CN103965853B - Combined surfactant and preparation method thereof - Google Patents
Combined surfactant and preparation method thereof Download PDFInfo
- Publication number
- CN103965853B CN103965853B CN201310044455.9A CN201310044455A CN103965853B CN 103965853 B CN103965853 B CN 103965853B CN 201310044455 A CN201310044455 A CN 201310044455A CN 103965853 B CN103965853 B CN 103965853B
- Authority
- CN
- China
- Prior art keywords
- surfactant
- polyoxyethylene polyoxypropylene
- water
- polyoxypropylene ether
- alkylol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
- 239000002888 zwitterionic surfactant Substances 0.000 claims abstract description 12
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 85
- -1 propoxyl group Chemical group 0.000 claims description 79
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 71
- 238000006243 chemical reaction Methods 0.000 claims description 62
- 235000002639 sodium chloride Nutrition 0.000 claims description 33
- 239000011734 sodium Substances 0.000 claims description 32
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 25
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 21
- 229960003237 betaine Drugs 0.000 claims description 21
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 20
- 229910052708 sodium Inorganic materials 0.000 claims description 18
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 14
- 239000002585 base Substances 0.000 claims description 14
- 229920001451 polypropylene glycol Polymers 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 230000006837 decompression Effects 0.000 claims description 8
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 8
- 150000007942 carboxylates Chemical class 0.000 claims description 7
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 7
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical class CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- 229940043237 diethanolamine Drugs 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical group [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 125000005265 dialkylamine group Chemical group 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000010612 desalination reaction Methods 0.000 claims description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims 3
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 2
- 125000005233 alkylalcohol group Chemical group 0.000 claims 1
- 238000006073 displacement reaction Methods 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 15
- 238000011084 recovery Methods 0.000 abstract description 10
- 125000000129 anionic group Chemical group 0.000 abstract description 2
- 239000003945 anionic surfactant Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 74
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 64
- 239000000243 solution Substances 0.000 description 29
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 28
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 19
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 17
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 13
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 12
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- NGSFWBMYFKHRBD-UHFFFAOYSA-M sodium lactate Chemical compound [Na+].CC(O)C([O-])=O NGSFWBMYFKHRBD-UHFFFAOYSA-M 0.000 description 12
- 238000002347 injection Methods 0.000 description 11
- 239000007924 injection Substances 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 238000012661 block copolymerization Methods 0.000 description 9
- 229960002668 sodium chloride Drugs 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000003213 activating effect Effects 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 6
- 239000004471 Glycine Substances 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- UXCXDXQIWXBVNI-UHFFFAOYSA-N ethanesulfonic acid;potassium Chemical compound [K].CCS(O)(=O)=O UXCXDXQIWXBVNI-UHFFFAOYSA-N 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 239000010779 crude oil Substances 0.000 description 5
- 239000008398 formation water Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 125000001421 myristyl 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])[H] 0.000 description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 241001044369 Amphion Species 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- 239000004530 micro-emulsion Substances 0.000 description 3
- 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 3
- 230000035699 permeability Effects 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VUQPJRPDRDVQMN-UHFFFAOYSA-N 1-chlorooctadecane Chemical compound CCCCCCCCCCCCCCCCCCCl VUQPJRPDRDVQMN-UHFFFAOYSA-N 0.000 description 2
- RNHWYOLIEJIAMV-UHFFFAOYSA-N 1-chlorotetradecane Chemical compound CCCCCCCCCCCCCCCl RNHWYOLIEJIAMV-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- SNRUBQQJIBEYMU-NJFSPNSNSA-N dodecane Chemical class CCCCCCCCCCC[14CH3] SNRUBQQJIBEYMU-NJFSPNSNSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- CLHYKAZPWIRRRD-UHFFFAOYSA-N 1-hydroxypropane-1-sulfonic acid Chemical compound CCC(O)S(O)(=O)=O CLHYKAZPWIRRRD-UHFFFAOYSA-N 0.000 description 1
- 235000016068 Berberis vulgaris Nutrition 0.000 description 1
- 241000335053 Beta vulgaris Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000007445 Chromatographic isolation Methods 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 210000000867 larynx Anatomy 0.000 description 1
- 125000000400 lauroyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005320 surfactant adsorption Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
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- 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
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Abstract
The present invention relates to combined surfactant and preparation method, the surfactant mainly solving to mainly comprise as oil displacement agent system in prior art exists that heat resistance is poor, interfacial activity is low, be especially unable to reach 10 when low concentration‑3The problem of mN/m ultralow interfacial tension value.The present invention, by using combined surfactant, includes following component: the zwitterionic surfactant of (1) 1 part in terms of mass fraction；The anionic and nonionic surfactant of (2) 0.01 ~ 50 parts；The technical scheme of the water of (3) 0.1 ~ 90 parts, preferably solves this problem, can be used in the tertiary oil recovery production in oil field.Wherein (1), the general molecular formula of (2) component are:(1)(2).
Description
Technical field
The present invention relates to a kind of combined surfactant and preparation method thereof.
Background technology
Along with the increase of world energy sources demand, the rational exploitation and utilization of oil has caused the very big attention of people, at the energy
Today of being becoming tight day, improve recovery ratio and become the key subjects of oil exploitation research, there are about the oil of 2/3 after water drive and be trapped in
In thinner or capillary channel that larynx footpath is narrower, it is in high dispersion state, because of the about 30mN/m of the interfacial tension between profit, displacement
This part oil, depends merely on increase pressure reduction difficulty the biggest.It is 9806.7Kpa because driving required pressure reduction, and during water filling, pressure reduction is only 196.1
～392.3Kpa, much smaller than driving pressure reduction.
Chemical flooding is the main method of tertiary oil recovery, and surfactant flooding occupies critical role in chemical flooding, surface
Activating agent either as host still as the auxiliary agent displacement of reservoir oil, all play immeasurable effect to increasing substantially recovery ratio.
The dominant mechanism using surfactant can improve oil recovery factor is: after oil field enters high water-cut stage, remaining oil is not to connect
Continuous oil film is by trap in the hole of reservoir rocks, and acting on oil droplet two main power is viscap,
If selecting suitable surfactant system, reduce the interfacial tension between profit, make interfacial tension between oil reservoirs profit from
20～30mN/m are down to relatively low or ultralow value (10-3～10-4MN/m), just can reduce oil droplet deformation when making remaining oil move to be carried
The resistance come, thus oil displacement efficiency is greatly improved.Surfactant flooding improves oil recovery factor and depends mainly on surfactant
Sweep efficiency in oil reservoir and oil displacement efficiency.
I.e. Er=E υ Ed
In formula: Er represents recovery ratio, %；E υ represents sweep efficiency, %；Ed represents oil displacement efficiency, %.
Therefore, improve Er to start with from improving Ev and Ed.Activating agent (including surfactant and alkali) is owing to having
Reduce the effects such as oil water interfacial tension, it is possible to increase Ed (oil displacement efficiency).This effect can be by comprehensive effect parameter capillary number
(N) describe:
Ed ∝ N
N=driving force/viscous force ∝ μ υ/YOw
In formula: μ represents injection phase viscosity；υ represents injection phase flow stream velocity；YOwRepresent interfacial tension between profit.
Have been proven in practice that, residual oil saturation to be effectively reduced, it is necessary to capillary number is improved 3～4 orders of magnitude.Due to
Oil reservoir injection rate and limited pressure, it is inadequate for therefore depending merely on raising μ and υ, but can be by oil water interfacial tension YOwReduce by 3
Or the higher order of magnitude, thus be greatly improved capillary number and make Ed (oil displacement efficiency) significantly improve, this is also that activating agent is main
Mechanism of oil displacement.And sweep efficiency to be improved, main way is to reduce the mobility of displacing fluid, and this point can be by adding polymer
Increase displacing fluid viscosity to realize.Adopt in operation three, use ASP ternary built composite reservoir oil displacement system, live by adding surface
Property agent can obtain the ultralow interfacial tension between profit make the displacement of reservoir oil effect (Ed) rate increase, by injection of polymer to increase injection
Fluid viscosity improves sweep efficiency (Ev), injects alkali to reduce surfactant adsorption.Make full use of useful the working in coordination with of ASP
Combined effect, improves oil recovery factor (Er).
Surfactant for EOR has anion surfactant, such as petroleum sulfonate, alkylsulfonate, olefin sulfonic acid at present
Salt and lignosulfonates etc..Use also having been reported that, such as Chinese patent CN 1528853, CN of cationic surfactant
1817431, CN 1066137 etc. in succession report bisamide type cationic, fluorine-containing cationic type and contain pyridine radicals cation pair
Sub-surface activating agent, but big, high in cost of production shortcoming is lost owing to cation has absorption, limit its making at Oil Field
With.The microemulsion flooding of foreign study report, as Kraft etc. has investigated under conditions of water-mineralizing degree is up to 220 g/L, 5%
The microemulsion system phase of APEO alkyl sodium carboxymethyl, phase transition temperature (PIT) rule and interfacial tension, result shows, should
Surfactant does not decomposes in 3 weeks at 95 DEG C, adsorption loss 0.4 mg/g, and without obvious chromatographic isolation, but due to
Surfactant usage amount is big, cost is high, and microemulsion flooding is restricted as oil displacement agent.
Combined surfactant application in tertiary oil recovery is mainly anion and nonionic combined surfactant,
Addition additive alkali is generally required in using, to reach ultralow oil/water interfacial tension, but owing to non-ionic heat resistance is poor,
Often the most ineffective when high temperature.Also there is report as surfactant oil displacement after different anions surfactant package
Lead, as Chinese patent CN1458219A discloses the ultralow interface of Surfactant/Polymer binary of a kind of tertiary oil recovery application
Tension composite drives formula, the surfactant wherein used be petroleum sulfonate or with petroleum sulfonate for host add diluent and
The combined surfactant of other surfactant package, the percentage by weight of its component is petroleum sulfonate 50～100%, alkane
Base sulfonate 0～50%, carboxylate 0～50%, alkylaryl sulfonates 0～35%, low-carbon alcohols 0～20%, this face bioactivator activity
Difference, oil displacement efficiency are low, and surfactant system is the most complicated.Zhang Xueqin etc. (the 3rd phase in 2002 volume 20, colloid be polymerized
Thing, P1～5) have studied anionic (SDS) and zwitterionic surfactant lauroyl
Forming micella ability and reducing the synergistic function of surface tension ability of amine CAB (LMB), finds SDS and LMB
Mass ratio synergistic effect in the range of 7:3 to 3:7 is notable, and the inorganic salts of low concentration can make surfactant package system surface open
Power and critical micelle concentration decline.
The studies above is not directed to the combined system of amphion and anion-nonionic surfactant, although SDS/LMB
Anion/amphion the combined surfactant formed has certain effect for reduction surface tension, synergy, but research is tied
Fruit is not directed to reduce the performances such as oil water interfacial tension, and the application to high-temperature low salt oil reservoir may also cannot be estimated.Therefore, for
The LOW PERMEABILITY RESERVOIR of high-temperature low salt, has invented one Stability Analysis of Structures at the formation temperature, and can form 10 with crude oil-3～10-4mN/m
The combined surfactant of ultralow interfacial tension, and preparation surfactant water both can be that running water is alternatively saline solution,
Can the usage amount of fresh-water-saving.The most this combined surfactant being applicable to high-temperature low salt LOW PERMEABILITY RESERVOIR of the present invention
And preparation method thereof.
Summary of the invention
One of the technical problem to be solved is the surface mainly comprised as oil displacement agent system in prior art
Activating agent exists that heat resistance is poor, interfacial activity is low, be especially unable to reach 10 when low concentration-3MN/m ultralow interfacial tension value
Problem, it is provided that a kind of new combined surfactant.For high-temperature low salt LOW PERMEABILITY RESERVOIR, prepare with this combined surfactant
The aqueous solution, in the concentration range of 0.005 ~ 0.3wt%, forms 10 to crude oil-3～10-4MN/m ultralow interfacial tension, thus
Improve the oil displacement efficiency of oil displacement agent system.
The two of the technical problem to be solved are to provide the described combined surfactant of one of above-mentioned technical problem
Preparation method.
In order to solve one of above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of combined surfactant,
Following component is included in terms of mass fraction:
The zwitterionic surfactant of (1) 1 part；
The anion-nonionic surfactant of (2) 0.01 ~ 50 parts；
The water of (3) 0.1 ~ 90 parts；
Wherein (1), the general molecular formula of (2) component are:
(1)
(2)
In formula, R1And R5Independently of one another selected from C8～C30Alkyl, by C4～C20The substituted phenyl of alkyl；A and c is the third oxygen
The adduction number of group PO, span independent of one another is 1～15；B and d is the adduction number of ethoxy group EO, value independent of one another
It is 1～30；R2And R3Independently of one another selected from C1～C5Alkyl or hydroxy alkyl, R4And R6Independently of one another selected from C1～C5Alkylene
Base or hydroxyl substituted alkylene；X- For-COO-Or-SO3 -, Y is-COOM or-SO3N, M and N are independently of one another selected from alkali metal or ammonium
Base.
In technique scheme, R1And R5It preferably is selected from C independently of one another12～C24Alkyl or by C8～C12The substituted benzene of alkyl
Base；A and c preferably value independently of one another is 2～12, b and d preferably value independently of one another is 1～10；R2、R3It is preferably independently of one another
Methyl, ethyl or ethoxy, R4And R6It preferably is selected from C independently of one another1～C3Alkylidene or hydroxyl replace propylidene；M and N is each other
Independent preferably sodium or potassium, more preferably sodium.
Combined surfactant key active ingredient of the present invention is (1) and (2), one skilled in the art will appreciate that in order to just
From the standpoint of transport and storage or onsite application etc., can be to use various supply forms, the most water-free solid-state form, or
The solid-state form that person is aqueous, or aqueous cream form, or aqueous solution form；Aqueous solution form includes being made into concentration with water
The form of liquid, is directly made into the solution form of on-the-spot displacement of reservoir oil desired concn, and key active ingredient content is the most by weight
The solution of 0.005～0.3wt% is the form that the on-the-spot displacement of reservoir oil is the most suitable.Wherein, water is not had particular/special requirement, can be from
Sub-water, running water, oil field stratum water or oilfield injection water, it is also possible to be inorganic salt solution, such as, the inorganic salts of 1 ~ 30wt%
The inorganic salt solution of the aqueous solution, especially 1 ~ 15wt%；Inorganic salts are preferably at least in sodium chloride, potassium chloride or ammonium chloride
At least one in kind, more preferably sodium chloride or potassium chloride.
Combined surfactant of the present invention, it is also possible to include displacement of reservoir oil component commonly used in the art, such as Polymer Used For Oil Displacement,
Displacement of reservoir oil foaming agent, displacement of reservoir oil solid or liquid base include NaOH, sodium carbonate, sodium acid carbonate, diethanol amine or three ethanol
The little molecule organic amine such as amine, organic molecule auxiliary agent includes short chain fatty alcohol, low carbon chain ketone, DMSO etc..
For solving the two of above-mentioned technical problem, the technical solution adopted in the present invention is as follows: group described in technique scheme
Close the preparation method of surfactant, comprise the following steps:
1) preparation of zwitterionic surfactant:
I. it is 1 by alkylol or alkyl phenol polyoxyethylene polyoxypropylene ether in molar ratio with thionyl chloride: (1 ~ 3) mixes,
Reacting 3 ~ 15 hours under the conditions of reaction temperature 50 ~ 120 DEG C, reaction obtains chloro alkylol or alkyl phenol after terminating after treatment
Polyoxyethylene polyoxypropylene ether；
Ii. by chloro alkylol synthesized in i or alkyl phenol polyoxyethylene polyoxypropylene ether and dialkylamine, water and
Low-carbon alcohols mixes, and is 40 ~ 100 DEG C in temperature and carries out tertiary-aminated reaction 3 ~ 20 hours, continues dropping sulfonating agent or the water of carboxylating agent
Solution, drips the complete reflux temperature that continues at and carries out quaterisation 5 ~ 30 hours, and the dialkyl group steaming low-carbon alcohols and excess is secondary
Amine, remove desalination, obtain alkylol or alkyl phenol polyoxyethylene polyoxypropylene ether carboxylic acid or sulfonate betaine；Wherein, dialkyl group
Secondary amine is dimethylamine, diethanol amine, and sulfonating agent is the alkali gold of the alkali metal salt of 3-chlorine-2-hydroxyl propane sulfonic acid, 2-chloroethanes sulfonic acid
Belonging to salt or PS, carboxylating agent is monoxone or chloroacetic alkali metal salt, and low-carbon alcohols is selected from C1~C3Fatty alcohol,
Chloro alkylol or alkyl phenol polyoxyethylene polyoxypropylene ether, dialkylamine are 1: (1 with the mol ratio of sulfonating agent or carboxylating agent
～3): (1～3)；
2) preparation of anion-nonionic surfactant:
By alkylol or alkyl phenol polyoxyethylene polyoxypropylene ether and sulfonating agent or carboxylating agent, alkali metal hydroxide solid
And solvent is mixed by required proportioning, react 3～15 hours at reaction temperature 50～130 DEG C, react after terminating through post-processing
Alkane alkylol or alkyl phenol polyoxyethylene polyoxypropylene ether sulfonate or carboxylate；Wherein, alkylol or alkyl phenol polyoxypropylene
The mol ratio of APEO, sulfonated reagent or carboxylating reagent and alkali metal hydroxide is 1: (1～4): (1～5), sulfonating agent
For 3-chlorine-2-hydroxyl propane sulfonic acid alkali metal salt, 2-chloroethanes sulfonic acid alkali metal salts or PS, carboxylating agent is chloroethene
Acid or monoxone alkali metal salt, at least one in solvent selected from acetone, benzene, toluene or dimethylbenzene；
3) by the desired amount of alkylol or alkyl phenol polyoxyethylene polyoxypropylene ether carboxylic acid or sulfonate betaine, alkylol
Or alkyl phenol polyoxyethylene polyoxypropylene ether sulfonate or carboxylate, water and low-carbon alcohols add in mixing container, it is warming up to 40 ~
100 DEG C are stirred 1～4 hour, and decompression boils off low-carbon alcohols, obtains required combined surfactant；In terms of mass fraction, alkylol
Or alkyl phenol polyoxyethylene polyoxypropylene ether carboxylic acid or sulfonate betaine, alkylol or alkyl phenol polyoxyethylene polyoxypropylene ether
The proportioning of sulfonate or carboxylate, low-carbon alcohols and water is 1 part: 0.01 ~ 50 part: 0.1 ~ 90 part: 0.1 ~ 90 part, and low-carbon alcohols is selected from C1
~C3Fatty alcohol.
In technique scheme, 1) alkylol or alkyl phenol polyoxyethylene polyoxypropylene ether and thionyl chloride in i step
Mol ratio is preferably 1: 1.2～2.0, and reaction temperature preferably 79 DEG C, the reaction time is preferably 4 ~ 10 hours；1) ii sulfonating agent is preferred
For 3-chlorine-2-hydroxyl propanesulfonate or 2-chloroethanes sodium sulfonate, carboxylating agent is preferably sodium chloroacetate, low-carbon alcohols preferably to ethanol,
Normal propyl alcohol or isopropanol, chloro alkylol or alkyl phenol polyoxyethylene polyoxypropylene ether, dialkylamine and sulfonating agent or carboxylation
The mol ratio of agent is preferably 1: 1.1～1.8: 1～2, and tertiary-aminated reaction temperature is preferably 65 ~ 85 DEG C, that the time is preferably 5 ~ 15 is little
Time, quaterisation is preferably reflux temperature, the time is preferably 6 ~ 20 hours；2) alkylol or alkyl phenol polyoxypropylene in step
The mol ratio of APEO, sulfonated reagent or carboxylating agent and alkali metal hydroxide is preferably 1:: (1～1.5): (1.5～
3.0), reaction temperature is preferably 50～110 DEG C, and the reaction time is preferably 5～12 hours.
Combined surfactant prepared by the present invention, after combining with zwitterionic surfactant due to anion-nonionic, i.e.
The advantages such as the increase of surface-active, the decline of critical micelle concentration, solubilising effect can be presented.This is because live in the moon-non-surface
Property agent in hydrophilic group and zwitterionic surfactant in positive charge there is electrostatic attraction effect, can reduce solution surface with
Plant the repulsive interaction between electric charge, and the hydrocarbon interchain of hydrophobic group of the two also has certain hydrophobic effect, promote different surfaces activity
Agent molecule takes more to be closely spaced mode, thus has higher surface-active, simultaneously because strong electrical function, two
After individual surfactant can form new " associated matter ", it is more likely formed micella in the solution, thus reduces aggregate surface activity
The critical micelle concentration of agent, and the introducing of the nonionic polyoxyalkylene group in the moon-non-surface-active agent both can increase aggregate surface and live
The hydrophily of property agent, simultaneously as steric effect reduces strongly interacting to avoid surfactant between combination agent
The generation of the phenomenons such as liquid-crystalization, precipitation.Two surfactants in combined surfactant are ionic, combination agent also table
Reveal the feature of ionic surface active agent, the most excellent heat resistance.Therefore, this surfactant had both had excellent temperature resistance
Can, there is again the interfacial activity of excellence, it is possible to resolve surfactant is unable to reach 10 when low concentration-3MN/m ultralow interfacial tension
The problem of value so that surfactant, in the migration process of down-hole, still can keep ultralow oil-water interfaces to open even if concentration is relatively low
Power such that it is able to improve oil displacement efficiency.
The present invention relates to the occasion of the concentration of combined surfactant, refer both to containing (1) in technique scheme and
(2) total concentration.
Using combined surfactant prepared by the present invention, by percentage to the quality, consumption is the model of 0.005～0.3wt%
In enclosing, can be used for formation temperature be 60 ~ 90 DEG C, salinity 500～10000 mg/litre, Mg2++Ca2+10 ~ 100 mg/litre
Jiangsu oilfield scene water and crude oil, determine the dynamical interfacial tension value between this aqueous surfactant solution and crude oil, up to
10-3～10-4The ultralow interfacial tension of mN/m, achieves preferable technique effect.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of alkyl phenol polyoxyethylene polyoxypropylene ether sulfonic acid salt form glycine betaine.
Fig. 2 is the infrared spectrogram of alkylol polyoxyethylene polyoxypropylene ether hydroxy-propanesulfonic acid salt.
Application U.S. Nicolet-5700 spectrometer, uses liquid-film method or pressed disc method to carry out infrared spectrum analysis (scanning model
Enclose 4000～400cm-1), determine the chemical constitution of sample, to reach the IR Characterization to compound of the present invention.By
Fig. 1 understands, 1600cm-1It is phenyl ring, 1250cm at Zuo You-1Place is aryl oxide C-O-C, 1060 ~ 11700cm-1There is oxirane ring at place
The characteristic peak of ehter bond, 1080-~ 1190cm in Ethylene Oxide-1Place is the stretching vibration of C-N, 1179,1030,620 cm-1For-SO3's
Absworption peak, it was demonstrated that the product of present invention synthesis is alkyl phenol polyethenoxy ether polyethenoxy ether sulphonate type glycine betaine surface really
Activating agent.As shown in Figure 2, wave number 2914cm-1、2860cm-1For methyl on alkyl chain and methylene C-H telescope features peak, at ripple
Several 726 cm-1The characteristic peak waved in chain alkyl C-H face occurs； 1350cm-1Peak, left and right is the characteristic peak of sulfonate, be by
Cause in the antisymmetric stretching vibration of S=O and the vibration of skeleton carbon；Wave number 1108cm-1Absworption peak for C-O-C key, it was demonstrated that this
The product of bright synthesis is alkylol polyoxyethylene polyoxypropylene ether sulfonic acid salt form the moon-non-surface-active agent really.
Fig. 3 is the variable concentrations oilfield injection water combined surfactant solution interfacial tension figure to dewatered oil.
Fig. 4 is the oil water interfacial tension change with ageing time of 0.1wt% oilfield injection water combined surfactant solution
Figure.
Fig. 5 is the variable concentrations oil field stratum water combined surfactant solution interfacial tension figure to dewatered oil.
Fig. 6 is the oil water interfacial tension change with ageing time of 0.05wt% oil field stratum water combined surfactant solution
Change figure.
The combined surfactant note that Fig. 7 is prepared for the same polymeric degree difference sequence polyethers compared with [embodiment 1]
Enter the aqueous solution interfacial tension figure to dewatered oil.
The combined surfactant ground that Fig. 8 is prepared for the same polymeric degree difference sequence polyethers compared with [embodiment 2]
The layer aqueous solution interfacial tension figure to dewatered oil.
The combined surfactant ground that Fig. 9 is prepared for the same polymeric degree random copolymerization polyethers compared with [embodiment 3]
The layer aqueous solution interfacial tension figure to dewatered oil.
Figure 10 is the amphion compared with [embodiment 1], anion-nonionic surfactant injects the aqueous solution to dehydration
The interfacial tension figure of crude oil.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
1) synthesis [a=8, b=2, the R of nonyl phenol poly-oxypropylene APEO glycine betaine2=CH3,R3=CH3,R4=CH2CH
(OH)CH2,X-=SO3 -]
I. to poly-equipped with adding nonyl phenol poly-oxypropylene in dry four mouthfuls of reaction bulbs of stirring, condensation and device for absorbing tail gas
Oxygen vinethene (a=8, b=2) 463.2 grams (0.6 mole), thionyl chloride 107.1 grams (0.9 mole), be heated to backflow, keep back
Stream reaction 6 hours, reaction changes distilling apparatus into and boils off the thionyl chloride of excess after terminating, obtain chloro nonyl phenol poly-oxypropylene and gather
Oxygen vinethene (a=8, b=2) 467.2g, yield 98.5%.
Ii. by chloro nonyl phenol poly-oxypropylene APEO (a=8, b=2) synthesized by i 237.2 g(0.3 mole) add
Enter in the four-hole boiling flask with reflux condensate device, thermometer and agitator, and add 33wt% dimethylamine agueous solution 61.4g
(0.45 mole), water 30g and isopropanol 90g phase mix, and are heated to 80 DEG C and react, and add 30wt% hydrogen-oxygen in course of reaction
Change sodium water solution to absorb the hydrogen chloride gas that reaction generates, and to keep pH value of reaction system be 7.5 ~ 9, after reacting 8 hours, to
Reactant liquor continues the aqueous solution 255.5 grams (0.39 mole) of dropping 30wt% 3-chlorine-2-hydroxyl propanesulfonate, drips complete
React 15 hours in reflux temperature.After reaction result, the salt solution of point sub-cloud, upper organic phase steams the two of isopropanol and excess
Methylamine, 60 DEG C of vacuum drying, obtain nonyl phenol poly-oxypropylene APEO glycine betaine [a=8, b=2, R2=CH3,R3=CH3,R4=
CH2CH(OH)CH2,X-=SO3 -]。
2) synthesis [c=2, d=4, the R of octadecyl polyoxyethylene polyoxypropylene ether hydroxypropionate sodium6=CH2CH(OH)
CH2,Y=SO3Na]
By octadecyl polyoxyethylene polyoxypropylene ether (c=2, d=4) 281 grams (0.5 mole) and 40 grams of (1 mole) hydrogen
Sodium oxide molybdena, 147.4 grams of (0.75 mole) 3-chlorine-2-hydroxyl propanesulfonates, 12.9 grams of TBABs and 900 milliliters of benzene mixing
In being furnished with four mouthfuls of reaction bulbs of 2000 milliliters of mechanical agitation, thermometer and reflux condensing tube, it is heated to 75 DEG C of reactions 8 little
Time.Cooling, is acidified to water layer pH=2 ~ 3, branch vibration layer with the hydrochloric acid of 15wt%, and organic layer concentrates and removes solvent, with 40wt% hydrogen-oxygen
Change sodium water solution neutralize, 60 DEG C of vacuum drying, obtain octadecyl polyoxyethylene polyoxypropylene ether hydroxypropionate sodium [c=2, d=4,
R6=CH2CH(OH)CH2,Y=SO3Na]。
Nonyl phenol poly-oxypropylene APEO glycine betaine [a=8, b=2, R to synthesis2=CH3,R3=CH3,R4=CH2CH
(OH)CH2,X-=SO3 -] carrying out infrared spectrum analysis, Fig. 1 is the infrared spectrum recorded；Octadecyl polyoxypropylene to synthesis
APEO hydroxypropionate sodium [c=2, d=4, R6=CH2CH(OH)CH2,Y=SO3Na] carry out infrared analysis, Fig. 2 is for recording
Infrared spectrum.
3) in terms of mass parts, 1 is taken) nonyl phenol poly-oxypropylene APEO glycine betaine [a=8, b=2, the R that synthesize2=CH3,
R3=CH3,R4=CH2CH(OH)CH2,X-=SO3 -] 30 parts, 2) octadecyl polyoxyethylene polyoxypropylene ether hydroxyl the third sulphur of synthesizing
Acid sodium [c=2, d=4, R6=CH2CH(OH)CH2,Y=SO3Na] 15 parts, 55 parts of ethanol and 60 parts of 3wt% sodium-chloride water solutions successively
Adding in reaction bulb, be warming up to 75 DEG C and stir 2 hours, ethanol is removed in decompression distillation, obtains the aggregate surface that concentration is 45.2wt%
Activating agent.
[embodiment 2]
1) synthesis [a=6, b=2, the R of dodecyl phenol polyoxyethylene polyoxypropylene ether glycine betaine2= CH2CH2OH,R3=
CH2CH2OH,R4=CH2CH2,X-=SO3 -]
I. dodecylphenol polyoxy third is added to equipped with in dry four mouthfuls of reaction bulbs of stirring, condensation and device for absorbing tail gas
Alkene APEO (a=6, b=2) 418.8 grams (0.6 mole), thionyl chloride 121.4 grams (1.02 moles), be heated to backflow, protects
Holding back flow reaction 7 hours, reaction post-processes with [embodiment 1] after terminating, and obtains chlorinated dodecane base phenol polyoxypropylene polyoxy second
Alkene ether (a=6, b=2) 418.7g, yield 97.4%.
Ii. chlorinated dodecane base phenol polyoxyethylene polyoxypropylene ether (a=6, b=2) 215.0 g(0.3 synthesized by i is rubbed
You) add in four-hole boiling flask with reflux condensate device, thermometer and agitator, and add diethanol amine 34.7g(0.33 and rub
You), water 20g and ethanol 60g phase mix, be heated to 75 DEG C and react, course of reaction is added 30wt% NaOH water-soluble
Liquid is to absorb the hydrogen chloride gas that reaction generates, and to keep pH value of reaction system be 7.5 ~ 9, after reacting 10 hours, to reactant liquor
Middle addition one is hydrated 2-chloroethanes sodium sulfonate 83.0 grams and (0.45 mole) water 150g, feeds complete in reflux temperature reaction
20 hours, reaction post-processed with [embodiment 1] after terminating, and obtains dodecyl phenol polyoxyethylene polyoxypropylene ether glycine betaine [a=
6,b=2,R2= CH2CH2OH,R3=CH2CH2OH,R4=CH2CH2,X-=SO3 -]。
2) synthesis [c=8, d=6, the R of nonyl phenol poly-oxypropylene APEO ethyl sulfonic acid potassium6=CH2CH2,Y=SO3K]
Except by nonyl phenol poly-oxypropylene APEO (c=8, d=6), hydration 2-chloroethanes sodium sulfonate and a hydroxide
The mol ratio of sodium is 0.5:: react at 0.75: 1, and toluene is that solvent reacts 5 hours in 100 DEG C, with the potassium hydroxide of 40wt%
The NaOH substituting 40wt% neutralizes, and other operation, with [embodiment 1], obtains nonyl phenol poly-oxypropylene APEO ethyl sulfonic acid
Potassium [c=8, d=6, R6=CH2CH2,Y=SO3K]
3) in terms of mass parts, 1 is taken) the dodecyl phenol polyoxyethylene polyoxypropylene ether glycine betaine that synthesizes [a=6, b=2,
R2= CH2CH2OH,R3=CH2CH2OH,R4=CH2CH2,X-=SO3 -] 50 parts, 2) the nonyl phenol poly-oxypropylene APEO that synthesizes
Ethyl sulfonic acid potassium [c=8, d=6, R6=CH2CH2,Y=SO3K] 20 parts, 30 parts of isopropanols and 35 parts of deionized water solutions are sequentially added into
In reaction bulb, being warming up to 80 DEG C and stir 2 hours, isopropanol is removed in decompression distillation, obtains the aggregate surface that concentration is 70.3wt% and lives
Property agent.
[embodiment 3]
1) synthesis [a=4, b=8, the R of myristyl polyoxyethylene polyoxypropylene ether glycine betaine2= CH3,R3= CH3,R4=
CH2CH2,X-=SO3 -]
I. myristyl polyoxypropylene is added to equipped with in dry four mouthfuls of reaction bulbs of stirring, condensation and device for absorbing tail gas
APEO (a=4, b=8) 478.8 grams (0.6 mole), thionyl chloride 85.7 grams (0.72 mole), be heated to backflow, keeps
Back flow reaction 8 hours, reaction post-processes with [embodiment 1] after terminating, obtains chloro-tetradecane base polyoxyethylene polyoxypropylene ether
(a=4, b=8) 478.6g, yield 97.7%.
Ii. by chloro-tetradecane base polyoxyethylene polyoxypropylene ether (a=4, b=8) synthesized by i 245.0 g(0.3 mole)
Add in the four-hole boiling flask with reflux condensate device, thermometer and agitator, and add 33wt% dimethylamine agueous solution 73.6g
(0.54 mole), water 30g and normal propyl alcohol 90g phase mix, and are heated to 85 DEG C and react, and add 30wt% hydrogen-oxygen in course of reaction
Change sodium water solution to absorb the hydrogen chloride gas that reaction generates, and to keep pH value of reaction system be 7.5 ~ 9, after reacting 6 hours, to
Reactant liquor adds hydration 2-chloroethanes sodium sulfonate 88.6 grams and (0.48 mole) water 150g, feeds complete in backflow temperature
Degree reaction 18 hours, reaction post-processes with [embodiment 1] after terminating, obtains myristyl polyoxyethylene polyoxypropylene ether glycine betaine
[a=4,b=8,R2=CH3,R3= CH3,R4=CH2CH2,X-=SO3 -]。
2) synthesis [c=2, d=4, the R of octadecyl polyoxyethylene polyoxypropylene ether hydroxypropionate sodium6=CH2CH(OH)
CH2,Y=SO3Na]
Except by octadecyl polyoxyethylene polyoxypropylene ether (c=2, d=4), 3-chlorine-2-hydroxyl propanesulfonate and hydroxide
The mol ratio of potassium is 0.5:: react at 0.6: 1.5, and acetone is that solvent reacts 12 hours in 55 DEG C, and other operation is with [embodiment
1], octadecyl polyoxyethylene polyoxypropylene ether hydroxypropionate sodium [c=2, d=4, R are obtained6=CH2CH(OH)CH2,Y=SO3Na]。
3) in terms of mass parts, 1 is taken) myristyl polyoxyethylene polyoxypropylene ether glycine betaine [a=4, b=8, the R that synthesize2=
CH3,R3= CH3,R4=CH2CH2,X-=SO3 -] 40 parts, 2) the octadecyl polyoxyethylene polyoxypropylene ether hydroxy-propanesulfonic acid that synthesizes
Sodium [c=2, d=4, R6=CH2CH(OH)CH2,Y=SO3Na] 10 parts, 50 parts of isopropanols and 55 parts of 5wt% sodium-chloride water solution water depend on
In secondary addition reaction bulb, being warming up to 80 DEG C and stir 3 hours, isopropanol is removed in decompression distillation, obtains the combination that concentration is 49.8wt%
Surfactant.
[embodiment 4]
1) synthesis [a=4, b=4, the R of octadecyl polyoxyethylene polyoxypropylene ether glycine betaine2= CH2CH2OH,R3=
CH2CH2OH,R4= CH2CH(OH)CH2,X-=SO3 -]
I. octadecyl polyoxypropylene is added to equipped with in dry four mouthfuls of reaction bulbs of stirring, condensation and device for absorbing tail gas
APEO (a=4, b=4) 406.8 grams (0.6 mole), thionyl chloride 107.1 grams (0.9 mole), be heated to backflow, keeps
Back flow reaction 6 hours, reaction post-processes with [embodiment 1] after terminating, obtains chlorooctadecane base polyoxyethylene polyoxypropylene ether
(a=4, b=4) 410.0g, yield 98.1%.
Ii. by chlorooctadecane base polyoxyethylene polyoxypropylene ether (a=4, b=4) 209.0g(0.3 mole synthesized by i)
Add in four-hole boiling flask with reflux condensate device, thermometer and agitator, and add diethanol amine 34.7g(0.33 and rub
You), water 20g and normal propyl alcohol 60g phase mix, be heated to 85 DEG C and react, course of reaction is added 30wt% NaOH water
Solution is to absorb the hydrogen chloride gas that reaction generates, and to keep pH value of reaction system be 7.5 ~ 9, after reacting 6 hours, to reactant liquor
The middle aqueous solution 353.7 grams (0.54 mole) continuing dropping 30wt% 3-chlorine-2-hydroxyl propanesulfonate, feeds complete in backflow
Thermotonus 12 hours, reaction post-processes with [embodiment 1] after terminating, obtains octadecyl polyoxyethylene polyoxypropylene ether beet
Alkali [a=4, b=4, R2= CH2CH2OH,R3= CH2CH2OH,R4= CH2CH(OH)CH2,X-=SO3 -]。
2) synthesis [c=8, d=6, the R of nonyl phenol poly-oxypropylene APEO ethyl sulfonic acid potassium6=CH2CH2,Y=SO3K]
Except by nonyl phenol poly-oxypropylene APEO (c=8, d=6), hydration 2-chloroethanes sodium sulfonate and a hydroxide
The mol ratio of sodium is 0.5:: react at 0.6: 1.5, and benzene is that solvent reacts 10 hours in 75 DEG C, replaces with the potassium hydroxide of 40wt%
NaOH for 40wt% neutralizes, and other operation, with [embodiment 1], obtains nonyl phenol poly-oxypropylene APEO ethyl sulfonic acid potassium
[c=8,d=6, R6=CH2CH2,Y=SO3K]。
3) in terms of mass parts, 1 is taken) octadecyl polyoxyethylene polyoxypropylene ether glycine betaine [a=4, b=4, the R that synthesize2=
CH2CH2OH,R3= CH2CH2OH,R4= CH2CH(OH)CH2,X-=SO3 -] 15 parts, 2) the nonyl phenol poly-oxypropylene polyoxy second that synthesizes
Alkene ether ethyl sulfonic acid potassium [c=8, d=6, R6=CH2CH2,Y=SO3K] 20 parts, 35 parts of ethanol and 62 parts of 8wt% sodium chloride/potassium chloride
The aqueous solution is sequentially added in reaction bulb, is warming up to 75 DEG C and stirs 3 hours, and ethanol is removed in decompression distillation, and obtaining concentration is 35.0wt%
Combined surfactant.
[embodiment 5]
1) synthesis [a=10, b=1, the R of docosyl polyoxyethylene polyoxypropylene ether glycine betaine2=CH2CH2OH,R3=
CH2CH2OH,R4= CH2,X-=COO-]
I. docosyl polyoxy third is added to equipped with in dry four mouthfuls of reaction bulbs of stirring, condensation and device for absorbing tail gas
Alkene APEO (a=10, b=1) 570 grams (0.6 mole), thionyl chloride 142.8 grams (1.2 moles), be heated to backflow, keeps
Back flow reaction 4 hours, reaction post-processes with [embodiment 1] after terminating, obtains chloro docosyl polyoxyethylene polyoxypropylene
Ether (a=10, b=1) 572.9g, yield 98.6%.
Ii. chloro docosyl polyoxyethylene polyoxypropylene ether (a=10, the b=1) 290.6g(0.3 synthesized by i is rubbed
You) add in four-hole boiling flask with reflux condensate device, thermometer and agitator, and add diethanol amine 34.7g(0.33 and rub
You), water 20g and ethanol 60g phase mix, be heated to 65 DEG C and react, course of reaction is added 30wt% NaOH water-soluble
Liquid is to absorb the hydrogen chloride gas that reaction generates, and to keep pH value of reaction system be 7.5 ~ 9, after reacting 6 hours, in reactant liquor
Continue the aqueous solution 96.1 grams (0.33 mole) of dropping 40wt% sodium chloroacetate, feed complete in reflux temperature reaction 7 hours, instead
Post-process with [embodiment 1] after should terminating, obtain docosyl polyoxyethylene polyoxypropylene ether glycine betaine [a=10, b=1, R2=
CH2CH2OH,R3= CH2CH2OH,R4= CH2,X-=COO-]。
2) synthesis [c=2, d=4, the R of octadecyl polyoxyethylene polyoxypropylene ether hydroxypropionate sodium6=CH2CH(OH)
CH2,Y=SO3Na]
Except by octadecyl polyoxyethylene polyoxypropylene ether (c=2, d=4), 3-chlorine-2-hydroxyl propanesulfonate and hydroxide
The mol ratio of sodium is 0.5:: react at 0.55: 1.5, and toluene is that solvent reacts 16 hours in 110 DEG C, and other operation is with [implementing
Example 1], obtain octadecyl polyoxyethylene polyoxypropylene ether hydroxypropionate sodium [c=2, d=4, R6=CH2CH(OH)CH2,Y=
SO3Na]。
3) in terms of mass parts, 1 is taken) the docosyl polyoxyethylene polyoxypropylene ether glycine betaine that synthesizes [a=10, b=1,
R2=CH2CH2OH,R3= CH2CH2OH,R4= CH2,X-=COO-] 25 parts, 2) the octadecyl polyoxyethylene polyoxypropylene ether that synthesizes
Hydroxypropionate sodium [c=2, d=4, R6=CH2CH(OH)CH2,Y=SO3Na] 5 parts, 35 parts of normal propyl alcohols and 75 parts of 10wt% sodium chloride
The aqueous solution is sequentially added in reaction bulb, is warming up to 85 DEG C and stirs 2 hours, and normal propyl alcohol is removed in decompression distillation, and obtaining concentration is
The combined surfactant of 31.1wt%.
[embodiment 6]
1) synthesis [a=6, b=2, the R of docosyl polyoxyethylene polyoxypropylene ether glycine betaine2=CH3,R3=CH3,R4=
CH2,X-=COO-]
I. docosyl polyoxy third is added to equipped with in dry four mouthfuls of reaction bulbs of stirring, condensation and device for absorbing tail gas
Alkene APEO (a=6, b=2) 457.2 grams (0.6 mole), thionyl chloride 121.4 grams (1.02 moles), be heated to backflow, protects
Holding back flow reaction 10 hours, reaction post-processes with [embodiment 1] after terminating, and obtains chloro docosyl polyoxypropylene polyoxy second
Alkene ether (a=6, b=2) 453.8g, yield 96.9%.
Ii. chloro docosyl polyoxyethylene polyoxypropylene ether (a=6, the b=2) 234.2g(0.3 synthesized by i is rubbed
You) add in the four-hole boiling flask with reflux condensate device, thermometer and agitator, and add 33wt% dimethylamine agueous solution
53.2g(0.39 mole), water 30g and ethanol 90g phase mix, be heated to 80 DEG C and react, course of reaction is added 30wt%
Sodium hydrate aqueous solution is to absorb the hydrogen chloride gas that reaction generates, and to keep pH value of reaction system be 7.5 ~ 9, reacts 8 hours
After, in reactant liquor, add monoxone 36.9 grams (0.39 mole) and 40wt% sodium hydrate aqueous solution 40g, feed complete in returning
Stream thermotonus 10 hours, reaction post-processes with [embodiment 1] after terminating, obtains docosyl polyoxyethylene polyoxypropylene ether
Glycine betaine [a=6, b=2, R2=CH3,R3=CH3,R4= CH2,X-=COO-]。
2) synthesis [c=2, d=4, the R of octadecyl polyoxyethylene polyoxypropylene ether hydroxypropionate sodium6=CH2CH(OH)
CH2,Y=SO3Na]
Except by octadecyl polyoxyethylene polyoxypropylene ether (c=2, d=4), 3-chlorine-2-hydroxyl propanesulfonate and hydroxide
The mol ratio of sodium is 0.5:: react at 0.75: 0.75, and toluene is that solvent reacts 7 hours in 95 DEG C, and other operation is with [implementing
Example 1], obtain octadecyl polyoxyethylene polyoxypropylene ether hydroxypropionate sodium [c=2, d=4, R6=CH2CH(OH)CH2,Y=
SO3Na]。
3) in terms of mass parts, 1 is taken) docosyl polyoxyethylene polyoxypropylene ether glycine betaine [a=6, b=2, the R that synthesize2=
CH3,R3=CH3,R4= CH2,X-=COO-] 15 parts, 2) the eight alkyl polyoxyethylene polyoxypropylene ether hydroxypropionate sodium [c that synthesize
=2,d=4, R6=CH2CH(OH)CH2,Y=SO3Na] 5 parts, 30 parts of isopropanols and 85 parts of 15wt% sodium-chloride water solutions are sequentially added into
In reaction bulb, being warming up to 85 DEG C and stir 2 hours, normal propyl alcohol is removed in decompression distillation, obtains the aggregate surface that concentration is 19.8wt% and lives
Property agent.
[embodiment 7]
The combined surfactant [embodiment 1 ~ 6] prepared adds Jiangsu Shanian Oilfield injection water, and (total salinity TDS is
800 mg/litre, Mg2++Ca2+It is 35 mg/litre) in, stir 2 hours in 30 DEG C, obtain 0.3wt% combined surfactant female
Liquid, is diluted to variable concentrations with the water of same salinity, measures combined surfactant solution former with the dehydration of Jiangsu Shanian Oilfield
The oil water interfacial tension of oil, test temperature is 85 DEG C, in the range of 0.005～0.3wt%, the combined surfactant aqueous solution
And the dynamical interfacial tension value between crude oil is up to 10-2～10-4The ultralow interfacial tension value of mN/m, as shown in Figure 3.Interface is opened
The TX500 type that power is produced by Texas ,Usa university rotates and drips interfacial tensimeter mensuration.
[embodiment 8]
With [embodiment 7], it is that 0.1wt% injects water that the combined surfactant that [embodiment 1 ~ 6] synthesizes is configured to concentration
Each 100 milliliters of solution, is respectively charged in the pressure vessel of 100 milliliters, puts into the baking oven of 110 DEG C after sealing, measures different old
Oil water interfacial tension (temperature measuring tension force is still 85 DEG C) during the change time.After aging 14 days of temperature 110 DEG C, 0.1wt%'s
The combined surfactant aqueous solution still can keep 10 with the interfacial tension of dewatered oil-3～10-4The ultralow value of mN/m, is shown in Fig. 4 institute
Show.
[embodiment 9]
With [embodiment 7], difference preparation surfactant water changes oil field stratum water into, and (total salinity TDS is
12000 mg/litre, Mg2++Ca2It is 45 mg/litre).In the range of 0.005～0.3wt%, the combined surfactant aqueous solution
And the dynamical interfacial tension value between crude oil is up to 10-2～10-4The ultralow interfacial tension value of mN/m, as shown in Figure 5.
[embodiment 10]
With [embodiment 8] into, aging temperature is changed 85 DEG C, use the formation water preparation 0.05wt% surface with [embodiment 9]
Activator solution, measures the oil water interfacial tension of different ageing time.After aging 90 days of temperature 85 DEG C, the combination of 0.05wt%
Aqueous surfactant solution still can keep 10 with the interfacial tension of dewatered oil-3～10-4The ultralow value of mN/m, as shown in Figure 6.
[comparative example 1]
Except substituting " the nonyl phenol of block copolymerization with " Nonyl pheno (2) polyoxypropylene (8) ether " of block copolymerization
Polyoxyethylene polyoxypropylene ether (a=8, b=2) " as preparing the initiation material of zwitterionic surfactant, remaining operation with
[embodiment 1].Open with the oil-water interfaces of [embodiment 7] mensuration variable concentrations injection aqueous solution with Jiangsu Shanian Oilfield dewatered oil
Power, test temperature is 85 DEG C, and in the range of 0.005～0.3wt%, dynamical interfacial tension value is up to 10-3MN/m is as shown in Figure 7.
[comparative example 2]
Except " octadecyl polyoxyethylene (4) polyoxypropylene (2) ether " with block copolymerization substitutes " the ten of block copolymerization
Eight alkyl polyoxyethylene polyoxypropylene ether (c=2, d=4) " as preparing the initiation material of anion-nonionic surfactant, remaining
Operation is with [embodiment 1].Measure variable concentrations with [embodiment 7] and inject the profit of the aqueous solution and Jiangsu Shanian Oilfield dewatered oil
Interfacial tension, test temperature is 85 DEG C, and in the range of 0.005～0.3wt%, dynamical interfacial tension value is up to 10-2～10- 3MN/m is as shown in Figure 7.
[comparative example 3]
Except " dodecyl phenol polyethenoxy (2) polyoxypropylene (6) ether " with block copolymerization substitutes block copolymerization
" dodecylphenol polyoxyethylene polyoxypropylene ether (a=6, b=2) " as preparing the initiation material of zwitterionic surfactant,
Remaining operation is with [embodiment 2].Variable concentrations formation water and Jiangsu Shanian Oilfield dewatered oil is measured with [embodiment 9]
Oil water interfacial tension, test temperature is 85 DEG C, and in the range of 0.005～0.3wt%, dynamical interfacial tension value is up to 10-3mN/m
As shown in Figure 8.
[comparative example 4]
Except substituting " the nonyl of block copolymerization with " Nonyl pheno (6) polyoxypropylene (8) ether " of block copolymerization
Phenol polyoxyethylene polyoxypropylene ether (c=8, d=6) " as preparing the initiation material of anion-nonionic surfactant, remaining operation
With [embodiment 2].The oil-water interfaces of variable concentrations formation water and Jiangsu Shanian Oilfield dewatered oil are measured with [embodiment 9]
Tension force, test temperature is 85 DEG C, and in the range of 0.005～0.3wt%, dynamical interfacial tension value is up to 10-2～103MN/m is shown in
Shown in Fig. 8.
[comparative example 5]
Except " myristyl polyoxyethylene (8) polyoxypropylene (4) ether " with random copolymerization substitutes " the 14 of block copolymerization
Alkyl polyoxyethylene polyoxypropylene ether (a=4, b=8) " as preparing the initiation material of zwitterionic surfactant, remaining behaviour
Make with [embodiment 3].Profit circle of variable concentrations formation water and Jiangsu Shanian Oilfield dewatered oil is measured with [embodiment 9]
Surface tension, test temperature is 85 DEG C, and in the range of 0.005～0.3wt%, dynamical interfacial tension value is up to 10-2～10-3mN/m
As shown in Figure 9.
[comparative example 6]
Except " octadecyl polyoxyethylene (4) polyoxypropylene (2) ether " replacement " the octadecyl polyoxy with random copolymerization
Propylene APEO (c=2, d=4) " as preparing the initiation material of anion-nonionic surfactant, remaining operation is with [real
Execute example 3].The oil water interfacial tension of variable concentrations formation water and Jiangsu Shanian Oilfield dewatered oil is measured with [embodiment 9],
Test temperature is 85 DEG C, and in the range of 0.005～0.3wt%, dynamical interfacial tension value is up to 10-2～10-3MN/m is shown in Fig. 9 institute
Show.
[comparative example 7]
Step 1) and 2) with [embodiment 1].
3) in terms of mass parts, 1 is taken) nonyl phenol poly-oxypropylene APEO glycine betaine [a=8, b=2, the R that synthesize2=
CH3,R3=CH3,R4=CH2CH(OH)CH2,X-=SO3 -] 45 parts and 55 parts of 3wt% sodium-chloride water solutions are sequentially added into mixing container
In, it is warming up to 75 DEG C and stirs 2 hours, obtain the zwitterionic surfactant that concentration is 45.0wt%.
Open with the oil-water interfaces of [embodiment 7] mensuration variable concentrations injection aqueous solution with Jiangsu Shanian Oilfield dewatered oil
Power, test temperature is 85 DEG C, and in the range of 0.005～0.3wt%, dynamical interfacial tension value is up to 10-2～10-3MN/m is shown in figure
Shown in 10.
[comparative example 8]
Step 1) and 2) with [embodiment 1].
3) in terms of mass parts, 2 are taken) synthesize) synthesis of octadecyl polyoxyethylene polyoxypropylene ether hydroxypropionate sodium
[c=2,d=4, R6=CH2CH(OH)CH2,Y=SO3Na] 45 parts and 55 parts of 3wt% sodium-chloride water solutions are sequentially added into mixing container
In, it is warming up to 75 DEG C and stirs 2 hours, obtain the anion-nonionic surfactant that concentration is 45.0wt%.Measure with [embodiment 7]
Variable concentrations injects the oil water interfacial tension of the aqueous solution and Jiangsu Shanian Oilfield dewatered oil, and test temperature is 85 DEG C, 0.005
～in the range of 0.3wt%, dynamical interfacial tension value is up to 10-1～10-3MN/m is as shown in Figure 10.
Claims (9)
1. a combined surfactant, includes following component in terms of mass fraction:
The zwitterionic surfactant of (1) 1 part；
The anion-nonionic surfactant of (2) 0.01～50 parts；
The water of (3) 0.1～90 parts；
Wherein (1), the general molecular formula of (2) component are:
In formula, R1And R5For independently of one another selected from C8～C30Alkyl or by C4～C20The substituted phenyl of alkyl；A and c is propoxyl group
The adduction number of group PO, span independent of one another is 1～15；B and d is the adduction number of ethoxy group EO, and value independent of one another is 1
～30；R2And R3Independently of one another selected from C1～C5Alkyl or hydroxy alkyl, R4And R6Independently of one another selected from C1～C5Alkylidene or
Hydroxyl substituted alkylene；X-For COO-Or SO3 -, Y is COOM or SO3N, M and N are independently of one another selected from alkali metal or ammonium.
Combined surfactant the most according to claim 1, it is characterised in that described R1And R5Independently of one another selected from C12~
C24Alkyl or by C8～C12The substituted phenyl of alkyl.
Combined surfactant the most according to claim 1, it is characterised in that described a and c value independent of one another be 2～
12, b and d values independent of one another are 1～10.
Combined surfactant the most according to claim 1, it is characterised in that described R2、R3Independently of one another selected from methyl, second
Base or ethoxy, R4And R6Independently of one another selected from C1～C3Alkylidene or hydroxyl replace propylidene.
Combined surfactant the most according to claim 1, it is characterised in that M and N is independently of one another selected from sodium or potassium.
Combined surfactant the most according to claim 1, it is characterised in that described water be deionized water, running water or
The inorganic salt solution of 1～30wt%.
Combined surfactant the most according to claim 6, it is characterised in that described water is the inorganic salts of 1～15wt%
The aqueous solution.
Combined surfactant the most according to claim 7, it is characterised in that described inorganic salts are sodium chloride, potassium chloride
Or at least one in ammonium chloride.
The preparation method of combined surfactant the most according to claim 1, comprises the following steps:
1) preparation of zwitterionic surfactant:
I. it is 1: 1～3 to mix, in reaction in molar ratio with thionyl chloride by alkylol or alkyl phenol polyoxyethylene polyoxypropylene ether
Reacting 3～15 hours under the conditions of temperature 50～120 DEG C, reaction obtains chloro alkylol or alkyl phenol polyoxy after terminating after treatment
Propylene APEO；
Ii. by chloro alkylol synthesized in i or alkyl phenol polyoxyethylene polyoxypropylene ether and dialkylamine, water and low-carbon (LC)
Alcohol mixes, and is 40～100 DEG C in temperature and carries out tertiary-aminated reaction 3～20 hours, and then dropping sulfonating agent or carboxylating agent is water-soluble
Liquid, drips the complete reflux temperature that continues at and carries out quaterisation 5～30 hours, and the dialkyl group steaming low-carbon alcohols and excess is secondary
Amine, remove desalination, obtain alkylol or alkyl phenol polyoxyethylene polyoxypropylene ether carboxylic acid or sulfonate betaine；Wherein, dialkyl group
Secondary amine is dimethylamine or diethanol amine, and sulfonating agent is the alkali gold of the alkali metal salt of 3-chlorine-2-hydroxyl propane sulfonic acid, 2-chloroethanes sulfonic acid
Belonging to salt or PS, carboxylating agent is monoxone or chloroacetic alkali metal salt, and low-carbon alcohols is selected from C1～C3Fat
Alcohol, chloro alkylol or alkyl phenol polyoxyethylene polyoxypropylene ether, dialkylamine are 1 with the mol ratio of sulfonating agent or carboxylating agent
: 1～3: 1～3；
2) preparation of anion-nonionic surfactant:
By alkylol or alkyl phenol polyoxyethylene polyoxypropylene ether and sulfonating agent or carboxylating agent, alkali metal hydroxide solid and molten
Agent is mixed by required proportioning, reacts 3～15 hours at reaction temperature 50～130 DEG C, reacts after terminating through post-processing to obtain alkyl
Alcohol or alkyl phenol polyoxyethylene polyoxypropylene ether sulfonate or carboxylate；Wherein, alkylol or alkyl phenol polyoxypropylene polyoxy second
The mol ratio of alkene ether, sulfonated reagent or carboxylating reagent and alkali metal hydroxide is 1: 1～4: 1～5, and sulfonating agent is the chloro-2-of 3-
Hydroxy-propanesulfonic acid alkali metal salt, 2-chloroethanes sulfonic acid alkali metal salts or PS, carboxylating agent is monoxone or chloroethene
Acid alkali metal salt, at least one in solvent selected from acetone, benzene, toluene or dimethylbenzene；
3) by the desired amount of alkylol or alkyl phenol polyoxyethylene polyoxypropylene ether carboxylic acid or sulfonate betaine, alkylol or alkane
Base phenol polyoxyethylene polyoxypropylene ether sulfonate or carboxylate, water and low-carbon alcohols add in mixing container, are warming up to 40～100 DEG C
Stirring 1～4 hour, decompression boils off low-carbon alcohols, obtains required combined surfactant；In terms of mass fraction, alkylol or alkane
Base phenol polyoxyethylene polyoxypropylene ether carboxylic acid or sulfonate betaine, alkylol or alkyl phenol polyoxyethylene polyoxypropylene ether sulfonic acid
The proportioning of salt or carboxylate, low-carbon alcohols and water is 1 part: 0.01～50 part: 0.1～90 part: 0.1～90 part, and low-carbon alcohols is selected from C1
～C3Fatty alcohol.
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