CN103834379B - A kind of vermiculate glues foam system and the method improving recovery ratio with it - Google Patents
A kind of vermiculate glues foam system and the method improving recovery ratio with it Download PDFInfo
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- CN103834379B CN103834379B CN201410003075.5A CN201410003075A CN103834379B CN 103834379 B CN103834379 B CN 103834379B CN 201410003075 A CN201410003075 A CN 201410003075A CN 103834379 B CN103834379 B CN 103834379B
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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
- C09K8/594—Compositions used in combination with injected gas, e.g. CO2 orcarbonated gas
Abstract
The present invention relates to the foam system that a kind of novel vermiculate glues strengthens, described system includes specific vermiculate glues and gas.Present invention also offers a kind of method that foam system using described vermiculate glues to strengthen improves oil recovery factor, it is characterised in that: by described vermiculate glues and gas alternately or described vermiculate glues bubbles in foam maker with gas after in injection oil bearing bed.The present invention uses vermiculate glues to strengthen foam can obtain highly stable foam system, and it can block Thief zone reservoir, but will not block low permeability reservoir, thus is greatly improved the oil recovery factor of foam flooding system.
Description
Technical field
The invention belongs to field of oilfield chemistry, relate to a kind of novel vermiculate glues foam system and use
It improves the method for recovery ratio.Described method can increase substantially the recovery ratio of crude oil tertiary oil recovery.
Background technology
During the oil extraction of underground, in underground reservoir, generally pierce extraction well.Due to oil reservoir
Self-generated pressure, crude oil automatically via extraction well stream to earth's surface, this is referred to as primary oil recovery.But, by
Self-generated pressure in oil reservoir quickly reduces, and primary oil recovery is only capable of a small amount of crude oil of extraction.In this case,
Need to carry out secondary oil recovery, water is injected in underground reservoir via water injection well, makes in underground reservoir rock
Crude oil along water injection well to the direction of extraction well flow, thus extraction crude oil.But, primary oil recovery and
Secondary oil recovery is only capable of producing about the 40% of underground crude oil, and major part crude oil is trapped in underground and needs out
Adopt.Therefore, the tertiary oil recoveries such as oil recovery by heating, chemical flooding, gas drive improve the exploitation of recovery efficiency technique should
With imperative.
Gas drive is one of the most rapid tertiary oil recovery technology of development in recent years, alkane, carbon dioxide, nitrogen
Gas even air all can be as the displacing agent of gas drive.But low-density, low viscosity and the height due to gas
Mobility, compared with water drive, is affected by reservoir heterogeneity bigger, is very easy to occur fingering existing
As, it is impossible to involve hyposmosis region, make raising oil recovery factor effect be restricted.
By add surfactant, make gas with the form displacement of aerated fluid, by foam stream body surface
See the increase of viscosity and reduce the flowing velocity in high permeability zone, improve sweep efficiency, can improve former
Oil recovery.It is surfactant due to foaming agent itself again, there is interfacial activity, it is possible to decrease oil/
Water interfacial tension, significantly increases capillary number, can play more preferable effect, the most significantly carry
High oil recovery factor.
But, a large amount of indoor and field test carrying out foam flooding method shows, foam system is not
Stability hinders the successful popularization and application of foam flooding technology.Accordingly, it would be desirable to strengthen in foam flooding system
The stability of foam.
Have two kinds of methods can strengthen the stability of foam at present, 1) adding polymer forms strengthening foam；
2) add solid phase particles and form heterogeneous foam.
CN101314710A discloses a kind of foam profile agent, and it is by the functional polymer aqueous solution and sends out
Infusion is formulated after mixing, and in profile control agent, density of foaming agent is 0.05～1wt%.
CN1651545A discloses a kind of method improving oil deposil erude petroleum recovery ratio, and it is by polyacrylamide
The mixed solution of amine, foaming agent and water replaces or according to underground liquid with gas: gas=1:0.01-2 volume ratio
Mixing is injected in water injection well.
Zhang Xiansong etc., " Polymer Enhanced Foam Composited Flooding System experimental study ", petroleum gas
Journal (Jianghan Petroleum College's journal), the 2nd phase of volume 28, discloses a kind of polymer reinforced for 2006 4
Foam flooding system, it can effectively block oil reservoir macropore, improve interlayer injectivity profile, it is thus possible to relatively
Oil recovery factor is significantly increased.
Li Binfei etc., " test of heterogeneous foam system transfer drive ", China University Of Petroleum Beijing's journal (natural science
Version), the 4th phase of volume 34, a kind of heterogeneous foam system for tertiary oil recovery in 2010, it is by multiple
Join foam and polymer gel micro-sphere and formed.
Li Zhaomin etc., " heterogeneous foam system deep profile controlling experimental study ", oil-gas geology and recovery ratio,
Volume 19 l phase, disclosing a kind of novel deep electrical structure in January, 2012, it is by by gel micro-ball
Compound with foam compound system (heterogeneous foam system) and formed, its have gel micro-ball deep profile controlling and
The feature that foam blocking ability is strong.
The polymer enhanced foam system of prior art and the heterogeneous foam containing solid phase particles can strengthen
Foam stability, but, large-sized polymer or solid particle while closure Thief zone reservoir,
Also can block low permeability reservoir, make hyposmosis region cannot involve and cause reservoir injury, make foam flooding
The raising oil recovery factor effect of system is restricted.
Invention summary
The present inventor finds through studying for a long period of time unexpectedly first, strengthens when using vermiculate glues
During foam, highly stable foam system can not only be obtained, play the effect of closure Thief zone reservoir.
The more important thing is, worm-like micelle systems is to be only the little molecule of 1～2nm non-covalent by molecular dimension
The Molecular Organized Assemblies formed under key effect, has the advantages that quickly dissociate and recombinate, and this makes compacted
The high stable foam system that worm shape micella is formed can not only effectively block Thief zone reservoir, it is also possible to
By the nano-scale pore structure of low permeability reservoir, so reach expansion involve region and to reservoir without wound
Evil, thus it is substantially improved the raising oil recovery factor effect of foam flooding system.
Therefore, it is an object of the invention to overcome described prior art shortcoming, provide a kind of novel first
Vermiculate glues strengthen foam system and with its improve oil recovery factor method.
Detailed Description Of The Invention
The present invention provides the foam system that a kind of vermiculate glues strengthens first, and described system includes spy
Fixed vermiculate glues and gas.Present invention also offers and a kind of use described vermiculate glues to strengthen
Foam system improves the method for oil recovery factor, it is characterised in that: by described vermiculate glues and gas
Alternately inject in oil bearing bed with gas after foam maker bubbles or by vermiculate glues.
Vermiculate glues used in the inventive method can be that the applicant submitted on July 18th, 2013
Chinese patent application 201310300604.3 described in vermiculate glues, described system comprises alkyl
Sulfobetaines, alkylsurfuric acid natrium surfactant and optional auxiliary agent.
Described alkyl sulfo betaines is selected from cetyl sulfobetaines, octadecyl sulfobetaines
Or a combination thereof, described sodium alkyl sulfate is selected from ten sodium alkyl sulfates, lauryl sodium sulfate, the tetradecane
Base sodium sulphate or a combination thereof.
Described worm-like micelle systems also can comprise auxiliary agent.Suitably auxiliary agent is known in the field.
Specifically, described auxiliary agent can be selected from one of following or combination: polycyclic epoxide sodium succinate, poly-sky
Winter propylhomoserin sodium, 1-hydroxy ethylidene-1,1-diphosphonic acid four sodium, ATMP five sodium, ethylenediamine tetraacetic methene phosphine
Acid five sodium, diethylenetriamines five methylenephosphonic acid five sodium.Described auxiliary agent can shield bivalent metal ion Ca2+
And Mg2+, improve this worm-like micelle systems interface performance relevant to oil displacement efficiency and viscoelastic property and
Foaming properties.
Worm-like micelle systems used in the present invention can be in total salinity 5000-20000mg/L, wherein
Containing Ca2+And Mg2+Total concentration be 200-3500mg/L mineralized water in use.Vermiform system of the present invention
Having the salt tolerance of excellence, it can be at Ca2+And Mg2+Total concentration is up in the mineralized water of 3500mg/L
Use.
In preferred embodiments, the worm-like micelle systems of the present invention comprise alkyl sulfo betaines,
Alkylsurfuric acid natrium surfactant and auxiliary agent.
Sodium alkyl sulfate in worm-like micelle systems of the present invention accounts for sodium alkyl sulfate and alkyl sulfobetaines beet
The molar fraction of alkali integral molar quantity is 0.2-0.6, preferably 0.2-0.4, more preferably 0.2-0.3.
The consumption of auxiliary agent is 0.0-0.5 mass %, and preferably 0.15-0.35 mass %, based on described worm
The gross mass of shape micelle volume.Gas used in the inventive method is to known to the skilled artisan
, such as and be not limited to lower paraffin hydrocarbon (such as methane, ethane, propane etc.), carbon dioxide, nitrogen,
Air, flue gas, natural gas etc..
In the methods of the invention, by vermiculate glues and gas alternately or described vermiculate glues and gas
Inject in oil bearing bed after foam maker bubbles.At described vermiculate glues with gas at foam
In the case of injecting oil bearing bed after generator bubbles, described worm-like micelle systems and described gas
Volume ratio at the standard conditions can be 1:1-1:10, preferably 1:1-1:5.
The present invention uses vermiculate glues to strengthen foam can obtain highly stable foam system, and it can seal
Stifled Thief zone reservoir, but low permeability reservoir will not be blocked, thus it is substantially improved the raising of foam flooding system
Oil recovery factor effect.
In particular it relates to following technical scheme:
1. vermiculate glues strengthen a foam system, described system include vermiculate glues and for
The gas bubbled, described vermiculate glues comprises alkyl sulfo betaines, sodium alkyl sulfate surface-active
Agent.
2. according to 1 system, wherein said alkyl sulfo betaines selected from cetyl sulfobetaines,
Octadecyl sulfobetaines or a combination thereof.
3. according to 1 or 2 system, wherein said sodium alkyl sulfate be selected from ten sodium alkyl sulfates, dodecane
Base sodium sulphate, sodium tetradecyl sulfate or a combination thereof.
4., according to the system any one of 1-3, described vermiculate glues also comprises auxiliary agent.
System the most according to claim 4, wherein said auxiliary agent is selected from one of following or combination: poly-
Epoxy radicals sodium succinate, poly (sodium aspartate), 1-hydroxy ethylidene-1,1-diphosphonic acid four sodium, ATMP
Five sodium, ethylene diamine tetra methylene phosphonic acid five sodium, diethylenetriamines five methylenephosphonic acid five sodium.
6., according to the system any one of 1-5, wherein sodium alkyl sulfate accounts for sodium alkyl sulfate and alkyl sulfobetaines
The molar fraction of glycine betaine integral molar quantity is 0.2-0.6, preferably 0.2-0.4, more preferably 0.2-0.3.
7., according to the system any one of 1-6, wherein said gas is lower paraffin hydrocarbon, carbon dioxide, nitrogen
Gas, air, flue gas or natural gas or its mixture.
8. the foam system raising oil recovering that the vermiculate glues used any one of 1-7 strengthens
The method of rate, it is characterised in that: described vermiculate glues and gas are alternately injecting in oil bearing bed,
Or inject in oil bearing bed after described vermiculate glues and gas are bubbled in foam maker.
9. according to 8 method, wherein said vermiculate glues and described gas body at the standard conditions
Long-pending ratio can be 1:1-1:10, preferably 1:1-1:5.
Embodiment
It is more fully described the present invention below by embodiment, but these embodiments are never in any form
Limit the scope of the present invention.
Embodiment 1: the foam flooding that cetyl sulfobetaines/lauryl sodium sulfate vermiculate glues strengthens
Oil systems
1. the preparation of vermiculate glues: weigh 0.28g lauryl sodium sulfate and 1.18g cetyl sulphur
(wherein lauryl sodium sulfate accounts for lauryl sodium sulfate and cetyl sulfobetaines to base glycine betaine
The molar fraction of integral molar quantity is 0.25) in 500ml beaker and add different amounts of total salinity and be
8951mg·L-1, wherein Ca2+Concentration is 200mg L-1, Mg2+Concentration is 100mg L-1Mineralized water.
At 35 DEG C, Germany's IKA-WATERKE mixer is utilized to stir 10 minutes under 200 revs/min to molten
Liquid mixes, and places 60 minutes.
2. vermiculate glues foam system foaming capacity and foam stability experiment
Prepared vermiculate glues solution 100ml uses paddling process the lower stirring 3 points of 7000 revs/min
Clock, is poured into rapidly in graduated cylinder and reads record foaming volume；Separate out with stopwatch record the most again
Time needed for 50ml liquid.
Table 1 below shows under variable concentrations, cetyl sulfobetaines/lauryl sodium sulfate mixing
The viscosity (η) of system and half foam life period, wherein test temperature is 60 DEG C, and lauryl sodium sulfate accounts for ten
The molar fraction of sodium dialkyl sulfate and cetyl sulfobetaines integral molar quantity is 0.25.Wherein table
Face activating agent mass fraction gross weight based on this system.As can be seen from Table 1, for this system when
When surfactant total mass fraction is higher than 0.22%, the viscosity of this system is higher than the viscosity of water, this table
Phaneroplasm system defines vermiculate glues；The foam stability forming worm-like micelle systems is significantly high
In conventional surfactants solution.When surfactant qualities mark is 0.73%, partly declining of foam
Phase is 3600 seconds.
| Surfactant qualities mark/% | Viscosity/mpa.s | Foaming volume/ml | Half foam life period/s |
| 0.07 | 0.56 | 380 | 272 |
| 0.15 | 1.15 | 360 | 410 |
| 0.22 | 2.01 | 350 | 683 |
| 0.30 | 4.61 | 330 | 1187 |
| 0.37 | 10.2 | 280 | 1620 |
| 0.55 | 52.8 | 240 | 3340 |
| 0.73 | 148.7 | 190 | 3600 |
3. laboratory simulation flooding experiment
(1) prepared by vermiculate glues foam system: above-mentioned cetyl sulfobetaines/dodecyl sulphur
Acid sodium, wherein total surfactant concentration is 0.73%, and the molar fraction of lauryl sodium sulfate is 0.25；
Foaming gas is air；Control gas liquid ratio is 1:1, bubbles in foam maker.
Jinzhou You Qu oil density 0.935g.cm-3, viscosity 82mPa.s (50 DEG C)；
Formula is 6s 60 DEG C of down cut speed-1Time viscosity 144.7mPa.s, mix with Jinzhou You Qu crude oil
After interfacial tension 2.0 × 10-2mN·m-1(60℃)；
(2) oil displacement efficiency experiment
Displacement of reservoir oil simulation fill out sand tube is prepared and master data (experimental temperature is 60 DEG C):
Sandpack column is Φ 25mm × 500mm, and it is 1169mD that water surveys permeability；
At 60 DEG C, it is simulated oil displacement experiment, first salt solution is driven to Produced Liquid moisture content 98%, then
Reinject the vermiculate glues foam flooding fluid of 1.2PV, change salt solution after having noted into and be driven to pressure reduction stably, send out
Referring now to the fill out sand tube of 1169mD, vermiculate glues foam flooding system can on the basis of water drive further
Improve oil recovery factor and reach 38.8%.
As can be seen here, the vermiculate glues foam system of the present invention is greatly improved oil recovery factor.
Comparative example 1
The total salinity is utilized to be according to the method described in Chinese patent application 201310300604.3
8951mg·L-1, wherein Ca2+Concentration is 200mg L-1, Mg2+Concentration is 100mg L-1Mineralising
The cetyl that molar fraction is 0.25 of water preparation worm-like micelle systems, i.e. lauryl sodium sulfate
Sulfobetaines/lauryl sodium sulfate system, finds at total surfactant concentration to be 0.73% time,
When sandpack column permeability is 1169mD, it is 23.2% that vermiculate glues drives raising recovery ratio.
By above-mentioned comparative example it can be seen that the vermiculate glues foam flooding system of the present invention is in phase
Carrying than the worm-like micelle systems described in Chinese patent application 201310300604.3 under conditions of Tong
High recovery rate effect exceeds 15.6%.
Embodiment 2
According to the program of embodiment 1, preparing vermiculate glues foam flooding system, difference is to make
By octadecyl sulfobetaines/lauryl sodium sulfate as raw material.
Research on the fill out sand tube of 988mD shows, this vermiculate glues foam flooding system can be at water
Improve oil recovery factor on the basis of driving further and reach 39.1%.
Embodiment 3
According to the program of embodiment 1, preparing vermiculate glues foam flooding system, difference is to make
With cetyl sulfobetaines/ten sodium alkyl sulfate as raw material.
Research on the fill out sand tube of 1260mD shows, this vermiculate glues foam flooding system can be at water
Improve oil recovery factor on the basis of driving further and reach 40.5%.
Embodiment 4
According to the program of embodiment 1, preparing vermiculate glues foam flooding system, difference is to make
With octadecyl sulfobetaines/ten sodium alkyl sulfate as raw material.
Research on the fill out sand tube of 895mD shows, this vermiculate glues foam flooding system can be at water
Improve oil recovery factor on the basis of driving further and reach 38.6%.
The present invention uses vermiculate glues to strengthen foam can obtain highly stable foam system, and it can seal
Stifled Thief zone reservoir, but low permeability reservoir will not be blocked, thus it is substantially improved the raising of foam flooding system
Oil recovery factor effect.
Claims (7)
1. vermiculate glues strengthen a foam system, described system comprise vermiculate glues and for
The gas bubbled, described vermiculate glues comprises alkyl sulfo betaines, sodium alkyl sulfate surface-active
Agent；Wherein said alkyl sulfo betaines is sweet selected from cetyl sulfobetaines, octadecyl sulfo group
Dish alkali or a combination thereof；Described sodium alkyl sulfate selected from ten sodium alkyl sulfates, lauryl sodium sulfate, ten
Tetraalkyl sodium sulphate or a combination thereof；Sodium alkyl sulfate accounts for sodium alkyl sulfate and alkyl sulfo betaines always rubs
Your molar fraction of amount is 0.2-0.6；Described vermiculate glues also comprises selected from one of following or combination
Auxiliary agent: polycyclic epoxide sodium succinate, poly (sodium aspartate), 1-hydroxy ethylidene-1,1-diphosphonic acid four sodium, amino
Three methylenephosphonic acid five sodium, ethylene diamine tetra methylene phosphonic acid five sodium, diethylenetriamines five methylenephosphonic acid five sodium.
System the most according to claim 1, wherein sodium alkyl sulfate accounts for sodium alkyl sulfate and alkyl sulfobetaines
The molar fraction of glycine betaine integral molar quantity is 0.2-0.4.
System the most according to claim 1, wherein sodium alkyl sulfate accounts for sodium alkyl sulfate and alkyl sulfobetaines
The molar fraction of glycine betaine integral molar quantity is 0.2-0.3.
System the most as claimed in one of claims 1-3, wherein said gas is lower paraffin hydrocarbon, dioxy
Change carbon, nitrogen, air, flue gas or natural gas or its mixture.
5. one kind uses the foam system that vermiculate glues as claimed in one of claims 1-4 strengthens
The method improving oil recovery factor, it is characterised in that: described vermiculate glues is alternately noted with gas
Enter in oil bearing bed, or injection after described vermiculate glues and gas are bubbled in foam maker
In oil bearing bed.
Method the most according to claim 5, wherein said vermiculate glues and described gas are at standard bar
Volume ratio under part is 1:1-1:10.
Method the most according to claim 5, wherein said vermiculate glues and described gas are at standard bar
Volume ratio under part is 1:1-1:5.
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| CN105134146A (en) * | 2015-07-07 | 2015-12-09 | 西北大学 | Method for oil displacement using carbon dioxide and foam |
| CN110157403B (en) * | 2019-05-08 | 2020-09-29 | 中国石油大学(北京) | Low-permeability oil reservoir oil displacement agent |
| CN110699057A (en) * | 2019-09-27 | 2020-01-17 | 中国石油化工股份有限公司 | Temperature-resistant high-strength foam system with synergistic lamellar nano-particles and preparation method thereof |
| CN112080269B (en) * | 2020-10-13 | 2021-06-25 | 中国石油大学(北京) | Micro-bubble fracturing fluid, preparation method and application |
| CN113136192A (en) * | 2021-04-06 | 2021-07-20 | 西安石油大油气科技有限公司 | Low-corrosivity foaming agent for air foam flooding for oil exploitation and preparation method thereof |
| CN113150762B (en) * | 2021-04-21 | 2023-11-14 | 中国石油大学(华东) | Supermolecule oil displacement system with viscoelasticity and ultralow interfacial tension and application thereof |
| CN113292982B (en) * | 2021-06-02 | 2023-02-17 | 中国石油大学(华东) | Viscoelastic surfactant foam system and preparation method and application thereof |
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| CN102020981B (en) * | 2010-10-27 | 2013-01-02 | 山东大学 | Temperature-resistant, salt-resistant and low-tension foam flooding agent and preparation method thereof |
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| CN102312666A (en) * | 2010-07-06 | 2012-01-11 | 中国石油天然气股份有限公司 | Method for improving oil-water displacement recovery ratio of low-permeable oil reservoir |
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