CN106279525A - Tertiary oil recovery surface-active polymer oil displacement agent and preparation method thereof - Google Patents
Tertiary oil recovery surface-active polymer oil displacement agent and preparation method thereof Download PDFInfo
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- CN106279525A CN106279525A CN201610643621.0A CN201610643621A CN106279525A CN 106279525 A CN106279525 A CN 106279525A CN 201610643621 A CN201610643621 A CN 201610643621A CN 106279525 A CN106279525 A CN 106279525A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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Abstract
The invention discloses a kind of tertiary oil recovery surface-active polymer oil displacement agent and preparation method thereof.The Heat Resistant and Salt Tolerant Polymer that the present invention provides has structure, wherein, by introducing containing naphthalenesulfonic acid group, ethanol group and pyrrolidone group unit on polyacrylamide, POLYPROPYLENE GLYCOL and polyvinyl alcohol molecule main chain, when making this Heat Resistant and Salt Tolerant Polymer be applied to the oil field displacement of reservoir oil, not only there is good high temperature resistant property, and there is good anti-salt property.Preparation process mild condition, step are simple, green non-pollution, can be effectively improved sweep efficiency and oil displacement efficiency, can keep oil field Sustainable high yield, especially can improve later stage Exploitation Level of Oilfield, have good application prospect.
Description
Technical field
The present invention relates to a kind of oil displacement agent and preparation method thereof, be specifically related to a kind of tertiary oil recovery surface-active polymer and drive
Oil preparation and preparation method thereof.
Background technology
The waterflooding extraction technology of China's onshore oil field is gradually improved, and in terms of exploitation matched process technology, have accumulated abundant
Practical experience.Under normal circumstances, primary oil recovery and secondary oil recovery can be gathered the crude oil of about 30%-40%, after secondary oil recovery
Residual production potential at about 60%-70%, therefore tertiary oil recovery is always the problem of countries in the world oil expert tackling key problem.Data shows
Showing, China's major part tertiary oil production in oil field is suitable for various technology of reservoir sweep, and potentiality are more than 5,000,000,000 tons of original oil in place.China is generation
The country that in boundary, tertiary oil recovery industrialization degree is the highest, polymer displacement of reservoir oil tech research is taken its place in the front ranks of the world with application.In recent years
The oil mass of tertiary oil recovery volume increase has accounted for the 6% of crude oil in China yield, and rises year by year.Carrying out tertiary oil recovery is that to slow down China many
Number oil field aging rate, maintenance crude oil in China stable yields, the minimizing China strategic requirement to external crude oil degree of dependence.Along with polymerization
The further genralrlization application of thing technology of reservoir sweep, the oil field being suitable for polymer flooding is fewer and feweri.More than 95% is not suitable for polymer flooding
Oil field tertiary oil recovery to be carried out, recovery ratio to be improved.
Polymer flooding oil process is polymer to be added in water filling increase the viscosity of water, owing to viscosity strengthens and uses certain
The water phase permeability that a little polymer are occurred reduces, and causes mobility ratio and reduces, and the reduction of mobility ratio increases volume and involves
Coefficient, decreases the oil saturation of swept zone, thus improves waterflood efficiency.At present in oil-gas mining polymer, permissible
That selects has partially hydrolyzed polyacrylamide (PHPA) (HPAM), acrylamide and the copolymer of the third vinyl monomer, biopolymer (yellow born of the same parents
Glue), cellulose ether compound, polyvinylpyrrolidone etc., oneself is through the extensive polymer oil-displacing agent for tertiary oil production in oil field
There is a few class of copolymer of HPAM and Xanthan gun, acrylamide and the third vinyl monomer, and based on HPAM.HPAM is own to be polymerized in China
It is widely used in the thing displacement of reservoir oil, and achieves good result.But HPAM product shear stability is poor, temperature-resistant anti-salt performance is not
Good.The anti-salt of Xanthan gun, anti-shear performance are excellent, but injection is poor and expensive with temperature tolerance.HPAM and Xanthan gun are all difficult to
Meet the needs of high temperature high salt concentration water.The copolymer of acrylamide and the third vinyl monomer is the focus of at present research, by with
Different function monomer copolymerization can improve the heat and salinity tolerance performance of polymer, and scholars gathers in the high performance raising of development
Rate water-soluble polymer aspect has carried out numerous studies work, achieves certain progress research.
Summary of the invention
The problems referred to above existed for prior art, the invention provides a kind of tertiary oil recovery surface-active polymer displacement of reservoir oil
Agent, it has the molecular structure being shown below
In wherein, m=3-9, n=50-73, p=3-8；The molecular weight of polymer is 3,500,000-1,000 ten thousand.
The preparation method of a kind of tertiary oil recovery surface-active polymer oil displacement agent, comprises the following steps:
A, water are solvent, are anti-with vinyl alcohol, propenyl, acrylamide, ethylene glycol, hydroxyl yrrolidone and beta-naphthalenesulfonic-acid
Answer thing, react at 40 DEG C-60 DEG C；
B, addition sodium hydroxide adjust pH to 8～9；
C, the monomer solution of b step is warming up to room temperature, logical nitrogen gas stirring 30 minutes；
D, in the monomer solution of step c add initiator ammonium sulfate-sodium sulfite, be warming up to 50 DEG C, persistently lead to nitrogen
Gas, reacts 9-11 hour；
E, product pelletize Step d obtained, dry, pulverizing, obtain novel surface active polymer flood agent.
Compared with existing tertiary oil recovery polymer oil-displacing agent, the present invention has feature highlighted below: wherein, by poly-third
It is simultaneously introduced containing naphthalenesulfonic acid group, ethanol group and pyrrolidone-base on acrylamide, POLYPROPYLENE GLYCOL and polyvinyl alcohol molecule main chain
Single group unit so that this polymer oil-displacing agent not only has good high temperature resistant property, and has good anti-salt property.
Accompanying drawing explanation
Fig. 1 novel surface living polymer infrared spectrum.
Detailed description of the invention
One, the preparation of polymer
Weigh a certain amount of deionized water, soda, vinyl alcohol, propenyl, acrylamide, ethylene glycol, hydroxyl yrrolidone
And beta-naphthalenesulfonic-acid is dissolved in deionized water, stirring completely, after logical nitrogen 20min, adds ammonium sulfate-sodium sulfite initiator, continues
It is passed through constant temperature 50 DEG C after nitrogen 20min, after polymerization 4h, 90 DEG C of hydrolysis 4h, pelletize, it is dried, pulverizes and sieves, obtain white powder
Shape solid, taking-up is cut into small pieces, and dry, pulverize and obtain white powder admittedly after repeatedly washing with ethanol in vacuum drying oven
Body.
Two, polymer performance evaluation
Utilizing FTIR spectrum to be characterized this polymer architecture, its result is as shown in Figure 1.As seen from Figure 1,
3221cm-1Place is N-H key stretching vibration absworption peak, 1650cm-1Place is C=O key stretching vibration absworption peak, at 1400cm-1 is
C-N bond bending vibration absorption peak, it is known that contain the characteristic absorption peak of acrylamide in copolymer thing.1065cm-1、980cm-1Place
Occur in that sulfonic characteristic absorption peak, illustrate that polymerizable surface active monomer take part in graft copolymerization.
Technical scheme below in conjunction with the embodiment of the present invention is clearly and completely described, and described embodiment is only this
Invent a part of embodiment.
Embodiment 1:
It is slowly added to the polymer oil-displacing agent sample prepared burn equipped with the saline that salinity is 8500mg L in advance
In Bei, it is configured to the polymer displacement of reservoir oil agent solution that concentration is 2000mg L, chooses tradition HPAM, HAWSP as comparison simultaneously
Group, investigates its molecule performance at ambient temperature.Result is as shown in table 1.Indoor under the conditions of normal saline solution, YM, routine are gathered
The basic physicochemical property of acrylamide (HPAM) and salt-resistant polymer (HAWSP) etc. is tested, and its result is as shown in table 1.
The molecule performance of table 1 polymer
As shown in Table 1, the basic physicochemical property of YM meets the technology requirement of Polymer Used For Oil Displacement, and is better than HPAM, reaches
Petroleum industry standard.
Embodiment 2:
At room temperature model evacuation, saturated formation water, obtain model pore volume；Under the conditions of 45 DEG C, model is saturated
Simulated oil, calculates oil saturation；Under the conditions of 45 DEG C, water drive is to specifying aqueous 98%, it is thus achieved that waterflood recovery efficiency factor；At 45 DEG C of bars
Under part, inject the polymer oil-displacing agent prepared, and compared with HPAM, HAWSP, injection pore volume multiple is
0.35, experimental result is shown in Table 2.
The indoor oil displacement experiment result of table 2
From table 2, polymer flooding is better than waterflooding effect；Under conditions of polymer volume is identical, novel surface activity
Polymer oil-displacing agent improves about 5% than traditional polymer oil-displacing agent.Analyze and understand, novel surface active polymers solution
Viscosity is relatively big, and flowing control ability is relatively strong, effectively expands swept volume, and has certain washing oil ability, therefore gathers
Rate amplification is bigger.
Embodiment 3:
It is slowly added to the polymer oil-displacing agent sample prepared burn equipped with the saline that salinity is 8500mg L in advance
In Bei, being configured to the polymer displacement of reservoir oil agent solution that concentration is 2500mg L, the most evacuated deoxygenation post package is in ampoule bottle
(control oxygen mass concentration ＜ 0.5mg L, take out after the most aging 0d, 10d, 30d, 90d, 120d, 150d in 90 DEG C of baking ovens,
At 40 DEG C and 7.23s-1Measure viscosity under shear rate, choose conventional propylene amide homopolymer as a control group simultaneously.Result is joined
It is shown in Table 3.
Table 3 polymer salt aqueous solution senile experiment result at 90 DEG C
From table 3 it can be seen that compared with methacrylamide homopolymer, the novel homopolymer synthesized herein shows preferably
Heat stability.The novel homopolymer of synthesis still keeps higher solution viscosity at 90 DEG C after 150d is aging, and the same terms
Under methacrylamide homopolymer solution be just down to 1.3mPa s merely through its viscosity of 30d.
As can be seen here: the basic physicochemical property of novel surface living polymer of synthesis meets the technology of Polymer Used For Oil Displacement to be wanted
Asking, solution viscosity is relatively big, and flowing control ability is relatively strong, effectively expands swept volume, and has certain washing oil ability；Warp
After crossing 90 DEG C of long-term ageings, viscosity is maintained at the target of more than 5mPa s.
The tertiary oil recovery surface-active polymer oil displacement agent that the present invention is developed, when being applied to the oil field displacement of reservoir oil, not only has
Well high temperature resistant property, and there is good anti-salt property.Preparation process mild condition, step are simple, green non-pollution,
Sweep efficiency and oil displacement efficiency can be effectively improved, oil field Sustainable high yield can be kept, especially can improve later stage Exploitation Level of Oilfield,
There is good application prospect.
Claims (2)
1. a tertiary oil recovery surface-active polymer oil displacement agent, it is characterised in that it has a molecular structure being shown below:
Wherein, m=3-9, n=50-73, p=3-8；The molecular weight of polymer is 3,500,000-1,000 ten thousand.
2. the preparation method of a tertiary oil recovery surface-active polymer oil displacement agent as claimed in claim 1, it is characterised in that
Comprise the following steps:
A, water are solvent, and vinyl alcohol, propenyl, acrylamide, ethylene glycol, hydroxyl yrrolidone and beta-naphthalenesulfonic-acid are reactant,
React at 40 DEG C-60 DEG C；
B, addition sodium hydroxide are adjusted to pH 8～9；
C, the monomer solution of b step is warming up to room temperature, logical nitrogen gas stirring 30 minutes；
D, in the monomer solution of step c add initiator ammonium sulfate-sodium sulfite, be warming up to 50 DEG C, maintaining nitrogen purge, instead
Answer 9-11 hour；
E, product pelletize Step d obtained, dry, pulverizing, obtain novel surface active polymer flood agent.
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Citations (7)
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|---|---|---|---|---|
| CN101205281A (en) * | 2007-12-12 | 2008-06-25 | 中国科学院长春应用化学研究所 | Water-soluble hydrophobic associated copolymer and preparation thereof |
| CN102093504A (en) * | 2011-01-04 | 2011-06-15 | 合肥工业大学 | High molecular weight salt-resistance and temperature-resistance biopolymer oil displacement agent and preparation method thereof |
| CN102304200A (en) * | 2011-05-27 | 2012-01-04 | 中国海洋石油总公司 | Crosslinked polymer microspheres and preparation method thereof |
| CN102838979A (en) * | 2012-09-07 | 2012-12-26 | 西南石油大学 | Polymer-surfactant dualistic compound oil-displacing agent |
| CN103665260A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Heat resistance and salt tolerance polymer for oil displacement and preparation method thereof |
| CN104628944A (en) * | 2013-11-15 | 2015-05-20 | 中国石油化工股份有限公司 | Acrylamide copolymer, as well as preparation method and application thereof |
| CN104974733A (en) * | 2015-06-10 | 2015-10-14 | 天津大港油田滨港集团博弘石油化工有限公司 | Polymer oil displacement agent and preparation method thereof |
-
2016
- 2016-08-08 CN CN201610643621.0A patent/CN106279525A/en active Pending
Patent Citations (7)
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| CN101205281A (en) * | 2007-12-12 | 2008-06-25 | 中国科学院长春应用化学研究所 | Water-soluble hydrophobic associated copolymer and preparation thereof |
| CN102093504A (en) * | 2011-01-04 | 2011-06-15 | 合肥工业大学 | High molecular weight salt-resistance and temperature-resistance biopolymer oil displacement agent and preparation method thereof |
| CN102304200A (en) * | 2011-05-27 | 2012-01-04 | 中国海洋石油总公司 | Crosslinked polymer microspheres and preparation method thereof |
| CN103665260A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Heat resistance and salt tolerance polymer for oil displacement and preparation method thereof |
| CN102838979A (en) * | 2012-09-07 | 2012-12-26 | 西南石油大学 | Polymer-surfactant dualistic compound oil-displacing agent |
| CN104628944A (en) * | 2013-11-15 | 2015-05-20 | 中国石油化工股份有限公司 | Acrylamide copolymer, as well as preparation method and application thereof |
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Application publication date: 20170104 |