CN103484149A - Self-crosslinking polyether demulsifier - Google Patents
Self-crosslinking polyether demulsifier Download PDFInfo
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- CN103484149A CN103484149A CN201310477804.6A CN201310477804A CN103484149A CN 103484149 A CN103484149 A CN 103484149A CN 201310477804 A CN201310477804 A CN 201310477804A CN 103484149 A CN103484149 A CN 103484149A
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Abstract
The invention discloses a self-crosslinking polyether demulsifier. The demulsifier is prepared from the following raw materials in percentage by weight: 50-90% of industrial polyether, 3-30% of acrylamide and 1-25% of N-hydroxymethyl acrylamide. The initiator accounts for 0.1-5 wt% of all the vinyl monomers, and the esterification catalyst accounts for 1-10 wt% of the N-hydroxymethyl acrylamide. The demulsifier can have a severe action on the oil-water interface of a crude oil emulsion, so that the crude oil emulsion is converted into a thermodynamically instable system, thereby implementing 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 chemical technical field, relate to a kind of Novel crude oil demulsifier, specifically a kind of self-cross linking type polyether demulsification agent that is applicable to crude oil emulsion is carried out breaking emulsion and dewatering.
Background technology
The breaking emulsion and dewatering of crude oil emulsion is important step in oil production and the defeated process of collection.Emulsion splitter is the indispensable chemical assistants in all oil fields, and it is bearing the task of emulsification crude oil demulsification dehydration.Along with constantly carrying out of Oil extraction, the continually developing and applying of oil recovery technique, it is more stable that crude oil emulsion becomes, and oil field produced most of crude oil is exploited out with the water-oil emulsion form, crude oil water content increases year by year, and this has just increased the weight of the task of emulsification crude oil demulsification dehydration.At present, the most frequently used crude oil demulsification method of petroleum industry is to add emulsion splitter in crude oil.From chemical type, domestic emulsion splitter mainly be take non-ionic polyoxyethylene polyoxypropylene block polymer as main, it is the kind difference of initiator, when preparing the higher molecular weight polyethers, side reaction is more, the polyether demulsification agent molecular weight ratio made is lower, dehydrating effect of emulsion breaker is undesirable, and to the wide spectrum bad adaptability of different crude oils oil product, particularly the low-temperature demulsification effect is unsatisfactory.
In order to improve the adaptability of this type of emulsion splitter, people had carried out modification to a certain degree to such emulsion splitter in recent years, to reach, improved breakdown of emulsion and strengthened adaptive effect, and chain extension and branching are exactly emulsion splitter to be carried out to the common method of pectination modification.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 the initiator effect, 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 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, realize the pectination modification to emulsion splitter thereby carry out esterification with industrial polyethers again, as 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, major part needs use the alcoholic solvent obtain solution, has increased difficulty to the oil field execute-in-place.In addition, owing in such emulsion splitter molecular structure, only containing the nonionic functional group, so do not have strong interaction for some electronegativity surfaces of crude oil, cause occurring the defect of the not good or bad adaptability of demulsification.
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 purpose of this invention is to provide a kind of self-cross linking type polyether demulsification agent.This emulsion splitter has that consumption is few, the rate of output water is fast, deviate from the characteristics such as water colour is clear, use range is wide.
The objective of the invention is to be achieved through the following technical solutions:
A kind of self-cross linking type polyether demulsification agent is characterized in that: the raw material weight of synthetic this emulsion splitter is in 100%, and wherein industrial polyethers is 50 ~ 90%, acrylamide 3 ~ 30%, N hydroxymethyl acrylamide 1 ~ 25%.The initiator add-on is 0.1 ~ 5% of whole vinyl monomer gross weights; The catalyst for etherification add-on is 1 ~ 10% of N hydroxymethyl acrylamide weight.
Industrial polyethers of the present invention comprises: 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; The alkyl phenolic resin block polyether, during synthetic initiator, alkylphenol commonly used is nonyl phenol; Phenol amine aldehyde resin block polyether, i.e. amino modified resol block polyether, the condensation product that initiator is alkylphenol, vinyl-amine compounds and formaldehyde.
Initiator of the present invention is the water soluble starters such as ammonium persulphate or Potassium Persulphate, and the oil-soluble initiators such as azo two isonitrile and benzoyl peroxide.
Catalyst for etherification of the present invention is one or both mixtures in phosphoric acid, sulfuric acid or tosic acid acid.
The synthetic method of this self-cross linking type polyether demulsification agent is as follows:
1) solvent is joined in the reaction flask with stirring, Dropping feeder and condenser, control temperature 75 ~ 95
oc, under agitation condition, add acrylamide, N hydroxymethyl acrylamide and initiator, and whole polymerization process was controlled in 1 ~ 3 hour, and reaction finishes follow-up continuation of insurance temperature reaction 1 hour, and then underpressure distillation obtains intermediate product except desolventizing; Described solvent can be the ethanol that concentration is 95%;
2) add industrial polyethers and solvent in above-mentioned intermediate product, after stirring, add catalyst for etherification, be warming up to 80 ~ 120
oc, continue stirring reaction and within 3 ~ 5 hours, obtain crude product, and underpressure distillation derives from the crosslinked polyether emulsion splitter except desolventizing.
In the present invention, contain the several functions groups such as amide group, methylol and ehter bond in the emulsion splitter molecular chain simultaneously, there is good adsorptivity, flocculence and water-soluble.At the breaking emulsion and dewatering temperature, self-crosslinking can occur or with natural surface active agent generation crosslinked actions such as system studies on asphaltenes and form pectination or reticulated structure mixture.With crude oil emulsion water-oil interface generation strong effect, make it change thermodynamic unstable system into, make crude oil emulsion oil-water interfacial film strength reduction, make it change thermodynamic unstable system into and realize oily water separation.
Emulsion splitter consumption of the present invention is few, the rate of output water is fast, deviate from that water colour is clear, use range is wide.
Embodiment
embodiment 1
A kind of self-cross linking type polyether demulsification agent is obtained by following methods:
1) by 100 gram 95% ethanol, the ethanol that solvent now is 95%, add in the reaction flask with stirring, Dropping feeder and water trap, 75
ounder the C agitation condition, add 30 gram acrylamides, 15 gram N hydroxymethyl acrylamides and ammonium persulphate 0.6 gram, whole polymerization process was controlled in 1 hour, and reaction finishes follow-up continuation of insurance temperature reaction 1 hour, and then underpressure distillation obtains intermediate product except desolventizing.
2) add industrial polyethers 150 grams (polyether demulsification agent AE0604 in above-mentioned intermediate product, Jurong Ningwu High-tech. Development Co., Ltd.'s product) and 100 gram Virahols, solvent now is Virahol, after stirring, add 0.5 gram tosic acid, be warming up to 90
oc continues stirring reaction and within 3 hours, obtains crude product.Underpressure distillation derives from the crosslinked polyether emulsion splitter except desolventizing.
embodiment 2
A kind of self-cross linking type polyether demulsification agent is obtained by following methods:
1) 110 gram 95% ethanol are added in the reaction flask with stirring, Dropping feeder and water trap, 80
ounder the C agitation condition, add 45 gram acrylamides, 5 gram N hydroxymethyl acrylamides and ammonium persulphate 0.6 gram, whole polymerization process was controlled in 2 hours, and reaction finishes follow-up continuation of insurance temperature reaction 1 hour, and then underpressure distillation obtains intermediate product except desolventizing.
2) add industrial polyethers 150 grams (polyether demulsification agent BP5921, Jurong Ningwu High-tech. Development Co., Ltd.'s product) and 100 gram Virahols in above-mentioned intermediate product, after stirring, add 0.2 gram tosic acid, be warming up to 100
oc continues stirring reaction and within 4 hours, obtains crude product.Underpressure distillation derives from the crosslinked polyether emulsion splitter except desolventizing.
embodiment 3
A kind of self-cross linking type polyether demulsification agent is obtained by following methods:
1) 70 gram 95% ethanol are added in the reaction flask with stirring, Dropping feeder and water trap, 85
ounder the C agitation condition, add 20 gram acrylamides, 10 gram N hydroxymethyl acrylamides and ammonium persulphate 0.2 gram, whole polymerization process was controlled in 3 hours, and reaction finishes follow-up continuation of insurance temperature reaction 1 hour, and then underpressure distillation obtains intermediate product except desolventizing.
2) add industrial polyethers 50 grams (polyether demulsification agent AE1910, Jurong Ningwu High-tech. Development Co., Ltd.'s product) and 35 gram Virahols in above-mentioned intermediate product, after stirring, add 0.3 gram tosic acid, be warming up to 110
oc continues stirring reaction and within 5 hours, obtains crude product.Underpressure distillation derives from the crosslinked polyether emulsion splitter except desolventizing.
Claims (4)
1. a self-cross linking type polyether demulsification agent, it is characterized in that: the synthesis material weight of this emulsion splitter is in 100%, and wherein industrial polyethers is 50 ~ 90%, acrylamide 3 ~ 30%, self-cross linking monomer N hydroxymethyl acrylamide 1 ~ 25%; The initiator add-on is 0.1 ~ 5% of whole vinyl monomer gross weights; The catalyst for etherification add-on is 1 ~ 10% of N hydroxymethyl acrylamide weight.
2. self-cross linking type polyether demulsification agent according to claim 1, it is characterized in that: described industrial polyethers comprises: the block polyether that the amine of take is initiator, amine used is polyethylene polyamine or quadrol; The block polyether that the alcohols of take is initiator, alcohol used is octadecanol or propylene glycol; The alkyl phenolic resin block polyether, alkylphenol during synthetic initiator is nonyl phenol; Phenol amine aldehyde resin block polyether, i.e. amino modified resol block polyether, the condensation product that initiator is alkylphenol, vinyl-amine compounds and formaldehyde.
3. self-cross linking type polyether demulsification agent according to claim 1, it is characterized in that: described initiator is ammonium persulphate or Potassium Persulphate water soluble starter, and azo two isonitrile and benzoyl peroxide oil-soluble initiator.
4. self-cross linking type polyether demulsification agent according to claim 1, it is characterized in that: described catalyst for etherification is one or both mixtures in phosphoric acid, sulfuric acid or tosic acid acid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310477804.6A CN103484149A (en) | 2013-10-14 | 2013-10-14 | Self-crosslinking polyether demulsifier |
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| CN201310477804.6A CN103484149A (en) | 2013-10-14 | 2013-10-14 | Self-crosslinking polyether demulsifier |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104673360A (en) * | 2014-04-01 | 2015-06-03 | 南通大学 | High-efficiency industrial application method of low-temperature type diesel oil demulsifier |
| CN105255514A (en) * | 2015-11-18 | 2016-01-20 | 北京石油化工学院 | Novel modified crude oil demulsifier preparing method |
| CN111088064A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Crude oil demulsifier and preparation method thereof |
| CN111088065A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Crude oil demulsifier and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317544A (en) * | 2001-04-18 | 2001-10-17 | 东南大学 | Polymer-type efficient demulsifier for emulsion of crude oil and its synthesizing process |
| WO2009097061A1 (en) * | 2008-01-31 | 2009-08-06 | General Electric Company | Methods for breaking crude oil and water emulsions |
| CN102311602A (en) * | 2011-06-07 | 2012-01-11 | 江苏大学 | Acrylate copolymer demulsifier with silica sol in-situ compound core-shell structure and preparation method thereof |
| CN102786639A (en) * | 2012-08-27 | 2012-11-21 | 句容宁武高新技术发展有限公司 | Preparation method of high performance demulsifier |
-
2013
- 2013-10-14 CN CN201310477804.6A patent/CN103484149A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317544A (en) * | 2001-04-18 | 2001-10-17 | 东南大学 | Polymer-type efficient demulsifier for emulsion of crude oil and its synthesizing process |
| WO2009097061A1 (en) * | 2008-01-31 | 2009-08-06 | General Electric Company | Methods for breaking crude oil and water emulsions |
| CN102311602A (en) * | 2011-06-07 | 2012-01-11 | 江苏大学 | Acrylate copolymer demulsifier with silica sol in-situ compound core-shell structure and preparation method thereof |
| CN102786639A (en) * | 2012-08-27 | 2012-11-21 | 句容宁武高新技术发展有限公司 | Preparation method of high performance demulsifier |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104673360A (en) * | 2014-04-01 | 2015-06-03 | 南通大学 | High-efficiency industrial application method of low-temperature type diesel oil demulsifier |
| CN104673360B (en) * | 2014-04-01 | 2016-07-06 | 南通大学 | The industrial application method of efficient low form diesel oil demulsifier |
| CN105255514A (en) * | 2015-11-18 | 2016-01-20 | 北京石油化工学院 | Novel modified crude oil demulsifier preparing method |
| CN111088064A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Crude oil demulsifier and preparation method thereof |
| CN111088065A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Crude oil demulsifier and preparation method thereof |
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Application publication date: 20140101 |