CN106582437A - Composite foaming agent and application thereof - Google Patents
Composite foaming agent and application thereof Download PDFInfo
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- CN106582437A CN106582437A CN201510661704.8A CN201510661704A CN106582437A CN 106582437 A CN106582437 A CN 106582437A CN 201510661704 A CN201510661704 A CN 201510661704A CN 106582437 A CN106582437 A CN 106582437A
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- 239000002131 composite material Substances 0.000 title claims abstract description 81
- 239000004088 foaming agent Substances 0.000 title claims abstract description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000004094 surface-active agent Substances 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 43
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 43
- 239000006260 foam Substances 0.000 claims abstract description 31
- 229920000570 polyether Polymers 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 18
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 15
- 239000003381 stabilizer Substances 0.000 claims abstract description 14
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- -1 organic acid salt Chemical class 0.000 claims description 16
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 10
- 229910001424 calcium ion Inorganic materials 0.000 claims description 10
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 244000007835 Cyamopsis tetragonoloba Species 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 4
- 229940088990 ammonium stearate Drugs 0.000 claims description 4
- JPNZKPRONVOMLL-UHFFFAOYSA-N azane;octadecanoic acid Chemical group [NH4+].CCCCCCCCCCCCCCCCCC([O-])=O JPNZKPRONVOMLL-UHFFFAOYSA-N 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 239000001913 cellulose Substances 0.000 claims 1
- 229920002678 cellulose Polymers 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 claims 1
- 239000000839 emulsion Substances 0.000 abstract description 18
- 238000005187 foaming Methods 0.000 abstract description 4
- 230000008719 thickening Effects 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 description 71
- 229960004424 carbon dioxide Drugs 0.000 description 40
- 238000006243 chemical reaction Methods 0.000 description 33
- 238000001228 spectrum Methods 0.000 description 30
- 239000002904 solvent Substances 0.000 description 27
- 239000013067 intermediate product Substances 0.000 description 26
- 238000002360 preparation method Methods 0.000 description 24
- 238000000034 method Methods 0.000 description 20
- 239000003921 oil Substances 0.000 description 20
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 239000007789 gas Substances 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 238000006068 polycondensation reaction Methods 0.000 description 15
- 238000007259 addition reaction Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 13
- 239000003960 organic solvent Substances 0.000 description 13
- 229920001568 phenolic resin Polymers 0.000 description 13
- 230000015556 catabolic process Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 10
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 10
- 238000010025 steaming Methods 0.000 description 10
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002736 nonionic surfactant Substances 0.000 description 9
- 239000001294 propane Substances 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000003213 activating effect Effects 0.000 description 8
- 238000004949 mass spectrometry Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 241000894007 species Species 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical class CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000000214 vapour pressure osmometry Methods 0.000 description 4
- 239000002569 water oil cream Substances 0.000 description 4
- MHCHQNXRVNQPHJ-UHFFFAOYSA-N 4-hexadecylphenol Chemical compound CCCCCCCCCCCCCCCCC1=CC=C(O)C=C1 MHCHQNXRVNQPHJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000005465 channeling Effects 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical class CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 2
- KJWMCPYEODZESQ-UHFFFAOYSA-N 4-Dodecylphenol Chemical class CCCCCCCCCCCCC1=CC=C(O)C=C1 KJWMCPYEODZESQ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 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 2
- 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 2
- 125000000913 palmityl 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])[H] 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- UMHJEEQLYBKSAN-UHFFFAOYSA-N Adipaldehyde Chemical compound O=CCCCCC=O UMHJEEQLYBKSAN-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- OOLBRPUFHUSCOS-UHFFFAOYSA-N Pimelic dialdehyde Chemical compound O=CCCCCCC=O OOLBRPUFHUSCOS-UHFFFAOYSA-N 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical class N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- ZNWNWEHQFXOPGK-UHFFFAOYSA-N decanedial Chemical compound O=CCCCCCCCCC=O ZNWNWEHQFXOPGK-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
本发明涉及一种复合发泡剂，该复合发泡剂含有：非离子型低聚表面活性剂、有机稳泡剂和水，所述非离子型低聚表面活性剂具有式(Ⅰ)或式(Ⅱ)所示的结构，其中，m为1-50中的任意整数，n为2-8中的任意整数，R1为C4-C20的烷基，R2为聚醚，形成所述聚醚的单体为环氧乙烷和/或环氧丙烷，所述聚醚的聚合度为5-100。本发明还涉及上述复合发泡剂在二氧化碳驱油中的应用。本发明的复合发泡剂在实际使用时用量低、增稠性好；而且，本发明的复合发泡剂用于二氧化碳驱油，形成的乳状液易破乳；本发明的复合发泡剂稳定性好、发泡性能好、适用范围广，可广泛应用于二氧化碳驱油领域。
The present invention relates to a kind of composite foaming agent, and this composite foaming agent contains: non-ionic oligomeric surfactant, organic foam stabilizer and water, described non-ionic oligomeric surfactant has formula (I) or formula The structure shown in (II), wherein, m is any integer in 1-50, n is any integer in 2-8, R 1 is C 4 -C 20 alkyl, R 2 is polyether, forming the The monomer of the polyether is ethylene oxide and/or propylene oxide, and the degree of polymerization of the polyether is 5-100. The present invention also relates to the application of the above composite blowing agent in carbon dioxide flooding. The composite foaming agent of the present invention has low dosage and good thickening property during actual use; moreover, the composite foaming agent of the present invention is used for carbon dioxide flooding, and the emulsion formed is easy to demulsify; the composite foaming agent of the present invention is stable Good performance, good foaming performance, wide application range, can be widely used in the field of carbon dioxide flooding.
Description
Technical field
The present invention relates to a kind of composite foamable agent, and the composite foamable agent is in carbon dioxide drive
Using.
Background technology
At present, the whole world there are about 75% raising recovery projects injection steam, carbon dioxide and light hydrocarbon.
Wherein, raising recovery ratio side of the carbon dioxide drive either as secondary oil recovery still after water drive
Method, is constantly subjected to industry attention.Carbon dioxide flooding oil tech is injected into carbon dioxide as oil displacement agent
In oil reservoir, carbon dioxide can reduce viscosity of crude, improve oil and water mobility ratio, makes crude oil volumetric expansion, from
And increase oil reservoir energy, improve oil-gas mining efficiency.The 50-60 ages in 20th century, because source of the gas enriches,
The U.S., Canada have carried out substantial amounts of field test.2005, the U.S. implemented the crude oil of inflating method and produces
Amount exceedes first thermal recovery annual production, becomes its topmost method for improving oil recovery factor.However, two
There are a series of technical barriers for needing and solving in actual application, also in carbonoxide technology of reservoir sweep.It is first
First, under reservoir conditions, carbon dioxide ratio of viscosities viscosity of crude is little 10-50 times, and unfavorable mobility ratio is caused
Viscous fingering cause gas early breakthrough, production gas-oil ratio high, low viscosity promotes carbon dioxide easily to enter
Enter high permeability formation etc., these reasons make mining site Flooding Efficiency economic benefit be deteriorated.On the other hand, carbon dioxide
Density contrast between crude oil produces Gravity Separation, and low density gas floats, and gravity segregation phenomenon occurs,
Reservoir top small part region can only be involved, the swept volume for causing gas declines, affect gas injection development effect
Really.Therefore, the key link for improving gas injection effect is the mobility for controlling carbon dioxide, slows down has channeling.
Carbon dioxide foaming is to slow down one of method of has channeling during current carbon dioxide drive.Research table
Bright, the apparent viscosity that foam is produced is about 100-1000 times of its gas viscosity, and aerated fluid has
Meet water to stablize, meet oily froth breaking, the characteristic that shut-off capacity increases as permeability increases.Can effectively lower
The relative permeability of gas in porous media, reduces the possibility that gas occurs infiltration to high permeability zone,
So as to expand its swept volume.Some research and development works are carried out to carbon dioxide flooding profile control foaming agent both at home and abroad
Make.The more carbon dioxide foaming agent of document report and practical application be nonionic surfactant, it is cloudy from
Sub- surfactant, Anionic-nonionic surfactant and the compound between them, although have
Certain profile control effect, but still there are problems that it is a lot, for example：
Patent US8857527 discloses a kind of formula of raising recovery ratio, including non-ionic surface active
Agent, the non-emulsified type surfactant of close carbon dioxide, can form stable foam with carbon dioxide and water.
The non-emulsified type surfactant of wherein close carbon dioxide is the surface containing polymeric oxygen ethyl and oxygen propyl group
Activating agent, and carbon dioxide has certain compatibility.Indoor Evaluating Experimentation shows, reaches can apparent viscosity
More than 100 times.But this usual large usage quantity of class surfactant, in actual application, into
This problem is probably one of its bottleneck.
Patent US8695718 discloses nonionic surface active agent for carbon dioxide foaming agent raising
The method of oil recovery factor.In implementation process, first nonionic surfactant and water can be noted from producing well
Enter oil reservoir, be subsequently injected into carbon dioxide, also the foam that three is formed can together be injected.Wherein, it is non-from
Sub- surfactant is the derivative for being based on glycerine, and containing polymeric oxygen ethyl, chain alkyl, consumption
For 0.001-5Vol%, Jing tests, the apparent viscosity of carbon dioxide foaming reaches as high as 140cP.Patent
CN103867169A reports gas soluble surfactants for the side of carbon dioxide drive fluidity control
Method.The ratio mixing of gas soluble surfactants and supercritical carbon dioxide 0.1-1.5% in mass ratio is equal
It is even, it is then injected into oil reservoir.Described gas soluble surfactants are Fatty alcohol polyoxyethylene polyoxypropylene ether
Or NPE.Displacement experiment is analyzed after simulation carbon dioxide flooding, and injection carries surface and lives
The carbon dioxide of property agent, rises can inlet pressure, illustrate to carry out carbon dioxide mobility by forming foam
Control is feasible.Although the addition of nonionic surfactant can solve has channeling in above-mentioned two patents
Problem, but the nonionic surfactant in above-mentioned two can make water and oil formation be difficult to the breast of breakdown of emulsion
Shape liquid.In petroleum production engineering, generally after water drive, when gas drive starts, water content is very high in oil reservoir for gas drive,
Producing well production fluid is the emulsion of oil and water, can cause the difficulty of following process.
Patent CN102660251A disclose a kind of carbon dioxide profile control temperature-resistant anti-salt foaming agent and its
Preparation method.The foaming agent is helped by 15-30% anion-nonionic surfactant hosts, 6-20% nonionics
Foaming agent, 2-5% organic molecules foam stabilizer and 50-77% water composition.The combination formula is applied to temperature
Not higher than 110 DEG C, salinity is not higher than the envelope of the geological conditions carbon dioxide drive of 150000ppm and alters tune
Cut open.But the anion-nonionic surfactant used by the invention equally exists follow-up oil-water emulsion and adds
Work difficult problem, while the anion-nonionic surfactant in foaming agent, with rock in stratum have compared with
High affinity, causes adsorption loss, and the surfactant amount of being actually added into substantially is reduced, during practical application
Forming the possibility of foam in the earth formation reduces.
And, the poor problem of existing foaming agent also existence and stability, and then affect its foam performance.
The content of the invention
The invention aims to overcome the drawbacks described above of composite foamable agent in prior art, there is provided a kind of
Consumption is little when using, easy breakdown of emulsion, the composite foamable agent of good stability, and the composite foamable agent is in dioxy
Change the application in the carbon displacement of reservoir oil.
The present inventor has found that under study for action it is formula (I) or formula to contain structure in composite foamable agent
(II) the nonionic oligo surfactant shown in,
Wherein, m is the arbitrary integer in 1-50, and n is the arbitrary integer in 2-8, R1For C4-C20
Alkyl, R2For polyethers, the monomer for forming the polyethers is oxirane and/or expoxy propane, described
The degree of polymerization of polyethers is 5-100.
Composite foamable agent consumption when actually used can be made little, the easy breakdown of emulsion of water-oil emulsion of formation, and
With high stability.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of composite foamable agent, should
Composite foamable agent contains：Nonionic oligo surfactant, organic foam stabilizer and water, the nonionic
Type oligo surfactant has formula (I) or the structure shown in formula (II),
Wherein, m is the arbitrary integer in 1-50, and n is the arbitrary integer in 2-8, R1For C4-C20
Alkyl, R2For polyethers, the monomer for forming the polyethers is oxirane and/or expoxy propane, described
The degree of polymerization of polyethers is 5-100.
Preferably, m is the arbitrary integer in 1-19.
Preferably, the degree of polymerization of polyethers is 7-50.
On the other hand, the invention provides application of the above-mentioned composite foamable agent in carbon dioxide drive.
Nonionic oligo surfactant in the composite foamable agent of the present invention, structure is between traditional single
Between chain, double-strand surfactant and high molecular surfactant molecule, relative to single-stranded, double-strand surface
Activating agent, has the advantages that low, the good surface-active of critical micelle concentration, rheological property are various, phase
For high molecular surfactant, there is that rate of dispersion is fast, anti-shear performance is good, and this
Nonionic oligo surfactant in bright is branching type, in the case of less than critical micelle concentration,
Netted aggregation is likely to form in aqueous, and these design features cause the composite foamable agent of the present invention to exist
Consumption is low when actually used, thickening property is good；And, the composite foamable agent of the present invention is used for carbon dioxide flooding
Oil, the easy breakdown of emulsion of emulsion of formation；The present invention composite foamable agent in surfactant concentration as little as
During 50ppm, remain to reach half foam life period more than 90 minutes, it is seen that the composite foamable agent of the present invention is steady
Qualitative good, foam performance is good；The applicable stratum water quality of the composite foamable agent of the present invention, total salinity highest
Up to 50000mg/L, calcium ions and magnesium ions concentration may be up to 2000mg/L, it is seen that the present invention's is composite foamed
Agent is applied widely, can be widely applied to carbon dioxide drive field.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Fig. 1 is the hydrogen spectrum spectrogram of the intermediate product of preparation example 1；
Fig. 2 is the carbon spectrum spectrogram of the intermediate product of preparation example 1；
Fig. 3 is the mass spectrogram of the intermediate product of preparation example 1.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
On the one hand, the invention provides a kind of composite foamable agent, the composite foamable agent contains：Nonionic
Oligo surfactant, organic foam stabilizer and water, the nonionic oligo surfactant has formula
(I) structure or shown in formula (II),
Wherein, m is the arbitrary integer in 1-50, and n is the arbitrary integer in 2-8, R1For C4-C20
Alkyl, R2For polyethers, the monomer for forming the polyethers is oxirane and/or expoxy propane, described
The degree of polymerization of polyethers is 5-100.
In the present invention, it is preferable that m is the arbitrary integer in 1-19 such that it is able to further improve multiple
Close the stability and easy breaking of foaming agent.
In the present invention, it is preferable that the degree of polymerization of polyethers is 7-50 such that it is able to further improve compound sending out
The stability of infusion and easy breaking.
In the present invention, organic foam stabilizer be preferably higher aliphatic, long chain organic acid, long chain organic acid salt,
At least one in carboxycellulose, polyacrylamide, soluble starch and modified guar.Wherein,
For higher aliphatic is without particular/special requirement, various higher aliphatics commonly used in the art can be adopted,
Preferably >=8, such as carbon chain lengths can be 8-20 to carbon chain lengths.For long chain organic acid is wanted without special
Ask, various long chain organic acids commonly used in the art, preferably stearic acid, for long-chain can be adopted
Acylate can adopt various salt commonly used in the art, preferably ammonium stearate without particular/special requirement.
The number-average molecular weight of polyacrylamide is preferably 100,000-2,000 ten thousand, more preferably 1,000,000-1,000 ten thousand.
For carboxycellulose, soluble starch and modified guar are without particular/special requirement, can be normal using this area
Various carboxycelluloses, soluble starch and modified guar.
In the present invention, water can be the conventional water for preparing foaming agent, the total ion concentration of water preferably≤
50000mg/L, calcium ions and magnesium ions concentration preferably≤2000mg/L.For the species of water is without particular/special requirement, example
Such as can be running water, well water, distilled water, or total ion concentration and calcium ions and magnesium ions concentration are accorded with
Close the mineralized water of above-mentioned requirements.
The no spy of content in the present invention, to nonionic oligo surfactant, organic foam stabilizer and water
Other restriction, can adopt the conventional content in this area.Preferably, it is with the gross weight of composite foamable agent
Benchmark, the content of nonionic oligo surfactant is 0.001-0.5 weight %, and organic foam stabilizer contains
Measure as 0.001-0.5 weight %, balance of water；It is highly preferred that on the basis of the gross weight of composite foamable agent,
The content of nonionic oligo surfactant is 0.005-0.2 weight %, and the content of organic foam stabilizer is
0.005-0.2 weight %, balance of water.The content of nonionic oligo surfactant and organic foam stabilizer
Can be the same or different.
In the present invention, for formula (I) or structure shown in formula (II) the oligomeric table of nonionic
The preparation method of face activating agent, can be thinkable various using those skilled in the art without particular/special requirement
Method, preferably includes：
(1) under the conditions of phenol-formaldehyde reaction, by structure be formula (III) or compound shown in (IV) with
Structure is that the compound shown in formula (V) carries out phenol-formaldehyde reaction；
(2) under the conditions of polycondensation reaction, the product that step (1) is obtained is with formaldehyde, structure
Compound shown in formula (III) or (IV) carries out polycondensation reaction；
(3) under the conditions of addition reaction, the product that step (2) is obtained is carried out with epoxyalkane
Addition reaction；
Wherein, R1For C4-C20Alkyl, n be 2-8 in arbitrary integer,
Wherein, in step (2), the product that step (1) is obtained is formula (III) with formaldehyde, structure
Or the mol ratio of the compound shown in (IV) is 1：4-210：4-210, it is in this case, obtained
M in nonionic oligo surfactant structural formula (I) or (II) is any whole in 1-50
Number；In step (3), the product that step (2) is obtained is 1 with the mol ratio of epoxyalkane：70-1000,
In this case, in the structural formula (I) of obtained nonionic oligo surfactant or (II)
The degree of polymerization of polyethers is 5-100, wherein, the epoxyalkane is oxirane and/or expoxy propane.
It will be understood by those skilled in the art that the nonionic in the composite foamable agent of the present invention is oligomeric
Surfactant has formula (I) or the structure shown in formula (II), therefore, in step (1) if
Using the compound shown in formula (III), then the compound being also adopted by step (2) shown in formula (III),
If using the compound shown in formula (IV), being then also adopted by formula (IV) in step (2) in step (1)
Shown compound.
In the present invention, in step (1), phenol-formaldehyde reaction condition is preferably included：Carry out in presence of an acid,
Temperature is 100-130 DEG C, and the time is 1-2 hours.
It should be appreciated by those skilled in the art, the phenol-formaldehyde reaction condition of step (1) can also be wrapped
Include：Carry out in a solvent.Wherein, the solvent can be the conventional organic solvent in this area, for example may be used
Think at least one in decahydronaphthalene, two methyl phenyl ethers anisoles and dimethylbenzene.As long as the consumption of solvent can be fully molten
Solution reaction raw materials, enable phenol-formaldehyde reaction to carry out in a solvent, as conventional quantity of solvent, and this is
It is known to one of skill in the art, will not be described here.
In the present invention, in step (1), compound and knot of the structure shown in formula (III) or (IV)
Structure is that the mol ratio of the compound shown in formula (V) is preferably 1：0.05-0.25.
It will be understood by those skilled in the art that acid serves as catalyst in step (1), for acid
Consumption, as long as conventional catalytic amount, it is preferable that the chemical combination with structure as formula shown in (V)
On the basis of the molal quantity of thing, the consumption of acid is 0.1-1.5 mole of %.
It should be appreciated by those skilled in the art, in order to reduce phenol-formaldehyde reaction in generate water to follow-up
The impact of polycondensation reaction, also needs to be post-processed, the side of post processing after step (1) phenol-formaldehyde reaction
Formula is preferably included：Water is steamed at 50-95 DEG C under 0.04-0.1MPa, 20-50 DEG C is then cooled to,
Wherein, solvent also can be steamed partly while water is steamed, different with the boiling point of solvent back and forth using water
Solvent is received, and recovered solvent is added in reaction system as follow-up contracting again after phenol-formaldehyde reaction terminates
The solvent of poly- reaction.
In the present invention, in step (2), polycondensation reaction condition is preferably included：Carry out in presence of an acid,
Temperature is 90-110 DEG C, and the time is 2-4 hours.
It should be appreciated by those skilled in the art, the polycondensation reaction condition of step (2) can also be wrapped
Include：Carry out in a solvent.Wherein, the solvent can be the conventional organic solvent in this area, for example may be used
Think at least one in decahydronaphthalene, two methyl phenyl ethers anisoles and dimethylbenzene.As long as the consumption of solvent can be fully molten
Solution reaction raw materials, enable polycondensation reaction to carry out in a solvent, as conventional quantity of solvent, and this is
It is known to one of skill in the art, will not be described here.
In the present invention, in step (2), the product that step (1) is obtained is formula with formaldehyde, structure
(III) mol ratio of the compound or shown in (IV) is preferably 1：8-80：8-80, when step (1)
The product for obtaining and formaldehyde, structure are that the mol ratio of formula (III) or the compound shown in (IV) is
1：8-80：During 8-80, the structural formula (I) of obtained nonionic oligo surfactant or (II)
In m be arbitrary integer in 1-19 such that it is able to further improve composite foamable agent stability and
Easy breaking.
It will be understood by those skilled in the art that acid serves as catalyst in step (2), for acid
Consumption, as long as conventional catalytic amount, it is preferable that with the product that step (1) is obtained
Molal quantity on the basis of, acid consumption be 0.1-1.5 mole of %.
It should be appreciated by those skilled in the art, in order to reduce polycondensation reaction in generate water to follow-up
The impact of addition reaction, also needs to be post-processed, the side of post processing after step (2) polycondensation reaction
Formula is preferably included：Water is steamed at 50-95 DEG C under 0.04-0.1MPa, 20-50 DEG C is then cooled to,
Wherein, solvent also can be steamed partly while water is steamed, different with the boiling point of solvent back and forth using water
Solvent is received, and is again added to recovered solvent after polycondensation reaction terminates in reaction system as subsequently adding
Into the solvent of reaction.
In the present invention, the acid in step (1) and step (2) is both preferably the concentrated sulfuric acid, concentrated hydrochloric acid and has
At least one in machine acid, organic acid is preferably toluene sulfonic acide and/or DBSA.Wherein,
Sour species in step (2) can be the same or different with the sour species in step (1), be
Simple to operate, the species of acid is identical with sour species in step (1) in step (2).This area
Technical staff should be understood that the concentrated sulfuric acid is H2SO4Concentration more than or equal to 70 weight % sulfuric acid
The aqueous solution, in the present invention, the concentrated sulfuric acid for 70-98 weight % the concentrated sulfuric acid, preferably 95-98 weight
The concentrated sulfuric acid of %.
In the present invention, in step (3), addition reaction condition is preferably included：In the presence of a base and inertia
Carry out under atmosphere, temperature is 130-160 DEG C, the time is 1-4 hours.
It should be appreciated by those skilled in the art, the addition reaction condition of step (3) can also be wrapped
Include：Carry out in a solvent.Wherein, the solvent can be the conventional organic solvent in this area, for example may be used
Think at least one in decahydronaphthalene, two methyl phenyl ethers anisoles and dimethylbenzene.As long as the consumption of solvent can be fully molten
Solution reaction raw materials, enable addition reaction to carry out in a solvent, as conventional quantity of solvent, and this is
It is known to one of skill in the art, will not be described here.
In the present invention, in step (3), product that step (2) is obtained and epoxyalkane mole
Than being preferably 1：170-850, when the product that step (2) is obtained is with the mol ratio of epoxyalkane
1：During 170-850, in the structural formula (I) of obtained nonionic oligo surfactant or (II)
The degree of polymerization of polyethers be 7-50 such that it is able to further improve the stability and easy breakdown of emulsion of composite foamable agent
Property.
It will be understood by those skilled in the art that alkali serves as catalyst in step (3), for alkali
Consumption, as long as conventional catalytic amount, it is preferable that with the product that step (2) is obtained
Molal quantity on the basis of, the consumption of alkali is 0.5-4 mole of %.
In the present invention, the alkali in step (3) is preferably in NaOH, potassium hydroxide and calcium hydroxide
At least one.
It will be understood by those skilled in the art that inert atmosphere can be provided by inert gas, for example may be used
To be provided by the one kind in nitrogen, helium and neon, preferably provided by nitrogen.
In the present invention, during practical operation, for convenience, the judgement of addition reaction terminal in step (3)
Method can for add epoxyalkane after be incubated to pressure at 130-160 DEG C no longer decline after be incubated again
0.5 hour.
In the present invention, can determine that preparing nonionic oligomeric surface lives by hydrogen spectrum, carbon spectrum and mass spectrum
Property agent during intermediate product and nonionic oligo surfactant structural formula, hydrogen spectrum, carbon spectrum and
Mass spectrographic method is known to the skilled person, and will not be described here.
Can be this area for the preparation method of composite foamable agent does not have special restriction in the present invention
The preparation method of conventional foaming agent, for example can be：By nonionic oligo surfactant, organic
Foam stabilizer and water are well mixed, so as to composite foamable agent is obtained, wherein, the mode of mixing can be ability
The conventional hybrid mode in domain.
On the other hand, the invention provides application of the above-mentioned composite foamable agent in carbon dioxide drive.
When actually used, supercritical carbon dioxide can be mixed to form with the composite foamable agent of the present invention
Foam system is injected in oil reservoir, it is also possible to hand over supercritical carbon dioxide with the composite foamable agent of the present invention
For being injected in oil reservoir, supercritical carbon dioxide is preferably with the weight ratio of the composite foamable agent of the present invention
1:3-3:1, more preferably 4:5-2:1, injection rate is preferably 0.3-1.5mL/min, more preferably
0.7-1.2mL/min.Supercritical carbon dioxide is mixed to form foam system with the composite foamable agent of the present invention,
Can be the conventional mixing condition in this area, for example, blended sliver for the condition of mixing is without particular/special requirement
Part can include：Temperature is 40-80 DEG C, and pressure is 8-12MPa.
Embodiment
Molecular weight refers to number-average molecular weight, and vapor-pressure osmometry measurement is with reference to People's Republic of China's standard
GB6597-86 methods are carried out.
Preparation example 1
By 98 weights of the 4- nonyl phenols of 1000 weight portions, the butanedial of 86 weight portions and 1 weight portion
The amount % concentrated sulfuric acids dissolve in the decahydronaphthalene of 200 weight portions, 1h are reacted at 100 DEG C, then in pressure
For 0.06MPa, temperature is to steam water at 75 DEG C, is cooled to 40 DEG C, obtains intermediate product；To steam
Organic solvent reclaim be added to again in reaction system, add the formaldehyde and 5280 weights of 720 weight portions
Amount part 4- nonyl phenols, reaction 3h is carried out at 90 DEG C, then pressure be 0.06MPa, temperature
To steam water at 75 DEG C, 25 DEG C are cooled to；The organic solvent for steaming is reclaimed and is added to reaction system again
In, the NaOH of 1.5 weight portions is added, and in a nitrogen atmosphere, it is passed through 12320 weight portions
Oxirane, be incubated to pressure at 130 DEG C after no longer declining be incubated again 0.5h show addition reaction tie
Beam, is obtained nonionic oligo surfactant A1.
Carry out hydrogen spectrum, carbon spectrum and mass spectroscopy, the hydrogen spectrum of intermediate product, carbon respectively to above-mentioned intermediate product
Spectrum and mass spectroscopy result respectively as shown in Figure 1, Figure 2 and Figure 3, by above-mentioned spectrogram it can be concluded that
The structural formula of intermediate product determines nonionic oligomeric surface as shown in (VI) using vapor-pressure osmometry
The molecular weight of activating agent A1, according to molecular weight and preparation method the structural formula such as (VII) of A1 are can be inferred that
It is shown that (in i.e. equivalent to structural formula (I), it is 2, R that m is 5, n1For nonyl, R2For polymerization
Spend the APEO for 10).
Preparation example 2
By the 4- dodecyl phenols of 5240 weight portions, the decanedial of 170 weight portions and 1.63 weight portions
DBSA dissolve in two methyl phenyl ethers anisoles of 30 weight portions, phenol-formaldehyde reaction is carried out at 130 DEG C
1.5h, is then 0.05MPa in pressure, and temperature is cooled to 30 DEG C, in obtaining to steam water at 65 DEG C
Between product；The organic solvent for steaming is reclaimed and is added in reaction system again, then add 360 weight simultaneously
The formaldehyde of part and the 4- dodecyl phenols of 3144 weight portions, carry out polycondensation reaction 2.5h at 110 DEG C,
Then it is 0.05MPa in pressure, temperature is cooled to 30 DEG C to steam water at 65 DEG C；By having for steaming
Machine solvent recovery is added in reaction system again, adds the calcium hydroxide of 0.4 weight portion, and in nitrogen
Under atmosphere, the oxirane of 7744 weight portions is passed through, is incubated to pressure at 160 DEG C after no longer declining again
Insulation 0.5h shows that addition reaction terminates, and nonionic oligo surfactant A2 is obtained.
Carry out hydrogen spectrum, carbon spectrum and mass spectroscopy, the hydrogen spectrum of intermediate product, carbon respectively to above-mentioned intermediate product
Spectrum and mass spectrogram are unlisted, the structural formula of intermediate product are inferred to by the spectrogram for determining, using steam
Pressure osmosis determines the molecular weight of nonionic oligo surfactant A2, so as to be inferred to the knot of A2
Shown in structure such as formula (I), wherein, it is 8, R that m is 2, n1For dodecyl, R2It is for the degree of polymerization
11 APEO.
Preparation example 3
By the 2- octyl phenols of 824 weight portions, 128 weight portions heptan dialdehyde and 2.58 weight portions to first
Base benzene sulfonic acid dissolves in the dimethylbenzene of 50 weight portions, phenol-formaldehyde reaction 2h is carried out at 110 DEG C, then
It is 0.04MPa in pressure, temperature is cooled to 20 DEG C, obtains intermediate product to steam water at 50 DEG C；
The organic solvent for steaming is reclaimed and is added in reaction system again, then add the first of 1080 weight portions simultaneously
The 2- octyl phenols of aldehyde and 7416 weight portions, carry out polycondensation reaction 3h, then in pressure at 100 DEG C
For 0.04MPa, temperature is to steam water at 50 DEG C, is cooled to 20 DEG C；The organic solvent for steaming is reclaimed
Again it is added in reaction system, adds the potassium hydroxide of 0.28 weight portion, and in a nitrogen atmosphere, leads to
Enter the expoxy propane of 16240 weight portions, be incubated to pressure at 150 DEG C after no longer declining and be incubated 0.5h again
Show that addition reaction terminates, nonionic oligo surfactant A3 is obtained.
Carry out hydrogen spectrum, carbon spectrum and mass spectroscopy, the hydrogen spectrum of intermediate product, carbon respectively to above-mentioned intermediate product
Spectrum and mass spectrogram are unlisted, the structural formula of intermediate product are inferred to by the spectrogram for determining, using steam
Pressure osmosis determines the molecular weight of nonionic oligo surfactant A3, so as to be inferred to the knot of A3
Shown in structure such as formula (II), wherein, it is 5, R that m is 8, n1For octyl, R2It is 7 for the degree of polymerization
Polyethenoxy ether.
Preparation example 4
By the 4- cetyl phenol of 3180 weight portions, the butanedial of 86 weight portions and 0.1 weight portion
The 98 weight % concentrated sulfuric acids dissolve in the decahydronaphthalene of 210 weight portions, and phenol-formaldehyde reaction is carried out at 120 DEG C
1.5h, is then 0.08MPa in pressure, and temperature is cooled to 50 DEG C, in obtaining to steam water at 85 DEG C
Between product；The organic solvent for steaming is reclaimed and is added in reaction system again, then add 2400 weights simultaneously
The formaldehyde of amount part and the 4- cetyl phenol of 25440 weight portions, carry out polycondensation reaction 4h at 90 DEG C,
Then it is 0.08MPa in pressure, temperature is cooled to 50 DEG C to steam water at 85 DEG C；By having for steaming
Machine solvent recovery is added in reaction system again, adds the NaOH of 0.8 weight portion, and in nitrogen
Under atmosphere, the oxirane of 36960 weight portions and the expoxy propane of 48720 weight portions are passed through, 140
It is incubated to pressure at DEG C after no longer declining and is incubated 0.5h again and shows that addition reaction terminates, nonionic is obtained
Oligo surfactant A4.
Carry out hydrogen spectrum, carbon spectrum and mass spectroscopy, the hydrogen spectrum of intermediate product, carbon respectively to above-mentioned intermediate product
Spectrum and mass spectrogram are unlisted, the structural formula of intermediate product are inferred to by the spectrogram for determining, using steam
Pressure osmosis determines the molecular weight of nonionic oligo surfactant A4, so as to be inferred to the knot of A4
Shown in structure such as formula (I), wherein, it is 2, R that m is 19, n1For cetyl, R2It is for the degree of polymerization
The polyethers that 10 polyoxyethylene is inlayed with polyoxypropylene.
Preparation example 5
By the ten of the 2-TBP of 1050 weight portions, the hexandial of 114 weight portions and 1 weight portion
Dialkyl benzene sulfonic acids dissolve in two methyl phenyl ethers anisoles of 50 weight portions, and phenol-formaldehyde reaction 2h is carried out at 100 DEG C,
Then it is 0.1MPa in pressure, temperature is cooled to 30 DEG C, obtains intermediate product to steam water at 95 DEG C；
The organic solvent for steaming is reclaimed and is added in reaction system again, then add the formaldehyde of 480 weight portions simultaneously
With the 2-TBP of 2400 weight portions, polycondensation reaction 3h is carried out at 100 DEG C, then in pressure
For 0.1MPa, temperature is to steam water at 95 DEG C, is cooled to 30 DEG C；The organic solvent for steaming is reclaimed into weight
Newly it is added in reaction system, adds the calcium hydroxide of 2.96 weight portions, and in a nitrogen atmosphere, is passed through
The oxirane of 26400 weight portions, is incubated to pressure after no longer declining at 150 DEG C and is incubated 0.5h again i.e.
Show that addition reaction terminates, nonionic oligo surfactant A5 is obtained.
Carry out hydrogen spectrum, carbon spectrum and mass spectroscopy, the hydrogen spectrum of intermediate product, carbon respectively to above-mentioned intermediate product
Spectrum and mass spectrogram are unlisted, the structural formula of intermediate product are inferred to by the spectrogram for determining, using steam
Pressure osmosis determines the molecular weight of nonionic oligo surfactant A5, so as to be inferred to the knot of A5
Shown in structure such as formula (II), wherein, it is 4, R that m is 3, n1For the tert-butyl group, R2It is 30 for the degree of polymerization
APEO.
Preparation example 6
By the 4- nonyl phenols of 1100 weight portions, the suberic aldehyde of 142 weight portions and 2 weight portions to first
Base benzene sulfonic acid dissolves in the dimethylbenzene of 80 weight portions, phenol-formaldehyde reaction 2h is carried out at 120 DEG C, then
It is 0.1MPa in pressure, temperature is cooled to 20 DEG C, obtains intermediate product to steam water at 90 DEG C；Will
The organic solvent that steams is reclaimed and is added in reaction system again, then add simultaneously 360 weight portions formaldehyde and
The 4- nonyl phenols of 2640 weight portions, carry out polycondensation reaction 2h at 110 DEG C, are then in pressure
0.1MPa, temperature is cooled to 20 DEG C to steam water at 90 DEG C；The organic solvent for steaming is reclaimed again
In being added to reaction system, the potassium hydroxide of 1.68 weight portions is added, and in a nitrogen atmosphere, be passed through
The expoxy propane of 46400 weight portions, is incubated to pressure after no longer declining at 130 DEG C and is incubated 0.5h again i.e.
Show that addition reaction terminates, nonionic oligo surfactant A6 is obtained.
Carry out hydrogen spectrum, carbon spectrum and mass spectroscopy, the hydrogen spectrum of intermediate product, carbon respectively to above-mentioned intermediate product
Spectrum and mass spectrogram are unlisted, the structural formula of intermediate product are inferred to by the spectrogram for determining, using steam
Pressure osmosis determines the molecular weight of nonionic oligo surfactant A6, so as to be inferred to the knot of A6
Shown in structure such as formula (I), wherein, it is 6, R that m is 2, n1For nonyl, R2It is 50 for the degree of polymerization
Polyethenoxy ether.
Preparation example 7
Method according to preparation example 4 prepares nonionic oligo surfactant, and except for the difference that, polycondensation is anti-
Ying Zhong, formaldehyde, the addition of 4- cetyl phenol are respectively 2520 weight portions and 26712 weight portions,
In addition reaction, the intake of oxirane is 38720 weight portions, and the intake of expoxy propane is 51040
Weight portion, is obtained nonionic oligo surfactant A7.
The molecular weight of nonionic oligo surfactant A7 is determined using vapor-pressure osmometry, A7 is drawn
Structural formula such as formula (I) shown in, wherein, it is 2, R that m is 20, n1For cetyl, R2It is poly-
Right is the polyethers that 10 polyoxyethylene is inlayed with polyoxypropylene.
Preparation example 8
Method according to preparation example 3 prepares nonionic oligo surfactant, and except for the difference that, addition is anti-
Ying Zhong, the addition of expoxy propane is 13920 weight portions, and nonionic oligo surfactant is obtained
A8。
The molecular weight of nonionic oligo surfactant A8 is determined using vapor-pressure osmometry, A8 is drawn
Structural formula such as formula (II) shown in, wherein, it is 5, R that m is 8, n1For octyl, R2For polymerization
Spend the polyethenoxy ether for 6.
Embodiment 1
The present embodiment is used to illustrate the composite foamable agent of the present invention.
By nonionic oligo surfactant A1, n-octyl alcohol and water (total ion obtained in preparation example 1
Concentration is 50000mg/L, wherein, calcium ions and magnesium ions concentration is 2000mg/L) it is well mixed, obtain
Composite foamable agent B1, wherein, the consumption of each component is caused on the basis of the gross weight of B1, and A1's contains
Measure as 0.01 weight %, the content of n-octyl alcohol is 0.01 weight %.
Embodiment 2
The present embodiment is used to illustrate the composite foamable agent of the present invention.
By nonionic oligo surfactant A2, stearic acid and water (total ion obtained in preparation example 2
Concentration is 30000mg/L, wherein, calcium ions and magnesium ions concentration is 1000mg/L) it is well mixed, obtain
Composite foamable agent B2, wherein, the consumption of each component is caused on the basis of the gross weight of B2, and A2's contains
Measure as 0.05 weight %, stearic content is 0.02 weight %.
Embodiment 3
The present embodiment is used to illustrate the composite foamable agent of the present invention.
It is 1,500,000 by nonionic oligo surfactant A3, number-average molecular weight obtained in preparation example 3
Polyacrylamide (be purchased from Shandong Wan Hua Chemical Industry Science Co., Ltd) and water (total ion concentration is
10000mg/L, wherein, calcium ions and magnesium ions concentration is 800mg/L) it is well mixed, obtain composite foamed
Agent B3, wherein, the consumption of each component is caused on the basis of the gross weight of B3, and the content of A3 is 0.005
Weight %, the content of polyacrylamide is 0.005 weight %.
Embodiment 4
The present embodiment is used to illustrate the composite foamable agent of the present invention.
Nonionic oligo surfactant A4, modified guar obtained in preparation example 4 (are purchased from into mountain
Dong Yun states Science and Technology Co., Ltd., model YZ-SP) and water (total ion concentration is 5000mg/L,
Wherein, calcium ions and magnesium ions concentration is 200mg/L) it is well mixed, composite foamable agent B4 is obtained, wherein,
The consumption of each component is caused on the basis of the gross weight of B4, and the content of A4 is 0.2 weight %, and be modified melon
The content of your glue is 0.2 weight %.
Embodiment 5
The present embodiment is used to illustrate the composite foamable agent of the present invention.
Nonionic oligo surfactant A5, carboxycellulose obtained in preparation example 5 (are purchased from and are appointed
Qiu Like Chemical Co., Ltd.s) and water (total ion concentration is 1000mg/L, wherein, calcium ions and magnesium ions are dense
Spend for 80mg/L) be well mixed, obtain composite foamable agent B5, wherein, the consumption of each component cause with
On the basis of the gross weight of B5, the content of A5 is 0.1 weight %, and the content of carboxycellulose is 0.05 weight
Amount %.
Embodiment 6
The present embodiment is used to illustrate the composite foamable agent of the present invention.
By nonionic oligo surfactant A6 obtained in preparation example 6, ammonium stearate and water (always from
Sub- concentration is 100mg/L, wherein, calcium ions and magnesium ions concentration is 0.5mg/L) it is well mixed, answered
Foaming agent B6 is closed, wherein, the consumption of each component is caused on the basis of the gross weight of B6, the content of A6
For 0.016 weight %, the content of ammonium stearate is 0.016 weight %.
Embodiment 7
The present embodiment is used to illustrate the composite foamable agent of the present invention.
Method according to embodiment 4 prepares composite foamable agent, except for the difference that, by nonionic oligomeric surface
Activating agent A4 replaces with nonionic oligo surfactant A7, obtains composite foamable agent B7.
Embodiment 8
The present embodiment is used to illustrate the composite foamable agent of the present invention.
Method according to embodiment 3 prepares composite foamable agent, except for the difference that, by nonionic oligomeric surface
Activating agent A3 replaces with nonionic oligo surfactant A8, obtains composite foamable agent B8.
Comparative example 1
Method according to embodiment 1 prepares composite foamable agent, except for the difference that, by nonionic oligomeric surface
Activating agent A1 replaces with Nonionic Anionic Surfactants NPS-10 (dodecylphenol polyoxy second
Alkene ether sulfuric ester salt, is purchased from Zibo Hai Jie Chemical Co., Ltd.s), and the content of surfactant is carried
Height obtains composite foamable agent D1 to 0.5 weight %.
Comparative example 2
Method according to embodiment 1 prepares composite foamable agent, except for the difference that, by nonionic oligomeric surface
Activating agent A1 replaces with nonionic surfactant NP-21, and (NPE, Qingdao day is prosperous
Chemical Co., Ltd.), obtain composite foamable agent D2.
Test case
The foam performance evaluation of test case 1
B1-B8, the D1-D2 for taking 100mL respectively pours the foaming dress of the high-temperature high-pressure air flow method with form into
In putting, then sealing is separately heated to design temperature (each foaming agent design temperature is shown in Table 1), toward solution
In be passed through carbon dioxide, be passed through to produce foam volume reach 500mL, then observe
Record foam volume is reduced to time (i.e. half-life t during original half0.5), the results are shown in Table 1.
The demulsification performance evaluation of test case 2
B1-B8, the D1-D2 for taking 60mL respectively is fitted in respective test tube, is being separately added into 3mL just
Decane, by test tube 40 DEG C are heated to, and are shaken with hands 2 minutes, it is found that oil occurs emulsification with water, so
Water-oil emulsion is placed at 40 DEG C afterwards, observes the situation of water-oil emulsion breakdown of emulsion, water-oil phase is complete
Separate and the time of interface is clear is the breakdown of emulsion time, the results are shown in Table 1.
Table 1
It will be understood by those skilled in the art that half foam life period can reflect stablizing for foaming agent
Property, the half-life is longer, and blowing agent stability is better, so as to illustrate that foam performance is better.The breakdown of emulsion time gets over
It is short, the easier breakdown of emulsion of emulsion for being formed is illustrated, illustrate that impact of the foaming agent to follow-up breakdown of emulsion is less.
B1 is compared respectively with D1 and D2 as can be seen that the composite foamable agent stability of the present invention
Good, foam performance is good, for the easy breakdown of emulsion of emulsion that profit is formed.
B4 and B7 is compared as can be seen that the nonionic in the composite foamable agent of the present invention is low
In the general structure of poly- surfactant, m is the arbitrary integer in 1-19, can further improve multiple
Close the stability and easy breaking of foaming agent.B3 and B8 are compared and can be seen that the present invention's
In the general structure of the nonionic oligo surfactant in composite foamable agent, R2The degree of polymerization be
7-50, can further improve the stability and easy breaking of composite foamable agent.
The composite foamable agent of present invention consumption when actually used is low, thickening property is good；And, it is of the invention
Composite foamable agent is used for carbon dioxide drive, the easy breakdown of emulsion of emulsion of formation；The composite foamable agent of the present invention
Good stability, foam performance are good, applied widely, can be widely applied to carbon dioxide drive field.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, the present invention is no longer separately illustrated to various possible combinations.
Additionally, can also be combined between a variety of embodiments of the present invention, as long as its
Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
Claims (11)
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