CN106188552A - The preparation method of chitosan class natural macromolecule modification crude oil desalting demulsifier - Google Patents
The preparation method of chitosan class natural macromolecule modification crude oil desalting demulsifier Download PDFInfo
- Publication number
- CN106188552A CN106188552A CN201610645497.1A CN201610645497A CN106188552A CN 106188552 A CN106188552 A CN 106188552A CN 201610645497 A CN201610645497 A CN 201610645497A CN 106188552 A CN106188552 A CN 106188552A
- Authority
- CN
- China
- Prior art keywords
- chitosan
- monomethyl ether
- glycol monomethyl
- crude oil
- polyethylene glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 104
- 239000010779 crude oil Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000011033 desalting Methods 0.000 title claims abstract description 28
- 230000018729 macromolecule modification Effects 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 58
- 125000004181 carboxyalkyl group Chemical group 0.000 claims abstract description 33
- 229920005615 natural polymer Polymers 0.000 claims abstract description 25
- 230000004048 modification Effects 0.000 claims abstract description 16
- 238000012986 modification Methods 0.000 claims abstract description 16
- 230000026030 halogenation Effects 0.000 claims abstract description 6
- 238000005658 halogenation reaction Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 65
- 239000002202 Polyethylene glycol Substances 0.000 claims description 53
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 34
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 26
- 238000004108 freeze drying Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000004821 distillation Methods 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical group [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 11
- 235000019270 ammonium chloride Nutrition 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 238000000502 dialysis Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 6
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical group CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 229910001923 silver oxide Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 230000008961 swelling Effects 0.000 claims description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 125000002346 iodo group Chemical group I* 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 230000006103 sulfonylation Effects 0.000 claims description 3
- 238000005694 sulfonylation reaction Methods 0.000 claims description 3
- HFRXJVQOXRXOPP-UHFFFAOYSA-N thionyl bromide Chemical compound BrS(Br)=O HFRXJVQOXRXOPP-UHFFFAOYSA-N 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 claims description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 230000031709 bromination Effects 0.000 claims description 2
- 238000005893 bromination reaction Methods 0.000 claims description 2
- 230000021523 carboxylation Effects 0.000 claims description 2
- 238000006473 carboxylation reaction Methods 0.000 claims description 2
- 230000002140 halogenating effect Effects 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 abstract description 10
- 150000003839 salts Chemical class 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 150000001768 cations Chemical class 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 3
- 150000003242 quaternary ammonium salts Chemical group 0.000 abstract description 3
- 229920000151 polyglycol Polymers 0.000 abstract 2
- 239000010695 polyglycol Substances 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 abstract 1
- 150000001924 cycloalkanes Chemical class 0.000 abstract 1
- 239000008187 granular material Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- -1 fatty acid salts Chemical class 0.000 description 29
- 238000001035 drying Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 229920000570 polyether Polymers 0.000 description 12
- 239000004721 Polyphenylene oxide Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 230000018044 dehydration Effects 0.000 description 11
- 238000006297 dehydration reaction Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 239000012265 solid product Substances 0.000 description 10
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004709 Chlorinated polyethylene Substances 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 3
- ALNUPAIRBMNLLB-UHFFFAOYSA-M dodecyl-dimethyl-(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1CO1 ALNUPAIRBMNLLB-UHFFFAOYSA-M 0.000 description 3
- 238000010291 electrical method Methods 0.000 description 3
- DYBLTIDRXDSCKH-UHFFFAOYSA-M hexadecyl-dimethyl-(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1CO1 DYBLTIDRXDSCKH-UHFFFAOYSA-M 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- GLIVMJADAWRCMK-UHFFFAOYSA-M dimethyl-(oxiran-2-ylmethyl)-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1CO1 GLIVMJADAWRCMK-UHFFFAOYSA-M 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000010358 mechanical oscillation Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LCPUCXXYIYXLJY-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)CC(F)(F)F LCPUCXXYIYXLJY-UHFFFAOYSA-N 0.000 description 1
- 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
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QNHFEURBGRDEDJ-UHFFFAOYSA-N [Cl-].C(C1CO1)[NH2+]CCCCCCCCCCCCCC Chemical compound [Cl-].C(C1CO1)[NH2+]CCCCCCCCCCCCCC QNHFEURBGRDEDJ-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- BXCCKEJWQJEUMS-UHFFFAOYSA-N formaldehyde;4-nonylphenol Chemical compound O=C.CCCCCCCCCC1=CC=C(O)C=C1 BXCCKEJWQJEUMS-UHFFFAOYSA-N 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-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
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000026045 iodination Effects 0.000 description 1
- 238000006192 iodination reaction Methods 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 125000005608 naphthenic acid group Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- GNBYZUQCDMNXML-UHFFFAOYSA-M sodium;2-chlorobutanoate Chemical compound [Na+].CCC(Cl)C([O-])=O GNBYZUQCDMNXML-UHFFFAOYSA-M 0.000 description 1
- RPOHBMAQTOJHKM-UHFFFAOYSA-M sodium;2-chloropropanoate Chemical compound [Na+].CC(Cl)C([O-])=O RPOHBMAQTOJHKM-UHFFFAOYSA-M 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
-
- 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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/323—Polymers modified by chemical after-treatment with inorganic compounds containing halogens
-
- 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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
-
- 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
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract
The present invention relates to the preparation method of a kind of chitosan class natural macromolecule modification crude oil desalting demulsifier.Specifically comprise the following steps that 1) poly glycol monomethyl ether is carried out halogenation modification；2) glycidyl dimethyl alkyl ammomium chloride is prepared；3) quaternized carboxyalkyl chitosan is prepared；4) by modified poly (ethylene glycol) monomethyl ether and quaternized carboxyalkyl chitosan reaction, obtain target product poly glycol monomethyl ether and be grafted quaternized carboxyalkyl chitosan.The present invention, with chitosan class natural polymer as raw material, has the plurality of advantages such as wide material sources, natural, nontoxic, sustainable, product bio-compatibility is good, degradable.The demulsifier that the present invention prepares not only breaking emulsion and dewatering is effective, simultaneously because containing substantial amounts of carboxyalkyl group and quaternary ammonium salt group on demulsifier molecule, it is that electronegative granule has the strongest binding ability to the electronegative ions such as metal cation, cycloalkanes acid group and surface, while breakdown of emulsion, therefore has the ability of removing oil-soluble salt concurrently.
Description
Technical Field
The invention relates to a preparation method of a chitosan natural polymer modified crude oil desalting demulsifier, belonging to the field of petrochemical industry.
Background
With the rapid development of industry, the demand of oil is more and more, and the improvement of oil recovery ratio has very important significance. The metal ion content in the crude oil gradually rises due to the increasing use amount of chemical flooding and the increasing heaviness and high acid value of the crude oil. The salts in crude oil are mainly inorganic salts, and are mostly dissolved in water contained in the crude oil, and the water and the oil form a stable water-in-oil (W/O) emulsion. The key to crude oil desalting is dewatering, which is demulsification. The natural emulsion in the crude oil is absorbed on an oil-water interface to form a viscoelastic film with certain strength, which causes kinetic barrier to coalescence of emulsion droplets and enables the crude oil emulsion to have stability. The principle of demulsification is a factor for destroying the stability of emulsion, and a plurality of demulsification methods are successfully developed for the demulsification research of crude oil at home and abroad. The oil field is most commonly added with a demulsifier, which is one of the essential chemical agents in the oil field and refinery at present. With the development of the petroleum industry, the demand of the demulsifier is increasing, and the performance requirement of the demulsifier is more severe. If a novel efficient deep desalting demulsifier is developed, the oil-soluble salt can be removed while demulsifying, and the novel efficient deep desalting demulsifier has very important significance for crude oil processing in China.
The crude oil demulsification method mainly comprises a chemical method, an electrical method, a centrifugal separation method, an ultrasonic method, a biological method and the like. The chemical method and the electrical method are most commonly used, but the electrical method has higher requirements on equipment and process conditions, is more complex to implement, and has higher early-stage investment and later-stage operation cost; chemical methods are an economical and rational process.
The demulsification process of the demulsifier is generally divided into 3 stages: (1) after the demulsifier is added into the crude oil emulsion, the demulsifier is dispersed in the whole oil phase and can enter emulsified water droplets; (2) the demulsifier permeates into the protective layer of the emulsified water droplets and makes the protective layer fragile, wrinkled and damaged, and after the protective layer is damaged, the emulsified water droplets approach and contact with each other; (3) the water droplets coalesce and the emulsified water droplets separate out from the continuous phase.
Barnickel reported from 1914 used 0.1% FeS04The solution is processed at 35-60 deg.c to demulsify emulsified crude oil, and the third-generation demulsifier is developed successively. In the 20 th to 30 th of the 20 th century, the first generation of low molecular ionic demulsifiers, such as anionic demulsifiers of fatty acid salts, naphthenic acid salts and the like and quaternary ammonium salt cationic demulsifiers, appeared for demulsification of oil-in-water crude oil emulsions. The demulsifier has the advantages of low price and the disadvantages of large dosage, poor effect, easy influence of electrolyte and the like. The industrialization of ethylene oxide production in the 20 th century from the 40 s to the 50 s has prompted the production of oxirane ringsThe appearance of oxypropylene block copolymers. From this, demulsifiers for water-in-oil emulsified crude oil of the second generation, mainly low molecular nonionic surfactants, were developed. Since the 60's of the 20 th century, third generation demulsifiers based on polyethers of high relative molecular mass were developed. A great deal of research is carried out on crude oil demulsifiers in China, and a great deal of patents are put forward. The most early nonionic surfactants as demulsifiers were prepared by graft copolymerization of a certain amount of ethylene oxide with alkylphenol and fatty alcohol as hydrophobic groups. With the large-scale field experiment of tertiary oil recovery technology, novel crude oil demulsifiers are continuously emerging. After 80 years, the simple ethylene oxide and propylene oxide block polyether demulsifier is replaced by polyamine, polymer and zwitterionic demulsifiers, and the minimum dosage is reduced to below 100 mg/L. However, these demulsifiers have the disadvantages of high specificity and poor adaptability. Therefore, people develop the composite demulsifier and the ultrahigh molecular weight high-efficiency demulsifier by modification or compounding, thereby pushing the application research of the demulsifier to a new step.
To solve the above problems, a method of preparing a crude oil demulsifier using multiple initiators has been developed in recent years. Chinese patent CN200510130345 introduces a polyether type crude oil demulsifier. The polyether is obtained by taking polyethylene polyamine or nonyl phenol-formaldehyde resin as an initiator, reacting with ethylene oxide and propylene oxide to obtain polyether, and then mixing and reacting the polyether with a chain extender and pyridine. The invention has the advantages of simple preparation process, small dosage, good demulsification and dehydration effects, low cost and the like, but the demulsifier can not achieve the effect of demulsification at low temperature to save heat energy. Chinese patent CN 201410710742 describes a low temperature crude oil demulsifier. The acrylic acid copolymer is obtained by copolymerizing glycidyl methacrylate and hexafluorobutyl methacrylate serving as initiators with acetone and acrylic acid. The defects of high temperature, long demulsification time and poor dehydration water quality of the conventional product are overcome. The emulsion breaking can be carried out at low temperature, the gas consumption per ton of oil is reduced, the energy is saved, and the economic benefit and the equipment treatment efficiency are improved. But the demulsifier has strong specificity and poor stability, and cannot be suitable for demulsifying various types of crude oil. Chinese patent CN201310289037.6 describes a polysaccharide modified crude oil demulsifier. Polysaccharide is used as an initiator, and is subjected to quaternization modification and polyether grafting modification, and the demulsifier has the advantages of wide source, naturalness, no toxicity, sustainability, good use safety and the like. The demulsifier has good demulsification and dehydration effects, and a large number of hydroxyl groups and other groups contained in demulsifier molecules have certain chelating capacity for metal ions, but the demulsifying agent has weak binding capacity, cannot remove different types and a large number of metal cations while dehydrating, and needs to be improved. Therefore, it is necessary to develop a demulsifier which can demulsify at low temperature, rapidly demulsify, expand the application range of the demulsifier to crude oil and has good dehydration and desalination effects.
Chitin is a second-most organic compound in the world, and has a wide source and a content second to cellulose. Chitosan is a product of chitosan deacetylation, and compared with xanthan gum and guar gum, a molecular chain contains amino groups with higher reactivity, so that grafting modification is easier. The chitosan natural polymer has excellent biocompatibility and environmental friendliness, large molecular weight, more active hydrogen, branched structure and unique rheological property. The derivative has stronger flocculation capacity, large occupied area at an oil-water interface, better temperature resistance and higher interfacial activity, and is an excellent candidate of the demulsifier initiator. The molecular chain of the chitosan is introduced with carboxyalkyl and quaternary ammonium salt groups, which have strong binding capacity to negatively charged ions such as metal cations, naphthenate radicals and the like in the crude oil. Meanwhile, a series of high-efficiency demulsifiers suitable for crude oil with different properties can be obtained by controlling the position and the degree of substitution of each substituent and the length of chain segments on polyether side chains, carboxyalkyl groups and quaternary ammonium salt groups, and oil-soluble salts can be removed while demulsifying.
Disclosure of Invention
The invention aims to provide a preparation method of a chitosan natural polymer modified crude oil desalting demulsifier aiming at the problems in the prior art, so as to obtain a series of high-efficiency demulsifiers suitable for crude oils with different properties, and remove oil-soluble salts while demulsifying.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the preparation method of the chitosan natural polymer modified crude oil desalting demulsifier is characterized by comprising the following steps:
1) halogenating the hydroxyl at the end of the polyethylene glycol monomethyl ether to obtain halogenated modified polyethylene glycol monomethyl ether;
2) preparation of glycidyl dimethyl alkyl ammonium chloride: dropwise adding epoxy chloropropane into N, N-dimethyl alkylamine, heating to 25-40 ℃, reacting at constant temperature for 6-30 h, and separating and purifying a reaction product to obtain glycidyl dimethyl alkyl ammonium chloride; wherein the carbon chain length of the alkyl group in the N, N-dimethyl alkylamine is C6‐C34；
3) Preparing quaternized carboxyalkyl chitosan: dissolving the carboxyalkyl chitosan by using a solvent A, and adjusting the pH value of the solution by using an alkali liquor; dissolving the glycidyl dimethyl alkyl ammonium chloride obtained in the step 2) in a solvent A, dropwise adding the solution into a reaction system, heating to 60-80 ℃, reacting for 8-24 hours, dialyzing the reaction solution, and freeze-drying to obtain a solid product, namely quaternized carboxyalkyl chitosan;
4) reacting modified polyethylene glycol monomethyl ether with quaternized carboxyalkyl chitosan: dissolving the quaternized carboxyalkyl chitosan obtained in the step 3) in a solvent B, stirring and heating to 60-100 ℃; dissolving the halogenated modified polyethylene glycol monomethyl ether obtained in the step 1) by using a solvent B, dropwise adding the solution into a reaction system, reacting at a constant temperature for 24-48 h, separating and purifying to obtain a target product, namely a chitosan natural polymer modified crude oil desalting demulsifier, namely polyethylene glycol monomethyl ether grafted quaternized carboxyalkyl chitosan.
According to the scheme, preferably, the specific steps of the halogenation modification in the step 1) are as follows: dissolving 0.5-1 molar part of polyethylene glycol monomethyl ether in a solvent C, stirring at 0-5 ℃ in an ice-water bath, adding 1-2 molar parts of a catalyst, slowly dropwise adding 1-2 molar parts of a chlorinating or brominating reagent into a reaction solution, heating for reflux reaction at 60-90 ℃ for 2-12 hours, separating and purifying the reaction solution, and freeze-drying to obtain chlorinated or brominated polyethylene glycol monomethyl ether; wherein the number average molecular mass of the polyethylene glycol monomethyl ether is 350, 500, 750, 1000, 1900 or 5000. Preferably, the solvent C is one or more of carbon tetrachloride, dichloromethane, chloroform, 1, 4-dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile and toluene. Preferably, the catalyst is pyridine or triethylamine. Preferably, the chlorinating or brominating agent is one of thionyl chloride, thionyl bromide, phosgene, oxalyl chloride, α -propionyl bromide, phosphorus tribromide. Preferably, the separation and purification specifically comprises: removing the solvent by reduced pressure distillation, dissolving the distillation residual solid with dichloromethane, washing with water, adding anhydrous sodium sulfate to remove water, performing suction filtration, and distilling the filtrate under reduced pressure to obtain a solid.
According to the scheme, preferably, the specific steps of the halogenation modification in the step 1) are as follows: dissolving 0.5-1 molar part of polyethylene glycol monomethyl ether in a solvent C, stirring at the temperature of 0-5 ℃ in an ice-water bath, adding 0.75-1.5 molar parts of a catalyst and 0.5-1 molar part of a sulfonylation reagent, slowly dropwise adding 0.1-0.2 molar part of a potassium iodide reagent into a reaction solution, reacting for 2-12 hours at room temperature, separating and purifying the reaction solution, and freeze-drying to obtain iodo polyethylene glycol monomethyl ether; wherein the number average molecular mass of the polyethylene glycol monomethyl ether is 350, 500, 750, 1000, 1900 or 5000. Preferably, the solvent C is one or more of carbon tetrachloride, dichloromethane, chloroform, 1, 4-dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile and toluene. Preferably, the catalyst is silver oxide. Preferably, the sulfonylating agent is p-toluenesulfonyl chloride. Preferably, the separation and purification specifically comprises: filtering the reaction solution to remove silver oxide, removing the solvent by reduced pressure distillation, adding the residual mixture into acetonitrile, heating to 60 ℃, continuously stirring for 2h, and carrying out column chromatography separation on the reaction solution by using a mobile phase of a mixed solution of dichloromethane and methanol.
According to the scheme, preferably, in the step 2), the mass part ratio of the N, N-dimethyl alkylamine to the epichlorohydrin is 1.93-2.97: 3.7.
according to the scheme, in the step 2), the separation and purification is performed by leaching with acetone and then vacuum drying.
According to the above scheme, preferably, the preparation method of the carboxyalkyl chitosan in the step 3) is as follows:
swelling 1.61 parts of chitosan by weight, adjusting the suspension to be alkaline by adopting alkali liquor, stirring overnight at the temperature of-15 to-25 ℃, adding 7.4 to 14.8 parts of sodium chloroalkyl as a carboxylation reagent, heating to 30 to 60 ℃, stirring for reaction for 3 to 12 hours, separating and purifying a reaction product, and freeze-drying to obtain the carboxyalkyl chitosan; wherein the length of the carbon chain of the sodium chloroalkyl acid is C2-C10. Preferably, the separation and purification specifically comprises: filtering, rinsing the obtained solid product with 80% ethanol and anhydrous ethanol respectively, drying at 60 deg.C for one day, dissolving the solid in water, and dialyzing.
According to the scheme, preferably, in the step 3), the mass part ratio of the carboxyalkyl chitosan to the glycidyl dimethyl alkyl ammonium chloride is 3.21: 1.93-7.7.
According to the scheme, preferably, in the step 3), the pH value range is 8-10.
According to the scheme, preferably, in the step 3), after the carboxyalkyl chitosan is dissolved by the solvent A and the pH value of the solution is adjusted by the alkali liquor, the solution is heated to 45-50 ℃ and reacts for 1 hour at constant temperature. The effect of this step is to allow the carboxyalkyl chitosan chains to be opened sufficiently for more uniform grafting.
According to the scheme, preferably, in the step 3), the solvent a is one or a mixture of distilled water, isopropanol, a sodium hydroxide solution, a hydrochloric acid solution, N dimethylformamide, N dimethylacetamide, dimethyl sulfoxide, acetic acid and methanol.
According to the scheme, preferably, in the step 4), the mass part ratio of the quaternized carboxyalkyl chitosan to the halogenated modified polyethylene glycol monomethyl ether is as follows: 0.47-1.05: 0.35-5.
According to the scheme, in the step 4), preferably, the solvent B is one or more of distilled water, isopropanol, sodium hydroxide solution, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, acetic acid, methanol and acetonitrile.
According to the scheme, preferably, in the step 4), when the modified polyethylene glycol monomethyl ether involved in the reaction in the step is chlorinated or brominated modified polyethylene glycol monomethyl ether, before the stirring and heating operation, the pH of the solution is adjusted to be alkaline by using alkali liquor, and a catalyst of potassium iodide is added.
According to the scheme, preferably, in the step 4), the specific steps of separating and purifying are as follows:
reduced pressure distillation, dialysis, freeze drying (when the modified polyethylene glycol monomethyl ether involved in the reaction in this step is a chlorinated or brominated modified polyethylene glycol monomethyl ether); or,
the distillation was carried out under reduced pressure, the remaining solid was washed with methylene chloride, the mixture was added to 10mL of a 50% acetic acid solution, stirred at room temperature for 4 hours, the reaction solution was poured into 500mL of an ice-ethanol and ether mixed solution, the precipitate was filtered, washed with acetone, and freeze-dried (when the modified polyethylene glycol monomethyl ether involved in the reaction in this step was iodo polyethylene glycol monomethyl ether).
According to the scheme, preferably, in each step, the alkali liquor is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
The synthetic route of the invention is as follows:
1. modification of polyethylene glycol monomethyl ether:
2. preparation of glycidyl dimethyl alkyl ammonium chloride:
3. performing carboxyl alkylation modification on chitosan, and reacting a quaternized modified product with modified polyethylene glycol monomethyl ether:
in the prior art, a traditional polyether demulsifier usually takes ethylene oxide and propylene oxide as main raw materials, selects a substance with active hydrogen as an initiator, and obtains a block polyether demulsifier through polymerization and etherification; as the oil field exploitation enters the later stage, a large amount of compound flooding is used in the exploitation process in a large amount, the process aggravates the crude oil emulsification degree and increases the demulsification difficulty, and the demulsification performance of the block polyether demulsifier is limited. 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 chitosan modified demulsifier obtained by modifying the polyethylene glycol monomethyl ether, the sodium chloroalkyl ate and the glycidyl dimethyl alkyl ammonium chloride has a high molecular weight, a multi-branched chain and a comb-shaped structure, and the carboxyalkyl and the dimethyl alkyl ammonium chloride in the side chain have strong binding capacity on negatively charged ions such as metal cations, naphthenate radicals and the like and particles with negative surfaces, so the chitosan modified natural polymer demulsifier has good dewatering and desalting effects;
3) according to the invention, when the carboxyalkyl chitosan is prepared, hydrogen bonds in chitosan molecules can be more easily opened by a low-temperature alkalization method, alkali liquor can more easily permeate into the chitosan molecules, and then carboxyalkyl side chains are more uniformly grafted onto a chitosan main chain, so that the obtained carboxyalkyl chitosan has a stable structure and good solubility.
4) According to the method for preparing the chitosan natural polymer modified crude oil desalting demulsifier, the molecular structure of the demulsifier, such as molecular weight, substitution degree, hydrophobic chain segment length aggregation state structure and the like, can be changed by selecting sodium carboxyalkyl, N, N-dimethylalkylamine and polyether with different carbon chain lengths, or changing the dosage ratio of reaction raw materials, or changing the conditions of reaction temperature, reaction time and the like of a reaction system, so that the desalting and dewatering effects of the synthesized high-efficiency demulsifier are regulated and controlled, and the method is suitable for crude oils with different properties (different producing areas and different salt and 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.
Example 1
The preparation method of the chitosan natural polymer modified crude oil desalting demulsifier specifically comprises the following steps:
(1) chlorination modification of polyethylene glycol monomethyl ether terminal hydroxyl: polyethylene glycol monomethyl ether (Mn 350)1.75g (5mmol) was dissolved in 40mL of 1, 4-dioxane, stirred in an ice-water bath (0 ℃ C.), added with 0.79g (10mmol) of pyridine and 1.19g (10mmol) of thionyl chloride, and reacted at 70 ℃ C under reflux for 2 hours. Removing the solvent by reduced pressure distillation, dissolving the distillation residue solid by dichloromethane, washing with water for 3 times, adding anhydrous sodium sulfate to remove water, performing suction filtration, distilling the filtrate under reduced pressure to obtain a solid, and freeze-drying to obtain chlorinated polyethylene glycol monomethyl ether;
(2) preparation of glycidyl dimethyldodecylammonium chloride: 2.13g of dodecyl dimethyl tertiary amine is added into a three-neck flask provided with a stirrer, a dropping funnel and a condensation reflux device, stirring is carried out continuously, 3.7g of epoxy chloropropane is added into the three-neck flask through the dropping funnel within 30min, the temperature is kept at 25 ℃, and the constant temperature reaction is carried out for 6 h. Stopping the reaction, leaching the product with acetone, and drying in vacuum to obtain the glycidyl dimethyl dodecyl ammonium chloride.
(3) Preparing carboxymethyl chitosan: adding 1.61g of chitosan into a 250mL flask, adding 10mL of isopropanol for swelling, adding 2.5mL of 10mol/L sodium hydroxide solution, continuing to stir for 30min, stirring overnight at-15 ℃, adding 7.4g of sodium chloroacetate, heating the reaction mixture to 60 ℃ after complete addition, and continuing to stir for reaction for 3 h. Filtering the reaction mixture after the reaction is finished to obtain a crude product, washing the crude product with 80% ethanol and absolute ethanol for 3 times respectively, putting the crude product into a drying box at 60 ℃ for drying for one day, dissolving the solid in water for dialysis for 3 days, and freeze-drying to obtain N, O-carboxymethyl chitosan;
(4) preparing quaternized carboxymethyl chitosan: weighing 3.21g N O-carboxymethyl chitosan in a three-neck flask, adding 40mL of distilled water, adjusting the pH value to 8-10 by using a sodium hydroxide solution, heating to 50 ℃, and reacting at constant temperature for 1 h; 2.78g of glycidyldodecylammonium chloride was dissolved in 20mL of water and added dropwise to the reaction system through a constant pressure funnel, and the temperature was raised to 80 ℃ to react for 8 hours. After the reaction is finished, dialyzing the reaction solution for 3-5 days, and freeze-drying to obtain a solid product quaternized carboxymethyl chitosan;
(5) reacting modified polyethylene glycol monomethyl ether with quaternized carboxymethyl chitosan: putting 0.47g of quaternized carboxymethyl chitosan into a 250mL three-neck flask, adding 30mL of dimethyl sulfoxide solution, dissolving, adding 0.8g of potassium carbonate solid and 0.166g of potassium iodide, stirring, heating to 80 ℃, and adding 0.35g of chlorinated polyethylene glycol monomethyl ether (M)n350) is dissolved in 10mL of dimethyl sulfoxide solution, the dropwise addition is completed within 10min, the reaction is carried out for 24h, the reaction solution is concentrated by reduced pressure distillation, the dialysis bag is used for dialysis for 3 days, and the residual solution in the bag is frozen and dried to obtain the target product, namely the polyethylene glycol monomethyl ether grafted quaternized carboxymethyl chitosan, which is the demulsifier 1.
Example 2
The preparation method of the chitosan natural polymer modified crude oil desalting demulsifier specifically comprises the following steps:
(1) bromination modification of polyethylene glycol monomethyl ether terminal hydroxyl: 3.75g (5mmol) of polyethylene glycol monomethyl ether (Mn. RTM. 750) was dissolved in 40mL of 1, 4-dioxane, stirred in an ice-water bath (2 ℃ C.), added with 1.18g (15mmol) of pyridine and 1.78g (15mmol) of thionyl bromide, and reacted at 70 ℃ for 4 hours under reflux. Removing the solvent by reduced pressure distillation, dissolving the distillation residual solid with dichloromethane, washing with water for 3 times, adding anhydrous sodium sulfate to remove water, performing suction filtration, removing the solvent from the filtrate by reduced pressure distillation to obtain a solid, and performing freeze drying to obtain the bromopolyethylene glycol monomethyl ether.
(2) Preparation of glycidyl dimethyltetradecylammonium chloride: 2.41g of tetradecyl dimethyl tertiary amine is added into a three-neck flask provided with a stirrer, a dropping funnel and a condensation reflux device, stirring is carried out continuously, 3.7g of epoxy chloropropane is added dropwise in 30min through the dropping funnel, the temperature is kept at 30 ℃, and the constant temperature reaction is carried out for 20 h. Stopping the reaction, leaching the product with acetone, and drying in vacuum to obtain the glycidyl dimethyltetradecyl ammonium chloride.
(3) Preparation of carboxyethyl chitosan: adding 1.61g of chitosan into a 250mL flask, adding 10mL of isopropanol for swelling, adding 2.5mL of 10mol/L sodium hydroxide solution, continuing to stir for 30min, stirring overnight at-20 ℃, adding 8.2g of sodium chloropropionate, heating the reaction mixture to 60 ℃ after the complete addition, and continuing to stir for reaction for 4 h. And after the reaction is finished, filtering the reaction mixture to obtain a solid product, washing the product for 3 times by using 80% ethanol and absolute ethanol respectively, drying the product in a drying box at the temperature of 60 ℃, dissolving the solid in water, dialyzing for 5 days, and freeze-drying to obtain a solid product N, O-carboxyethyl chitosan.
(4) Preparing quaternized carboxyethyl chitosan: weighing 3.21g N O-carboxyethyl chitosan into a three-neck flask, adding 40mL of distilled water, adjusting the pH value to 8-10 by using a sodium hydroxide solution, heating to 45 ℃, and reacting at constant temperature for 1 h. 2.78g of glycidyl tetradecyl ammonium chloride was dissolved in 20mL of water, and the solution was added dropwise to the reaction system through a constant pressure funnel, and the temperature was raised to 70 ℃ for 16 hours. And after the reaction is finished, dialyzing the reaction solution for 5 days, and freeze-drying to obtain a solid product of quaternized carboxyethyl chitosan.
(5) Reacting modified polyethylene glycol monomethyl ether with quaternized carboxyethyl chitosan: putting 0.53g of quaternized carboxyethyl chitosan into a 250mL three-neck flask, adding 30mL of dimethyl sulfoxide solution, adding 0.8g of potassium carbonate solid and 0.166g of potassium iodide after dissolving, stirring and heating to 90 ℃, dissolving 1.5g of brominated polyethylene glycol monomethyl ether (Mn & gt 750) into 10mL of dimethyl sulfoxide solution, completing dropwise addition within 10min, reacting for 30h, carrying out reduced pressure distillation to concentrate reaction liquid, dialyzing for 3 days by using a dialysis bag, and freeze-drying residual liquid in the bag to obtain a target product, namely the quaternized carboxyethyl chitosan grafted with polyethylene glycol monomethyl ether, which is demulsifier 2.
Example 3
The preparation method of the chitosan natural polymer modified crude oil desalting demulsifier specifically comprises the following steps:
(1) iodination modification of polyethylene glycol monomethyl ether terminal hydroxyl: polyethylene glycol monomethyl ether (Mn ═ 1000)5g (5mmol) was dissolved in 40mL of toluene, stirred in an ice-water bath (5 ℃ c), and 1.73g (7.5mmol) of silver oxide, 0.166g (1mmol) of potassium iodide and 1g (5mmol) of p-toluenesulfonyl chloride were added and reacted at room temperature for 12 hours. The silver oxide was removed by filtration, the solvent was removed by distillation under reduced pressure, and the remaining mixture was added to 30mL of acetonitrile, warmed to 60 ℃ and stirred for 2 h. And (3) carrying out column chromatography separation on the reaction solution by using a mobile phase of dichloromethane and methanol, and freeze-drying to obtain iodo-polyethylene glycol monomethyl ether.
(2) Preparation of glycidyl dimethylhexadecylammonium chloride: 2.69g of hexadecyl dimethyl tertiary amine is added into a three-neck flask provided with a stirrer, a dropping funnel and a condensation reflux device, stirring is carried out continuously, 3.7g of epoxy chloropropane is added into the flask by the dropping funnel within 30min, the temperature is kept at 40 ℃, the reaction is stopped after 30 hours of constant temperature reaction. The product was washed with acetone and dried under vacuum to give glycidyl dimethylhexadecylammonium chloride.
(3) Preparation of carboxypropyl chitosan: adding 1.61g of chitosan into a 250mL flask, adding 10mL of isopropanol for swelling, adding 2.5mL of 10mol/L sodium hydroxide solution, continuing to stir for 30min, stirring overnight at-25 ℃, adding 9.5g of sodium chlorobutyrate, heating the reaction mixture to 30 ℃ after the complete addition, and continuing to stir for reaction for 12 h. And after the reaction is finished, filtering the reaction mixture to obtain a solid product, washing the product for 3 times by using 80% ethanol and absolute ethanol respectively, drying the product in a drying box at the temperature of 60 ℃, dissolving the solid in water, dialyzing for 4 days, and freeze-drying to obtain a solid product N, O-carboxypropyl chitosan.
(4) Preparing quaternized carboxypropyl chitosan: weighing 3.21g N O-carboxypropyl chitosan, adding 40mL of distilled water into a three-neck flask, adjusting the pH value to 8-10 by using a sodium hydroxide solution, heating to 45 ℃, and reacting for 1h at constant temperature. 2.86g of glycidyl dimethylhexadecyl ammonium chloride is dissolved in 20mL of water and is dripped into the reaction system through a constant pressure funnel, the temperature is raised to 60 ℃, and the reaction is carried out for 24 hours. And after the reaction is finished, dialyzing the reaction solution for 5 days, and freeze-drying to obtain a solid product of quaternized carboxypropyl chitosan.
(5) Reacting modified polyethylene glycol monomethyl ether with quaternized carboxypropyl chitosan: 0.64g of quaternized carboxypropyl chitosan is placed in a 250mL three-neck flask, 30mL of acetonitrile solution is added, magnetic stirring is carried out, the temperature is raised to 60 ℃, 2g of iodinated polyethylene glycol monomethyl ether (Mn is 1000) is dissolved in 10mL of acetonitrile, the dropwise addition is completed within 10min, and the reaction is carried out for 24 h. The distillation was performed under reduced pressure, and the remaining solid was washed several times with methylene chloride, and the mixture was added to 10mL of a 50% acetic acid solution and stirred at room temperature for 4 hours. And pouring the reaction solution into 500mL of mixed solution of ice ethanol and ether, washing the precipitate with acetone for several times, and freeze-drying to obtain the target product, namely the polyethylene glycol monomethyl ether grafted quaternized carboxypropyl chitosan, which is the demulsifier 3.
Example 4
The preparation method of the chitosan natural polymer modified crude oil desalting demulsifier specifically comprises the following steps:
(1) chlorination modification of polyethylene glycol monomethyl ether terminal hydroxyl: polyethylene glycol monomethyl ether (Mn. RTM. 5000)5g (1mmol) was dissolved in 40mL of 1, 4-dioxane, stirred in an ice-water bath (0 ℃ C.), added with 0.158g (2mmol) of pyridine and 0.252g (2mmol) of oxalyl chloride, and reacted at 90 ℃ C. under reflux for 12 hours. Removing the solvent by reduced pressure distillation, dissolving the distillation residue solid by dichloromethane, washing with water for 3 times, adding anhydrous sodium sulfate to remove water, performing suction filtration, distilling the filtrate under reduced pressure to obtain a solid, and freeze-drying to obtain chlorinated polyethylene glycol monomethyl ether;
(2) preparation of glycidyl dimethyl tridodecylammonium chloride: 2.97g of dotriacontanyl dimethyl tertiary amine is added into a three-neck flask provided with a stirrer, a dropping funnel and a condensation reflux device, stirring is carried out continuously, 3.7g of epoxy chloropropane is added dropwise in 30min through the dropping funnel, the temperature is kept at 40 ℃, and the constant temperature reaction is carried out for 30 h. Stopping the reaction, leaching the product with acetone, and drying in vacuum to obtain the glycidyl dimethyl dodecyl ammonium chloride.
(3) Preparation of carboxynonyl Chitosan: adding 1.61g of chitosan into a 250mL flask, adding 10mL of isopropanol for swelling, adding 2.5mL of 10mol/L sodium hydroxide solution, continuing to stir for 30min, stirring overnight at-20 ℃, adding 14.8g of sodium chlorodecanoate, heating the reaction mixture to 60 ℃ after complete addition, and continuing to stir for reaction for 3 h. Filtering the reaction mixture after the reaction is finished to obtain a crude product, washing the crude product with 80% ethanol and absolute ethanol for 3 times respectively, putting the crude product into a drying box at 60 ℃ for drying for one day, dissolving the solid in water for dialysis for 3 days, and freeze-drying to obtain N, O-carboxynonyl chitosan;
(4) preparing quaternized carboxynonyl chitosan: weighing 3.21g N, putting O-carboxymethyl chitosan into a three-neck flask, adding 40mL of dimethyl sulfoxide, adjusting the pH value to 8-10 with a sodium hydroxide solution, heating to 50 ℃, and reacting at constant temperature for 1h (fully opening carboxymethyl chitosan chains and ensuring that grafting is more uniform); 7.7g of glycidyl tridodecylammonium chloride is dissolved in 20mL of dimethyl sulfoxide, and the solution is dripped into the reaction system through a constant pressure funnel, and the temperature is raised to 80 ℃ for reaction for 8 hours. After the reaction is finished, dialyzing the reaction solution for 3-5 days, and freeze-drying to obtain a solid product of quaternized carboxynonyl chitosan;
(5) reacting modified polyethylene glycol monomethyl ether with quaternized carboxynonyl chitosan: putting 1.05g of quaternized carboxynonyl chitosan into a 250mL three-neck flask, adding 30mL of dimethyl sulfoxide solution, dissolving, adding 0.8g of potassium carbonate solid and 0.166g of potassium iodide, stirring, heating to 80 ℃, and adding 5g of chlorinated polyethylene glycol monomethyl ether (M)n5000) is dissolved in 10mL of dimethyl sulfoxide solution, the dropwise addition is completed within 10min, the reaction is carried out for 48h, the reaction solution is concentrated by reduced pressure distillation, the dialysis bag is used for dialysis for 3 days, and the residual solution in the bag is frozen and dried to obtain the target product, namely the polyethylene glycol monomethyl ether grafted quaternized carboxynonyl chitosan, which is the demulsifier 4.
Comparative example 1
The quaternized carboxymethyl chitosan prepared in step (4) in example 1 was used as the demulsifier in comparative example 1.
Comparative example 2
A crude oil demulsifier modified by chitosan natural polymer prepared according to the method of example 1 in the publication of chinese patent application CN201310289037.6 was used as comparative demulsifier 2.
Comparative example 3
And a commercial product number JL series demulsifier is used as the demulsifier comparative example 3.
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 60-80 ℃, and the concentration of a demulsifier in the crude oil is 70-120 ppm. The demulsification performances of the demulsifiers 1-4 prepared in examples 1-4 and the demulsifier comparative examples 1-3 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 time (5min, 15min, 30min, 60min and 120min), and observing and recording the sewage color and the oil-water interface condition when the sedimentation is stopped.
The experimental result shows that compared with the comparative demulsifier 1-3, the demulsifier 1-4 obtained by the method has better dehydration and desalination effects within the ranges of the dehydration temperature of 60-80 ℃ and the demulsifier concentration of 70-120 ppm, and the effect is optimal particularly when the concentration is 90ppm and the dehydration temperature is 65 ℃.
The demulsifiers 1 to 4 prepared in examples 1 to 4 and the demulsifiers of comparative examples 1 to 3 provided in comparative examples 1 to 3 showed the results of the demulsification and dehydration experiments in Table 1 and the demulsification and desalination experiments in Table 2 under the above-mentioned optimum concentration and temperature conditions.
TABLE 1
TABLE 2
Claims (10)
1. The preparation method of the chitosan natural polymer modified crude oil desalting demulsifier is characterized by comprising the following steps:
1) halogenating the hydroxyl at the end of the polyethylene glycol monomethyl ether to obtain halogenated modified polyethylene glycol monomethyl ether;
2) preparation of glycidyl dimethyl alkyl ammonium chloride: dropwise adding epoxy chloropropane into N, N-dimethyl alkylamine, heating to 25-40 ℃, reacting at constant temperature for 6-30 h, and separating and purifying a reaction product to obtain glycidyl dimethyl alkyl ammonium chloride; wherein the alkyl group of the N, N-dimethyl alkylamineHas a carbon chain length of C6‐C34；
3) Preparing quaternized carboxyalkyl chitosan: dissolving the carboxyalkyl chitosan by using a solvent A, and adjusting the pH value of the solution by using an alkali liquor; dissolving the glycidyl dimethyl alkyl ammonium chloride obtained in the step 2) in a solvent A, dropwise adding the solution into a reaction system, heating to 60-80 ℃, reacting for 8-24 hours, dialyzing the reaction solution, and freeze-drying to obtain quaternized carboxyalkyl chitosan;
4) reacting modified polyethylene glycol monomethyl ether with quaternized carboxyalkyl chitosan: dissolving the quaternized carboxyalkyl chitosan obtained in the step 3) in a solvent B, stirring and heating to 60-100 ℃, dissolving the halogenated modified polyethylene glycol monomethyl ether obtained in the step 1) by using the solvent B, then dropwise adding the dissolved halogenated modified polyethylene glycol monomethyl ether into a reaction system, reacting at a constant temperature for 24-48 h, separating and purifying to obtain the target product chitosan natural polymer modified crude oil desalting demulsifier polyethylene glycol monomethyl ether grafted quaternized carboxyalkyl chitosan.
2. The preparation method of the chitosan natural polymer modified crude oil desalting demulsifier according to claim 1, wherein the halogenation modification in the step 1) comprises the following specific steps:
dissolving 0.5-1 molar part of polyethylene glycol monomethyl ether in a solvent C, stirring at 0-5 ℃ in an ice-water bath, adding 1-2 molar parts of a catalyst, slowly dropwise adding 1-2 molar parts of a chlorinating or brominating reagent into a reaction solution, heating for reflux reaction at 60-90 ℃ for 2-12 hours, separating and purifying the reaction solution, and freeze-drying to obtain chlorinated or brominated polyethylene glycol monomethyl ether; wherein the number average molecular mass of the polyethylene glycol monomethyl ether is 350, 500, 750, 1000, 1900 or 5000.
3. The preparation method of the chitosan natural polymer modified crude oil desalting demulsifier according to claim 1, wherein the halogenation modification in the step 1) comprises the following specific steps:
dissolving 0.5-1 molar part of polyethylene glycol monomethyl ether in a solvent C, stirring at the temperature of 0-5 ℃ in an ice-water bath, adding 0.75-1.5 molar parts of a catalyst and 0.5-1 molar part of a sulfonylation reagent, slowly dropwise adding 0.1-0.2 molar part of a potassium iodide reagent into a reaction solution, reacting for 2-12 hours at room temperature, separating and purifying the reaction solution, and freeze-drying to obtain iodo polyethylene glycol monomethyl ether; wherein the number average molecular mass of the polyethylene glycol monomethyl ether is 350, 500, 750, 1000, 1900 or 5000.
4. The preparation method of the chitosan natural polymer modified crude oil desalting demulsifier according to claim 2, wherein the preparation method comprises the following steps:
the solvent C is one or more of carbon tetrachloride, dichloromethane, chloroform, 1, 4-dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile and toluene;
the catalyst is pyridine or triethylamine;
the chlorination or bromination reagent is one of thionyl chloride, thionyl bromide, carbonyl chloride, oxalyl chloride, alpha-propionyl bromide and phosphorus tribromide;
in the step 4), adjusting the pH of the solution to be alkaline by adopting alkali liquor before stirring and heating, and adding a catalyst potassium iodide;
in the step 4), the specific steps of separation and purification are reduced pressure distillation, dialysis and freeze drying.
5. The preparation method of the chitosan natural polymer modified crude oil desalting demulsifier according to claim 3, wherein the preparation method comprises the following steps:
the solvent C is one or more of carbon tetrachloride, dichloromethane, chloroform, 1, 4-dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile and toluene;
the catalyst is silver oxide;
the sulfonylation reagent is p-toluenesulfonyl chloride;
the separation and purification in the halogenation modification specifically comprises the following steps: filtering the reaction solution to remove silver oxide, removing the solvent by reduced pressure distillation, adding the residual mixture into acetonitrile, heating to 60 ℃, continuously stirring for 2h, and carrying out column chromatography separation on the reaction solution by using a mobile phase of a mixed solution of dichloromethane and methanol;
in the step 4), the specific steps of separation and purification are as follows: distilling under reduced pressure, washing the residual solid with dichloromethane, adding the mixture into acetic acid solution, stirring at room temperature for 4h, pouring the reaction solution into the mixed solution of ice ethanol and diethyl ether, filtering the precipitate, washing with acetone, and freeze-drying.
6. The preparation method of the chitosan natural polymer modified crude oil desalting demulsifier according to claim 1, wherein in the step 2), the mass part ratio of the N, N-dimethylalkylamine to the epichlorohydrin is 1.93-2.97: 3.7.
7. the method for preparing the chitosan natural polymer modified crude oil desalting demulsifier according to claim 1, wherein the preparation method of the carboxyalkyl chitosan in the step 3) is as follows:
swelling 1.61 parts of chitosan by weight, adjusting the suspension to be alkaline by adopting alkali liquor, stirring overnight at the temperature of-15 to-25 ℃, adding 7.4 to 14.8 parts of sodium chloroalkyl as a carboxylation reagent, heating to 30 to 60 ℃, stirring for reaction for 3 to 12 hours, separating and purifying a reaction product, and freeze-drying to obtain the carboxyalkyl chitosan; wherein the length of the carbon chain of the sodium chloroalkyl acid is C2‐C10。
8. The method for preparing the demulsifier for desalting of crude oil modified by chitosan natural polymers according to claim 1, wherein in step 3),
the mass part ratio of the carboxyalkyl chitosan to the glycidyl dimethyl alkyl ammonium chloride is 3.21: 1.93-7.7;
the pH value range is 8-10;
the solvent A is one or more of distilled water, isopropanol, sodium hydroxide solution, hydrochloric acid solution, N, N dimethylformamide, N, N dimethylacetamide, dimethyl sulfoxide, acetic acid and methanol.
9. The preparation method of the chitosan natural polymer modified crude oil desalting demulsifier according to claim 1, wherein in the step 3), after the carboxyalkyl chitosan is dissolved by the solvent A and the pH value of the solution is adjusted by the alkali liquor, the solution is heated to 45-50 ℃ and reacts for 1 hour at constant temperature.
10. The method for preparing the demulsifier for desalting of crude oil modified by chitosan natural polymers according to claim 1, wherein in step 4),
the mass part ratio of the quaternized carboxyalkyl chitosan to the halogenated modified polyethylene glycol monomethyl ether is as follows: 0.47-1.05: 0.35-5;
the solvent B is one or a mixture of more of distilled water, isopropanol, sodium hydroxide solution, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, acetic acid, methanol and acetonitrile.
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