CN101570696B - Demulsifier for ternary combination flooding produced fluid and preparation method thereof - Google Patents
Demulsifier for ternary combination flooding produced fluid and preparation method thereof Download PDFInfo
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- CN101570696B CN101570696B CN2008101056564A CN200810105656A CN101570696B CN 101570696 B CN101570696 B CN 101570696B CN 2008101056564 A CN2008101056564 A CN 2008101056564A CN 200810105656 A CN200810105656 A CN 200810105656A CN 101570696 B CN101570696 B CN 101570696B
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- emulsion splitter
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Abstract
The invention relates to a preparation method for a demulsifier for a ternary combination flooding produced fluid. The method comprises the following steps: adopting A styrene and B acrylate or methacrylate as monomers, benzoperoxide or azodiisobutylnitrile as an initiating agent, and methylbenzene or dimethylbenzene as a polymerization solvent; reacting the mixture at a temperature of between 70 and 120 DEG C for 5 to 8 hours to obtain a polymer-type initiator of which the molecular weight is between 1,000 and 5,000; and under the action of potassium hydroxide, performing addition reaction onthe initiator synthesized in the first step with propylene oxide and ethylene oxide to obtain the demulsifier, wherein the molar ratio of the monomer A to the monomer B is between 1:1 and 1:4; the do sage of the initiating agent accounts for 0.5 to 5 percent of the mass of the monomers; the dosage of the potassium hydroxide accounts for 0.1 to 0.8 percent of the mass of the initiator; the molar ratio of the initiator to the propylene oxide is between 1:50 and 1:300; the molar ratio of the initiator to the ethylene oxide is between 1:50 and 1:300; and the oil content in sewage is lower than 200milligrams per liter, and the water content in emulsified oil is lower than 10 percent.
Description
Technical field:
The present invention relates to a kind of ternary combination flooding produced liquid oily water separation with high molecular polyether type emulsion splitter and preparation method thereof.
Technical background:
Extraction liquid breaking emulsion and dewatering is failed and processes all very important to crude oil production, collection.The ternary composite driving technology becomes one of gordian technique of oilfield stimulation stable yields gradually, but because the emulsified state of extraction liquid is complicated, emulsion is very stable, causes very difficulty of breaking emulsion and dewatering, brings many difficult problems to production.Abroad because of not forming mass-producing ternary composite driving The Application of Technology, thus very few to the research of demulsifier for ternary combination flooding produced fluid.More domestic research units only carry out preliminary study to the breakdown of emulsion mechanism of ternary combination flooding produced liquid, also do not develop to be fit to the emulsion splitter that ternary combination flooding produced liquid is used.
At present the comparatively general emulsion splitter of domestic and international application is that the resin with alcohol, amine, hydroxyl or amino-contained is initiator addition propylene oxide and oxyethane; The synthetic polyether type demulsifying agent; Like AE1910, TA1031, SP169, F3111 etc., solved the breaking emulsion and dewatering problem of water drive extraction liquid preferably.But it is lower to be used for this type of emulsion splitter molecular weight ratio, can not satisfy the requirement of ternary combination flooding produced liquid breaking emulsion and dewatering.For this reason, people have obtained certain progress to polyether type demulsifying agent modification or composite, but still can not solve the breaking emulsion and dewatering difficult problem of ternary combination flooding produced liquid.
Patent US6080794, US5472617, US5100852 are polymerization single polymerization monomer synthetic polymer type emulsion splitter with vinylformic acid and propenoate.Patent CN1100584C is the synthetic non-polyether polymer type emulsion splitter of polymerization single polymerization monomer with vinylbenzene, methyl acrylate, TEB 3K, Bing Xisuandingzhi, vinylformic acid, methylacrylic acid, molecular weight 5.3 * 10
3～69.9 * 10
3, the affinity of this type of emulsion splitter and crude oil is better.Patent CN1883740A is the synthetic non-polyether polymer type emulsion splitter of polymerization single polymerization monomer with vinylformic acid, methylacrylic acid, propenoate, methacrylic ester, molecular weight 5 * 10
3～100 * 10
3, the affinity of this type of emulsion splitter and crude oil is better.Above-mentioned emulsion splitter all belongs to non-polyethers, polymer-type emulsion splitter from a structural point, and this type of emulsion splitter has certain demulsification to common extraction liquid, but can not satisfy the breaking emulsion and dewatering requirement of ternary combination flooding produced liquid.
Summary of the invention
The purpose of this invention is to provide a kind of demulsifier for ternary combination flooding produced fluid and preparation method thereof.
The preparation method of emulsion splitter provided by the invention comprised for two steps: the first step is a monomer with vinylbenzene, propenoate or methacrylic ester, synthetic polymer type initiator; Second step synthetic initiator addition propylene oxide and the oxyethane.
The first step
Adopt solution polymerization process; With vinylbenzene, propenoate or methacrylic ester is monomer; With Lucidol or azobisisobutyronitrile is initiator; With toluene or YLENE is polymer solvent, under 70～120 ℃ of temperature, reacts 5～8 hours, can obtain the polymer-type initiator of molecular weight 1000～5000.Its structural formula is following:
In the said structure formula, m, n are positive integer, R
1Be H or CH
3, R
2Be C
2H
4Or C
3H
6,
Monomer: A is a vinylbenzene; B is Hydroxyethyl Acrylate, vinylformic acid hydroxy propyl ester, Rocryl 400, Rocryl 410;
Two kinds of monomeric mol ratios of A and B: 1: 1～1: 4
Temperature of reaction: 70～120 ℃
Reaction times: 5～8 hours
Initiator amount: be 0.5%～5% of monomer A and B total mass
Toluene or YLENE consumption and monomer A and B total mass equivalent;
Second step
Under the effect of Pottasium Hydroxide,, obtain the target emulsion splitter, molecular weight 1x10 with first synthetic initiator addition propylene oxide and oxyethane
4～5x10
4
The structure of emulsion splitter is following:
In the said structure formula, m, n, p, q are positive integer, R
1Be H or CH
3, R
2Be C
2H
4Or C
3H
6
Pottasium Hydroxide consumption: account for 0.1～0.8% of initiator quality;
The mol ratio of initiator and propylene oxide: 1: 50～1: 300;
The mol ratio of initiator and oxyethane: 1: 50～1: 300.
Said emulsion splitter has breakdown of emulsion preferably to ternary combination flooding produced liquid in grand celebration four factory's apricots two, and sewage with oil is lower than 200mg/L, for WWT lays a good foundation; Oil in water emulsion is moisture to be lower than 10%, reaches into electricity and takes off and be lower than 20% requirement.
Embodiment
Embodiment 1
Taking by weighing 26 gram vinylbenzene, 59 gram Hydroxyethyl Acrylate and 80 gram YLENE packs in the 250ml there-necked flask that has whisking appliance; With 5 gram xylene soluble, 0.85 gram Lucidol; Under 80 ℃, drip initiator (approximately needing 1 hour) gradually, after dropwising, under 85 ℃ of temperature, continue reaction 5 hours; Remove under the vacuum and desolvate, obtain the emulsion splitter initiator.
Take by weighing 6 gram gained initiators in autoclave,, add 0.13 gram Pottasium Hydroxide then the still sealing; Be heated to 120 ℃, drip continuously then 14 the gram propylene oxide, treat that the autoclave internal pressure is reduced to normal pressure after; Renew and drip 11 gram oxyethane, treat that the autoclave internal pressure is reduced to normal pressure after, continued again to keep 1 hour; Gained affixture meter is made A-1, (m, n, p, q are respectively 6,12,480,520 in the structure of A-1).
Embodiment 2
Taking by weighing 16 gram vinylbenzene, 68 gram Rocryl 410s and 80 gram YLENE packs in the 250ml there-necked flask that has whisking appliance; With 8 gram xylene soluble, 1.3 gram Lucidols; Under 80 ℃, drip initiator (approximately needing 1 hour) gradually, after dropwising, under 85 ℃ of temperature, continue reaction 5 hours; Remove under the vacuum and desolvate, obtain the emulsion splitter initiator.
Take by weighing 4 gram gained initiators in autoclave,, add 0.19 gram Pottasium Hydroxide then the still sealing; Be heated to 120 ℃, drip continuously then 21 the gram propylene oxide, treat that the autoclave internal pressure is reduced to normal pressure after; Drip continuously again 16 the gram oxyethane, treat that the autoclave internal pressure is reduced to normal pressure after, continued again to keep 1 hour; Gained affixture meter is made A-2, (m, n, p, q are respectively 6,18,1056,1230 in the structure of A-2).
The said emulsion splitter of this patent is listed table 1 with the contrast emulsion splitter in to the breaking emulsion and dewatering effect of grand celebration four factory's ternary combination flooding produced liquids.Evaluation method is following:
Measure in 100ml grand celebration four factory's apricots two ternary combination flooding produced liquid in encloses container, add the said emulsion splitter of 30mg/L this patent, shake evenly after, under 40 ℃ of conditions, the static placement 30 minutes.The sampling analysis effect.
The static demulsification of table 1
| Emulsion splitter | Oil-containing/mg/L in the water | Oil in water emulsion is moisture/% | Water-oil interface |
| Contrast medium | 1132.6 | 33.2 | Uneven |
| A-1 | 114.5 | 5.62 | Together |
| A-2 | 180.8 | 8.26 | Together |
Table 1 shows that the said emulsion splitter of this patent has breakdown of emulsion preferably to ternary combination flooding produced liquid in grand celebration four factory's apricots two, and sewage with oil is lower than 200mg/L, for WWT lays a good foundation; Oil in water emulsion is moisture to be lower than 10%, reaches into electricity and takes off and be lower than 20% requirement.
Claims (2)
1. the preparation method of a demulsifier for ternary combination flooding produced fluid is characterized in that:
The first step
With vinylbenzene, propenoate or methacrylic ester is monomer; With Lucidol or Diisopropyl azodicarboxylate is initiator; With toluene or YLENE is polymer solvent; Under 70～120 ℃ of temperature, reacted 5～8 hours, obtain molecular weight 1000～5000 polymer-type initiators, its structural formula is following:
In the said structure formula, m, n are positive integer, R
1Be H or CH
3, R
2Be C
2H
4Or C
3H
6
Monomer: A is a vinylbenzene; B is Hydroxyethyl acrylate, Propylene glycol monoacrylate, Rocryl 400 or Rocryl 410;
Two kinds of monomeric mol ratios of A and B: 1: 1～1: 4
Temperature of reaction: 70～120 ℃
Reaction times: 5～8 hours
Initiator amount: be 0.5%～5% of monomer A and B total mass
Toluene or YLENE consumption and monomer A and B total mass equivalent;
Second step
Under the effect of Pottasium Hydroxide, with the first step synthetic initiator addition propylene oxide and oxyethane, obtain the target emulsion splitter, molecular weight 1 * 10
4～5 * 10
4
The structure of emulsion splitter is following:
In the said structure formula, m, n, p, q are positive integer, R
1Be H or CH
3, R
2Be C
2H
4Or C
3H
6
Pottasium Hydroxide consumption: account for 0.1～0.8% of initiator quality;
The mol ratio of initiator and propylene oxide: 1: 50～1: 300;
The mol ratio of initiator and oxyethane: 1: 50～1: 300.
2. a demulsifier for ternary combination flooding produced fluid is characterized in that: the molecular weight 1 * 10 of this emulsion splitter
4～5 * 10
4Structure as shown in the formula:
In the said structure formula, m, n, p, q are positive integer, R
1Be H or CH
3, R
2Be C
2H
4Or C
3H
6
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|---|---|---|---|
| CN2008101056564A CN101570696B (en) | 2008-04-30 | 2008-04-30 | Demulsifier for ternary combination flooding produced fluid and preparation method thereof |
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| CN101570696A CN101570696A (en) | 2009-11-04 |
| CN101570696B true CN101570696B (en) | 2012-07-18 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102533314B (en) * | 2012-02-16 | 2014-03-19 | 中国海洋石油总公司 | Quick petroleum deemulsifier and preparation method thereof |
| CN104031258B (en) * | 2014-06-12 | 2015-06-24 | 南京师范大学 | Phosphate group containing terpolymer as well as preparation method and application thereof |
| CN106318444B (en) * | 2016-10-21 | 2017-11-28 | 中国海洋石油总公司 | A kind of polymer-type thick oil demulsifier and preparation method thereof |
| CN108276571A (en) * | 2017-12-25 | 2018-07-13 | 威海翔泽新材料科技有限公司 | A kind of preparation of the dedicated efficient dehydration of tar agent of coking of coal |
| CN109593189B (en) * | 2018-11-27 | 2021-02-05 | 句容宁武高新技术发展有限公司 | Ultrahigh molecular weight demulsifier rich in multi-ring structure and preparation method thereof |
| CN113773431A (en) * | 2021-09-23 | 2021-12-10 | 九江蓝卓新材料科技有限公司 | Novel high-molecular copolymer demulsifier and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1288901A (en) * | 1999-09-07 | 2001-03-28 | 现代电子产业株式会社 | Organic polymer for anti-reflection coating and its preparation method thereof |
| CN1506388A (en) * | 2002-12-06 | 2004-06-23 | 中国石油天然气股份有限公司 | Terpolymer pour point reducer and its prepn |
-
2008
- 2008-04-30 CN CN2008101056564A patent/CN101570696B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1288901A (en) * | 1999-09-07 | 2001-03-28 | 现代电子产业株式会社 | Organic polymer for anti-reflection coating and its preparation method thereof |
| CN1506388A (en) * | 2002-12-06 | 2004-06-23 | 中国石油天然气股份有限公司 | Terpolymer pour point reducer and its prepn |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2006-232947A 2006.09.07 |
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