A kind of synthetic method of poly ion liquid crude oil modified emulsion splitterTechnical field
The invention belongs to petroleum industry field of chemicals, relate to a kind of synthetic method that is applicable to crude oil emulsion to carry out the poly ion liquid crude oil modified emulsion splitter of breaking emulsion and dewatering.
Background technology
Emulsion splitter is the indispensable chemical assistants in all oil fields, and it is bearing the task of emulsification crude oil demulsification dehydration.At present, the exploitation in domestic many oil fields all enters tertiary phase substantially, and in the crude oil of extraction, water ratio increases year by year, and the multiple remaining chemical agent after produced-water reinjection in crude oil makes emulsification crude oil demulsification dehydration more complicated and difficult.At present, the emulsion splitter of research, from chemical type, mainly be take non-ionic polyoxyethylene polyoxypropylene block polymer as main both at home and abroad, just the kind difference of initiator, the emulsion splitter adaptability of this structure is poor, and particularly low-temperature demulsification effect is unsatisfactory.
Comb type polymeric surface active agent became the study hotspot in emulsion splitter field in recent years, being on the one hand such emulsion splitter will obviously be better than common polymeric surface active agent reducing surface tension and have aspect lower micelle-forming concentration, that it has higher relative molecular mass than conventional block polyether on the other hand, the emulsion splitter of this high molecular weight can play bridge formation, connect the effect of large small droplets in emulsion of crude oil in breakdown of emulsion process, thereby make drop coalescence gradually, reach the object of oily water separation.Pectination emulsion splitter is synthetic generally by polymerization and esterification or esterification and polymerization two step process implementations.The people such as China researchist Chen Mei in 2002 and Yang little Long are by vinylformic acid and maleic anhydride esterification for polyether type demulsifying agent, and esterification products polymerization under initiator effect, has synthesized vinylformic acid chain extension modified emulsion breaker.Shang Shaocheng, Zhang Zhongyang etc. all studied the preparation method of Demulsifiers Modified by Acrylic Acid, although the polymer modification emulsion splitter obtaining has certain demulsification, but find the water-soluble not good enough of emulsion splitter in actual application, and because functional group is single, so emulsion splitter adaptability is not strong.In order to improve the solvability of emulsion splitter, improve its functionally active, people by water-soluble monomer as acrylamide and acrylic acid copolymer after, thereby carry out esterification with industrial polyethers again and realize the pectination modification to emulsion splitter, emulsion splitter as described in number of patent application CN01113543.3, CN201010274323.1.In recent years, the industrial polyethers that our seminar also makes tens of kinds of initiators with vinylformic acid has carried out chain extension and branched modification, find that this class modified emulsion breaker is water-soluble poor, on-the-spot emulsion splitter solution preparation needs with an organic solvent, not only to environment, and there is potential safety hazard while using.In addition, owing to only containing nonionic functional group in such emulsion splitter molecular structure, so there is not strong interaction for some electronegativity surfaces of crude oil, cause occurring the defect of the not good or bad adaptability of demulsification.
Adopt vinyl imidazole class ionic liquid monomer and acrylic copolymer to carry out the technical scheme of crude oil modified emulsion splitter, have no any patent and bibliographical information.
Summary of the invention
In order to overcome polyacrylic acid modified polyether demulsification agent poorly water-soluble, functional group is single, and the deficiency of bad adaptability, the object of this invention is to provide a kind of preparation method of cation-modified emulsion splitter.Emulsion splitter consumption that the method obtains is few, the rate of output water fast, deviate from that water colour is clear, use range is wide.
The object of the invention is to be achieved through the following technical solutions:
A synthetic method for poly ion liquid crude oil modified emulsion splitter, is characterized in that this synthetic method is as follows:
1) solvent is joined in the reaction flask with stirring, Dropping feeder and condenser, control temperature 75 ~ 95oc, under agitation condition, adds vinyl imidazole class ionic liquid monomer, vinylformic acid and initiator, and whole polymerization process was controlled in 1 ~ 3 hour, had reacted follow-up continuous insulation reaction, and then underpressure distillation removes desolventizing and obtains intermediate product; Described solvent is that concentration is 95% ethanol;
2) in above-mentioned intermediate product, add industrial polyethers and solvent, after stirring, add esterifying catalyst, be warming up to 100 ~ 160oc, continues stirring reaction and within 3 ~ 5 hours, obtains crude product, and underpressure distillation removes desolventizing and obtains poly ion liquid crude oil modified emulsion splitter, and described solvent is toluene.
In the present invention, the raw material weight of synthetic this emulsion splitter is in 100%, industrial polyethers 50-80% wherein, vinylformic acid 2-30%, vinyl imidazole class ionic liquid monomer 2-25%.Initiator add-on is 0.2 ~ 6% of whole vinyl monomer gross weights, and esterifying catalyst add-on is 0.2 ~ 5% of vinylformic acid weight.
Industrial polyethers of the present invention, comprising: the block polyether that the amine of take is initiator, and amine used is polyethylene polyamine or quadrol; The block polyether that the alcohols of take is initiator, alcohol used is octadecanol or propylene glycol; Alkyl phenolic resin block polyether, during synthetic initiator, conventional alkylphenol is nonyl phenol; Phenol amine aldehyde resin block polyether, i.e. amino modified resol block polyether, initiator is the condensation product of alkylphenol, vinyl-amine compounds and formaldehyde.
Initiator of the present invention is Diisopropyl azodicarboxylate in azo or the oil-soluble initiators such as benzoyl peroxide in peroxide; Or the water soluble starter such as ammonium persulphate or Potassium Persulphate.
Vinyl imidazole class ionic liquid monomer of the present invention is chlorination 1-allyl group-3-Methylimidazole (AMIMCl) or chlorination 1-vinyl-3-Methylimidazole or their nitrate.
Esterifying catalyst of the present invention is sulfuric acid or the phosphoric acid in mineral acid, the p-methyl benzenesulfonic acid in organic acid or heteropolyacid.
Emulsion splitter of the present invention is by vinyl imidazole class ionic liquid monomer and acrylic acid copolymer, the chain extension effect of pfpe molecule to be obtained.The emulsion splitter that the present invention obtains contains positively charged ion and nonionic functional group simultaneously in molecular chain, can strong effect occur with some electronegativity surfaces of crude oil, makes it change thermodynamic unstable system into and realizes oily water separation.The emulsion splitter that the method obtains has that consumption is few, the rate of output water is fast, deviate from the features such as water colour is clear, use range is wide, belongs to crude oil demulsifier of new generation.
Embodiment
embodiment 1
A kind of poly ion liquid crude oil modified emulsion splitter synthetic method is as follows:
1) ethanol that is 95% by 150 grams of concentration, solvent is now that concentration is 95% ethanol; Join in the reaction flask with stirring, Dropping feeder and condenser, control temperature 75oc, under agitation condition, add 50 grams of chlorination 1-allyl group-3-Methylimidazole ionic liquids, 20 grams of vinylformic acid and 0.8 gram of ammonium persulphate, whole polymerization process was controlled in 1 hour, reacted follow-up continuous insulation reaction 1 hour, then underpressure distillation removes desolventizing and obtains intermediate product.
2) in above-mentioned intermediate product, add 200 grams of industrial polyethers (polyether demulsification agent AE31, Jurong Ningwu High-tech. Development Co., Ltd.'s product) and 100 grams of toluene, solvent is now toluene.After stirring, add 0.5 gram of tosic acid, be warming up to 120oc, continues stirring reaction and within 5 hours, obtains crude product, and underpressure distillation removes desolventizing and obtains poly ion liquid crude oil modified emulsion splitter.
embodiment 2
A kind of poly ion liquid crude oil modified emulsion splitter synthetic method is as follows:
1) ethanol that is 95% by 150 grams of concentration joins in the reaction flask with stirring, Dropping feeder and condenser, controls temperature 85oc, under agitation condition, add 35 grams of chlorination 1-allyl group-3-Methylimidazole ionic liquids, 35 grams of vinylformic acid and 1 gram of ammonium persulphate, whole polymerization process was controlled in 2 hours, reacted follow-up continuous insulation reaction 1 hour, then underpressure distillation removes desolventizing and obtains intermediate product.
2) in above-mentioned intermediate product, add 180 grams of industrial polyethers (polyether demulsification agent BP5921, Jurong Ningwu High-tech. Development Co., Ltd.'s product) and 90 grams of toluene, after stirring, add 0.6 gram of tosic acid, be warming up to 130oc, continues stirring reaction and within 4 hours, obtains crude product, and underpressure distillation removes desolventizing and obtains poly ion liquid crude oil modified emulsion splitter.
embodiment 3
A kind of poly ion liquid crude oil modified emulsion splitter synthetic method is as follows:
1) ethanol that is 95% by 210 grams of concentration joins in the reaction flask with stirring, Dropping feeder and condenser, controls temperature 90oc, under agitation condition, add 65 grams of chlorination 1-allyl group-3-Methylimidazole ionic liquids, 35 grams of vinylformic acid and 1.2 grams of ammonium persulphates, whole polymerization process was controlled in 3 hours, reacted follow-up continuous insulation reaction 1 hour, then underpressure distillation removes desolventizing and obtains intermediate product.
2) in above-mentioned intermediate product, add 200 grams of industrial polyethers (polyether demulsification agent TA1031, Jurong Ningwu High-tech. Development Co., Ltd.'s product) and 100 grams of toluene, after stirring, add 0.5 gram of tosic acid, be warming up to 140oc, continues stirring reaction and within 3 hours, obtains crude product, and underpressure distillation removes desolventizing and obtains poly ion liquid crude oil modified emulsion splitter.