CN103484150B - Polyion-liquid-modified crude oil demulsifier - Google Patents
Polyion-liquid-modified crude oil demulsifier Download PDFInfo
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- CN103484150B CN103484150B CN201310477814.XA CN201310477814A CN103484150B CN 103484150 B CN103484150 B CN 103484150B CN 201310477814 A CN201310477814 A CN 201310477814A CN 103484150 B CN103484150 B CN 103484150B
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Abstract
The invention discloses a polyion-liquid-modified crude oil demulsifier. The demulsifier is synthesized from the following raw materials in percentage by weight: 50-80% of industrial polyether, 2-30% of acrylic acid and 2-25% of vinyl imidazole ionic liquid monomer. An initiator accounts for 0.2-6 wt% of all the vinyl monomers, and an esterification catalyst accounts for 0.2-5 wt% of the acrylic acid. The demulsifier can have a severe action on some electronegative surfaces of crude oil to achieve the goal of oil-water separation. The demulsifier has the advantages of low consumption, low water outlet rate, clear dehydrated water and width application range.
Description
Technical field
the invention belongs to petroleum industry field of chemicals, relate to a kind of Polyion-liquid-modifcrude crude oil demulsifier being applicable to carry out crude oil emulsion breaking emulsion and dewatering.
Background technology
Emulsion splitter is the indispensable chemical assistant in all oil fields, and it carries 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 it is more complicated and difficult that the multiple remaining chemical agent after produced-water reinjection in crude oil makes emulsification crude oil demulsification dewater.At present, the emulsion splitter of domestic and international research chemically type is seen, mainly based on non-ionic polyoxyethylene polyoxypropylene block polymer, just the kind of initiator is different, the emulsion splitter adaptability of this structure is poor, and particularly low-temperature demulsification effect is unsatisfactory.
Combed polymeric surface active agent became the study hotspot in emulsion splitter field in recent years, that such emulsion splitter is reducing surface tension and having in lower micelle-forming concentration and will obviously be better than common polymeric surface active agent on the one hand, that it has higher relative molecular mass than the block polyether of routine 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, thus make drop coalescence gradually, reach the object of oily water separation.The synthesis of pectination emulsion splitter is generally by polymerization and esterification or esterification and polymerization two step process implementation.The people such as China researchist Chen Mei and Yang little Long in 2002 are by polyether type demulsifying agent vinylformic acid and maleic anhydride esterification, and esterification products is polymerized 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 obtained has certain demulsification, but find the water-soluble not good enough of emulsion splitter in actual application, and due to functional group 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 after acrylamide and acrylic acid copolymer, carry out esterification with industrial polyether again thus realize the pectination modification to emulsion splitter, emulsion splitter as described in number of patent application CN01113543.3, CN201010274323.1.In recent years, our seminar has also carried out chain extension and branched modification by the industrial polyether that vinylformic acid is obtained to tens of kinds of initiators, find that this kind of 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 when using.In addition, due in such emulsion splitter molecular structure only containing nonionic functional group, 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 cation-modified emulsion splitter.This emulsion splitter consumption is few, the rate of output water is 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 kind of Polyion-liquid-modifcrude crude oil demulsifier, is characterized in that: synthesize the raw material weight of this emulsion splitter in 100%, wherein industrial polyether 50-80%, vinylformic acid 2-30%, vinyl imidazole class ionic liquid monomer 2-25%.Initiator add-on is 0.2 ~ 6% of whole vinyl monomer gross weight, and esterifying catalyst add-on is 0.2 ~ 5% of vinylformic acid weight.
Industrial polyether of the present invention, comprising: the block polyether taking amine as initiator, and amine used is polyethylene polyamine or quadrol; Take alcohols as the block polyether of initiator, alcohol used is octadecanol or propylene glycol; Alkyl phenolic resin block polyether, during synthesis 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 the oil-soluble initiator such as the Diisopropyl azodicarboxylate in azo or the 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 in mineral acid or phosphoric acid, the p-methyl benzenesulfonic acid in organic acid or heteropolyacid.
The synthetic method of Polyion-liquid-modifcrude crude oil demulsifier of the present invention is as follows:
1) solvent is joined with stirring, in the reaction flask of Dropping feeder and condenser, control temperature 75 ~ 95
oc, under agitation, add vinyl imidazole class ionic liquid monomer, vinylformic acid and initiator, whole polymerization process controls in 1 ~ 3 hour, has reacted follow-up continuous insulation reaction 1 hour, and then underpressure distillation removes desolventizing and obtains intermediate product.Described solvent to be concentration be 95% ethanol;
2) in above-mentioned intermediate product, add industrial polyether and solvent, after stirring, add esterifying catalyst, be warming up to 100 ~ 160
oc, continue stirring reaction and obtain crude product in 3 ~ 5 hours, underpressure distillation removes desolventizing and namely obtains Polyion-liquid-modifcrude crude oil demulsifier, and described solvent is toluene.
By vinyl imidazole class ionic liquid monomer and acrylic acid copolymer, the chain extension effect to pfpe molecule obtains emulsion splitter of the present invention., simultaneously containing positively charged ion and nonionic functional group in molecular chain, strong effect can be there is with some electronegativity surfaces of crude oil, make it change thermodynamic unstable system into and realize oily water separation in the emulsion splitter that the present invention obtains.This emulsion splitter 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 Polyion-liquid-modifcrude crude oil demulsifier, synthetic method is as follows:
1) be the ethanol of 95% by 150 grams of concentration, solvent to be now concentration be 95% ethanol; Join with stirring, in the reaction flask of Dropping feeder and condenser, control temperature 75
oc, under agitation, 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 controls 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 industrial polyether 200 grams of (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 120
oc, continue stirring reaction and obtain crude product in 5 hours, underpressure distillation removes desolventizing and namely obtains Polyion-liquid-modifcrude crude oil demulsifier.
embodiment 2
A kind of Polyion-liquid-modifcrude crude oil demulsifier, synthetic method is as follows:
1) by 150 grams of concentration be that 95% ethanol joins with stirring, in the reaction flask of Dropping feeder and condenser, control temperature 85
oc, under agitation, 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 controls 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 industrial polyether 180 grams (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 130
oc, continue stirring reaction and obtain crude product in 4 hours, underpressure distillation removes desolventizing and namely obtains Polyion-liquid-modifcrude crude oil demulsifier.
embodiment 3
A kind of poly ion liquid crude oil modified breakdown of emulsion, agent synthetic method is as follows:
1) by 210 grams of concentration be that 95% ethanol joins with stirring, in the reaction flask of Dropping feeder and condenser, control temperature 90
oc, under agitation, 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 controls 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 industrial polyether 200 grams (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 140
oc, continue stirring reaction and obtain crude product in 3 hours, underpressure distillation removes desolventizing and namely obtains Polyion-liquid-modifcrude crude oil demulsifier.
Claims (4)
1. a Polyion-liquid-modifcrude crude oil demulsifier, is characterized in that: this emulsion splitter synthesis raw material weight in 100%, wherein industrial polyether 50 ~ 80%, vinylformic acid 2 ~ 30%, vinyl imidazole class ionic liquid monomer 2 ~ 25%; Initiator add-on is 0.2 ~ 6% of whole vinyl monomer gross weight, and esterifying catalyst add-on is 0.2 ~ 5% of vinylformic acid weight; Described vinyl imidazole class ionic liquid monomer is chlorination 1-allyl group-3-Methylimidazole or chlorination 1-vinyl-3-Methylimidazole or their nitrate.
2. Polyion-liquid-modifcrude crude oil demulsifier according to claim 1, is characterized in that: described industrial polyether, comprising: the block polyether taking amine as initiator, and amine used is polyethylene polyamine or quadrol; Take alcohols as the block polyether of initiator, alcohol used is octadecanol or propylene glycol; Alkyl phenolic resin block polyether, alkylphenol during synthesis initiator 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.
3. Polyion-liquid-modifcrude crude oil demulsifier according to claim 1, is characterized in that: described initiator is the Diisopropyl azodicarboxylate in azo or the benzoyl peroxide oil-soluble initiator in peroxide; Or ammonium persulphate or Potassium Persulphate water soluble starter.
4. Polyion-liquid-modifcrude crude oil demulsifier according to claim 1, is characterized in that: described esterifying catalyst is sulfuric acid in mineral acid or phosphoric acid, the p-methyl benzenesulfonic acid in organic acid, or heteropolyacid.
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| CN110387255A (en) * | 2018-04-23 | 2019-10-29 | 盘锦富隆化工有限公司 | A kind of non-ionic water-soluble heavy crude desalination demulsifier and preparation method thereof |
| CN113684053B (en) * | 2021-10-25 | 2021-12-21 | 胜利油田海发环保化工有限责任公司 | Composite demulsifier and preparation process thereof |
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| US5660717A (en) * | 1995-03-27 | 1997-08-26 | Nalco/Exxon Energy Chemicals, L. P. | Abatement of hydrolyzable cations in crude oil |
| CN1137247C (en) * | 2001-04-18 | 2004-02-04 | 东南大学 | Polymer-type efficient demulsifier for emulsion of crude oil and its synthesizing process |
| DE102009019177A1 (en) * | 2009-04-28 | 2010-11-11 | Clariant International Ltd. | Use of biodegradable alkoxylated (meth) acrylate copolymers as crude oil emulsion breakers |
| CN102229814B (en) * | 2011-06-07 | 2013-06-19 | 句容宁武高新技术发展有限公司 | Demulsifier compounded from amido ionic liquid and polyether and preparation method thereof |
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