CN111848943A - Modified polyether, composite crude oil demulsifier, and preparation method and application thereof - Google Patents
Modified polyether, composite crude oil demulsifier, and preparation method and application thereof Download PDFInfo
- Publication number
- CN111848943A CN111848943A CN202010756787.XA CN202010756787A CN111848943A CN 111848943 A CN111848943 A CN 111848943A CN 202010756787 A CN202010756787 A CN 202010756787A CN 111848943 A CN111848943 A CN 111848943A
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- China
- Prior art keywords
- modified polyether
- crude oil
- oil
- absorption
- demulsifier
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- 239000010779 crude oil Substances 0.000 title claims abstract description 164
- 229920000570 polyether Polymers 0.000 title claims abstract description 131
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 129
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000003921 oil Substances 0.000 claims abstract description 89
- 238000003756 stirring Methods 0.000 claims abstract description 52
- 239000007864 aqueous solution Substances 0.000 claims abstract description 47
- -1 alkyl compound Chemical class 0.000 claims abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 39
- 238000001816 cooling Methods 0.000 claims abstract description 26
- 239000013067 intermediate product Substances 0.000 claims abstract description 13
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 11
- 239000004593 Epoxy Substances 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 9
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 238000007789 sealing Methods 0.000 claims abstract description 4
- 238000010521 absorption reaction Methods 0.000 claims description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 46
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 230000018044 dehydration Effects 0.000 claims description 35
- 238000006297 dehydration reaction Methods 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 28
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 21
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 21
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000004094 surface-active agent Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 16
- 238000002329 infrared spectrum Methods 0.000 claims description 15
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 8
- 239000008098 formaldehyde solution Substances 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 5
- 230000000149 penetrating effect Effects 0.000 claims description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 4
- 229920000053 polysorbate 80 Polymers 0.000 claims description 4
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 229940077386 sodium benzenesulfonate Drugs 0.000 claims description 3
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 2
- 229920002334 Spandex Polymers 0.000 claims 1
- 239000004759 spandex Substances 0.000 claims 1
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000007670 refining Methods 0.000 abstract description 2
- 150000002989 phenols Chemical class 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 44
- 208000005156 Dehydration Diseases 0.000 description 34
- 238000005070 sampling Methods 0.000 description 20
- 239000012071 phase Substances 0.000 description 11
- 239000010963 304 stainless steel Substances 0.000 description 10
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 150000008378 aryl ethers Chemical class 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000001993 wax Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 239000013049 sediment Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000007655 standard test method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 238000011144 upstream manufacturing Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 3
- 239000002199 base oil Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 229960001124 trientine Drugs 0.000 description 3
- VKIGAWAEXPTIOL-UHFFFAOYSA-N 2-hydroxyhexanenitrile Chemical compound CCCCC(O)C#N VKIGAWAEXPTIOL-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000008351 acetate buffer Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 235000015096 spirit Nutrition 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- YEECOJZAMZEUBB-UHFFFAOYSA-N 2,2,3,3,6,6,7,7-octamethyloctane Chemical compound CC(C)(C)C(C)(C)CCC(C)(C)C(C)(C)C YEECOJZAMZEUBB-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 101100293608 Hordeum vulgare NAS9 gene Proteins 0.000 description 1
- 206010034701 Peroneal nerve palsy Diseases 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
- C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Polyethers (AREA)
Abstract
The invention relates to a modified polyether, a composite crude oil demulsifier, a preparation method and application thereof, wherein the preparation method of the modified polyether comprises the following steps: sealing and preheating phenols and vinylamine at 50-70 ℃ for 30-50min under normal pressure; then at a stirring speed in N2Or raising the temperature to 110-130 ℃ within 30-60 min under inert atmosphere, then dropwise adding a formaldehyde water solution, raising the pressure to 0.2-0.6MPa, and reacting at the constant temperature of 110-130 ℃ for 2-5 hours; under the condition of keeping the stirring speed before the stirring, adding alkali into the first intermediate product, dropwise adding an epoxy alkyl compound aqueous solution at the temperature of 110-130 ℃ under the pressure of 0.2-0.6MPa, stirring at constant temperature and constant pressure for 5-7 hours, and then cooling to 70-90 ℃; reducing the pressure to normal pressure, cooling to room temperature, neutralizing and purifying to obtain the modified polyether. The composite crude oil demulsifier provided by the invention has the advantages of wide source of raw materials, low cost and no generation of oil refining equipment in the follow-up processCorrosion, so that the cost can be saved and the utilization rate of equipment can be improved.
Description
Technical Field
The invention belongs to the field of oilfield chemical additives, and particularly relates to a modified polyether, a composite crude oil demulsifier, and a preparation method and application thereof.
Background
Crude oil is a very complex multi-component mixture composed primarily of hydrocarbons of different molecular weights, structures and properties, as well as non-hydrocarbon compounds and impurities. At present, oil field exploitation enters a high water-cut period, and various enhanced oil recovery technical measures are applied, so that the water content of a crude oil emulsion is increased greatly, and the difficulty of crude oil dehydration is increased. Because the crude oil and the water are strongly mixed to form the emulsified crude oil with different stabilities, the dehydration difficulty of the crude oil is increased, and the prior demulsifier can not be adapted to the requirements of demulsification and dehydration treatment of the crude oil with high water content or thick oil and crude oil with high wax content; the main reasons are as follows: the dehydration temperature of the crude oil is reduced, wax in the crude oil is separated out, the viscosity of the emulsified crude oil is increased, the emulsified crude oil is usually in a water-in-oil state, and demulsifier molecules are difficult to disperse in the crude oil and cannot rapidly act on an oil-water interface film.
At present, the demulsifier used in Ilac Luke oil West Guerna second-stage oil field has poor adaptability, raised well head back pressure, unstable and reduced daily liquid yield, slow crude oil dehydration rate and higher heat energy consumption.
Disclosure of Invention
In view of the above, the main object of the present invention is to provide a modified polyether, a composite crude oil demulsifier, a preparation method and an application thereof, wherein the composite crude oil demulsifier has the advantages of strong demulsification capability, good permeability, good solubility in crude oil, high dehydration speed, etc.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. The preparation method of the modified polyether provided by the invention comprises the following steps:
a, sealing and preheating a phenol compound and a vinylamine compound at 50-70 ℃ for 30-50min under normal pressure; then heating to 110-130 ℃ in N2 or inert atmosphere within 30-60 min under a stirring rotation speed, then dropwise adding a formaldehyde water solution, raising the pressure to 0.2-0.6MPa, and reacting at the constant temperature of 110-130 ℃ for 2-5 hours to obtain a first intermediate product;
b, under the condition of keeping the stirring speed before, adding alkali into the first intermediate product, dropwise adding an epoxy alkyl compound aqueous solution at the temperature of 110-130 ℃ under the pressure of 0.2-0.6MPa, stirring at constant temperature and constant pressure for reaction for 5-7 hours, and then cooling to 70-90 ℃ to obtain a second intermediate product;
c, decompressing the second intermediate product to normal pressure, cooling to room temperature, neutralizing and purifying to obtain modified polyether;
the cloud point of the modified polyether is 30-35 degrees; the infrared spectrum of the modified polyether is 1265-1220cm-1And 1300 + 990cm-12C-O telescopic vibration absorption peaks are respectively arranged between the two adjacent vibration absorption peaks, and the peak length is 3300--1Has an O-H telescopic absorption peak between the two and is 1720-1700cm-1C-O absorption vibration peak is arranged between the two, and the absorption vibration peak is 1200cm at 1320--1And C-O stretching vibration peaks are arranged between the two.
The purpose of the invention and the technical problem to be solved are further realized by adopting the following technical scheme.
Preferably, in the preparation method of the modified polyether, in the step a, the mass ratio of the phenol compound to the vinylamine compound is (0.8-6): 1.
preferably, in the preparation method of the modified polyether, in step a, the phenol compound is phenol, o-cresol, m-cresol or p-cresol.
Preferably, in the preparation method of the modified polyether, in step a, the vinylamine compound is diethylenetriamine, diethylenediamine, triethylenediamine or triethylenetetramine.
Preferably, in the preparation method of the modified polyether, in the step a, the mass ratio of the formaldehyde solution to the vinylamine compound is (0.1-0.6): 1; the concentration of the formaldehyde aqueous solution is 30-35 wt%; the dropping rate of the formaldehyde solution is 30-35 drops/min.
Preferably, in the preparation method of the modified polyether, in the step b, the alkali is sodium hydroxide solution or potassium hydroxide solution; the mass ratio of the alkali to the vinylamine compound is (0.5-4): 40.
preferably, in the preparation method of the modified polyether, in the step b, the alkylene oxide compound is at least one selected from ethylene oxide and propylene oxide; the mass ratio of the epoxy alkyl compound solution to the vinylamine compound is (0.4-2.5): 1; the concentration of the ethylene oxide solution and the concentration of the propylene oxide solution are both 99 wt%; the dropping speed of the ethylene oxide solution and the dropping speed of the propylene oxide solution are both 20-25 drops/min.
Preferably, in the preparation method of the modified polyether, in the step a and the step b, the rotation speed of the stirring is 150-250 rpm/min.
Preferably, the preparation method of the modified polyether further comprises step b1 after step b and before step c: adding at least one of grafting agent and catalyst, and reacting at 80-85 deg.C for 1-2 hr.
Preferably, in the preparation method of the modified polyether, in step b1, the grafting agent is selected from one of acetic anhydride, maleic anhydride, acetic acid, formic acid, concentrated sulfuric acid and dilauric acid; the mass ratio of the grafting agent to the vinylamine compound is (0.35-1.6): 1.
preferably, in the step b1, the catalyst is selected from one of p-toluenesulfonic acid, sodium benzenesulfonate, sodium dodecylsulfate, dibutyltin dilaurate, dicumyl oxide (DCP), and di-tert-butyl peroxide (DTBP); the mass ratio of the catalyst to the vinylamine compound is (1-4): 30.
preferably, the preparation method of the modified polyether further comprises a step b2 after the step b1 and before the step c: adding cross-linking agent, and heating at 80-85 deg.C for 5-6 hr.
Preferably, in the step b2, the crosslinking agent is at least one selected from the group consisting of acrylic acid, dibenzoyl peroxide, diisopropylbenzene hydroperoxide and 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane; the mass ratio of the cross-linking agent to the vinylamine compound is (0.5-0.8): 1.
the purpose of the invention and the technical problem to be solved can be realized by adopting the following technical scheme. According to the modified polyether provided by the invention, the cloud point of the modified polyether is 30-35 ℃; the infrared spectrum of the modified polyether is 1265-1220cm-1And 1300 + 990cm-12C-O telescopic vibration absorption peaks are respectively arranged between the two adjacent vibration absorption peaks, and the peak length is 3300--1Has an O-H telescopic absorption peak between the two and is 1720-1700cm-1C-O absorption vibration peak is arranged between the two, and the absorption vibration peak is 1200cm at 1320--1C-O stretching vibration peaks are arranged between the two groups; the modified polyether is prepared by the method.
The purpose of the invention and the technical problem to be solved can be realized by adopting the following technical scheme. The invention provides a composite crude oil demulsifier, which is prepared from the following components in percentage by mass (0.5-2): 1: (1-4): (2-4) the modified polyether, the solvent oil, the surfactant and the alcohol-water solution; the cloud point of the modified polyether is 30-35 degrees; the infrared spectrum of the modified polyether is 1265-1220cm-1And 1300 + 990cm-12C-O telescopic vibration absorption peaks are respectively arranged between the two adjacent vibration absorption peaks, and the peak length is 3300--1Has an O-H telescopic absorption peak between the two and is 1720-1700cm-1C-O absorption vibration peak is arranged between the two, and the absorption vibration peak is 1200cm at 1320--1And C-O stretching vibration peaks are arranged between the two.
The purpose of the invention and the technical problem to be solved are further realized by adopting the following technical scheme.
Preferably, the method for preparing the complex crude oil demulsifier comprises the step of preparing the complex crude oil demulsifier, wherein the alcohol aqueous solution is selected from methanol aqueous solution or ethanol aqueous solution, and the concentration of the alcohol aqueous solution is 95-99 wt%.
Preferably, the preparation method of the complex crude oil demulsifier is described above, wherein the mineral spirit is selected from one of 1000# mineral spirit, 1800# mineral spirit, 1500# mineral spirit, 100# mineral spirit and 200# mineral spirit.
Preferably, in the preparation method of the composite crude oil demulsifier, the surfactant is selected from fatty alcohol-polyoxyethylene ether, a penetrant JFY, a penetrant JFC, and one of span 80/tween 80/polyether surfactant in a mass ratio of 1:1: 1.
Preferably, in the preparation method of the composite crude oil demulsifier, the composite crude oil demulsifier is a brown yellow transparent oil-soluble liquid, the density is 0.85-0.9g/ml, the viscosity is 30-55mpa.s, and the flash point is 61-65 ℃.
The purpose of the invention and the technical problem to be solved can be realized by adopting the following technical scheme. The invention provides a preparation method of a composite crude oil demulsifier, which comprises the following steps:
heating the modified polyether to 40-60 ℃ at the normal-pressure stirring speed of 100 plus 200rpm/min, sequentially adding the surfactant and the alcohol aqueous solution for 30-60 min, adding the solvent oil, and cooling to room temperature after 30-60 min to obtain the composite crude oil demulsifier; the cloud point of the modified polyether is 30-35 degrees; the infrared spectrum of the modified polyether is 1265-1220cm-1And 1300 + 990cm-12C-O telescopic vibration absorption peaks are respectively arranged between the two adjacent vibration absorption peaks, and the peak length is 3300--1Has an O-H telescopic absorption peak between the two and is 1720-1700cm-1C-O absorption vibration peak is arranged between the two, and the absorption vibration peak is 1200cm at 1320--1And C-O stretching vibration peaks are arranged between the two.
The purpose of the invention and the technical problem to be solved can be realized by adopting the following technical scheme. The invention provides a demulsification and dehydration method of water-in-oil emulsified oil, which comprises the following steps:
diluting the composite crude oil demulsifier with methanol aqueous solution, adding the demulsifier into the water-in-oil emulsified oil, uniformly mixing, and performing demulsification and dehydration.
Preferably, the method for demulsifying and dehydrating the water-in-oil emulsified oil liquid comprises the steps of preparing the methanol aqueous solution with the concentration of 95-99 wt%; the dilution ratio is 1 (8-10); the demulsification temperature is 30-80 ℃.
Compared with the prior art, the modified polyether, the composite crude oil demulsifier, the preparation method and the application thereof have the following advantages:
1. the composite crude oil demulsifier has the advantages of wide source of raw materials, low cost and no corrosion to subsequent oil refining equipment, thereby saving the cost and improving the utilization rate of the equipment.
2. The composite crude oil demulsifier provided by the invention is used for producing and extracting oil in Ilack Lukexigulna second-stage oil fields, has good surface property and permeability, can be quickly dissolved in Ilack Lukexigulna second-stage oil field crude oil, reduces the heat energy consumption and the electric power cost of local first-stage and second-stage oil extraction plants and gathering and transportation stations, has the advantages of high dehydration rate and high dehydration degree, and can be suitable for special environments such as acidification operation.
3. The composite crude oil demulsifier provided by the invention can obviously reduce the load of the pumping unit and stabilize the daily liquid production amount when being added into a single well of an oil field in the secondary stage of Ilake Lux Welchurona.
4. The preparation method of the composite crude oil demulsifier can realize automatic continuous production, has high mechanization degree, and is suitable for popularization and industrial production.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be given to the specific embodiments, features and properties of the modified polyether, the composite crude oil demulsifier, and the preparation method thereof according to the present invention with reference to the preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The following materials or reagents are commercially available unless otherwise specified.
The invention provides a preparation method of modified polyether, which comprises the following steps:
a, sealing and preheating a phenol compound and a vinylamine compound at 50-70 ℃ for 30-50min under normal pressure; then stirring at a stirring speed of 150-250rpm/min under N2Or raising the temperature to 110-130 ℃ within 30-60 min under inert atmosphere, then dropwise adding a formaldehyde water solution, raising the pressure to 0.2-0.6MPa, and reacting at the constant temperature of 110-130 ℃ for 2-5 hours to obtain a first intermediate product;
b, adding alkali into the first intermediate product, dropwise adding an epoxy alkyl compound aqueous solution at the temperature of 110-130 ℃ under the pressure of 0.2-0.6MPa, reacting for 5-7 hours at constant temperature and constant pressure, and cooling to 70-90 ℃ to obtain a second intermediate product;
c, decompressing the second intermediate product to normal pressure, cooling to room temperature, neutralizing and purifying to obtain modified polyether;
the cloud point of the modified polyether is 30-35 degrees; the infrared spectrum of the modified polyether is 1265-1220cm-1And 1300 + 990cm-12C-O stretching vibration absorption peaks are respectively arranged between the modified polyether and the polyether, which indicates that the aromatic ether exists in the modified polyether; at 3300 and 2800cm-1An O-H telescopic absorption peak is formed between the modified polyether and the polyether, which indicates that hydroxyl exists in the modified polyether; at 3300 and 2800cm-1Has a wide and strong O-H telescopic absorption peak between the two and is 1720-1700cm-1C-O absorption vibration peak is arranged between the two, and the absorption vibration peak is 1200cm at 1320--1The stretching vibration peak of C-O is formed between the two, which indicates that the modified polyether has carboxyl.
In the step a, the mass ratio of the phenol compound to the vinylamine compound is (0.8-6): 1, preferably (1-4): 1, more preferably 2:1, so that the viscosity and density of the demulsifier prepared at the later stage can be relatively low after optimization; if the phenol is excessive, since phenol is easily crystallized at a low temperature, it is difficult to remove phenol mixed in the product at the time of later purification; if the vinylamine is excessive, the excessive vinylamine is well controlled, and the excessive vinylamine can volatilize and is toxic, so the reaction is carried out in a well controlled amount and is consumed as far as possible.
In specific implementation, in step a, the phenol compound may be phenol, o-cresol, m-cresol or p-cresol, and preferably p-cresol or phenol; because methyl has electronic attraction to the phenol functional group (the-OH bond on the benzene ring), and is relatively active; while it is less reactive towards methylphenol, which has no methyl functional groups, thus excluding the effect of electron cloud attraction.
In a specific implementation, in step a, the vinylamine compound may be diethylenetriamine, diethylenediamine, triethylenediamine, or triethylenetetramine, preferably diethylenetriamine or diethylenediamine; triethylene diamine and triethylene tetramine are unstable, and can be decomposed by self reaction if the storage time is too long, for example, more than 1 month, because pi electron cloud on a covalent bond of ethylene is very active and is easy to oxidize amine groups after the ethylene is polymerized, so that more impurities are generated, the impurities can influence the reaction during the synthesis of polyether at the later stage, and unnecessary treatment stages can be generated during the purification of polyether at the later stage; considering storage, and the influence of by-products, diethylenetriamine or diethylenediamine is generally selected.
In the step a, the mass ratio of the formaldehyde solution to the vinylamine compound is (0.1-0.6): 1, preferably (0.2-0.5): 1, which preferably later facilitates the reaction and better oxygen barrier; the concentration of the formaldehyde aqueous solution is 30-35 wt%; the dropping rate of the formaldehyde solution is 30-35 drops/min; the function of formaldehyde: the first is used as a catalyst, and the second is used as a raw material, wherein the pi electron cloud of the C ═ O bond of the formaldehyde and the C ═ O covalent bond can be subjected to a bonding reaction with the previous product, and meanwhile, the formaldehyde solution can volatilize a little formaldehyde gas, so that the formaldehyde in the upper air can also play a role in isolating oxygen.
In a specific implementation, in the step b, the alkali may be sodium hydroxide or potassium hydroxide; the mass ratio of the alkali to the vinylamine compound is (0.5-4): 40; preferably (0.6-3.3): 40; this preference helps to better adjust the pH of the reaction system and to catalyze the reaction.
In step b, the alkylene oxide compound may be at least one selected from ethylene oxide and propylene oxide; the mass ratio of the epoxy alkyl compound solution to the vinylamine compound is (0.4-2.5): 1, preferably (0.4-2): 1; the concentration of the ethylene oxide solution and the concentration of the propylene oxide solution are both 99 wt%; the dropping rate of the ethylene oxide solution and the dropping rate of the propylene oxide solution are both 20-25 drops/min; ethylene oxide and propylene oxide are selected because the ethylene oxide and the propylene oxide have-C-C cyclic structures, are relatively active, require relatively low chemical energy consumption and are easy to chain scission and graft, while other epoxy alkyl compounds are generally not commonly used, mainly because of being relatively stable, the cyclic structures of the ethylene oxide and the propylene oxide are relatively difficult to break, the grafting difficulty is large, and the energy consumption is high; further, since an alkylene oxide having a large number of carbon atoms is easily self-polymerized, the alkylene oxide having a large number of carbon atoms generally has a large number of terminal carbon atoms, but tends to form waste when it is grafted to a polyether. Epoxy resins and epoxy curing agents, which are pastes like glues, are themselves very stable and their activity is very low, and are essentially used to terminate the polymerization.
In specific implementation, after step b and before step c, step b1 may be further included: adding at least one of grafting agent and catalyst, and reacting at 80-85 deg.C for 1-2 hr.
In step b1, the grafting agent may be one selected from acetic anhydride, maleic anhydride, acetic acid, formic acid, concentrated sulfuric acid and dilauric acid, and is preferably acetic anhydride, because it has strong acidity, strong oxidizing property, strong activation at tail end and grafting (capable of changing the tail end function of original chain), and low cost. The mass ratio of the grafting agent to the vinylamine compound is (0.35-1.6): 1; preferably (0.375-1.5): 1, which preferably later contributes to better tail activation and easier grafting. The catalyst is selected from one of paratoluenesulfonic acid, sodium benzenesulfonate, sodium dodecyl sulfate, dibutyltin dilaurate, dicumyl oxide (DCP) and di-tert-butyl peroxide (DTBP), preferably paratoluenesulfonic acid, which also participates in the reaction in the system and finally becomes a part of a product, so that the paratoluenesulfonic acid is preferred because the paratoluenesulfonic acid is strong in acidity and can be oleophilic at an oil-water interface because the benzene ring contains the benzene ring which is oleophilic, so that the demulsifier can be left in crude oil after use without causing water pollution, otherwise, water needs to be treated in a later period to remove residual demulsifier; other catalysts are toxic, have more byproducts and low synthesis rate, or are easy to be oxidized by heat and unstable; the mass ratio of the catalyst to the vinylamine compound is (1-4): 30, preferably (1-3): 30, so that the branched chain of the demulsifier can be increased by increasing sulfo and carboxyl together with the grafting agent, because the sulfo and the carboxyl have H-O bonds to facilitate oil-water interface contact; the addition of 2 is preferable because the number of active chains is large and different, which is advantageous in increasing the dehydration rate.
In specific implementation, after step b1 and before step c, the method may further include step b 2: adding cross-linking agent, and heating at 80-85 deg.C for 5-6 hr.
In step b2, the cross-linking agent is at least one selected from acrylic acid, dibenzoyl peroxide, diisopropylbenzene hydroperoxide and 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide, preferably acrylic acid and dibenzoyl peroxide; the mass ratio of the cross-linking agent to the vinylamine compound is (0.5-0.8): 1, preferably (0.75-0.7): 1, so that the crosslinking agent can better crosslink the previous epoxyalkyl compound such as ethylene oxide or propylene oxide, and can also attach the functional group on the grafting agent to the main chain and can increase the reactive functional group; if no cross-linking agent is added, the reaction conditions are relatively harsh, and the required requirements are relatively high; if the cross-linking agent is added, the reaction time is shortened, the polymerization speed of grafting is controlled, meanwhile, the by-products are few, the effective components of the demulsifier are naturally more, and the initial dehydration rate is different.
The cloud point of the modified polyether prepared by the method is 30-35 ℃; the infrared spectrum of the modified polyether is 1265-1220cm-1And 1300 + 990cm-12C-O stretching vibration absorption peaks are respectively arranged between the modified polyether and the polyether, which indicates that the aromatic ether exists in the modified polyether; at 3300 and 2800cm-1An O-H telescopic absorption peak is formed between the modified polyether and the polyether, which indicates that hydroxyl exists in the modified polyether; at 3300 and 2800cm-1Has a wide and strong O-H telescopic absorption peak between the two and is 1720-1700cm-1C-O absorption vibration peak is arranged between the two, and the absorption vibration peak is 1200cm at 1320--1The stretching vibration peak of C-O is formed between the two, which indicates that the modified polyether has carboxyl.
The invention also provides a composite crude oil demulsifier, which comprises the following components in percentage by mass (0.5-2): 1: (1-4): and (2-4) modified polyether, solvent oil, surfactant and alcohol-water solution.
In specific implementation, the alcohol-water solution is selected from methanol-water solution or ethanol-water solution, and the concentration of the alcohol-water solution is 95-99 wt%, and the preferred concentration is 99 wt%; if the concentration is relatively low, the miscella is oil-based, and thus, delamination may occur.
In specific implementation, the solvent oil is selected from one of 1000# solvent oil, 1800# solvent oil, 1500# solvent oil, 100# solvent oil and 200# solvent oil, preferably 200# solvent oil, so that the viscosity and density of the prepared demulsifier are preferably relatively low, and the demulsifier is well suspended in a crude oil system and is well miscible with crude oil, thereby facilitating dehydration.
In specific implementation, the surfactant is selected from fatty alcohol-polyoxyethylene ether, a penetrating agent JFY, a penetrating agent JFC and one of span 80/Tween 80/polyether surfactant with the mass ratio of 1:1:1, preferably fatty alcohol-polyoxyethylene ether, so that the viscosity and density of the prepared demulsifier are relatively low after optimization, and the demulsifier is well suspended in a crude oil system and then well mixed with crude oil, thereby being beneficial to dehydration.
The composite crude oil demulsifier is a brown yellow transparent oil-soluble liquid, the density is 0.85-0.9g/ml, the viscosity is 30-55mpa.s, and the flash point is 61-65 ℃.
The invention also provides a preparation method of the composite crude oil demulsifier, which comprises the following steps:
heating the modified polyether to 40-60 ℃ at the normal-pressure stirring speed of 100 plus 200rpm/min, sequentially adding the surfactant and the alcohol aqueous solution for 30-60 min, adding the solvent oil, and cooling to room temperature after 30-60 min to obtain the composite crude oil demulsifier. The purpose of sequentially adding and mixing is that after the polyether is mixed and dispersed by the surfactant and the alcohol-water solution, the methanol can form oil-water amphoteric medium in the system, and then the solvent oil is added for dissolving to form uniform and transparent emulsion; the mineral spirits do not dissolve the polyethers directly because the polyethers are not soluble in mineral spirits; if the modified polyether, the surfactant, the alcohol-water solution and the solvent oil are uniformly mixed, mixed white turbid matters are obtained, and the demulsification effect cannot be achieved.
The invention also provides a demulsification and dehydration method of the water-in-oil emulsified oil, which comprises the following steps:
diluting the composite crude oil demulsifier with methanol aqueous solution, adding the demulsifier into the water-in-oil emulsified oil, uniformly mixing, and performing demulsification and dehydration.
In specific implementation, the concentration of the methanol aqueous solution is 95-99 wt%; the dilution ratio is 1 (8-10); the demulsification temperature is 30-80 ℃, and preferably 60-70 ℃, so that the demulsification effect is better after optimization.
In specific implementation, 0.1M triethylammonium acetate buffer solution can be added to adjust the pH value to 8 after the water-in-oil emulsified oil liquid is added, so that the demulsifying effect of the demulsifier is better, and the water content of the water-in-oil emulsified crude oil can be reduced from 16% vol to below 0.1% vol.
The crude oil of the Iraq oilfield contains 1.65 wt% of wax, 10% of asphaltene, 4.5 wt% of sulfide, a pour point of-42 ℃, a boiling point of 47 ℃, an API density of 21 and a viscosity of 2.85, and the crude oil is high in wax content, particularly high in asphaltene, and the asphalt is a very viscous slow-flowing liquid, so that the crude oil is high in viscosity, high in consistency and poor in fluidity. And the modified polyether has a hydrophilic group such as a hydroxyl group O-H, a carboxyl group COOH and a lipophilic group such as an aromatic ether group C6H5C-O-C, etc., so the application adopts the modified polyether to increase when designing the composite demulsifierBenzene ring structure and carbon-carbon double bond to improve the intersolubility of modified polyether and asphaltene and wax in crude oil, so that hydrophilic groups such as hydroxyl O-H in the modified polyether are contacted with emulsified water wrapped by the asphaltene and the wax to form hydrogen bonds, and the aim of quickly and completely removing the emulsified water wrapped by the asphaltene and the wax is fulfilled.
In the specific implementation, the composite crude oil demulsifier can utilize hydrophilic groups (such as hydroxyl group O-H and carboxyl group COOH) to penetrate into the water phase, and lipophilic R groups (such as aromatic ether group C)6H5-C-O-C, etc.) into the organic phase of the crude oil, which reduces the surface energy of the oil-water interface, and strips the emulsified water from the crude oil to form free water for dehydration, thereby exhibiting rapid demulsification characteristics in performance.
The present invention is further illustrated by the following specific examples, which are not to be construed as limiting the invention thereto.
Example 1
Weighing p-methyl phenol and diethylenetriamine respectively according to the mass ratio of 4:1, adding the total weight of the p-methyl phenol and the diethylenetriamine into a sealed 1L 304 stainless steel reaction tank, and preheating for 30min at the temperature of 60 ℃ under normal pressure; replacing the air in the tank with N2 or inert gas for 30 min; then the stirring was started, the stirring rate was maintained at 200rpm/min and the temperature was raised to 130 ℃ within 30 min. Then 5g of formaldehyde aqueous solution with the concentration of 30 wt% is slowly dripped, the dripping speed is controlled to be 30 drops/min, the pressure in the tank is increased to 0.4MPa, the reaction temperature is 130 ℃, and the constant temperature reaction is carried out for 2 hours. Then adding 1.65g of solid sodium hydroxide, keeping the pressure in the tank at 0.4MPa, keeping the temperature constant at 130 ℃, dropwise adding 10g of 99 wt% ethylene oxide aqueous solution and 10g of 99 wt% propylene oxide aqueous solution, controlling the dropwise adding rate of both the ethylene oxide aqueous solution and the propylene oxide aqueous solution to be 20 drops/min, after reacting at constant temperature and constant pressure for 3 hours, cooling to 85 ℃, adding 15g of acetic anhydride and 1g of p-toluenesulfonic acid, stirring and reacting at 85 ℃ (200rpm/min) for 1.5 hours, finally adding 10g of acrylic acid and 1g of dibenzoyl peroxide, stirring and reacting at 85 ℃ (200rpm/min) for 5 hours, reducing the pressure to normal pressure, cooling to room temperature, neutralizing and purifying (after sodium hydroxide solution is neutralized to neutrality, adding 50g of xylene, heating to boiling to obtain the productRemoving excessive water in polyether) to obtain modified polyether JM-169 with cloud point of 33 degrees, wherein the infrared spectrum of the modified polyether JM-169 is 1220cm-1And 1000cm-12C-O stretching vibration absorption peaks appear, which indicates that aromatic ether exists in the modified polyether; at 3000cm-1A wide and strong O-H stretching absorption peak appears, which indicates that hydroxyl exists in the modified polyether; at 3000 and 2800cm-1A wide and strong O-H telescopic absorption peak appears between the two and is 1706-1700cm-1A C-O absorption vibration peak appears between the two peaks, which is 1210-1200cm-1The existence of a C-O stretching vibration peak is indicated, and the existence of a carboxyl functional group in the modified polyether is indicated.
Weighing 50g of modified polyether, placing the modified polyether in a 500ml 304 stainless steel reaction tank, starting mechanical stirring, heating to 50 ℃, sequentially adding 10g of fatty alcohol-polyoxyethylene ether and 10g of methanol aqueous solution (99 wt%), stirring for 30min at normal pressure, then stirring at 100rpm/min, adding 50g of solvent oil No. 100, continuing stirring for 30min at 50 ℃ at normal pressure, cooling to room temperature, and obtaining the composite crude oil demulsifier RD-1029, wherein the density is 0.90g/ml, the viscosity is 40mpa.s, and the flash point is 61 ℃.
The basic data for the irakrux valner second phase oil field crude is shown in table 1 below.
TABLE 1
| Region(s) | The crude oil contains water | Export API @15 deg.C | Density of external transportation @ deg.C | Pour point of external transportation | Treatment temperature C |
| WQ-2 | 6–11％ | 23.8 | 0.9099 | -27 | 50 |
The testing steps are as follows:
(1) crude oil sampling
1.1 use clean/dry glass beaker 1L;
1.2 before sampling, please ensure that no other crude oil demulsifiers are injected upstream of the sampling point;
1.3 taking 1L of single-well crude oil samples of the Lux West Guerner second-stage oil field from a crude oil inlet sampling port;
1.4 the water content of the crude oil is 10 percent by a distillation method (refer to China petrochemical Q/SH CG 66-2013);
(2) crude oil breaking bottle test
1.1, 100ml of scales are marked on the outer walls of 10 clean screening test tubes, and the interval of each scale line is 1 ml;
1.2 using 200-1000 μ L liquid-transferring gun to add 100ppm demulsifier into 10 test tubes respectively;
1.3 in the test tube of the 1.2, adding crude oil samples of single well of Lux West Guerner second-stage oil field slowly until the scale mark of 100 ml;
1.4 screwing the test tube cover, and sequentially placing into HT-110X30 water bath shaking table (Shanghai Haitian scientific instruments Co., Ltd.), setting rotation speed at 100r/min, rotation time at 5min, and temperature at 50 deg.C;
1.5, after shaking is finished, timing for 15min, 30min, 60min and 90min, respectively reading and recording the dehydration rate in the pipe and the interface leveling data which are correspondingly timed;
(3) crude oil breaking bottle test results
The performance of the composite crude oil demulsifier prepared in example 1 of the present invention was evaluated by referring to petrochemical Q/SH CG66-2013 standard, SY/T5281-2000 "method for testing demulsifier use performance (bottle test method)," standard test method for measuring water and sediments in crude oil by centrifugation ", and the evaluation results are shown in table 2 below.
TABLE 2
As can be seen from the data in table 2, the composite crude oil demulsifier RD-1029 prepared in example 1 of the present invention corresponds to 10 different single well crude oils, and has similar dehydration rates, faster dehydration rate and wide adaptability under the same chemical concentration of 100ppm, and is suitable for demulsification of crude oils of different single wells in the il rak luck west gulna second-phase oil field.
Example 2
Respectively weighing 50g of phenol and 50g of diethylenetriamine according to the mass ratio of 4:1, pouring the weighed phenol and 50g of diethylenetriamine into a sealed 1L 304 stainless steel reaction tank, and preheating for 30min at 50 ℃ under normal pressure; replacing the air in the tank with N2 or inert gas for 30 min; then the stirring was started, the stirring rate was maintained at 200rpm/min and the temperature was raised to 125 ℃ within 30 min. Then slowly dripping 5g of 30 wt% formaldehyde aqueous solution, controlling the dripping speed at 30 drops/min, raising the pressure in the tank to 0.4MPa, and reacting at 125 ℃ for 4 hours at constant temperature. Then adding 2g of solid sodium hydroxide, keeping the pressure in the tank at 0.4MPa and the temperature constant at 125 ℃, dropwise adding 20g of 99 wt% ethylene oxide aqueous solution, controlling the dropping rate of the ethylene oxide aqueous solution to be 20 drops/min, reacting at constant temperature and constant pressure for 3 hours, cooling to 85 ℃, adding 1g of p-toluenesulfonic acid, stirring at 85 ℃ for reacting for 5 hours, finally decompressing to normal pressure, cooling to normal temperature, neutralizing and purifying (adding 25g of dimethylbenzene after the sodium hydroxide solution is neutralized to be neutral, heating to boil to remove excessive water in polyether) to obtain modified polyether JM-169 with the cloud point of 32 ℃, wherein the modified polyether JM-169 has an infrared spectrum of 1260cm-1And 1050cm-12C-O stretching vibration absorption peaks appear, which indicates the modificationThe presence of aromatic ethers in the polyether; at 3300cm-1A wide and strong O-H stretching absorption peak appears, which indicates that hydroxyl exists in the modified polyether; at 3100--1A wide and strong O-H telescopic absorption peak appears between the two and is 1720--1A C-O absorption vibration peak appears between the two, which is 1300cm at 1320--1The existence of a C-O stretching vibration peak is indicated, and the existence of a carboxyl functional group in the modified polyether is indicated.
Weighing 50g of modified polyether, placing the modified polyether in a 500ml 304 stainless steel reaction tank, starting mechanical stirring, wherein the stirring speed is 200rpm/min, heating to 45 ℃, sequentially adding 10g of penetrating agent JFY and 10g of 99 wt% methanol aqueous solution, stirring for 30min at normal pressure, then stirring at 200rpm/min, adding 50g of solvent oil 1000#, continuing stirring for 30min at 45 ℃ at normal pressure, cooling to room temperature, and obtaining the composite crude oil demulsifier RD-1029, wherein the composite crude oil demulsifier has the density of 0.90g/ml, the viscosity of 45mpa.s and the flash point of 63 ℃ through detection.
The base oil data for the Luksi Gulna second phase oil field of Iraq is shown in Table 3 below.
TABLE 3
| Region(s) | The crude oil contains water | Export API @15 deg.C | Density of external transportation @ deg.C | Pour point of external transportation | Treatment temperature C |
| WQ-2 | 6–11％ | 23.8 | 0.9099 | -27 | 50 |
The testing steps are as follows:
(1) crude oil sampling
1.6 use clean/dry glass beaker 1L;
1.7 before sampling, please ensure that no other crude oil demulsifiers are injected upstream of the sampling point;
1.8 taking 1L of single-well crude oil samples of the Lux West Guerner second-stage oil field from a crude oil inlet sampling port;
1.9 the water content of the crude oil is 10 percent by a distillation method (refer to China petrochemical Q/SH CG 66-2013);
(2) crude oil breaking bottle test
1.10 the outer walls of 10 clean screening test tubes are marked with 100ml of scales, and the interval of each scale line is 1 ml;
1.11 using a 200-1000uL pipette to add 100ppm of demulsifier to 10 test tubes respectively;
1.12 in the test tube of the 1.11, adding crude oil samples of single well of the Lux West Guerner second-stage oil field into each test tube correspondingly and slowly until the scale mark is 100 ml;
1.13 tightening the test tube cover, and sequentially placing into HT-110X30 water bath shaking table (Shanghai Hutian scientific instruments Co., Ltd.), setting rotation speed at 100r/min, rotation time at 5min, and temperature at 50 deg.C;
1.14 after shaking is finished, timing for 15min, 30min, 60min and 90min, respectively reading and recording the dehydration rate in the pipe and the interface leveling data correspondingly timed;
(3) crude oil breaking bottle test results
The performance of the composite crude oil demulsifier prepared in example 2 of the present invention was evaluated with reference to petrochemical Q/SH CG66-2013 standard, SY/T5281-2000 "method for testing demulsifier use performance (bottle test method)," standard test method for measuring water and sediments in crude oil by centrifugation ", and the evaluation results are shown in table 4 below.
TABLE 4
As can be seen from the data in Table 4, RD-1029 corresponds to 10 different single well crude oils, under the condition of the same dosing concentration of 100ppm, the dehydration rate is similar, the dehydration rate is high, the adaptability is wide, and the demulsification agent can be adapted to the demulsification of different single well crude oils in the Iraq Luc Welchurona second-phase oil field.
Example 3
Respectively weighing 50g of phenol and 50g of diethylene diamine according to the mass ratio of 1:1, pouring the weighed phenol and 50g of diethylene diamine into a sealed 1L 304 stainless steel reaction tank, preheating the reaction tank at the temperature of 60 ℃ under normal pressure for 30min, and replacing the air in the tank by N2 or inert gas for 30 min; then the stirring was started, the stirring rate was maintained at 200rpm/min and the temperature was raised to 110 ℃ within 30 min. Then 5g of formaldehyde aqueous solution with the concentration of 30 wt% is slowly dripped, the dripping speed is controlled to be 30 drops/min, the pressure in the tank is increased to 0.4MPa, the reaction temperature is 110 ℃, and the constant temperature reaction is carried out for 5 hours. Then adding 2g of solid potassium hydroxide, keeping the pressure in a tank at 0.4MPa, keeping the temperature constant at 110 ℃, dropwise adding 10g of propylene oxide aqueous solution with the concentration of 99 wt%, controlling the dropwise adding rate of the propylene oxide aqueous solution to be 30 drops/min, reacting at constant temperature and constant pressure for 7 hours, cooling to 80 ℃, adding 2g of p-toluenesulfonic acid, stirring at 80 ℃ for reacting for 5 hours, finally decompressing to normal pressure, cooling to normal temperature, neutralizing and purifying (adding 25g of dimethylbenzene after neutralizing to be neutral by adding sodium hydroxide solution, heating to boil to remove excessive water in polyether) to obtain modified polyether JM-169 with the cloud point of 32 ℃, wherein in the infrared spectrum of the modified polyether JM-169, 1220cm of infrared spectrum-1And 1000cm-12C-O stretching vibration absorption peaks appear, which indicates that aromatic ether exists in the modified polyether; at 2800cm-1A strong O-H stretching absorption peak appears, which indicates that hydroxyl exists in the modified polyether; at 3300 and 3150cm-1A wide and strong O-H stretching absorption peak appears between the two and is 1700cm-1The C-O absorption vibration peak appears at 1300-1290cm-1The existence of a C-O stretching vibration peak is indicated, and the existence of a carboxyl functional group in the modified polyether is indicated.
50g of modified polyether is weighed and placed in a 500ml 304 stainless steel reaction tank, mechanical stirring is started, the stirring speed is 100rpm/min, the temperature is raised to 45 ℃, 10g of penetrant JFC and 10g of methanol water solution with the concentration of 99 wt% are sequentially added, after stirring for 10min at normal pressure, the stirring speed is 100rpm/min, 30g of solvent oil 1800# is added, after stirring for 30min at 45 ℃ at normal pressure, cooling to room temperature is carried out, and the composite crude oil demulsifier RD-1029 is obtained, and the detection shows that the density is 0.88g/ml, the viscosity is 55mpa.s, and the flash point is 62 ℃.
The crude oil base data for the Lux-Welchuronan second phase oil field of Iraq are shown in Table 5 below.
TABLE 5
| Region(s) | The crude oil contains water | Export API @15 deg.C | Density of external transportation @ deg.C | Pour point of external transportation | Treatment temperature C |
| WQ-2 | 6–11％ | 23.8 | 0.9099 | -27 | 50 |
The experimental steps are as follows:
(1) crude oil sampling
1.15 use clean/dry glass beaker 1L;
1.16 before sampling, please ensure that no other crude demulsifiers are injected upstream of the sampling point;
1.17 taking 1L of single-well crude oil samples of the Lux West Guerner second-stage oil field from a crude oil inlet sampling port;
1.18 measuring the water content of the crude oil by a distillation method (refer to China petrochemical Q/SH CG66-2013) to be 10 percent;
(2) crude oil breaking bottle test
1.19 the outer walls of 10 clean screening test tubes are marked with 100ml of scales, and the interval of each scale line is 1 ml;
1.20 Using a 200-1000 μ L pipette gun, 100ppm demulsifier was added to 10 tubes, respectively;
1.21 in the test tube of the 1.2, adding crude oil samples of single well of the Lux West Guerner second-stage oil field into each test tube correspondingly and slowly until the scale mark is 100 ml;
1.22 the test tube cover is screwed, and then put into HT-110X30 water bath shaking table (Shanghai Hutian scientific instruments Co., Ltd.) in sequence, the set rotation speed is 100r/min, the rotation time is 5min, and the temperature is 50 ℃;
1.23, starting timing for 15min, 30min, 60min and 90min after the shaking is finished, and respectively reading and recording the dehydration rate in the pipe and the interface flushing data correspondingly timed.
(3) Crude oil breaking bottle test results
The performance of the composite crude oil demulsifier prepared in example 3 of the present invention was evaluated with reference to petrochemical Q/SH CG66-2013 standard, SY/T5281-2000, "method for testing demulsifier use performance (bottle test method)," standard test method for measuring water and sediments in crude oil by centrifugation ", and the evaluation results are shown in table 6 below.
TABLE 6
From the data in table 6, it can be seen that the composite crude oil demulsifier RD-1029 in example 3 of the present invention corresponds to 10 crude oils of different single wells, and has similar dehydration rate, faster dehydration rate and wide adaptability under the condition of the same chemical concentration of 100ppm, and can be adapted to demulsification of different crude oils of different single wells in the secondary stage of ilankux.
Example 4
Weighing phenol and diethylenetriamine respectively according to the mass ratio of 1:1, wherein the total weight of the phenol and the diethylenetriamine is 80g, pouring the phenol and the diethylenetriamine into a sealed 1L 304 stainless steel reaction tank, preheating the reaction tank at the temperature of 50 ℃ under normal pressure for 30min, and replacing the air in the tank by adopting N2 or inert gas for 30 min; then the stirring was started, the stirring rate was maintained at 200rpm/min and the temperature was raised to 125 ℃ within 30 min. Then slowly dripping 10g of 30 wt% formaldehyde aqueous solution, controlling the dripping speed to be 30 drops/min, raising the pressure in the tank to 0.4MPa, and reacting at 125 ℃ for 4 hours at constant temperature. Then adding 0.66g of solid sodium hydroxide, keeping the pressure in the tank at 0.4MPa and keeping the temperature constant at 125 ℃, dropwise adding 20g of 99 wt% ethylene oxide aqueous solution and 15g of 99 wt% propylene oxide aqueous solution, controlling the dropwise adding rate of both the ethylene oxide aqueous solution and the propylene oxide aqueous solution to be 20 drops/min, after reacting at constant temperature and constant pressure for 6 hours, cooling to 85 ℃, adding 15g of acetic acid, stirring and reacting at 80-85 ℃, finally decompressing to normal pressure, cooling to normal temperature, neutralizing and purifying (after neutralizing to neutrality by adding sodium hydroxide solution, adding 45g of xylene, heating to boiling to remove excessive water in polyether) to obtain modified polyether JM-cloud point 169 with the temperature of 33 ℃, wherein the modified polyether JM-169 has an infrared spectrum of 1265cm-1And 1010cm-12C-O stretching vibration absorption peaks appear, which indicates that aromatic ether exists in the modified polyether; at 3300cm-1A sharp O-H stretching absorption peak appears, which indicates that hydroxyl exists in the modified polyether; in 3300--1A wide and strong O-H telescopic absorption peak appears between the two and is 1720-1700cm-1C-O absorption vibration peak appears between the two peaks, namely 1260cm at 1280--1The existence of a C-O stretching vibration peak is indicated, and the existence of a carboxyl functional group in the modified polyether is indicated.
Weighing 50g of modified polyether, placing the modified polyether in a 500ml 304 stainless steel reaction tank, starting mechanical stirring, heating to 50 ℃, sequentially adding 5g of compound surfactant (the mass ratio of span 80/Tween 80/polyether surfactant is 1:1:1) and 10g of 99 wt% methanol aqueous solution, stirring at 100rpm/min after stirring at normal pressure for 60min, adding 50g of solvent oil 100#, continuing stirring at 50 ℃ for 60min at normal pressure, cooling to room temperature to obtain the demulsifier RD-1029 of the composite crude oil, and detecting that the demulsifier has the density of 0.90g/ml, the viscosity of 40mpa.s and the flash point of 65 ℃.
The base oil data for the Luksi Gulna second phase oil field of Iraq is shown in Table 7 below.
TABLE 7
| Region(s) | The crude oil contains water | Export API @15 deg.C | Density of external transportation @ deg.C | Pour point of external transportation | Treatment temperature C |
| WQ-2 | 6–11％ | 23.8 | 0.9099 | -27 | 50 |
The experimental steps are as follows:
(1) crude oil sampling
1.24 use clean/dry glass beaker 1L;
1.25 before sampling, please ensure that no other crude demulsifier is injected upstream of the sampling point;
1.26 taking 1L of single-well crude oil samples of the Lux West Guerner second-stage oil field from a crude oil inlet sampling port;
1.27 the water content of the crude oil is 10% measured by a distillation method (refer to China petrochemical Q/SH CG 66-2013);
(2) crude oil breaking bottle test
1.28 the outer walls of 10 clean screening test tubes are marked with 100ml of scales, and the interval of each scale line is 1 ml;
1.29 using a 200-1000uL pipette to add 100ppm demulsifier RD-1029 to 10 tubes respectively;
1.30 in the test tube in the 1.2, correspondingly and slowly adding crude oil samples of single well of the Lux West Guerner second-stage oil field in each test tube until the volume reaches 100ml of scale mark;
1.31 tightening the test tube cover, sequentially placing into HT-110X30 water bath shaking table (Shanghai Hutian scientific instruments Co., Ltd.), setting rotation speed of 100r/min, rotation time of 5min, and temperature of 50 deg.C;
after 1.32 shaking is finished, timing for 15min, 30min, 60min and 90min, respectively reading and recording the dehydration rate in the pipe and the interface flushing data which are correspondingly timed;
(3) crude oil breaking bottle test results
The performance of the composite crude oil demulsifier RD-1029 prepared in example 4 of the present invention is evaluated by referring to petrochemical Q/SH CG66-2013 standard, SY/T5281-2000 (method for testing demulsifier use performance (bottle test method)), and International ASTM D4007 (Standard test method for measuring Water and sediment in crude oil by centrifugation), and the evaluation results are shown in Table 8 below.
TABLE 8
As can be seen from the data in table 8, the composite crude oil demulsifier RD-1029 in example 4 of the present invention corresponds to crude oils of 10 different single wells, and has similar dehydration rates, faster dehydration rate and wide adaptability under the same chemical concentration of 100ppm, and is suitable for demulsification of crude oils of different single wells in the second-phase oil field of ruxsiel gulner in iraq.
Example 5
Weighing p-methyl phenol and diethylenetriamine respectively according to the mass ratio of 2:1, adding the total amount of 90g into a sealed 1L 304 stainless steel reaction tank, preheating for 30min at the normal pressure at the temperature of 50 ℃, and replacing the air in the tank with N2 or inert gas for 30 min; then the stirring was started, the stirring rate was maintained at 200rpm/min and the temperature was raised to 130 ℃ within 30 min. Then slowly dropping 10g of 30 wt% formaldehyde aqueous solution, controlling the dropping speed at 30 drops/min, raising the pressure in the tank to 0.4MPa, and reacting at 120 ℃ for 3 hours at constant temperature. Then adding 0.66g of solid sodium hydroxide, keeping the pressure in the tank at 0.4MPa and keeping the temperature constant at 120 ℃, dropwise adding 20g of 99 wt% ethylene oxide aqueous solution and 15g of 99 wt% propylene oxide aqueous solution, controlling the dropwise adding rate of both the ethylene oxide aqueous solution and the propylene oxide aqueous solution to be 20 drops/min, after 5 hours of constant temperature and pressure reaction, cooling to 80 ℃, adding 15g of acetic anhydride and 1g of p-toluenesulfonic acid, stirring and reacting for 1.5 hours at 80 ℃, finally adding 20g of acrylic acid and 1g of dibenzoyl peroxide, still stirring and reacting for 6 hours at 80 ℃, reducing the pressure to normal pressure, cooling to normal temperature, neutralizing and purifying (adding 50g of dimethylbenzene after sodium hydroxide solution is neutralized, heating to boiling to remove excessive water in polyether) to obtain modified polyether-169 with a cloud point of 32 ℃, the modified polyether JM-169 has an infrared spectrum of 1250cm-1And 990cm-12C-O stretching vibration absorption peaks appear, which indicates that aromatic ether exists in the modified polyether; at 3100--1A wide and strong O-H telescopic absorption peak appears in the interval, which indicates that hydrophilic group hydroxyl exists in the modified polyether; at 2950 and 2900cm-1A wide and strong O-H telescopic absorption peak appears in the interval and is within 1710--1The C ═ O absorption vibration peak appears at 1260--1The stretching vibration peak of C-O appears, which indicates that the modified polyether has carboxylThe presence of a radical functional group.
Weighing 30g of modified polyether, placing the modified polyether in a 500ml 304 stainless steel reaction tank, starting mechanical stirring, wherein the stirring speed is 100rpm/min, heating to 50 ℃, sequentially adding 15g of fatty alcohol-polyoxyethylene ether and 15g of 99 wt% methanol aqueous solution, stirring for 30min at normal pressure, then stirring at 100rpm/min, adding 50g of solvent oil 200#, continuing stirring for 30min at 45 ℃ at normal pressure, cooling to room temperature, and obtaining the composite crude oil demulsifier RD-1029, wherein the composite crude oil demulsifier has the density of 0.85g/ml, the viscosity of 30mpa.s and the flash point of 65 ℃ through detection.
The base oil data for the Luksi Gulna second phase oil field of Iraq is shown in Table 9 below.
TABLE 9
| Region(s) | The crude oil contains water | Export API @15 deg.C | Density of external transportation @ deg.C | Pour point of external transportation | Treatment temperature C |
| WQ-2 | 6–11％ | 23.8 | 0.9099 | -27 | 50 |
The experimental steps are as follows:
(1) crude oil sampling
1.33 use clean/dry glass beaker 1L;
1.34 before sampling, please ensure that no other crude demulsifiers are injected upstream of the sampling point;
1.35 taking 1L of single-well crude oil samples of the Lux West Guerner second-stage oil field from a crude oil inlet sampling port;
1.36 the water content of the crude oil is 10% measured by a distillation method (refer to China petrochemical Q/SH CG 66-2013);
(2) crude oil breaking bottle test
1.37 the outer walls of 10 clean screening test tubes are marked with 100ml of scales, and the interval of each scale line is 1 ml;
1.38 using 200 and 1000 μ L pipette gun to add 100ppm demulsifier RD-1029 to 10 tubes;
1.39 in the test tube of the 1.2, crude oil samples of single wells of the Lux West Guerner II-phase oil field are correspondingly and slowly added into each test tube until the volume reaches 100ml of scale marks;
1.40 screwing test tube covers, sequentially placing into HT-110X30 water bath shaking table (Shanghai Hutian scientific instruments Co., Ltd.), setting rotation speed at 100r/min, rotation time at 5min, and temperature at 50 deg.C;
1.41, starting timing for 15min, 30min, 60min and 90min after shaking is finished, and respectively reading and recording the dehydration rate in the pipe and the interface flushing data which are correspondingly timed;
(3) crude oil breaking bottle test results
The performance of the composite crude oil demulsifier RD-1029 prepared in example 5 of the present invention is evaluated by referring to petrochemical Q/SH CG66-2013 standard, SY/T5281-2000 (method for testing demulsifier use performance (bottle test method)), and International ASTM D4007 (Standard test method for measuring Water and sediment in crude oil by centrifugation), and the evaluation results are shown in Table 10 below.
Watch 10
From the data in table 10, it can be seen that the composite crude oil demulsifier RD-1029 in example 5 of the present invention corresponds to 10 different single well crude oils, and has similar dehydration rate, faster dehydration rate and wide adaptability under the same dosing concentration of 100ppm, and can be adapted to demulsification of crude oils of different single wells in the second-phase oil field of ruksxigulna of iraq.
The composite crude oil demulsifier RD-1029 prepared in example 5 of the invention is used for single well feeding of Iraq petroleum Welchurona second-stage oil field to obtain obvious pressure reduction and yield stabilization effects, and the test effect data are shown in Table 11.
The testing steps are as follows:
(1) selecting 5 different crude oil single wells at different layers, wherein the daily liquid production of the selected single well is 5-16m3；
(2) Adding drug RD-1029 into the single well in the step (1), and keeping the set daily dosage constant for 7 days;
(3) and recording the corresponding wellhead back pressure and daily liquid production data of the single well after 7 days.
TABLE 11
As can be seen from the data in table 11, since the modified polyether is used as the main component in the composite crude oil demulsifier RD-1029 of example 5 of the present invention, the contact area of the polyether small molecules is increased, the accommodation foot drop point of the polyether modified product is also increased, the contact angle of gas and liquid in crude oil can be reduced, and the surface tension of gas and crude oil can be reduced, so as to achieve the purpose of increasing the yield; the 200# solvent oil is matched with the modified polyether, a small amount of methanol aqueous solution (industrial grade methanol) is added, the dispersibility of precipitates in the composite crude oil demulsifier RD-1029 is enhanced, and the viscosity and the density of the precipitates are reduced, so that most components in the RD-1029 are well dissolved in a crude oil system, and only a few hydrophilic parts are suspended and dispersed in oil, so that the resistance of the crude oil at corners and other positions in a pipeline is reduced, the freezing point of the crude oil is also reduced, and the paraffin formation of the crude oil in an oil pipe is reduced, thereby further achieving the purpose of increasing the yield.
Example 6 composite crude oil demulsifier clear water test
The invention provides a demulsification and dehydration method of water-in-oil emulsified oil (with the water content of 15-16 wt%), which uses the composite crude oil demulsifier provided by the invention;
the conditions for demulsification and dehydration are generally as follows: diluting the composite crude oil demulsifier stock solution to 1:8 by adopting a 99 wt% methanol solution, adding the diluted composite crude oil demulsifier stock solution into an oil/water type crude oil emulsion, and completely and uniformly mixing, wherein the demulsification temperature is 65-80 ℃, and the optimal selection is 70 ℃; and 0.1M triethylammonium acetate buffer can be added to adjust the pH value to 8, so that the demulsifying effect of the demulsifier is better, and the water content of the water-in-oil emulsified crude oil can be reduced from 16% vol to 0.08% vol.
When the composite crude oil demulsifier in the embodiment 5 of the invention is used at 70 ℃ and the addition amounts of 30mg/L, 50mg/L, 100mg/L, 120mg/L, 150mg/L, 180mg/L and 200mg/L, and the dosage of the demulsifier is 100mg/L, the water content of the water-in-oil emulsified crude oil can be reduced to 0.2% vol, the salt content is reduced to 20mg/L, the cleanliness reaches NAS9 level, the qualified parameters of the water content (less than 0.2% vol) and the salt content (less than 30mg/L) of the exported crude oil are reached, and the appearance and the acid value of the oil product are improved.
Comparative example
Commercially available demulsifiers KD-25G, KD-25F and KD-25A are used for single well feeding of the Illackluk West Guerna second-stage oil field, and a pressure reduction and yield stabilization test is carried out, wherein the test data are shown in Table 12.
The testing steps are as follows:
(1) selecting different 5 crude oil single wells at different layers, wherein the daily liquid production of the selected single well is 5-16m3；
(2) Adding KD-25G, KD-25F and KD-25A into the single well in the step (1), and keeping the daily dosage constant for 7 days;
(3) recording corresponding wellhead back pressure and daily liquid production data of the single well after 7 days;
TABLE 12
Combining the data in the tables 11 and 12, it can be seen that after the commercially available demulsifiers KD-25G, KD-25F and KD-25A are added to the same 5 single wells with the same dosage as the composite crude oil demulsifier RD-1029 in the table 11, the well-head back pressure after adding the dosage is higher than that of RD-1029, and the daily fluid production is also lower than that of RD-1029; the reason is that the modified polyether in the 3 kinds of commercially available demulsifiers is different from the modified polyether JM-169 in the composite crude oil demulsifier RD-1029 in Table 11, and a small amount of methanol aqueous solution (industrial grade methanol) is not used, so that the densities of KD-25G, KD-25F and KD-25A are all higher than RD-1029, the viscosity is higher than RD-1029, the crude oil is not easy to suspend and disperse in the crude oil, the resistance of the crude oil at corners and other positions in a pipeline cannot be effectively reduced, the paraffin coagulation generation rate of the crude oil in an oil pipe is higher, the wellhead back pressure and the daily product volume after single well dosing are not changed, even the wellhead back pressure is increased, and the daily product volume is reduced.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (17)
1. The preparation method of the modified polyether is characterized by comprising the following steps:
a, sealing and preheating a phenol compound and a vinylamine compound at 50-70 ℃ for 30-50min under normal pressure; then at a stirring speed in N2Or raising the temperature to 110-130 ℃ within 30-60 min under inert atmosphere, then dropping formaldehyde aqueous solution, raising the pressure to 0.2-0.6MPa,reacting at 110-130 ℃ for 2-5 hours to obtain a first intermediate product;
b, under the condition of keeping the stirring speed before, adding alkali into the first intermediate product, dropwise adding an epoxy alkyl compound aqueous solution at the temperature of 110-130 ℃ under the pressure of 0.2-0.6MPa, stirring at constant temperature and constant pressure for reaction for 5-7 hours, and then cooling to 70-90 ℃ to obtain a second intermediate product;
c, decompressing the second intermediate product to normal pressure, cooling to room temperature, neutralizing and purifying to obtain modified polyether;
the cloud point of the modified polyether is 30-35 degrees; the infrared spectrum of the modified polyether is 1265-1220cm-1And 1300 + 990cm-12C-O telescopic vibration absorption peaks are respectively arranged between the two adjacent vibration absorption peaks, and the peak length is 3300--1Has an O-H telescopic absorption peak between the two and is 1720-1700cm-1C-O absorption vibration peak is arranged between the two, and the absorption vibration peak is 1200cm at 1320--1And C-O stretching vibration peaks are arranged between the two.
2. The method for preparing modified polyether according to claim 1, wherein in step a, the mass ratio of the phenol compound to the vinylamine compound is (0.8-6): 1.
3. the method of claim 2, wherein in step a, the phenol compound is phenol, o-cresol, m-cresol or p-cresol; the vinylamine compound is diethylenetriamine, diethylenediamine, triethylenediamine or triethylenetetramine.
4. The method for preparing modified polyether according to claim 1, wherein in the step a, the mass ratio of the formaldehyde solution to vinylamine is (0.1-0.6): 1; the concentration of the formaldehyde aqueous solution is 30-35 wt%; the dropping rate of the formaldehyde solution is 30-35 drops/min.
5. The method of claim 1, wherein in step b, the base is sodium hydroxide or potassium hydroxide; the mass ratio of the alkali to the vinylamine compound is (0.5-4): 40.
6. the process for producing a modified polyether according to claim 1, wherein in the step b, the alkylene oxide compound is at least one selected from the group consisting of ethylene oxide and propylene oxide; the mass ratio of the epoxy alkyl compound solution to the vinylamine compound is (0.4-2.5): 1; the concentration of the ethylene oxide solution and the concentration of the propylene oxide solution are both 99 wt%; the dropping rate of the ethylene oxide solution and the dropping rate of the propylene oxide solution are both 20-25 drops/min; in the step a and the step b, the rotation speed of the stirring is 150-250 rpm/min.
7. The method of claim 1, further comprising step b1, after step b and before step c: adding at least one of grafting agent and catalyst, and reacting at 80-85 deg.C for 1-2 hr.
8. The method of claim 7, wherein in step b1, the grafting agent is selected from one of acetic anhydride, maleic anhydride, acetic acid, formic acid, concentrated sulfuric acid, and dilauric acid; the mass ratio of the grafting agent to the vinylamine compound is (0.35-1.6): 1; the catalyst is selected from one of p-toluenesulfonic acid, sodium benzene sulfonate, sodium dodecyl sulfate, dibutyltin dilaurate, dicumyl oxide and di-tert-butyl peroxide; the mass ratio of the catalyst to the vinylamine compound is (1-4): 30.
9. the method of claim 7, further comprising, after step b1 and before step c, step b 2: adding cross-linking agent, and heating at 80-85 deg.C for 5-6 hr.
10. The method of claim 9, wherein in step b2, the crosslinking agent is at least one selected from the group consisting of acrylic acid, dibenzoyl peroxide, diisopropylbenzene hydroperoxide, and 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane; the mass ratio of the cross-linking agent to the vinylamine compound is (0.5-0.8): 1.
11. a modified polyether prepared by the process of any one of claims 1-10, wherein the modified polyether has a cloud point of 30 to 35 degrees; the infrared spectrum of the modified polyether is 1265-1220cm-1And 1300 + 990cm-12C-O telescopic vibration absorption peaks are respectively arranged between the two adjacent vibration absorption peaks, and the peak length is 3300--1An O-H telescopic absorption peak is arranged between the two groups; and at 1720--1C-O absorption vibration peak is arranged between the two, and the absorption vibration peak is 1200cm at 1320--1And C-O stretching vibration peaks are arranged between the two.
12. The composite crude oil demulsifier is characterized by comprising the following components in percentage by mass (0.5-2): 1: (1-4): (2-4) the modified polyether, the solvent oil, the surfactant and the alcohol-water solution; the cloud point of the modified polyether is 30-35 degrees; the infrared spectrum of the modified polyether is 1265-1220cm-1And 1300 + 990cm-12C-O telescopic vibration absorption peaks are respectively arranged between the two adjacent vibration absorption peaks, and the peak length is 3300--1Has an O-H telescopic absorption peak between the two and is 1720-1700cm-1C-O absorption vibration peak is arranged between the two, and the absorption vibration peak is 1200cm at 1320--1And C-O stretching vibration peaks are arranged between the two.
13. The complex crude oil demulsifier of claim 12, wherein the aqueous alcohol solution is selected from aqueous methanol or aqueous ethanol having a concentration of 95 to 99 wt%; the solvent oil is selected from one of 1000# solvent oil, 1800# solvent oil, 1500# solvent oil, 100# solvent oil and 200# solvent oil; the surfactant is selected from fatty alcohol-polyoxyethylene ether, a penetrating agent JFY, a penetrating agent JFC and a spandex 80/Tween 80/polyether surfactant with the mass ratio of 1:1: 1.
14. The composite crude oil demulsifier of claim 13, wherein the composite crude oil demulsifier is a brown yellow transparent oil-soluble liquid having a density of 0.85 to 0.9g/ml, a viscosity of 30 to 55mpa.s, and a flash point of 61 to 65 ℃.
15. The preparation method of the composite crude oil demulsifier is characterized by comprising the following steps:
heating the modified polyether to 40-60 ℃ at the normal-pressure stirring speed of 100 plus 200rpm/min, sequentially adding the surfactant and the alcohol aqueous solution for 30-60 min, adding the solvent oil, and cooling to room temperature after 30-60 min to obtain the composite crude oil demulsifier; the mass ratio of the modified polyether to the solvent oil to the surfactant to the alcohol-water solution is (2-10): 1: (1-2): (3-10); the cloud point of the modified polyether is 30-35 degrees; the infrared spectrum of the modified polyether is 1265-1220cm-1And 1300 + 990cm-12C-O telescopic vibration absorption peaks are respectively arranged between the two adjacent vibration absorption peaks, and the peak length is 3300--1Has an O-H telescopic absorption peak between the two and is 1720-1700cm-1C-O absorption vibration peak is arranged between the two, and the absorption vibration peak is 1200cm at 1320--1And C-O stretching vibration peaks are arranged between the two.
16. A demulsification dehydration method of water-in-oil emulsified oil is characterized by comprising the following steps:
the complex crude oil demulsifier of any one of claims 12 to 14 is diluted with a methanol aqueous solution with a concentration of 95 to 99 wt%, and then added to the water-in-oil emulsified oil liquid, mixed uniformly, and demulsified and dehydrated.
17. The method for demulsifying and dehydrating of claim 16 wherein the dilution ratio is 1 (8-10); the demulsification temperature is 30-80 ℃.
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