mN/m.After injecting said surfactant preparaton (being called " surfactant flooding ") or preferred microemulsion flooding, can be through water (" water drive ") or more high viscosity water solution (" polymer flooding ") the injection stratum that preferably has a polymer of remarkable thickening effect be keep-uped pressure.Yet, the also known technology of Action of Surfactant that wherein at first make in the stratum.Another known technology is the solution that injects surfactant and thickening polymer, injects thickening polymer solution then.Those skilled in the art know the details of the industrial implementation of " surfactant flooding ", " water drive " and " polymer flooding ", and use suitable technique according to the oil reservoir type.
As far as the inventive method, use the aqueous formulation of the surfactant of said general formula.Outside dewatering, said preparaton also can be chosen wantonly and comprise water miscibility or organic substance or other materials of water dispersible at least.This type additive is particularly useful in storage or surface of stability activator solution during being transported to the oil field.Yet the amount of other solvents of this type should be no more than 50 weight % usually, preferred 20 weight %.In the particularly advantageous embodiment of the present invention, only water is used for preparation.The instance of water miscibility solvent comprises that especially alcohol is like methyl alcohol, ethanol, propyl alcohol, butanols, sec-butyl alcohol, amylalcohol, butyl glycol, butyldiglycol or butyl triethylene glycol.
In the preferred embodiment of the invention, said aqueous surfactant preparaton comprises at least a alkyl alkoxy sulfate or alkyl alkoxy sulfonated type anion surfactant.This anion surfactant is present in the said aqueous surfactant preparaton with the concentration higher than desired cationic surfactant; Be anion surfactant and the ratio of cationic surfactant is 5.5:4.5 at least based on mole; Be preferably 6:4 at least; 7:3 at least more preferably, because charge neutralization, it is solvable to obtain settled solution that said surfactant solution keeps to guarantee.
In a preferred embodiment of the invention, said aqueous surfactant preparaton comprises at least a alkylaryl sulfonates type anion surfactant.This anion surfactant is present in the said aqueous surfactant preparaton with the concentration higher than desired cationic surfactant; Be anion surfactant and the ratio of cationic surfactant is 5.5:4.5 at least based on mole; Be preferably 6:4 at least; 7:3 at least more preferably, because charge neutralization, it is solvable to obtain settled solution that said surfactant solution keeps to guarantee.
According to the present invention, the ratio of the existing all surface activating agent of said general formula surfactant comprise (being the surfactant and the optional surfactant that exists of said general formula) is for being not more than 49 weight %.Preferred this ratio is for being not more than 30 weight %.
Can the mixture that the present invention is used be preferred for the surfactant flooding of oil reservoir.Be particularly suited for Winsor III type microemulsion flooding (in Winsor III scope the displacement of reservoir oil or have the displacement of reservoir oil in the bicontinuous microemulsions phase scope).The technology of microemulsion flooding is described in detail at the beginning part.
Except said surfactant, said preparaton also can comprise other components, for example C
4-C
8Alcohol and/or basic salt (so-called " displacement of reservoir oil of basic surface activating agent ").This type additive for example can be used for reducing the delay in the stratum.Yet based on the ratio of the alcohol of used surfactant total amount be at least usually 1:1-, also can use significantly excessive alcohol.The amount of basic salt can be 0.1-5 weight % usually.
Wherein use the oil reservoir of said method to have usually and be at least 10 ° of C, for example the temperature of 10-150 ° of C preferably has at least 15 ° of C to 120 ° of C, more preferably has the temperature of 15-90 ° of C.All surface activating agent total concentration together is 0.05-5 weight % based on said aqueous surfactant preparaton total amount, is preferably 0.1-2.5 weight %.Those skilled in the art especially make suitable choice according to the condition in the said mineral oil reservoir according to desired properties.At this moment, it will be apparent for a person skilled in the art that said surfactant concentrations can be owing to this preparaton can mix with formation water after injecting the stratum, perhaps surfactant also can be absorbed on the surface of solids on stratum and changes.The huge advantage of the used mixture of the present invention is that said surfactant causes good especially interfacial tension to reduce dissolubility that effect has surfactant simultaneously to obtain settled solution.
Certainly and preferably at first prepare the concentrate of diluted on site only to the desired concn that is used for injecting the stratum.Surfactant total concentration in this concentrate is generally 10-45 weight %.
Hereinafter embodiment is intended to set forth in detail the present invention:
Part I: surfactant synthetic
Universal method 1: through KOH catalysis alkoxylate
In the 2L autoclave, will treat oxyalkylated alcohol (1.0 equivalent) and the KOH aqueous solution that comprises 50 weight %KOH.The amount of KOH is 0.3 weight % of product to be prepared.Under agitation, with this mixture in 100 ° of C and 20 millibars dehydration 2 hours down.Then, use N
2Purge 3 times, set up the N of about 1.3 crust
2Admission pressure, and temperature risen to 120-130 ° of C.So that remaining on the mode of 125-135 ° of C (under the situation of ethylene oxide) or 130-140 ° of C (under the situation of propylene oxide), temperature is metered into oxyalkylene.Under 125-135 ° of C, stirred again 5 hours then, use N
2Purge, be cooled to 70 ° of C, and empty agitated reactor.By in the acetate with alkaline crude product.Perhaps also available commercially available magnesium silicate neutralizes, then with its filtering.By at CDCl
3In
1H-NMR spectrum, gel permeation chromatography and OH pH-value determination pH characterize light product, and measure productive rate.
Universal method 2: through the chlorosulfonic acid sulphation
In the 1L round-bottomed flask, will treat that Sulfated alkyl alkoxylates (1.0 equivalent) is dissolved in the carrene (based on weight %) of 1.5 times of amounts and is cooled to 5-10 ° of C.So that temperature be no more than the mode of 10 ° Cs drip chlorosulfonic acid (1.1 equivalent) thereafter.Make this mixture get warm again after a cold spell to room temperature and under this temperature at N
2Stirred 4 hours in the stream, being up under 15 ° of C, above-mentioned reactant mixture is dropped in the NaOH aqueous solution of half volume then.The amount of calculating NaOH is excessive for a little based on used chlorosulfonic acid to obtain.Gained pH value is about pH9-10.Being up under 50 ° of C, under gentle vacuum, removing carrene on the rotary evaporator.
Product is used
1H-NMR characterizes, and measures the water content (about 70%) of this solution.
Universal method 3: the alkoxylate of amine
In the 2L autoclave, will treat that oxyalkylated primary amine (1.0 equivalent) mixes with low amounts of water (0.1 equivalent).Then, use N
2Purge 3 times, set the N of about 1.3 crust
2Initial pressure, and temperature risen to 120-130 ° of C.So that temperature remains on the oxyalkylene that the mode of 125-135 ° of C is metered into 2.0 equivalents.After this, under 125-135 ° of C, stirred 5 hours again, use N
2Purge, be cooled to 70 ° of C, and the sky agitated reactor that inclines.By in the acetate with alkaline crude product.By at CDCl
3In
1H-NMR spectrum, gel permeation chromatography and OH pH-value determination pH and amine value characterize light product, and measure productive rate.
Randomly, can with the amine of 2.0 equivalent reactions of alkylene oxide and the KOH aqueous solution that comprises 50 weight %KOH.The amount of KOH is 0.3 weight % of product to be prepared.Under agitation, with this mixture in 100 ° of C and 20 millibars dehydration 2 hours down.After this, use N
2Purge 3 times, set the N of about 1.3 crust
2Initial pressure, and temperature risen to 120-130 ° of C.So that remaining on the mode of 125-135 ° of C (as far as ethylene oxide) or 130-140 ° of C (as far as propylene oxide), temperature is metered into oxyalkylene.After this, under 125-135 ° of C, stirred 5 hours again, use N
2Purge, be cooled to 70 ° of C, and the sky agitated reactor that inclines.By at CDCl
3In
1H-NMR spectrum, gel permeation chromatography and OH pH-value determination pH and amine pH-value determination pH characterize light product, and measure productive rate.
Universal method 4: amine and dimethyl suflfate quaternized
It is optional with the water-reducible quaternized amine (1.0 equivalent) of treating of same amount at first in the 2L glass flask, to pack into.Then under agitation, so that being no more than the mode of 60 ° of C, temperature slowly drips dimethyl suflfate (1.0 equivalent).By amine pH-value determination pH conversion ratio.Continuing to stir until quaternized degree is 95% or bigger.Can choose wantonly and use a small amount of excessive dimethyl suflfate (0.1 equivalent).Said excess sulfuric acid dimethyl ester can be through destroying with the of short duration boiling of water.By at CDCl
3In
1H-NMR spectrum, gel permeation chromatography and amine pH-value determination pH characterize light product, and measure productive rate.
Following alkohol and amine is used to synthesize:
Performance test
Use the gained surfactant to test as follows, whether be suitable for tertiary recovery mineral oil to evaluate it.
A) dissolubility
At room temperature, alkyl alkoxy sulfate and cationic surfactant being dissolved in saliferous injects water or from the recovered water (total concentration is 500-3000ppm) of oil reservoir, said solution is risen to reservoir temperature.The optional butyldiglycol (BDG) of adding.After 24 hours, said sample is carried out visual evaluation and only has further application under the settled solution.The injection glassware for drinking water of said two oil reservoirs has the salinity of 4000-30000ppm TDS (salt of total dissolving).Said reservoir temperature is respectively 18 ° of C and 32 ° of C.
B) interfacial tension
In addition, through directly measuring interfacial tension at two kinds of degassed crudes (every kind API is about 14) and the initial saliferous injection method of dripping of revolving under the reservoir temperature of 18 ° of C and 32 ° of C waterborne.For this reason, use the surfactant solution of preparation in a).Under reservoir temperature, oil droplet is introduced in this settled solution, after 2 hours, read interfacial tension.
Test result
The result is shown among the table 1-6.
Table 1 is under 18 ° of C, in the dissolubility of injecting water
Can find out from table 1, exist some under specified criteria, to cause clarifying the combination of surfactant preparaton.
Table 2 is under 18 ° of C, at crude oil I and injection aquatic measurement
Yet compare with table 2, obviously the cationic surfactant based on the group with 12 carbon atoms provides the 6 remarkable poorer interfacial tensions than embodiment.This is surprisingly, because have the surfactant of longer alkyl better interfacial tension is provided usually.Can find out that from embodiment 7 surfactant required for protection not only all provides < the interfacial tension of 0.01mN/>m in low salinity (embodiment 6, total salt content 12500ppm) and under the situation of total salt content for the more high salinity of about 24300ppm.
Table 3 is under 18 ° of C, in the dissolubility of injecting water
In table 3,, can not produce solubility problem even use the surfactant preparaton that comprises higher ethoxylation cationic surfactant yet.
Table 4 is under 18 ° of C, at crude oil I and injection aquatic measurement
Can find out that from table 4 being combined in the wide salinity range of alkyl alkoxy sulfate and higher ethoxylation cationic surfactant has the < interfacial tension of 0.01mN/>m.
Table 5 is under 32 ° of C, in the dissolubility of injecting water
In table 5, the dissolubility of said surfactant preparaton is suitable for having the oil reservoir (32 ° of C, but not 18 ° of C) of higher temperature.Except that said test, said preparaton also comprises the alkali that is the NaOH form.
Table 6 is under 32 ° of C, at crude oil II and injection aquatic measurement
Can find out from table 6, can obtain 0.02mN/m or lower low interfacial tension (embodiment 2-4) by the cation cosurfactant that contains alkyl with 6-10 carbon atom.Demonstrate the interfacial tension of a high one magnitude once more than the cationic surfactant of long-chain among the control Example C1.
Claims (13)
1. the surfactant of a following general formula:
R
1N
+(R
2)
m(R
3)
n(R
4)X
-
Wherein
R
1Be the straight or branched with 6-10 carbon atom, saturated or undersaturated aliphatic series and/or aromatic hydrocarbyl,
R
2And R
3Be methyl, ethyl and benzyl independently of one another, or inferior ethoxyl, inferior propoxyl group and/or inferior butoxy and/or inferior amoxy,
R
4Be alkyl or hydroxyalkyl, benzyl or phenyl-CH with 1-4 carbon atom
2-CH
2-or phenyl-CH (CH
3)-,
M is 1-8,
N is 1-8, and wherein the m+n sum is 2-8, and
X is an anion.
2. according to the surfactant of claim 1, R wherein
2And R
3Be methyl, ethyl or benzyl independently of one another, and n=m=1.
3. according to the surfactant of claim 1, R wherein
2And R
3Inferior ethoxyl and R respectively do for oneself
4Be methyl or ethyl.
4. according to the surfactant of claim 1 or 3, wherein the n+m sum is 2-5.
5. surfactant preparaton that comprises the surfactant of at least a following general formula,
R
1N
+(R
2)
m(R
3)
n(R
4)X
-
Wherein
R
1Be the straight or branched with 6-10 carbon atom, saturated or undersaturated aliphatic series and/or aromatic hydrocarbyl,
R
2And R
3Be methyl, ethyl and benzyl independently of one another, or inferior ethoxyl, inferior propoxyl group and/or inferior butoxy and/or inferior amoxy,
R
4Be alkyl or hydroxyalkyl, benzyl or phenyl-CH with 1-4 carbon atom
2-CH
2-or phenyl-CH (CH
3)-,
M is 1-8,
N is 1-8, and wherein the m+n sum is 2-8, and
X is an anion.
6. according to the surfactant preparaton of claim 5, R wherein
2And R
3Be methyl, ethyl or benzyl independently of one another, and n=m=1.
7. according to the surfactant preparaton of claim 5 or 6, wherein all surface activating agent concentration together is 0.05-5 weight % based on the total amount of said aqueous surfactant preparaton.
8. one kind is passed through the method that Winsor III type microemulsion flooding is exploited mineral oil; To be used for wherein the interfacial tension between the profit is reduced to that < the aqueous surfactant preparaton that comprises at least a ionic surfactant of 0.1mN/>m injects well via at least one and injects the mineral oil reservoir; And from said oil reservoir, extract crude oil out via at least one extraction well, wherein said surfactant preparaton comprises the surfactant of at least a following general formula:
R
1N
+(R
2)
m(R
3)
n(R
4)X
-
Wherein
R
1Be the straight or branched with 6-10 carbon atom, saturated or undersaturated aliphatic series and/or aromatic hydrocarbyl,
R
2And R
3Be methyl, ethyl and benzyl independently of one another, or inferior ethoxyl, inferior propoxyl group and/or inferior butoxy and/or inferior amoxy,
R
4Be alkyl or hydroxyalkyl, benzyl or phenyl-CH with 1-4 carbon atom
2-CH
2-or phenyl-CH (CH
3)-,
M is 1-8,
N is 1-8, and wherein the m+n sum is 2-8, and
X is an anion.
9. according to Claim 8 method, wherein the m+n sum is 2-5.
10. according to the mineral oil recovery method of claim 9, R wherein
2And R
3Be methyl, ethyl or benzyl independently of one another, and n=m=1.
11. each method according to Claim 8-10; Wherein said aqueous surfactant preparaton comprises the anion surfactant of at least a alkyl alkoxy sulfate or alkyl alkoxy sulfonated type, and it is present in the said aqueous surfactant preparaton with the amount bigger than desired cationic surfactant.
12. each method according to Claim 8-10; Wherein said aqueous surfactant preparaton also comprises alkylaryl sulfonates type anion surfactant, and it is present in the said aqueous surfactant preparaton with the amount bigger than desired cationic surfactant.
13. each method according to Claim 8-11, wherein all surface activating agent concentration together is 0.05-5 weight % based on the total amount of said aqueous surfactant preparaton.
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| EP10002490.0 | 2010-03-10 | ||
| EP10002490 | 2010-03-10 | ||
| PCT/EP2011/053552 WO2011110601A2 (en) | 2010-03-10 | 2011-03-09 | Method for producing crude oil using cationic surfactants comprising a hydrophobic block having a chain length of 6 - 10 carbon atoms |
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|---|---|
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| CN103965853A (en) * | 2013-02-05 | 2014-08-06 | 中国石油化工股份有限公司 | Combined surfactant and its preparation method |
| CN106590592A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Composite surfactant for improving crude oil recovery rate |
| CN109169654A (en) * | 2018-10-28 | 2019-01-11 | 扬州润达油田化学剂有限公司 | A kind of heavy oil wells Produced Liquid viscosity reduction fungicide and preparation method thereof |
| CN111566183A (en) * | 2017-05-30 | 2020-08-21 | 巴斯夫欧洲公司 | Method for extracting petroleum from underground oil reservoir with high temperature and salinity |
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| JP6063879B2 (en) | 2011-03-18 | 2017-01-18 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Integrated circuit device, optical device, micromachine, and method for manufacturing mechanical precision device having patterned material layer having a line width of 50 nm or less |
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- 2011-03-09 WO PCT/EP2011/053552 patent/WO2011110601A2/en active Application Filing
- 2011-03-09 JP JP2012556510A patent/JP2013521122A/en active Pending
- 2011-03-09 RU RU2012142938/04A patent/RU2012142938A/en not_active Application Discontinuation
- 2011-03-09 EP EP11707668A patent/EP2544810A2/en not_active Withdrawn
- 2011-03-09 CA CA2792305A patent/CA2792305A1/en not_active Abandoned
- 2011-03-09 MX MX2012010277A patent/MX2012010277A/en not_active Application Discontinuation
- 2011-03-09 CN CN2011800182983A patent/CN102834170A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103965853A (en) * | 2013-02-05 | 2014-08-06 | 中国石油化工股份有限公司 | Combined surfactant and its preparation method |
| CN103965853B (en) * | 2013-02-05 | 2016-08-24 | 中国石油化工股份有限公司 | Combined surfactant and preparation method thereof |
| CN106590592A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Composite surfactant for improving crude oil recovery rate |
| CN106590592B (en) * | 2015-10-20 | 2019-11-08 | 中国石油化工股份有限公司 | Improve the complexed surfactant of oil recovery factor |
| CN111566183A (en) * | 2017-05-30 | 2020-08-21 | 巴斯夫欧洲公司 | Method for extracting petroleum from underground oil reservoir with high temperature and salinity |
| CN109169654A (en) * | 2018-10-28 | 2019-01-11 | 扬州润达油田化学剂有限公司 | A kind of heavy oil wells Produced Liquid viscosity reduction fungicide and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2544810A2 (en) | 2013-01-16 |
| WO2011110601A2 (en) | 2011-09-15 |
| JP2013521122A (en) | 2013-06-10 |
| WO2011110601A3 (en) | 2012-01-19 |
| MX2012010277A (en) | 2012-11-21 |
| CA2792305A1 (en) | 2011-09-15 |
| RU2012142938A (en) | 2014-04-20 |
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