CN108865222B - Multi-branched crude oil demulsifier and preparation method thereof - Google Patents
Multi-branched crude oil demulsifier and preparation method thereof Download PDFInfo
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- CN108865222B CN108865222B CN201810803797.7A CN201810803797A CN108865222B CN 108865222 B CN108865222 B CN 108865222B CN 201810803797 A CN201810803797 A CN 201810803797A CN 108865222 B CN108865222 B CN 108865222B
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- CN
- China
- Prior art keywords
- chitosan
- polyethylene glycol
- glycol monomethyl
- crude oil
- monomethyl ether
- Prior art date
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- 239000010779 crude oil Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920001661 Chitosan Polymers 0.000 claims abstract description 97
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 54
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 125000004181 carboxyalkyl group Chemical group 0.000 claims abstract description 18
- 230000004048 modification Effects 0.000 claims abstract description 13
- 238000012986 modification Methods 0.000 claims abstract description 13
- 238000005576 amination reaction Methods 0.000 claims abstract description 10
- 238000005917 acylation reaction Methods 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 230000010933 acylation Effects 0.000 claims abstract description 3
- 230000029936 alkylation Effects 0.000 claims abstract description 3
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000004108 freeze drying Methods 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical group CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical group ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 229940014800 succinic anhydride Drugs 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000012716 precipitator Substances 0.000 claims description 5
- 230000008961 swelling Effects 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 230000006103 sulfonylation Effects 0.000 claims description 4
- 238000005694 sulfonylation reaction Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 150000001718 carbodiimides Chemical class 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims 1
- 239000000839 emulsion Substances 0.000 abstract description 23
- 239000004721 Polyphenylene oxide Chemical group 0.000 abstract description 13
- 229920000570 polyether Chemical group 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 231100000956 nontoxicity Toxicity 0.000 abstract description 3
- 125000002252 acyl group Chemical group 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- 125000001424 substituent group Chemical group 0.000 abstract 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 16
- 239000003921 oil Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 11
- 150000004676 glycans Chemical class 0.000 description 11
- 229920001282 polysaccharide Polymers 0.000 description 11
- 239000005017 polysaccharide Substances 0.000 description 11
- 238000011033 desalting Methods 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 235000019270 ammonium chloride Nutrition 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
- -1 nitrophenyl ester Chemical class 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 125000003277 amino group Chemical group 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 4
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 4
- 230000006196 deacetylation Effects 0.000 description 4
- 238000003381 deacetylation reaction Methods 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- PKHMTIRCAFTBDS-UHFFFAOYSA-N hexanoyl hexanoate Chemical compound CCCCCC(=O)OC(=O)CCCCC PKHMTIRCAFTBDS-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920005615 natural polymer Polymers 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229920000867 polyelectrolyte Polymers 0.000 description 3
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 150000001720 carbohydrates Chemical group 0.000 description 2
- 230000021523 carboxylation Effects 0.000 description 2
- 238000006473 carboxylation reaction Methods 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000010358 mechanical oscillation Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000007764 o/w emulsion Substances 0.000 description 2
- RAFYDKXYXRZODZ-UHFFFAOYSA-N octanoyl octanoate Chemical compound CCCCCCCC(=O)OC(=O)CCCCCCC RAFYDKXYXRZODZ-UHFFFAOYSA-N 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- GNBYZUQCDMNXML-UHFFFAOYSA-M sodium;2-chlorobutanoate Chemical compound [Na+].CCC(Cl)C([O-])=O GNBYZUQCDMNXML-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001285 xanthan gum Polymers 0.000 description 2
- 239000000230 xanthan gum Substances 0.000 description 2
- 235000010493 xanthan gum Nutrition 0.000 description 2
- 229940082509 xanthan gum Drugs 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- FLJFMDYYNMNASJ-UHFFFAOYSA-N 6-methyl-5,6-dihydrothieno[2,3-b]thiopyran-4-one Chemical compound S1C(C)CC(=O)C2=C1SC=C2 FLJFMDYYNMNASJ-UHFFFAOYSA-N 0.000 description 1
- 241000239223 Arachnida Species 0.000 description 1
- 241000238421 Arthropoda Species 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 241000238424 Crustacea Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 101001134681 Drosophila melanogaster Protein nubbin Proteins 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 238000010795 Steam Flooding Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- MSWZFWKMSRAUBD-IVMDWMLBSA-N glucosamine group Chemical group OC1[C@H](N)[C@@H](O)[C@H](O)[C@H](O1)CO MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- LSACYLWPPQLVSM-UHFFFAOYSA-N isobutyric acid anhydride Chemical compound CC(C)C(=O)OC(=O)C(C)C LSACYLWPPQLVSM-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- DUCKXCGALKOSJF-UHFFFAOYSA-N pentanoyl pentanoate Chemical compound CCCCC(=O)OC(=O)CCCC DUCKXCGALKOSJF-UHFFFAOYSA-N 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1033—Oil well production fluids
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Cosmetics (AREA)
Abstract
The invention relates to a multi-branched crude oil demulsifier and a preparation method thereof. The structural general formula of the multi-branched crude oil demulsifier is shown as formula I, and the preparation method comprises the following steps: 1) performing acylation modification on chitosan to obtain N-acylated chitosan; 2) carrying out carboxyl alkylation modification on the N-acylated chitosan to obtain N-acylated carboxyalkyl chitosan; 3) carrying out amination modification on terminal hydroxyl of the polyethylene glycol monomethyl ether to obtain aminated polyethylene glycol monomethyl ether; 4) the modified polyethylene glycol monomethyl ether reacts with the N-acylated carboxyalkyl chitosan to obtain the target product polyethylene glycol monomethyl ether grafted N-acylated carboxyalkyl chitosan. The invention takes chitosan natural high molecular compound as raw material, and has the advantages of wide source, naturalness, no toxicity, good biocompatibility, degradability and the like. The carboxyl alkyl, acyl and polyether side chain are introduced into the chitosan molecular chain, and a series of high-efficiency demulsifiers suitable for oil-in-water (O/W) type emulsion are obtained by controlling the position and the degree of substitution of each substituent.
Description
Technical Field
The invention relates to a multi-branched crude oil demulsifier and a preparation method thereof, belonging to the field of petrochemical industry.
Background
In the process of oil field exploitation, along with the implementation of oil extraction process technologies such as steam flooding, surfactant, polymer and ternary complex flooding, the water content of the crude oil emulsion is increased, the stability is enhanced, and the demulsification difficulty of the crude oil is increased. The formation of emulsions can pose a serious hazard to the recovery, transportation and processing of petroleum. The crude oil is emulsified with water, so that the difficulty in extracting the crude oil is increased; transporting the crude oil containing water by pipeline or tank car increases the load of the pump and the transportation cost. Therefore, it is essential to desalt and dewater crude oil emulsions prior to crude oil transportation and processing.
The emulsion is a very complex dispersion system, mainly water-in-oil (W/O) type, and oil-in-water (O/W) type emulsion gradually appears in produced liquid along with the application of new oil extraction technology. The common demulsification methods include flotation, chemical coagulation, chemical and electrochemical technologies, chemical demulsification, membrane separation, biotechnology and the like, and the most widely applied demulsification methods are chemical demulsification methods. The demulsifier required by the chemical demulsification method has been updated for one generation in the past hundred years, and the demulsifier has better and better effect and less dosage. However, as the emulsion becomes more complex, the specificity of the demulsifier becomes stronger. At present, the crude oil demulsifier used in oil fields in China is mainly based on block polymers and tends to develop in the direction of ultrahigh molecular weight. The polysaccharide natural polymer has wide sources, excellent biocompatibility and environmental friendliness, large molecular weight, more active hydrogen, a branch structure and unique rheological property, occupies a large area at an oil-water interface, has good temperature resistance, high interfacial activity and no pollution to the environment, and is an excellent candidate for the demulsifier initiator. Guo Dong hong, etc. uses xanthan gum or guar gum as initiator, and adds with epoxyethane and epoxypropane to synthesize polysaccharide natural high-molecular demulsifier with polyether branch structure, and makes simple evaluation on its demulsification performance. Xu et al found that ethyl cellulose can effectively remove 90% of water in asphalt emulsion and systematically studied its demulsification mechanism. Wangli and the like take polysaccharide and the like as initiators to synthesize five polysaccharide crude oil demulsifiers, and the demulsification performance of the five polysaccharide crude oil demulsifiers is evaluated to a certain extent. Fan and the like synthesize a series of chitosan crude oil demulsifiers, have certain demulsification and dehydration effects on water-in-oil (W/O) crude oil emulsion under the condition that the demulsification temperature is 60 ℃, and discuss the demulsification mechanism.
Chitosan is a natural macromolecule which is produced second to cellulose in nature, widely exists in wings and shells of arthropods (arachnids, crustaceans), and also exists in cell walls of fungi and algae, and has excellent biocompatibility and environmental friendliness. Compared with polysaccharide such as xanthan gum and cellulose, the chitosan contains more active amino groups and is easier to graft and modify. Carboxymethyl chitosan can be obtained by carboxymethylation of chitosan, and the solubility of chitosan is greatly changed due to the introduction of hydrophilic group carboxyl; the carboxymethyl chitosan is modified by quaternization, so that the amphoteric polyelectrolyte with both carboxyl and quaternary ammonium salt groups in the molecule can be obtained. Chinese patent CN 201310289037.6 describes a polysaccharide modified crude oil demulsifier. Polysaccharide is used as an initiator, and quaternary amination modification and polyether grafting modification are carried out on the polysaccharide to obtain the polysaccharide modified crude oil demulsifier. Chinese patent CN 201610644945.6 describes a preparation method of polyelectrolyte type crude oil desalting demulsifier. Glycidyl dimethyl alkyl ammonium chloride and amination modified polyether are grafted to carboxymethyl chitosan to obtain the polyelectrolyte type crude oil desalting demulsifier. In Chinese patent CN201610644992.0, glycidyl dimethyl alkyl ammonium chloride and isocyanate modified polyether are grafted to carboxymethyl chitosan to obtain a novel efficient crude oil desalting demulsifier. In the Chinese patent CN201610644943.7, glycidyl dimethyl alkyl ammonium chloride and polyether modified by acrylic acid esterification are grafted to carboxymethyl chitosan to obtain the comb-shaped polymer crude oil desalting demulsifier. In Chinese patent CN201610644993.5, glycidyl dimethyl alkyl ammonium chloride and aldehyde modified polyether are grafted to carboxymethyl chitosan to obtain a polyether grafted chitosan derivative crude oil desalting demulsifier. In the Chinese patent CN201610645442.0, glycidyl dimethyl alkyl ammonium chloride and polyether modified by nitrophenyl ester are grafted to carboxymethyl chitosan to obtain the efficient crude oil desalting demulsifier. China patent CN201610645444.X glycidyl dimethyl alkyl ammonium chloride and epoxy modified polyether are grafted onto carboxymethyl chitosan to obtain the chitosan crude oil desalting demulsifier. In the Chinese patent CN201610645497.1, glycidyl dimethyl alkyl ammonium chloride and polyether after halogenation modification are grafted to carboxymethyl chitosan to obtain a chitosan natural polymer modified crude oil desalting demulsifier. In Chinese patent CN201610648933.0, glycidyl dimethyl alkyl ammonium chloride and esterified and modified polyether are grafted to carboxymethyl chitosan to obtain a double-ion type crude oil desalting demulsifier. The demulsifier has the advantages of wide source of the polysaccharide demulsifier, naturalness, innocuity, sustainability, good use safety and the like, and can remove oil-soluble salts in crude oil emulsion while demulsifying. However, these chitin demulsifiers are mainly aimed at water-in-oil (W/O) crude oil emulsions.
With the heavy use of new oil recovery technology, the oil-in-water (O/W) emulsion has larger proportion and stronger stability while improving the recovery ratio of crude oil. Oil-in-water (O/W) emulsions are complex in composition and generally include dirty oil, scale, organic matter, corrosive gases, sludge and clays, surfactants and co-surfactants, and the like. Due to the presence of these substances, the oil-water interfacial tension and the zeta potential of the oil droplet surface can be greatly reduced, and the high polymer contained in the emulsion can increase the viscosity of water, so that a very stable oil-in-water (O/W) emulsion is formed, and the emulsion breaking and separation of the emulsion are very difficult.
At present, the domestic demulsifiers aiming at oil-in-water (O/W) type emulsions are only CW-01, PDM-1, BH-1, RD-1 and the like. The demulsifiers are poor in environmental friendliness and easy to cause irreversible secondary pollution; in addition, each oil field crude oil production fluid has more or less different compositions and properties, and a demulsifier capable of treating all types of crude oil production fluids does not exist. Therefore, the development of a novel and environmentally friendly oil-in-water (O/W) demulsifier to solve the problems caused by the new technology of oil recovery has become an important and urgent problem to be solved in the later development of oil fields.
Disclosure of Invention
The invention provides a multi-branched crude oil demulsifier and a preparation method thereof aiming at the problems in the prior art. The demulsifier takes chitosan natural high molecular compounds as raw materials, and acyl, alkyl and polyether side chains are introduced to a chitosan molecular chain, so that the obtained demulsifier can realize high-efficiency demulsification on oil-in-water (O/W) crude oil emulsion. The preparation method of the demulsifier has the advantages of wide raw material source, naturalness, no toxicity, sustainability, good biocompatibility of the product, degradability and the like.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the multi-branched crude oil demulsifier is characterized by having a general structural formula shown in the following formula (I):
the invention also provides a preparation method of the multi-branched crude oil demulsifier, which comprises the following steps:
the preparation method of the multi-branched crude oil demulsifier is characterized by comprising the following steps:
1) performing acylation modification on amino on chitosan to obtain N-acylated chitosan, which comprises the following specific steps:
dissolving chitosan in an organic acid aqueous solution, adding organic alcohol for dilution, adding acid anhydride according to 0.5 time of the amount of substances of amino groups on the chitosan under the condition of stirring, standing at room temperature for 24-48 h, adding a precipitator, washing the precipitate, and freeze-drying to obtain N-acylated chitosan; preferably, the organic alcohol is used in an amount of 80% by volume or more of the whole system. (acylation reaction is carried out in a homogeneous system consisting of organic alcohol, organic acid and water, the content of the organic alcohol in the system is as high as 80%. the acylation reaction is preferentially carried out on amino groups of sugar rings due to the competition effect of hydroxyl groups of the organic alcohol, so that the system has excellent selectivity, and the acylation reaction is carried out on the amino group at the C2 position only.)
2) The N-acylated chitosan is subjected to carboxyl alkylation modification to obtain the N-acylated carboxyalkyl chitosan, and the specific steps are as follows:
dissolving or swelling the N-acylated chitosan prepared in the step 1) in a solvent A, and adding alkali liquor to alkalize for 1-2 h; alkaliAfter the reaction is finished, adding a carboxylation reagent sodium chloroalkyl ate into the reaction liquid, heating to 50-100 ℃ after the addition is finished, reacting for 2-7 hours, and adding an acid solution to adjust the pH of the reaction liquid to be neutral; carrying out suction filtration on the reaction product, washing and dialyzing a filter cake, and freeze-drying to obtain N-acylated carboxyalkyl chitosan; wherein, preferably, the carbon chain length of the sodium chloroalkylate is C2-C18；
3) The method comprises the following steps of carrying out amination modification on terminal hydroxyl of polyethylene glycol monomethyl ether to obtain aminated polyethylene glycol monomethyl ether:
dissolving 1 mol part of polyethylene glycol monomethyl ether in a solvent B at room temperature, carrying out a reaction in an inert gas environment, adding 1-5 mol parts of a catalyst, dissolving 2.5-5 mol parts of a sulfonylation reagent in the solvent B, slowly dropwise adding the solution into a reaction solution, carrying out an ice-water bath reaction for 3-5 h, carrying out reduced pressure distillation, adding a solvent C for recrystallization, adding a recrystallized product into 10-20 mol parts of an amination reagent, carrying out a reflux reaction at 140-160 ℃ for 6-8 h, carrying out reduced pressure distillation, and carrying out freeze drying to obtain the aminated polyethylene glycol monomethyl ether; wherein, the number average molecular mass of the polyethylene glycol monomethyl ether is preferably 350-5000;
4) the method comprises the following steps of reacting aminated polyethylene glycol monomethyl ether with N-acylated carboxyalkyl chitosan:
dissolving the aminated polyethylene glycol monomethyl ether prepared in the step 3) in a solvent B, adding dianhydride, reacting for 12-24 h at 20-100 ℃, dissolving or swelling the N-acylated carboxyalkyl chitosan prepared in the step 2) in a solvent D, then dropwise adding the solvent D into a reaction system, adding a certain amount of catalyst, stirring and heating to 80-120 ℃, reacting for 12-24 h at a constant temperature, separating and purifying the reaction liquid, and freeze-drying to obtain the target product modified polyethylene glycol monomethyl ether grafted N-acylated carboxyalkyl chitosan.
According to the scheme, the organic alcohol in the step 1) is preferably one or more of aliphatic alcohols with 1-10 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and the like; the acid anhydride is one or more of acetic anhydride, propionic anhydride, n-butyric anhydride, isobutyric anhydride, n-valeric anhydride, n-hexanoic anhydride, n-octanoic anhydride and other anhydrides corresponding to fatty acid with 2-10 carbon atoms; the precipitant is acetone.
According to the scheme, preferably, in the step 2), the mass part ratio of the N-acylated chitosan to the sodium chloroalkyl ate is (1-1.256): (4.6-15.48).
According to the scheme, preferably, in the step 2), in the process of dissolving or swelling the N-acylated chitosan in the solvent A and adding alkali liquor for alkalization, the alkali liquor is added in a small amount for multiple times; after the alkalization is finished, the carboxylation reagent sodium chloroalkyl ate is added in a small amount for multiple times.
According to the scheme, preferably, in the step 3), the catalyst is pyridine or triethylamine; the sulfonylation reagent is p-toluenesulfonyl chloride; the amination reagent is ammonia water; the inert gas is nitrogen or argon.
According to the scheme, in the step 4), the mass part ratio of the N-acylated carboxyalkyl chitosan to the aminated polyethylene glycol monomethyl ether is (0.289-0.821) (0.898-10.198).
According to the scheme, in the step 4), preferably, the dianhydride is succinic anhydride; the catalyst is one or more of carbodiimide, dicyclohexylcarbodiimide and N-hydroxysuccinimide.
According to the scheme, preferably, the solvent A is one or a mixture of more of distilled water, isopropanol, sodium hydroxide solution, hydrochloric acid solution, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, acetic acid and methanol.
According to the scheme, preferably, the solvent B is one or more of dichloromethane, chloroform, carbon tetrachloride, N-dimethylformamide and N, N-dimethylacetamide.
According to the scheme, preferably, the solvent C is one or more of diethyl ether, isopropyl ether and methyl tert-butyl ether.
According to the scheme, preferably, the solvent D is one or more of distilled water, isopropanol, sodium hydroxide solution, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, acetic acid and methanol.
The synthetic route of the invention is as follows:
1. carrying out amination modification on the terminal hydroxyl of the polyethylene glycol monomethyl ether, wherein the modified polyethylene glycol monomethyl ether is marked as MPEG-M:
2. preparing N-acylated carboxyalkyl chitosan, synthesizing polyethylene glycol monomethyl ether grafted N-acylated carboxyalkyl chitosan:
compared with the prior art, the invention has the following beneficial effects:
1) the invention takes chitosan natural high molecular compound as raw material, and has the advantages of wide source, naturalness, no toxicity, biodegradability, compatibility, sustainability, good use safety and the like.
2) The modified polyethylene glycol monomethyl ether grafted N-acylated carboxyalkyl chitosan prepared by the invention is a high-efficiency crude oil demulsifier. The demulsifier has a comb-shaped structure, has large molecular weight and more branched chains, occupies a large area at an oil-water interface, and has high interfacial activity. The demulsifier has strong competitive adsorption capacity on an oil-water interface, is easy to adsorb and replace natural emulsifiers such as asphalt, paraffin, resin and the like adsorbed on the interface on the oil-water interface, and can realize high-efficiency demulsification on oil-in-water (O/W) crude oil emulsion. The emulsion breaker is added to enable emulsion droplets to be aggregated to form larger oil droplets and destroy an oil-water interface film, so that the emulsion breaking and deoiling effects are achieved, a water phase after emulsion breaking is clear, an oil-water interface is neat, and the deoiling efficiency is high.
3) According to the method for preparing the chitosan natural polymer modified crude oil demulsifier, the molecular structure of the demulsifier, such as molecular weight, substitution degree, hydrophobic chain segment length aggregation structure and the like, can be changed by selecting sodium carboxylate and alkyl chains with different carbon chain lengths, or changing the using amount ratio of reaction raw materials, or changing the conditions of reaction temperature, reaction time and the like of a reaction system, so that the deoiling effect of the synthesized high-efficiency demulsifier is regulated and controlled, and the method is suitable for crude oils with different properties (different producing areas and different oil-containing water contents).
Detailed Description
For a better understanding of the present invention, the following examples are given to further illustrate the present invention, but the present invention is not limited to the following examples.
All the starting materials mentioned in the examples below are, unless otherwise specified, commercially available.
Example 1
The method for preparing the N-N-butyrylated carboxymethyl chitosan grafted by the polyethylene glycol monomethyl ether comprises the following specific steps:
(1) synthesis of N-acylated chitosan: mixing 2g Chitosan (CS) (M)w179.17kDa, degree of deacetylation>95 percent and the viscosity of 100-200 mPas) is dissolved in 40mL of 10 percent acetic acid aqueous solution, 160mL of methanol is added for dilution, 5.9mmol of N-butyric anhydride is added under the stirring condition, the mixture is placed for 24 hours at room temperature, 260mL of acetone is added as a precipitator, the precipitate is washed three times by methanol and ether respectively, and the white water-soluble solid N-N-butyrylated chitosan (A) is obtained after freeze drying4CS)。
Wherein the dosage of the n-butyric anhydride is 0.5 times of the dosage of amino substances contained in the chitosan, and the specific calculation method is as follows:
the saccharide units of chitosan are glucosamine residues, the molecular weight of this residue (saccharide units of chitosan) is 161, 2g of chitosan (degree of deacetylation > 95%) contains the amount of amino groups: 2 g/161 g/mol × 95% ═ 0.0118mol, i.e. 11.8 mmol; the mass of n-butyric anhydride is then: 0.5 × 11.8mmol ═ 5.9 mmol.
(2) Carboxymethylation of N-butyrylated chitosan: fetch 1g A4CS is added into a 250mL three-neck flask, 100mL of distilled water is added until the solution is completely dissolved at room temperature, 10mL of 10% sodium hydroxide solution is divided into 5 parts, added into the reaction solution for 5 times at intervals of 5min, and alkalized for 1 h. After the alkalization is finished, 4.6g of sodium chloroacetate is divided into 5 parts, one part is added into the reaction liquid every 1min, and the solution is increased after the addition is finishedThe temperature is raised to 60 ℃, the reaction is carried out for 2h, and the pH of the reaction solution is adjusted to be neutral by acetic acid. After the reaction is finished, performing suction filtration, washing a filter cake for three times by using acetone, dialyzing for three days after washing, and performing freeze drying to obtain the N-N-butyrylated carboxymethyl chitosan (A)4CMC)。
(3) Synthesis of aminated polyethylene glycol monomethyl ether: taking polyethylene glycol monomethyl ether (M)n5000)5g (1mmol) was dissolved in 10mL of dichloromethane, the reaction was maintained under an argon atmosphere, 0.3mL (2mmol) of triethylamine was added, 0.95g (5mmol) of p-toluenesulfonyl chloride was dissolved in dichloromethane and slowly added dropwise to the reaction solution, and the mixture was reacted in an ice water bath (0 ℃ C.) for 5 hours. The mixture was distilled under reduced pressure, 100mL of diethyl ether was added for recrystallization, and the recrystallized product was added to 38.5mL (10mol) of ammonia water and heated to 140 ℃ for reflux reaction for 8 hours. Vacuum distilling, freeze drying to obtain aminated polyethylene glycol monomethyl ether (MPEG-NH)2)。
(4) Synthesizing N-N-butyrylated carboxymethyl chitosan grafted by polyethylene glycol monomethyl ether: 10.198g of aminated polyethylene glycol monomethyl ether is put in a 250mL three-neck flask, 10mL of dichloromethane solution is added, 10mL of succinic anhydride is added, and the reaction is carried out for 24h at 30 ℃; then 0.289g A is taken4CMC is dissolved in 50mL of dimethyl sulfoxide, 1 drop of N-hydroxysuccinimide as a catalyst is added dropwise, the mixture is added dropwise into a reaction system within 10min through a constant pressure dropping funnel, the temperature is raised to 110 ℃, and the reaction is carried out for 24 h. And dialyzing the reaction solution for 3 days after the reaction is finished, and freeze-drying to obtain the polyethylene glycol monomethyl ether grafted N-N-butyrylated carboxymethyl chitosan serving as the demulsifier 1.
Example 2
The method for preparing the N-N-hexanoyl carboxymethyl chitosan grafted by the polyethylene glycol monomethyl ether comprises the following steps:
(1) synthesis of N-acylated chitosan: mixing 2g Chitosan (CS) (M)w179.17kDa, degree of deacetylation>95 percent and 100-200 mPas) is dissolved in 40mL of 10 percent acetic acid water solution, 160mL of methanol is added for dilution, 5.9mmol of N-hexanoic anhydride is added according to 0.5 time of the amount of amino substances under the condition of stirring, 260mL of acetone is added as a precipitator after the mixture is placed for 24 hours at room temperature, the precipitate is washed three times by methanol and ether respectively, and the white water-soluble solid N-N-hexanoylated chitosan (A) is obtained by freeze drying6CS)。The calculation of the amount of n-hexanoic anhydride used was as described in step (1) of example 1.
(2) Carboxymethylation of N-hexanoylated chitosan: take 1.128g A6CS is added into a 250mL three-neck flask, 100mL of distilled water is added until the solution is completely dissolved at room temperature, 10mL of 10% sodium hydroxide solution is divided into 5 parts, added into the reaction solution for 5 times at intervals of 5min, and alkalized for 1 h. After the alkalization is finished, 4.6g of sodium chloroacetate is divided into 5 parts, one part is added into the reaction liquid every 1min, the temperature is raised to 60 ℃ after the addition is finished, the reaction is carried out for 2h, and the pH value of the reaction liquid is adjusted to be neutral by acetic acid. After the reaction is finished, carrying out suction filtration, washing a filter cake for three times by using acetone, dialyzing for three days after washing, and carrying out freeze drying to obtain the N-N-hexanoyl carboxymethyl chitosan (A)6CMC)。
(3) Synthesis of aminated polyethylene glycol monomethyl ether: taking polyethylene glycol monomethyl ether (M)n1900)1.9g (1mmol) was dissolved in 10mL of dichloromethane, the reaction was kept under an argon atmosphere, 0.15mL (1mmol) of triethylamine was added, 0.48g (2.5mmol) of p-toluenesulfonyl chloride was dissolved in dichloromethane and slowly added dropwise to the reaction solution, and the mixture was reacted in an ice water bath (0 ℃ C.) for 3 hours. The mixture was distilled under reduced pressure, 100mL of diethyl ether was added for recrystallization, and the recrystallized product was added to 38.1mL (10mol) of ammonia water and heated to 150 ℃ for reflux reaction for 8 hours. Carrying out reduced pressure distillation, and freeze-drying to obtain aminated polyethylene glycol monomethyl ether;
(4) synthesizing polyethylene glycol monomethyl ether grafted N-N-hexanoyl carboxymethyl chitosan: 3.998g of aminated polyethylene glycol monomethyl ether is put in a 250mL three-neck flask, 10mL of dichloromethane solution is added, 10mL of succinic anhydride is added, and the reaction is carried out for 24h at 30 ℃; then take 0.317g A6CMC is dissolved in 50mL of dimethyl sulfoxide, 1 drop of N-hydroxysuccinimide as a catalyst is added dropwise, the mixture is added dropwise into a reaction system within 10min through a constant pressure dropping funnel, the temperature is raised to 110 ℃, and the reaction is carried out for 24 h. And dialyzing the reaction solution for 3 days after the reaction is finished, and freeze-drying to obtain the polyethylene glycol monomethyl ether grafted N-N-hexyl acylated carboxymethyl chitosan which is the demulsifier 2.
Example 3
The preparation method of the N-N-octanoylated carboxymethyl chitosan grafted by the polyethylene glycol monomethyl ether comprises the following specific steps:
(1) synthesis of N-acylated chitosan: 2g Chitosan (CS) (M)w179.17kDa, degree of deacetylation>95 percent and 100 to 200 mPas) is dissolved in 40mL of 10 percent acetic acid water solution, 160mL of methanol is added for dilution, 5.9mmol of N-caprylic anhydride is added according to 0.5 time of the amount of amino substances under the condition of stirring, 260mL of acetone is added as a precipitator after the mixture is placed for 24 hours at room temperature, the precipitate is washed three times by methanol and ether respectively, and the white water-soluble solid N-N-octanoylated chitosan (A) is obtained by freeze drying8CS). The method for calculating the amount of n-octanoic anhydride used is described in reference to step (1) in example 1.
(2) Carboxymethylation of N-octanoylated chitosan: get 1.256g A8CS is added into a 250mL three-neck flask, 100mL of distilled water is added, when the solution is completely dissolved at room temperature, 10mL of 10% sodium hydroxide solution is added into the reaction solution for alkalization for 1h in 5 times at intervals of 5 min. After the alkalization is finished, 4.6g of sodium chloroacetate is divided into 5 parts, one part is added into the reaction liquid every 1min, and after the addition is finished, the temperature is raised to 60 ℃ for reaction for 2 h. After the reaction is finished, carrying out suction filtration, washing a filter cake for three times by using acetone, dialyzing for three days after washing, and carrying out freeze drying to obtain the N-N-octanoyl carboxymethyl chitosan (A)8CMC)。
(3) Synthesis of aminated polyethylene glycol monomethyl ether: taking polyethylene glycol monomethyl ether (M)n750. times.0.75 g (1mmol) was dissolved in 10mL of dichloromethane, the reaction was maintained under an argon atmosphere, 0.38mL (2.5mmol) of triethylamine was added, 0.95g (5mmol) of p-toluenesulfonyl chloride was dissolved in dichloromethane and slowly added dropwise to the reaction solution, and the reaction was carried out in an ice water bath (0 ℃ C.) for 5 hours. The mixture was distilled under reduced pressure, 100mL of diethyl ether was added for recrystallization, and the recrystallized product was added to 38.1mL (10mol) of ammonia water and heated to 140 ℃ for reflux reaction for 8 hours. Carrying out reduced pressure distillation, and freeze-drying to obtain aminated polyethylene glycol monomethyl ether;
(4) synthesizing N-N-octanoyl carboxymethyl chitosan grafted by polyethylene glycol monomethyl ether: taking 1.698g of aminated polyethylene glycol monomethyl ether in a 250mL three-neck flask, adding 50mL of dichloromethane, adding 10mL of succinic anhydride, reacting at 30 ℃ for 24h, and taking 0.345g A8CMC is dissolved in 10mL dimethyl sulfoxide solution, 1 drop of N-hydroxysuccinimide is added as catalyst, and then a constant pressure dropping funnel is usedDropwise adding the mixture into a reaction system within 10min, heating to 110 ℃, and reacting for 24 h. And dialyzing the reaction solution for 3 days after the reaction is finished, and freeze-drying to obtain the N-N-octanoylated carboxymethyl chitosan grafted by the polyethylene glycol monomethyl ether, which is the demulsifier 3.
Example 4
The preparation method of the N-N-octanoylated carboxypropyl chitosan grafted by the polyethylene glycol monomethyl ether comprises the following specific steps:
(1) the same procedure as in step (1) of example 3 gave N-N-octanoylated chitosan (A)8CS)。
(2) Carboxypropylation of N-N-octanoylated chitosan: get 1.256g A8CS is added into a 250mL three-neck flask, 100mL of isopropanol solution is added, the mixture is fully swelled at room temperature, 10mL of 10% sodium hydroxide solution is taken and added into the reaction solution for alkalization for 1h in 5 times at intervals of 5min each time. After the alkalization is finished, 5.76g of sodium chlorobutyrate is divided into 5 parts, one part of sodium chlorobutyrate is added into the reaction liquid every 1min, and the temperature is raised to 70 ℃ after the addition, so that the reaction is carried out for 7 h. After the reaction is finished, carrying out suction filtration, washing a filter cake for three times by using acetone, dialyzing for three days after washing, and carrying out freeze drying to obtain the N-N-octanoyl carboxypropyl chitosan (A)8CPC)。
(3) Synthesis of aminated polyethylene glycol monomethyl ether: taking polyethylene glycol monomethyl ether (M)n350) was dissolved in 10mL of carbon tetrachloride, the reaction was maintained under an argon atmosphere, 0.76mL (5mmol) of triethylamine was added, 0.95g (5mmol) of p-toluenesulfonyl chloride was dissolved in dichloromethane and slowly added dropwise to the reaction solution, and the mixture was reacted in an ice water bath (0 ℃ C.) for 8 hours. The mixture was distilled under reduced pressure, 100mL of isopropyl ether was added for recrystallization, and the recrystallized product was added to 76.2mL (20mol) of ammonia water and heated to 160 ℃ for reflux reaction for 7 hours. Carrying out reduced pressure distillation, and freeze-drying to obtain aminated polyethylene glycol monomethyl ether;
(4) synthesizing N-N-octanoyl carboxypropyl chitosan grafted by polyethylene glycol monomethyl ether: 0.898g of aminated polyethylene glycol monomethyl ether was placed in a 250mL three-necked flask, 50mL of carbon tetrachloride was added, 10mL of succinic anhydride was added, and the mixture was reacted at 30 ℃ for 24 hours. Take 0.377g A8Dissolving CPC in 10mL of N, N-dimethylformamide solution, dropwise adding 1 drop of N-hydroxysuccinimide as catalyst, and dropwise adding into the reactant within 10min through a constant pressure dropping funnelIn the reaction system, the temperature is raised to 120 ℃ and the reaction lasts 18 h. And dialyzing the reaction solution for 3 days after the reaction is finished, and freeze-drying to obtain the N-N-octanoylated carboxypropyl chitosan grafted by the polyethylene glycol monomethyl ether, namely the demulsifier 4.
Comparative example 1
And a commercial product number SP series demulsifier is used as a demulsifier comparative example 1.
Comparative example 2
And a commercial product number JL series demulsifier is used as the demulsifier comparative example 2.
Demulsification effect experiment of demulsifier
Crude oil provided by Wuhan division of China petrochemical company Limited is used as the oil for demulsification experiments to carry out experiments, and the water content in the crude oil is measured to be 50 percent according to GB/T8929-88 (distillation method).
The dehydration temperature is set to be 40-80 ℃, and the concentration of a demulsifier in the crude oil is 70-220 ppm. The demulsification performances of the demulsifiers 1-4 prepared in examples 1-4 and the demulsifier comparative examples 1-2 prepared in comparative examples were tested with reference to "crude oil demulsifier usability detection method (bottle test method)" of the national petroleum and gas industry standard SY/T5281-2000, and a mechanical oscillation method was used as an oscillation method for a dehydration test bottle in the test.
The method comprises the following specific steps: pouring the crude oil emulsion sample into a 100mL measuring cylinder with a plug, and heating in a constant-temperature water bath for 30 min; adding a certain amount of crude oil demulsifier solution into the measuring cylinder with the plug by using a pipette; adopting a mechanical oscillation method, enabling the amplitude to be larger than 20cm, enabling the oscillation time to be 5min, fully mixing uniformly, and then placing the measuring cylinder with the plug in a constant-temperature water bath again for standing and settling; timing, recording the dehydration amount at different times (20min, 40min, 60min, 80min, 100min and 120min), and observing and recording the color of the sewage when the sedimentation is stopped.
The experimental result shows that compared with the comparative demulsifier examples 1-4, the demulsifier 1-4 obtained by the method has better dehydration and desalination effects within the ranges of the dehydration temperature of 40-80 ℃ and the demulsifier concentration of 70-220 ppm, and particularly has the best effect at the concentration of 200ppm and the dehydration temperature of 50 ℃.
The demulsifiers 1-4 prepared in examples 1-4 and the demulsifiers provided in comparative examples 1-2, the effect of the demulsification and dehydration experiments under the above-mentioned optimum concentration and temperature conditions, are shown in Table 1.
TABLE 1
Claims (10)
1. The preparation method of the multi-branched crude oil demulsifier comprises the following general structural formula shown in formula (I):
R＝H or COCH3R0，R1＝H or R5COOH or MPEG-NH-COCH2CH2CO
R2＝H or CH3(CH2)aCO(a＝0，1，2，3...8)or R5COOH or MPEG-NH-COCH2CH2CO
R5＝(CH2)b(b＝1，2，3，4，5，6...17)
(I)
the method is characterized by comprising the following steps:
1) carrying out acylation modification on amino on chitosan:
dissolving chitosan in an organic acid aqueous solution, adding organic alcohol, adding acid anhydride according to 0.5 time of the amount of amino substances on the chitosan, standing for 24-48 h, adding a precipitator, washing the precipitate, and freeze-drying to obtain N-acylated chitosan;
2) carrying out carboxyl alkylation modification on the N-acylated chitosan:
dissolving or swelling the N-acylated chitosan prepared in the step 1) in a solvent A, adding alkali liquor for alkalization, adding sodium chloroalkyl into reaction liquid after alkalization is finished, heating to 50-100 ℃, reacting for 2-7 h, separating and purifying the reaction liquid, and freeze-drying to obtain the N-acylated carboxyalkyl chitosan(ii) a Wherein the length of the carbon chain of the sodium chloroalkyl acid is C2-C18；
3) Carrying out amination modification on terminal hydroxyl of the polyethylene glycol monomethyl ether to obtain aminated polyethylene glycol monomethyl ether;
4) reacting aminated polyethylene glycol monomethyl ether with N-acylated carboxyalkyl chitosan:
dissolving the aminated polyethylene glycol monomethyl ether prepared in the step 3) in a solvent B, adding dianhydride, reacting for 12-24 h at 20-100 ℃, dissolving or swelling the N-acylated carboxyalkyl chitosan prepared in the step 2) in a solvent D, then dropwise adding the solvent D into a reaction system, adding a catalyst, heating to 80-120 ℃, reacting for 12-24 h, separating and purifying the reaction solution, and freeze-drying to obtain the modified polyethylene glycol monomethyl ether grafted N-acylated carboxyalkyl chitosan.
2. The method for preparing the multi-branched crude oil demulsifier according to claim 1, wherein the organic alcohol is used in an amount of 80% by volume or more based on the whole system in step 1).
3. The method for preparing the multi-branched crude oil demulsifier according to claim 1, wherein in step 1), the organic alcohol is one or more of fatty alcohols having 1 to 10 carbon atoms; the acid anhydride is one or more of acid anhydrides corresponding to fatty acid with 2-10 carbon atoms; the precipitant is acetone.
4. The method for preparing the multi-branched crude oil demulsifier according to claim 1, wherein the mass part ratio of the N-acylated chitosan to the sodium chloroalkyl ate in step 2) is (1-1.256): (4.6-15.48).
5. The method for preparing the multi-branched crude oil demulsifier according to claim 1, wherein in step 2), the alkali solution is added in small amounts and a plurality of times; the addition mode of the sodium chloroalkyl is small-amount multiple addition.
6. The method for preparing the multi-branched crude oil demulsifier according to claim 1, wherein the mass part ratio of the N-acylated carboxyalkyl chitosan to the aminated polyethylene glycol monomethyl ether in step 4) is (0.289-0.821) (0.898-10.198).
7. The method for preparing the multi-branched crude oil demulsifier according to claim 1, wherein in step 4), the dianhydride is succinic anhydride; the catalyst is one or more of carbodiimide, dicyclohexylcarbodiimide and N-hydroxysuccinimide.
8. The method for preparing the multi-branched crude oil demulsifier according to any one of claims 1 to 7, wherein the solvent A is a mixture of one or more of distilled water, isopropanol, sodium hydroxide solution, hydrochloric acid solution, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, acetic acid, and methanol; the solvent B is one or more of dichloromethane, chloroform, carbon tetrachloride, N-dimethylformamide and N, N-dimethylacetamide; the solvent D is one or more of distilled water, isopropanol, sodium hydroxide solution, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, acetic acid and methanol.
9. The method for preparing the multi-branched crude oil demulsifier according to claim 8, wherein the specific steps of step 3) are as follows:
dissolving 1 mol part of polyethylene glycol monomethyl ether in a solvent B at room temperature, carrying out a reaction in an inert gas environment, adding 1-5 mol parts of a catalyst, dissolving 2.5-5 mol parts of a sulfonylation reagent in the solvent B, slowly dropwise adding the solution into a reaction solution, carrying out an ice-water bath reaction for 3-5 h, carrying out reduced pressure distillation, adding a solvent C for recrystallization, adding a recrystallized product into 10-20 mol parts of an amination reagent, carrying out a reflux reaction at 140-160 ℃ for 6-8 h, carrying out reduced pressure distillation, and carrying out freeze drying to obtain the aminated polyethylene glycol monomethyl ether; wherein the number average molecular mass of the polyethylene glycol monomethyl ether is 350-5000.
10. The method for preparing the multi-branched crude oil demulsifier according to claim 9, wherein the catalyst is pyridine or triethylamine; the sulfonylation reagent is p-toluenesulfonyl chloride; the amination reagent is ammonia water; the inert gas is nitrogen or argon; the solvent C is one or more of diethyl ether, isopropyl ether and methyl tert-butyl ether.
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| WO2004050801A1 (en) * | 2002-12-03 | 2004-06-17 | M-I L.L.C. | Demulsifiers for crude oil emulsions |
| CN103320158A (en) * | 2013-07-10 | 2013-09-25 | 武汉工程大学 | Natural polysaccharide macromolecule-modified crude oil demulsifier |
| CN106221728A (en) * | 2016-08-09 | 2016-12-14 | 武汉工程大学 | A kind of preparation method of polyelectrolyte type crude oil desalting demulsifier |
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| WO2004050801A1 (en) * | 2002-12-03 | 2004-06-17 | M-I L.L.C. | Demulsifiers for crude oil emulsions |
| CN103320158A (en) * | 2013-07-10 | 2013-09-25 | 武汉工程大学 | Natural polysaccharide macromolecule-modified crude oil demulsifier |
| CN106221728A (en) * | 2016-08-09 | 2016-12-14 | 武汉工程大学 | A kind of preparation method of polyelectrolyte type crude oil desalting demulsifier |
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