CN106967406A - A kind of oil displacement system and flooding method for heterogeneous reservoir - Google Patents
A kind of oil displacement system and flooding method for heterogeneous reservoir Download PDFInfo
- Publication number
- CN106967406A CN106967406A CN201710193004.XA CN201710193004A CN106967406A CN 106967406 A CN106967406 A CN 106967406A CN 201710193004 A CN201710193004 A CN 201710193004A CN 106967406 A CN106967406 A CN 106967406A
- Authority
- CN
- China
- Prior art keywords
- oil displacement
- displacement system
- oil
- polymer
- surfactant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
- C09K8/584—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
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
Abstract
Include association polymer the invention provides a kind of oil displacement system for heterogeneous reservoir；The molecular weight of the association polymer is 103.6~4021.5 ten thousand；In mole percent, the association polymer is polymerize with 0~15.4% function monomer by acrylamide, 0.11%~9.96% hydrophobic monomer and obtained；The concentration of association polymer is 400~3500mg/L in the oil displacement system.Compared with prior art, the present invention uses and the association polymer that a small amount of hydrophobic monomer and function monomer are obtained is introduced on polymer molecule backbone, hydrophobic grouping is mutually associated with spacial framework in aqueous, improve system viscosity, set up high resistant force coefficient and high residual resistance factor, Relative High Permeability region permeability is effectively reduced, with preferable profile control effect；Function monomer is introduced and spacial framework, so that system has good heat and salinity tolerance anti-shearing and ageing stability, having to heterogeneous reservoir preferably improves oil and water mobility ratio effect, improves injection water sweep efficiency, so as to preferably improve heterogeneous reservoir recovery ratio.
Description
Technical field
The invention belongs to technical field of petroleum extraction, more particularly to a kind of oil displacement system and the displacement of reservoir oil for heterogeneous reservoir
Method.
Background technology
With sharply increasing for energy demand, heterogeneous reservoir proportion is more and more, cause domestic and foreign scholars and
The great attention of oil company.Reservoir heterogeneity refers to reservoir under the influence of environment and active force, in spatial distribution and interior
There is uneven change on portion's reservoir physical, it has a significant impact to petrol-gas permeation fluid and recovery ratio.Reservoir
Property be broadly divided into plain heterogeneity, in reservoir layer and heterogeneity, in plane, water is injected during waterflooding extraction along high permeability zone
Fingering, causes high permeability zone washing degree at a relatively high, and hyposmosis band sweep efficiency is smaller, and water filling is produced effects poor, causes residue
Oily skewness in the plane；In reservoir layer and interlayer, each region water logging degree difference is larger, Thief zone position percolation flow velocity
Comparatively fast, water flooding degree is higher, and hyposmosis position percolation flow velocity is slower, and water flooding degree is relatively low, and remaining oil is relative to be enriched with；It is strong heterogeneous
Reservoir high hypotonic complex distribution, particularly thorny between longitudinal direction, plane and different reservoir, when causing waterflooding extraction, injection water is easy
Advanced by leaps and bounds along high permeability zone and crack, withdrawal well water breakthrough is early, has had a strong impact on heterogeneous reservoir waterflooding development effect, has needed new carry badly
High recovery rate method.
For heterogeneous reservoir, the polymer flooding in chemical flooding is obtained with its excellent performance as a kind of important method
Extensive concern is arrived.Because polymer can increase displacement fluid viscosity, improvement mobility ratio, the high vadose zone formed is blocked
Or crack, expand water drive swept volume, reduction Relative High Permeability region permeability adjusts inhomogeneous formation water injection profile, employs low
Infiltration layer, is finally reached the purpose for improving recovery ratio, with suitable application potential.Meanwhile, the surfactant flooding in chemical flooding
And caustic waterflooding can play a part of effectively reducing oil water interfacial tension, itself and polymer flooding are compounded to be formed poly-/table binary,
Poly-/table/alkali ternary system.Surfactant can be given full play to and alkali reduction interfacial tension improves displacement efficiency and polymer changes
The performance advantage of kind intake profile, reduces cost, also of great interest.It is the emphasis studied at present.
In the practical application of polymer flooding, for heterogeneous reservoir, natural polymer by season and territorial restrictions and
Cost is higher, and heat endurance and biological stability are relatively poor, easily degrades, thus the application in high temperature and high salt oil deposit by
To limitation；Although most widely used polyacrylamide can improve solution viscosity to a certain extent in synthesis macromolecule,
But it is easy in work progress because Strong shear effect makes molecule long-chain occur mechanical degradation；It is vulnerable to ground environment (temperature
Degree, salinity etc.) influence, there is problems with：1) when being applied under the conditions of high temperature and high salinity, polyacrylamide when temperature is higher
The hydrolysis of amine is serious；2) after formation temperature is more than 75 DEG C, as formation temperature is raised, hydrolyzed polyacrylamide, which precipitates to be formed, to be added
It hurry up；3) high temperature and high salt is easily caused hydrolyzed polyacrylamide and is precipitated out from the aqueous solution, and the more high this phenomenon of degree of hydrolysis is more
Significantly；4) solution viscosity is very sensitive to temperature and salinity, and the reservation viscosity of solution is very low in high temperature and high salt environment.So it is poly-
Acrylamide is applied under slightly harsh reservoir condition and is extremely restricted.Importantly, being influenceed by reservoir condition, heterogeneous reservoir
Being generally used for the polymer of the displacement of reservoir oil should meet under low concentration with viscosity higher, can set up higher resistance coefficient and remnants
Resistance coefficient, and polymer molecular weight and molecular coil chi can be carried out according to reservoir high hypotonic size and permeability extreme difference situation
Very little regulation etc. is required.Polyacrylamide will obtain viscosity higher, it is necessary to increase polymer concentration and molecular weight, and cost significantly increases
Plus；Due to determining that its molecular coil dimension adjustable parameter is more single, with heterogeneous reservoir permeability and permeability extreme difference
Poor with property, the resistance coefficient of foundation, residual resistance factor is smaller, it is impossible to preferably reduces Relative High Permeability region permeability, adjusts
Whole inhomogeneous formation water injection profile, expands swept volume and closure water drive alters the effect of stand in channel.Add surfactant and alkali
When being configured to binary (ternary) system, polyacrylamide and most surfactant, alkali act on its viscosity and elasticity all can
Different degrees of reduction, and then reduce fluidity control ability (generation negative coopertive effect).For problem above, plain polypropylene acyl
Amine can only adjust molecular weight and degree of hydrolysis and adjustable range is limited due to it, be difficult on the basis of its existing molecular structure
Further overcome, it is thus impossible to meet the Efficient Development demand in heterogeneous oil field.
The content of the invention
In view of this, the technical problem to be solved in the present invention be to provide a kind of oil displacement system for heterogeneous reservoir and
Flooding method, the oil displacement system consumption is small, superior performance, can set up real high resistant force coefficient and high residual resistance factor,
And heterogeneous reservoir water drive and poly- drive recovery ratio can be increased substantially.
The invention provides a kind of oil displacement system for heterogeneous reservoir, including association polymer；The associtation polymer
The molecular weight of thing is 103.6~4021.5 ten thousand；In mole percent, the association polymer by acrylamide, 0.11%~
9.96% hydrophobic monomer polymerize with 0~15.4% function monomer to be obtained；The concentration of association polymer in the oil displacement system
For 400~3500mg/L；
The hydrophobic monomer is selected from N- alkyl-substituted acrylamides and its derivative, alkyl acrylate, methacrylic acid
Arrcostab, the alkyl acrylate of fluorine substitution, alkyl methacrylate, allyl alkyl quaternary ammonium salt, the acryloyl of fluorine substitution
Amine alkyl sulfonic acid and its sulfonate, alkylphenol-polyethenoxy acrylate and one kind or many in acrylic acid polyxyethylated ester
Kind；
The function monomer is selected from sulfonic acid and its sulfonate derivatives containing end alkenyl with containing end alkenyl
One or more in Hete rocyclic derivatives.
It is preferred that, the N- alkyl-substituted acrylamides and its derivative, alkyl acrylate, methacrylate
Ester, allyl alkyl quaternary ammonium salt, acrylic acid alkyl sulfonic acid and its sulfonate, alkylphenol-polyethenoxy acrylate, acrylic acid gather
The carbon number of alkyl is each in the alkyl methacrylate of oxygen vinyl alkyl ester, the alkyl acrylate of fluorine substitution and fluorine substitution
From independently being 4~40.
It is preferred that, the function monomer is selected from 2- acrylamide-2-methylpro panesulfonic acids and its sulfonate, vinyl sulfonic acid
And its one or more in sulfonate, styrene sulfonic acid and its sulfonate and NVP.
It is preferred that, in addition to surfactant；The quality of the surfactant is the 0.001% of associtation polymer amount of substance
~0.76%.
It is preferred that, the surfactant is petroleum sulfonate analog anion surfactants, alkyl benzene sulfonate the moon
Ionic surface active agent, alpha-alkene sulfonate anionoid surfactant, betaines both sexes surfactant, alkanolamide class nonionic
Surfactant, non-ionic gemini surface active agent, anionic gemini surfactant, alkylnaphthalene sulfonate, lignin sulfonic acid
One or more in salt, vegetable oil carboxylate, petroleum carboxylate, biological species surfactant and complexed surfactant.
It is preferred that, in addition to alkaline matter；The quality of the alkaline matter for associtation polymer amount of substance 0.09%~
2.1%.
It is preferred that, the alkaline matter is NaOH, Na2CO3With the one or more in amine organic base.
It is preferred that, the permeability extreme difference of the heterogeneous reservoir is 1.1~30.7.
Present invention also offers a kind of flooding method of heterogeneous reservoir, using the above-mentioned displacement of reservoir oil body for heterogeneous reservoir
System carries out the displacement of reservoir oil.
Compared with prior art, associtation polymer is included the invention provides a kind of oil displacement system for heterogeneous reservoir
Thing；The molecular weight of the association polymer is 103.6~4021.5 ten thousand；In mole percent, the association polymer is by third
Acrylamide, 0.11%~9.96% hydrophobic monomer polymerize with 0~15.4% function monomer to be obtained；Formed in the oil displacement system
The concentration for closing polymer is 400~3500mg/L；The hydrophobic monomer is selected from N- alkyl-substituted acrylamides and its derivative, third
Olefin(e) acid Arrcostab, alkyl methacrylate, the alkyl acrylate of fluorine substitution, alkyl methacrylate, the alkene of fluorine substitution
Propyl alkyl quaternary ammonium salt, acrylamide alkyl sulfonic acid and its sulfonate, alkylphenol-polyethenoxy acrylate and acrylic acid polyoxy
One or more in vinyl alkyl ester；The function monomer is selected from sulfonic acid and its sulfonate containing end alkenyl and derived
Thing and the one or more in the Hete rocyclic derivatives containing end alkenyl.Compared with prior art, the present invention is using in polymer point
Association polymer that a small amount of hydrophobic grouping and function monomer obtain is introduced on son as oil displacement system, is drawn on polymer molecular chain
Enter the association polymer that a small amount of hydrophobic monomer and function monomer are obtained, with the introducing of hydrophobic grouping, these macromoleculars are interior or divide
Hydrophobic grouping between son is mutually associated due to hydrophobic effect in aqueous, forms reversible three dimensions dynamic physical cross-linked network
Network, so that can have higher viscosity and elasticity in low concentration, it is significantly cost-effective, due to the introducing of hydrophobic monomer, drive
High resistant force coefficient and high residual resistance factor can be set up when oily, heterogeneous reservoir improves waterflood recovery efficiency factor, increases residual resistive
Coefficient contribution rate is more than increase resistance coefficient, and high residual resistance factor advantageously reduces high permeability zone permeability, adjusts heterogeneous
Stratum water injection profile, closure water drive alters the effect of stand in channel, and with preferable " transfer drive " effect, improvement is subsequently implanted into ripples and effect
Rate；This reversible construction has strong
The characteristic recovered is broken and be able to when shear action reduces or disappears under shear action, solves conventional polymeric
The problem of thing is acted on irreversible loss viscosity by Strong shear；Function monomer is introduced and association spacial framework intensity is with molten
Liquid polarity increases and increased so that system has good heat and salinity tolerance anti-shearing and ageing stability, has to heterogeneous reservoir
Preferably improve oil and water mobility ratio effect, molecular coil size can be changed by content of hydrophobic monomers, species and the change of molecular weight,
So as to match with heterogeneous reservoir permeability and permeability extreme difference, it is ensured that injection, oil displacement efficiency is improved；Due to three in solution
The presence of dimension space dynamic physical cross-linked network, system elasticity is significantly raised, and polymer microscopic oil displacement efficiency is improved, so as to more
Recovery ratio after the water drive of good raising heterogeneous reservoir；When addition surfactant and alkali are configured to binary (ternary) system,
While ensureing association polymer advantage, the performances such as system viscosity and elasticity (generation positive coopertive effect) can be increased substantially,
And the surfactant and alkali added can increase substantially system displacement efficiency, so that in the heterogeneous reservoir condition of High water cut
Under can increase substantially water drive and poly- drive recovery ratio.
Test result indicates that, provided by the present invention for heterogeneous reservoir solution concentration between 400~3500mg/L it
Between, 3.1~1696.7mPa.s of viscosity, mechanical shearing viscosity retention ratio is 61.43%~99.13%, and aged viscosity retains within 90 days
Rate is 60.90%~98.58%, and recovery ratio degree is 12.13%~32.85% during moisture content 98%, improves recovery ratio degree
For 15.25%~39.24%.
Embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, all
Belong to the scope of protection of the invention.
The present invention provides a kind of oil displacement system for heterogeneous reservoir, including association polymer；The association polymer
Molecular weight be 103.6~4021.5 ten thousand；In mole percent, the association polymer by acrylamide, 0.11%~
9.96% hydrophobic monomer polymerize with 0~15.4% function monomer to be obtained；The concentration of association polymer in the oil displacement system
For 400~3500mg/L；The hydrophobic monomer is selected from N- alkyl-substituted acrylamides and its derivative, alkyl acrylate, first
Base alkyl acrylate, the alkyl acrylate of fluorine substitution, alkyl methacrylate, the allyl alkyl quaternary ammonium of fluorine substitution
In salt, acrylamide alkyl sulfonic acid and its sulfonate, alkylphenol-polyethenoxy acrylate and acrylic acid polyxyethylated ester
One or more；The function monomer is selected from sulfonic acid and its sulfonate derivatives containing end alkenyl with containing end alkene
One or more in the Hete rocyclic derivatives of base.
In some embodiments that the present invention is provided, the molecular weight of the association polymer is preferably 103.6 ten thousand；In this hair
In some embodiments of bright offer, the molecular weight of the association polymer is preferably 201.5 ten thousand；Some realities provided in the present invention
Apply in example, the molecular weight of the association polymer is preferably 603.8 ten thousand；It is described to form in some embodiments that the present invention is provided
The molecular weight for closing polymer is preferably 587.4 ten thousand；In some embodiments that the present invention is provided, the molecule of the association polymer
Amount is preferably 15,330,000；In some embodiments that the present invention is provided, the molecular weight of the association polymer is preferably 39,880,000；
In other embodiments that the present invention is provided, the molecular weight of the association polymer is preferably 4002.8 ten thousand.
In some embodiments that the present invention is provided, the content of the hydrophobic monomer is preferably 0.12%；Carried in the present invention
In some embodiments supplied, the content of the hydrophobic monomer is preferably 3.2%；In some embodiments that the present invention is provided, institute
The content for stating hydrophobic monomer is preferably 0.89%；In some embodiments that the present invention is provided, the content of the hydrophobic monomer is excellent
Elect 6.24% as；In some embodiments that the present invention is provided, the content of the hydrophobic monomer is preferably 4.63%；In the present invention
In other embodiments provided, the content of the hydrophobic monomer is preferably 9.96%.
The hydrophobic monomer is selected from N- alkyl-substituted acrylamides and its derivative, alkyl acrylate, methacrylic acid
Arrcostab, the alkyl acrylate of fluorine substitution, alkyl methacrylate, allyl alkyl quaternary ammonium salt, the acryloyl of fluorine substitution
Amine alkyl sulfonic acid and its sulfonate, alkylphenol-polyethenoxy acrylate and one kind or many in acrylic acid polyxyethylated ester
Kind；Wherein, the N- alkyl-substituted acrylamides and its derivative, alkyl acrylate, alkyl methacrylate, pi-allyl
Alkyl quaternary ammonium salts, acrylic acid alkyl sulfonic acid and its sulfonate, alkylphenol-polyethenoxy acrylate, acrylic acid are polyxyethylated
Alkyl methacrylate, allyl alkyl quaternary ammonium salt, the acrylamide alkane of ester, the alkyl acrylate of fluorine substitution and fluorine substitution
The carbon number of alkyl in base sulfonic acid and its sulfonate, alkylphenol-polyethenoxy acrylate or acrylic acid polyxyethylated ester
4~40, more preferably 4~30 are each independently, is further preferably 6~20.
The N- alkyl-substituted acrylamides derivative preferably comprises the derivative of benzene ring structure；The alkyl phenol polyoxy second
Alkene acrylate is preferably 7~20 independently of one another with the polyoxyethylated degree of polymerization in acrylic acid polyxyethylated ester, more excellent
Elect 7~16 as；The number of fluorine atom is each in the alkyl methacrylate that the alkyl acrylate of the fluorine substitution replaces with fluorine
From independently be preferably 4~10, more preferably 6~8, most preferably 2- (N- ethylperfluoros sulfanilic acid) EMAs or
2- (N- ethylperfluoros octane) butyl methacrylate；Heretofore described hydrophobic monomer is most preferably dodecyl acrylate, third
Olefin(e) acid hexadecyl ester, octadecyl acrylate, lauryl methacrylate, hexadecyl metrhacrylate, octadecyl methacrylate, N-
Dodecylacrylamide, N- cetyls acrylamide, N- phenethyl acrylamides, 2- acrylamido -2- methyl 20
Five sodium alkyl sulfonates, N- octyl groups propionamide, 2- acrylamido -2- methyl docosyls sodium sulfonate, N- myristyl propylene
Acid amides, N, N- dioctyl acrylamides, Hexafluorobutyl mathacrylate, cetyl pi-allyl dibrominated tetramethylethylenediamine,
2- acrylamido tetradecanes sodium sulfonate, 2- acrylamido -2- methyl dodecane sulfonic acids sodium, Nonyl pheno acrylic acid
Ester, dodecyl polyoxyethylene acrylate, octadecyl pi-allyl dibrominated tetramethylethylenediamine, cetyl polyoxyethylene
Acrylate, N- cetyls acrylamide, N- octyl acrylamides, the ammonium of sodium dodecyl allyl base dibrominated tetramethyl fourth two,
Myristyl pi-allyl dichloride tetramethyl butane diamine and one in (4- acrylamidos) phenyl normal-butyl ditallowdimethyl ammonium bromide
Plant or a variety of.
In mole percent, the content of function monomer is preferably 2%~15% in the association polymer, more preferably
2.47%~14.79%；In some embodiments that the present invention is provided, the content of the function monomer is preferably 0%；In this hair
In some embodiments of bright offer, the content of the function monomer is preferably 15.4%；Some embodiments provided in the present invention
In, the content of the function monomer is preferably 14.6%；In some embodiments for providing of the present invention, the function monomer contains
Amount is preferably 2.47%；In some embodiments that the present invention is provided, the content of the function monomer is preferably 5.76%；At this
Invent in some embodiments provided, the content of the function monomer is preferably 6.11%；Some implementations provided in the present invention
In example, the content of the function monomer is preferably 14.72%；In other embodiments that the present invention is provided, the function list
The content of body is preferably 8.83%.
The function monomer is selected from sulfonic acid and its sulfonate derivatives containing end alkenyl with containing end alkenyl
One or more in Hete rocyclic derivatives；The carbon number of the function monomer is preferably 2~20, and more preferably 2~15, then it is excellent
Elect 2~10 as；In the present invention, the function monomer is most preferably 2- acrylamide-2-methylpro panesulfonic acids and its sulfonate, second
One or more in olefin sulfonic acid and its sulfonate, styrene sulfonic acid and its sulfonate and NVP.
Provided by the present invention for the oil displacement system of heterogeneous reservoir；The heterogeneous reservoir is that those skilled in the art are ripe
The heterogeneous reservoir known, has no special limitation, the permeability extreme difference of heretofore described heterogeneous reservoir is preferably 1.1
~30.7.
The oil displacement system includes association polymer, in the oil displacement system concentration of association polymer for 400~
3500mg/L；In some embodiments that the present invention is provided, the concentration of association polymer is preferably in the oil displacement system
400mg/L；In some embodiments that the present invention is provided, the concentration of association polymer is preferably in the oil displacement system
1000mg/L；In some embodiments that the present invention is provided, the concentration of association polymer is preferably in the oil displacement system
1800mg/L；In some embodiments that the present invention is provided, the concentration of association polymer is preferably in the oil displacement system
2200mg/L；In some embodiments that the present invention is provided, the concentration of association polymer is preferably in the oil displacement system
3000mg/L；In some embodiments that the present invention is provided, the concentration of association polymer is preferably in the oil displacement system
3200mg/L；In some embodiments that the present invention is provided, the concentration of association polymer is preferably in the oil displacement system
2600mg/L；In some embodiments that the present invention is provided, the concentration of association polymer is preferably in the oil displacement system
1600mg/L；In some embodiments that the present invention is provided, the concentration of association polymer is preferably in the oil displacement system
1350mg/L；In some embodiments that the present invention is provided, the concentration of association polymer is preferably in the oil displacement system
2500mg/L；In some embodiments that the present invention is provided, the concentration of association polymer is preferably in the oil displacement system
1500mg/L；In some embodiments that the present invention is provided, the concentration of association polymer is preferably in the oil displacement system
1750mg/L；In other embodiments that the present invention is provided, the concentration of association polymer is preferably in the oil displacement system
2000mg/L。
The present invention uses and the association polymer work that a small amount of hydrophobic grouping and function monomer are obtained is introduced on polymer molecule
For oil displacement system, the association polymer that a small amount of hydrophobic monomer and function monomer are obtained is introduced on polymer molecular chain, with thin
The introducing of water base group, in these macromoleculars or intermolecular hydrophobic grouping is mutually associated due to hydrophobic effect in aqueous,
Reversible three dimensions dynamic physical cross-linked network is formed, so as to can have higher viscosity and elasticity in low concentration, significantly
It is cost-effective, high resistant force coefficient and high residual resistance factor, heterogeneous oil can be set up due to the introducing of hydrophobic monomer, during the displacement of reservoir oil
Hide and improve waterflood recovery efficiency factor, increase residual resistance factor contribution rate is more than increase resistance coefficient, high residual resistance factor is conducive to
High permeability zone permeability is reduced, inhomogeneous formation water injection profile is adjusted, closure water drive alters the effect of stand in channel, with preferable
" transfer drive " effect, improvement is subsequently implanted into water sweep efficiency；This reversible construction, which has, is broken and is worked as under intensive shear effect
Shear action reduces or is able to when disappearing the characteristic recovered, and solves traditional polymer viscous by the irreversible loss of Strong shear effect
The problem of spending；Function monomer is introduced and association spacial framework intensity increases as solution polarity increases so that system has
There is good heat and salinity tolerance anti-shearing and ageing stability, having to heterogeneous reservoir preferably improves oil and water mobility ratio effect, can
Molecular coil size is changed by content of hydrophobic monomers, species and the change of molecular weight, so that with heterogeneous reservoir permeability and oozing
Saturating rate extreme difference matches, it is ensured that injection, improves oil displacement efficiency；Because three dimensions dynamic physical cross-linked network is deposited in solution
Significantly is raised in, system elasticity, improve polymer microscopic oil displacement efficiency, after the water drive so as to preferably improve heterogeneous reservoir
Recovery ratio；When addition surfactant and alkali are configured to binary (ternary) system, while association polymer advantage is ensured, energy
The performances such as system viscosity and elasticity (generation positive coopertive effect) are enough increased substantially, and the surfactant and alkali that add can be big
Amplitude improves system displacement efficiency, so as to can increase substantially water drive under the conditions of the heterogeneous reservoir of High water cut and poly- drive is adopted
Yield.
The oil displacement system that the present invention is provided preferably also includes surfactant, and the quality of the surfactant is poly- for association
The 0.001%~0.76% of compound quality；In some embodiments that the present invention is provided, the surfactant is preferably association
The 0.05% of polymer quality；In some embodiments that the present invention is provided, the surfactant is preferably association polymer
The 0.12% of quality；In some embodiments that the present invention is provided, the surfactant is preferably associtation polymer amount of substance
0.69%；In some embodiments that the present invention is provided, the surfactant is preferably associtation polymer amount of substance
0.011%；In some embodiments that the present invention is provided, the surfactant is preferably associtation polymer amount of substance
0.096%；In some embodiments that the present invention is provided, the surfactant is preferably associtation polymer amount of substance
0.001%；In some embodiments that the present invention is provided, the surfactant is preferably associtation polymer amount of substance
0.69%；In some embodiments that the present invention is provided, the surfactant is preferably the 0.15% of associtation polymer amount of substance；
In some embodiments that the present invention is provided, the surfactant is preferably the 0.0098% of associtation polymer amount of substance；At this
Invent in other embodiments provided, the surfactant is preferably the 0.73% of associtation polymer amount of substance.
The surfactant is surfactant well known to those skilled in the art, has no special limitation, this
It is preferably petroleum sulfonate analog anion surfactants, alkyl benzene sulfonate anion surfactant, α-alkene in invention
Sulfonated hydrocarbon anionoid surfactant, betaines both sexes surfactant, alkanolamide class non-ionic surfactant, non-ionic Shuangzi
Surfactant, anionic gemini surfactant, alkylnaphthalene sulfonate, lignosulfonates, vegetable oil carboxylate, oil
One or more in carboxylate, biological species surfactant and complexed surfactant.
The oil displacement system that the present invention is provided preferably also includes alkaline matter, and the quality of the alkaline matter is association polymer
The 0.09%~2.1% of quality.Now, oil displacement system is ASP ternary composite drivings, its main mechanism of oil displacement be alkali with crude oil
Acidic components act on in-situ generation soaps, are acted synergistically with the surfactant of addition, produce ultralow interfacial tension；Surface-active
The mineral generation ion exchange of alkali, alkali and rock surface is added in agent/polymeric system, becomes rock surface mineral composition
Change, improve rock particles surface electrical behavior, reduce the higher surfactant of price and polymer adsorbing on a rock surface, stagnant
Loss is stayed, dosage of surfactant needed for can making combination flooding is substantially reduced, cost-effective.
In some embodiments that the present invention is provided, the quality of the alkaline matter is preferably association polymer quality
0.09%；In some embodiments that the present invention is provided, the quality of the alkaline matter is preferably association polymer quality
0.27%；In some embodiments that the present invention is provided, the quality of the alkaline matter is preferably association polymer quality
0.83%；In some embodiments that the present invention is provided, the quality of the alkaline matter is preferably association polymer quality
2.1%；In some embodiments that the present invention is provided, the quality of the alkaline matter is preferably association polymer quality
0.85%；In some embodiments that the present invention is provided, the quality of the alkaline matter is preferably association polymer quality
0.12%；In some embodiments that the present invention is provided, the quality of the alkaline matter is preferably association polymer quality
0.35%；In some embodiments that the present invention is provided, the quality of the alkaline matter is preferably association polymer quality
0.18%；In some embodiments that the present invention is provided, the quality of the alkaline matter is preferably association polymer quality
0.89%；In some embodiments that the present invention is provided, the quality of the alkaline matter is preferably association polymer quality
0.35%；In some embodiments that the present invention is provided, the quality of the alkaline matter is preferably association polymer quality
0.74%；In other embodiments that the present invention is provided, the quality of the alkaline matter is preferably association polymer quality
1.9%.
The alkaline matter is alkaline matter well known to those skilled in the art, has no special limitation, the present invention
In be preferably NaOH, Na2CO3With the one or more in amine organic base.
The present invention uses and the association polymer work that a small amount of hydrophobic grouping and function monomer are obtained is introduced on polymer molecule
For oil displacement system, the association polymer that a small amount of hydrophobic monomer and function monomer are obtained is introduced on polymer molecular chain, with thin
The introducing of water base group, in these macromoleculars or intermolecular hydrophobic grouping is mutually associated due to hydrophobic effect in aqueous,
Reversible three dimensions dynamic physical cross-linked network is formed, so as to can have higher viscosity and elasticity in low concentration, significantly
It is cost-effective, high resistant force coefficient and high residual resistance factor, heterogeneous oil can be set up due to the introducing of hydrophobic monomer, during the displacement of reservoir oil
Hide and improve waterflood recovery efficiency factor, increase residual resistance factor contribution rate is more than increase resistance coefficient, high residual resistance factor is conducive to
High permeability zone permeability is reduced, inhomogeneous formation water injection profile is adjusted, closure water drive alters the effect of stand in channel, with preferable
" transfer drive " effect, improvement is subsequently implanted into water sweep efficiency；This reversible construction, which has, is broken and is worked as under intensive shear effect
Shear action reduces or is able to when disappearing the characteristic recovered, and solves traditional polymer viscous by the irreversible loss of Strong shear effect
The problem of spending；Function monomer is introduced and association spacial framework intensity increases as solution polarity increases so that system has
There is good heat and salinity tolerance anti-shearing and ageing stability, having to heterogeneous reservoir preferably improves oil and water mobility ratio effect, can
Molecular coil size is changed by content of hydrophobic monomers, species and the change of molecular weight, so that with heterogeneous reservoir permeability and oozing
Saturating rate extreme difference matches, it is ensured that injection, improves oil displacement efficiency；Because three dimensions dynamic physical cross-linked network is deposited in solution
Significantly is raised in, system elasticity, improve polymer microscopic oil displacement efficiency, after the water drive so as to preferably improve heterogeneous reservoir
Recovery ratio；When addition surfactant and alkali are configured to binary (ternary) system, while association polymer advantage is ensured, energy
The performances such as system viscosity and elasticity (generation positive coopertive effect) are enough increased substantially, and the surfactant and alkali that add can be big
Amplitude improves system displacement efficiency, so as to can increase substantially water drive under the conditions of the heterogeneous reservoir of High water cut and poly- drive is adopted
Yield.
Present invention also offers a kind of flooding method of heterogeneous reservoir, using the above-mentioned displacement of reservoir oil body for heterogeneous reservoir
System carries out the displacement of reservoir oil.
In order to further illustrate the present invention, what is with reference to embodiments the present invention provided is a kind of for heterogeneous reservoir
Oil displacement system and flooding method are described in detail.
Reagent used is commercially available in following examples.
1st, when oil displacement system only includes association polymer and water, its evaluation rubric standard is as follows：
1.1 prepared polymer mother liquors
Open water-bath and be warming up to demand temperature, the water of amount of calculation is weighed in beaker (need to first use 500 eye mesh screens with water filling
Filtering), and be put into water-bath, vertical stirrer is opened, suitable rotational speed is selected, the formation whirlpool of the water in cup is preheated.
The polymer dry powder of amount of calculation is weighed, is uniformly sprinkled into along whirlpool wall, the mother liquor of the concentration to needed for being dissolved as is stirred.
1.2 prepare certain density target liquid
As needed, take appropriate polymer mother liquor and add the water of amount of calculation, using vertical stirrer under appropriate rotating speed
1h is stirred, the target liquid of concentration needed for being diluted to.
1.3 determination of solution viscosity
From Brookfield viscosimeters, a certain amount of polymer target solution is taken to be fitted into Sheng sample cylinder, in required temperature
It is lower to be preheated.Choose to take the mean after appropriate rotor and rotating speed, measure 3,5,8min viscosity numbers and obtain target fluid viscosity value.
1.4 mechanical shearing retention rates
Appropriate polymer target liquid is taken, solution viscosity (viscosity before shearing) is determined.Using waring agitators under I grades it is right
The solution stands froth breaking at normal temperatures after being stirred shearing 30s.Froth breaking takes clear liquid after finishing, and determines its viscosity and (is glued after shearing
Degree).Mechanical shearing retention rate is the ratio between viscosity and the preceding viscosity of shearing after shearing.
1.5 90 days aged viscosity retention rates
The polymer target solution configured for determining viscosity is led into nitrogen to carry out after deoxygenation, packing to multiple ampoule bottles
In and high temperature sintering sealing, ampoule bottle is positioned in the baking oven of relevant temperature, every certain number of days take out one determine its viscosity,
Compare 90 days interpolymer target solution viscosity B coefficents, the ratio of solution viscosity and initial viscosity when its viscosity retention ratio is 90 days
Value.
1.6 resistance coefficients are determined with residual resistance factor
The natural core or artificial core for having measured basic parameter are chosen, and is put it into core holding unit,
Plus appropriate ring pressure；Or the fill out sand tube for having measured basic parameter is chosen, it is put into the baking oven for rise to experimental temperature and adds
Heat.
Load intermediate receptacle after water used in experiment and the polymer target solution prepared are filtered.Using precision
Pump is first with appropriate flow velocity to rock core or fill out sand tube saturation water；After saturation water is finished, continue to be filled to pressure stability P1；With with note
Water identical flow velocity injection of polymer target solution is to pressure value stabilization P2, export the viscosity stabilization of efflux；Finally again with phase
The steady P of pressure is filled to speed3。
Resistance coefficient is P2 and P1 ratio.
Residual resistance factor is P3 and P1 ratio.
1.7 improve recovery ratio degree
Heterogeneous reservoir oil displacement experiment can use artificial multilayer heterogeneous core, and sand tube, homogeneous people lithogenesis in parallel are filled out in parallel connection
The heart and natural core in parallel, below by taking the artificial side's core oil-displacement test in parallel for measuring parameters as an example：
Connect after pipeline, setting oven temperature, every rock core (filling out sand tube) is carried out respectively first using suitable flow rate
Saturation water operation.After saturation water terminates, saturation crude oil or simulation oil operation are carried out, efflux is collected, the oil of outflow is recorded
Water volume, seal core or fill out sand tube cure certain time immediately after saturated oils process terminates, and are ready for water drive experiment.
When water drive is tested, rock core outlet is first opened, is discharged in model from oil spout untill no longer fuel-displaced, record is from oil spout
Volume, and it is deducted from saturation oil mass.By clamper outlet connection oil water separator, by constant speed pump into rock core according to
It is required that flow velocity carries out water filling, port of export efflux, and the liquid above and below certain time pressure of record, oil water separator are collected
Face, effluent volume, calculate instantaneous liquid outlet quantity, instantaneous moisture content, instantaneous oil yield, overall recovery factor and injection pore volume times
Number；When instantaneous moisture content reaches the poly- condition of requirement metaideophone, metaideophone gathers immediately.
During polymer flooding, stop water filling, liquid is collected using desired flow velocity injection of polymer, and in exit.Often
10min reads pressure, liquid level, effluent volume above and below oil water separator, and record calculate instantaneous liquid outlet quantity, it is instantaneous aqueous
Rate, instantaneous oil yield, overall recovery factor and injection pore volume multiple；Reach that experiment will when injection of polymer solution adds up liquid outlet quantity
During the polymer injection rate asked, turn sequent water flooding immediately.
During sequent water flooding, stop injection of polymer, flow velocity water filling as requested collects liquid in the port of export；Read per 10min
Liquid level, effluent volume above and below pressure, oil water separator, and record calculate instantaneous liquid outlet quantity, it is instantaneous moisture content, instantaneous
Oil yield, overall recovery factor and injection pore volume multiple；When displacement to oil-free output or moisture content reaches requirement, terminate real
Test.
Certain density demulsifier is added in oil water separator and is well mixed, stands to read after 24 h under experimental temperature and divides
From fluid value above and below device, and raising recovery ratio value (now overall recovery factor subtracts early stage waterflood recovery efficiency factor) now is calculated, with reality
Raising recovery ratio at the end of testing just compares, and amendment may caused recovery ratio error due to emulsification of crude oil.
Oil displacement system is evaluated according to this standard, it is 3~51mD to obtain evaluating heterogeneous reservoir permeability, and permeability extreme difference is
When 17, the composition that the performance test results of oil displacement system are shown in Table polymer in 2, oil displacement system is shown in Table 1, and using molecular weight as 1000
Ten thousand polyacrylamide is used as comparative example 1.
Experiment condition：
Temperature：82℃；TDS：75000mg/L；Calcium ions and magnesium ions：12000mg/L；Viscosity of crude：250mPa.s；Rock core is advised
Lattice：Two 4.5 × 4.5 × 30cm artificial cores in parallel；Injection rate 3m/d improves recovery ratio amplitude, moisture content 98% after water drive
When metaideophone poly- 0.3PV after continue water drive to moisture content 98%.
The composition of polymer in the oil displacement system of table 1
The performance test results of oil displacement system when the permeability extreme difference of table 2 is 17
Oil displacement system is evaluated according to this standard, it is 452~504mD permeability extreme differences to obtain evaluating heterogeneous reservoir permeability
For 1.1 when, the composition that the performance test results of oil displacement system are shown in Table polymer in 4, oil displacement system is shown in Table 3, and using molecular weight as
18000000 polyacrylamide is used as comparative example 2.
Experiment condition：
Temperature：80℃；TDS：40000mg/L；Calcium ions and magnesium ions：3500mg/L；Viscosity of crude：500mPa.s；Rock core specification：
Two 4.5 × 4.5 × 30cm artificial cores in parallel；Injection rate 3m/d, improves recovery ratio amplitude after water drive, during moisture content 98%
Continue water drive after the poly- 0.3PV of metaideophone to moisture content 98%.
The composition of polymer in the oil displacement system of table 3
The performance test results of oil displacement system when the permeability extreme difference of table 4 is 1.1
Oil displacement system is evaluated according to this standard, it is 201~1042mD, permeability pole to obtain evaluating heterogeneous reservoir permeability
When difference is 5.2, the composition that the performance test results of oil displacement system are shown in Table polymer in 6, oil displacement system is shown in Table 5, and with molecular weight
Comparative example 3 is used as 20,000,000 polyacrylamide.
Experiment condition：
Temperature：75℃；TDS：32000mg/L；Calcium ions and magnesium ions：2000mg/L；Viscosity of crude：900mPa.s；Rock core specification：
Two 4.5 × 4.5 × 30cm artificial cores in parallel；Injection rate 3m/d, improves recovery ratio amplitude after water drive, during moisture content 98%
Continue water drive after the poly- 0.3PV of metaideophone to moisture content 98%.
The composition of polymer in the oil displacement system of table 5
The performance test results of oil displacement system when the permeability extreme difference of table 6 is 5.2
Oil displacement system is evaluated according to this standard, it is 324~9947mD permeabilities pole to obtain evaluating heterogeneous reservoir permeability
When difference is 30.7, the performance test results of oil displacement system are shown in Table polymer composition in 8, oil displacement system and are shown in Table 7, and using molecular weight as
28000000 polyacrylamide is used as comparative example 4.
Experiment condition：
Temperature：70℃；TDS：75000mg/L；Calcium ions and magnesium ions：18000mg/L；Viscosity of crude：2000mPa.s；Rock core is advised
Lattice：Two 4.5 × 4.5 × 30cm artificial cores in parallel；Injection rate 3m/d, improves recovery ratio amplitude, moisture content after water drive
Continue water drive when 98% after the poly- 0.3PV of metaideophone to moisture content 98%.
The composition of polymer in the oil displacement system of table 7
The performance test results of oil displacement system when the permeability extreme difference of table 8 is 30.7
2nd, when oil displacement system include association polymer and surfactant when, as binary combination flooding when, evaluation criterion is such as
Under：
2.1 prepared polymer mother liquors
Open water-bath and be warming up to demand temperature, the water of amount of calculation is weighed in beaker (need to first use 500 eye mesh screens with water filling
Filtering), and be put into water-bath, vertical stirrer is opened, suitable rotational speed is selected, the formation whirlpool of the water in cup is preheated.
The polymer dry powder of amount of calculation is weighed, is uniformly sprinkled into along whirlpool wall, the mother liquor of the concentration to needed for being dissolved as is stirred.
2.2 prepare certain density target liquid
As needed, take appropriate polymer mother liquor and add corresponding the species surfactant solution and water of amount of calculation, adopt
1h is stirred under appropriate rotating speed with vertical stirrer, the binary system target liquid of concentration needed for being configured to.
2.3 determination of solution viscosity
From Brookfield viscosimeters, a certain amount of binary system target solution is taken to be fitted into Sheng sample cylinder, in required temperature
Degree is lower to be preheated.Choose to take the mean after appropriate rotor and rotating speed, measure 3,5,8min viscosity numbers and obtain target fluid viscosity
Value.
2.4 mechanical shearing retention rates
Appropriate binary system target liquid is taken, solution viscosity (viscosity before shearing) is determined.Using waring agitators under I grades
Froth breaking is stood at normal temperatures after shearing 30s is stirred to the solution.Froth breaking takes clear liquid after finishing, and determines its viscosity (after shearing
Viscosity).Mechanical shearing retention rate is the ratio between viscosity and the preceding viscosity of shearing after shearing.
2.5 90 days aged viscosity retention rates
The binary system target solution configured that viscosity (initial viscosity) will be determined is led to after nitrogen progress deoxygenation, packing
Into multiple ampoule bottles, simultaneously high temperature sintering sealing, ampoule bottle is positioned in the baking oven of relevant temperature, and one is taken out every certain number of days
Branch determines its viscosity, compares binary system target solution viscosity B coefficent in 90 days, and solution glues when its viscosity retention ratio is 90 days
The ratio of degree and initial viscosity.
2.6 resistance coefficients are determined with residual resistance factor
The natural core or artificial core for having measured basic parameter are chosen, and is put it into core holding unit,
Plus appropriate ring pressure；Or the fill out sand tube for having measured basic parameter is chosen, it is put into the baking oven for rise to experimental temperature and adds
Heat.
Load intermediate receptacle after water used in experiment and the binary system target solution prepared are filtered.Using essence
Close pump is first with appropriate flow velocity to rock core or fill out sand tube saturation water；After saturation water is finished, continue to be filled to pressure stability P1；With with
Water filling identical flow velocity injects binary system target solution to pressure value stabilization P2, export the viscosity stabilization of efflux；Again finally
The steady P of pressure is filled to identical speed3。
Resistance coefficient is P2 and P1 ratio.
Residual resistance factor is P3 and P1 ratio.
2.7 improve recovery ratio degree
Heterogeneous reservoir oil displacement experiment can use artificial multilayer heterogeneous core, and sand tube, homogeneous people lithogenesis in parallel are filled out in parallel connection
The heart and natural core in parallel, below by taking the artificial side's core oil-displacement test in parallel for measuring parameters as an example：
Connect first after device pipeline, setting oven temperature, saturation water operation is carried out to rock core using suitable flow rate.Treat
After saturation water terminates, saturation crude oil or simulation oil operation are carried out, efflux is collected, the profit volume of outflow is recorded, hole is calculated
Gap volume and saturation oil mass；Close fill out sand tube curing certain time immediately after saturated oils process terminates, be ready for water drive real
Test.When water drive is tested, rock core outlet is first opened, discharges in model from oil spout untill no longer fuel-displaced, records blowing oil volume,
And deduct it from saturation oil mass.By clamper outlet connection oil water separator, by constant speed pump into rock core as requested
Flow velocity carries out water filling, collects port of export efflux, and liquid level, stream above and below certain time pressure of record, oil water separator
Go out liquid product, calculate instantaneous liquid outlet quantity, instantaneous moisture content, instantaneous oil yield, recovery ratio and injection pore volume multiple；Work as wink
When moisture content reach the poly- condition of requirement metaideophone metaideophone binary system immediately.
When binary system drives, stop water filling, binary system is injected using desired flow velocity, and liquid is collected in exit.
Pressure is read per 10min, liquid level, effluent volume above and below oil water separator, and record and calculate instantaneous liquid outlet quantity, instantaneously contain
Water rate, instantaneous oil yield, overall recovery factor and injection pore volume multiple；Reality is reached when injection binary system solution adds up liquid outlet quantity
When testing the binary system injection rate of requirement, turn sequent water flooding immediately.
During sequent water flooding, stop injection binary system, flow velocity water filling as requested collects liquid in the port of export；Per 10min
Liquid level, effluent volume above and below pressure of reading, oil water separator, and record calculates instantaneous liquid outlet quantity, instantaneous moisture content, wink
When oil yield, overall recovery factor and injection pore volume multiple；When displacement to oil-free or moisture content reaches required value, terminate real
Test.
Certain density demulsifier is added in oil water separator and is well mixed, stands to read after 24h under experimental temperature and divides
From fluid value above and below device, and raising recovery ratio value (now overall recovery factor subtracts early stage waterflood recovery efficiency factor) now is calculated, with reality
Raising recovery ratio at the end of testing just compares, and amendment may caused recovery ratio error due to emulsification of crude oil.
Oil displacement system is evaluated according to this standard, it is 3~51mD to obtain evaluating heterogeneous reservoir permeability, and permeability extreme difference is
When 17, the composition that the performance test results of binary combination flooding oil displacement system are shown in Table polymer in 10, oil displacement system is shown in Table 9, and with
Molecular weight is used as comparative example 5 for 10,000,000 polyacrylamide.
Experiment condition：
Temperature：82℃；TDS：75000mg/L；Calcium ions and magnesium ions：12000mg/L；Viscosity of crude：250mPa.s；Rock core is advised
Lattice：Two 4.5 × 4.5 × 30cm artificial cores in parallel；Injection rate 3m/d, improves recovery ratio amplitude, moisture content after water drive
Continue water drive when 98% after the poly- 0.3PV of metaideophone to moisture content 98%.
The composition of polymer in the oil displacement system of table 9
The performance test results of binary combination flooding oil displacement system when the permeability extreme difference of table 10 is 17
Oil displacement system is evaluated according to this standard, it is 452~504mD permeability extreme differences to obtain evaluating heterogeneous reservoir permeability
For 1.1 when, the composition that the performance test results of binary combination flooding oil displacement system are shown in Table polymer in 12, oil displacement system is shown in Table 11,
And it is used as comparative example 6 by 18,000,000 polyacrylamide of molecular weight.
Experiment condition：
Temperature：80℃；TDS：40000mg/L；Calcium ions and magnesium ions：3500mg/L；Viscosity of crude：500mPa.s；Rock core specification：
Two 4.5 × 4.5 × 30cm artificial cores in parallel；Injection rate 3m/d, improves recovery ratio amplitude after water drive, during moisture content 98%
Continue water drive after the poly- 0.3PV of metaideophone to moisture content 98%.
The composition of polymer in the oil displacement system of table 11
The performance test results of binary combination flooding oil displacement system when the permeability extreme difference of table 12 is 1.1
Oil displacement system is evaluated according to this standard, it is 201~1042mD permeabilities pole to obtain evaluating heterogeneous reservoir permeability
When difference is 5.2, the composition that the performance test results of binary combination flooding oil displacement system are shown in Table polymer in 14, oil displacement system is shown in Table
13, and it is used as comparative example 7 by 20,000,000 polyacrylamide of molecular weight.
Experiment condition：
Temperature：75℃；TDS：32000mg/L；Calcium ions and magnesium ions：2000mg/L；Viscosity of crude：900mPa.s；Rock core specification：
Two 4.5 × 4.5 × 30cm artificial cores in parallel；Injection rate 3m/d, improves recovery ratio amplitude after water drive, during moisture content 98%
Continue water drive after the poly- 0.3PV of metaideophone to moisture content 98%.
The composition of polymer in the oil displacement system of table 13
The performance test results of binary combination flooding oil displacement system when the permeability extreme difference of table 14 is 5.2
Oil displacement system is evaluated according to this standard, it is 324~9947mD permeabilities pole to obtain evaluating heterogeneous reservoir permeability
When difference is 30.7, the composition that the performance test results of binary combination flooding oil displacement system are shown in Table polymer in 16, oil displacement system is shown in Table
15, and it is used as comparative example 8 by 28,000,000 polyacrylamide of molecular weight.
Experiment condition：
Temperature：70℃；TDS：75000mg/L；Calcium ions and magnesium ions：18000mg/L；Viscosity of crude：2000mPa.s；Rock core is advised
Lattice：Two 4.5 × 4.5 × 30cm artificial cores in parallel；Injection rate 3m/d, improves recovery ratio amplitude, moisture content after water drive
Continue water drive when 98% after the poly- 0.3PV of metaideophone to moisture content 98%.
The composition of polymer in the oil displacement system of table 15
Binary combination flooding oil displacement system the performance test results when the permeability extreme difference of table 16 is 30.7
3rd, when oil displacement system includes association polymer, surfactant and during alkaline matter, as ternary composite driving when, comment
Price card is accurate as follows：
3.1 prepared polymer mother liquors
Open water-bath and be warming up to demand temperature, the water of amount of calculation is weighed in beaker (need to first use 500 eye mesh screens with water filling
Filtering), and be put into water-bath, vertical stirrer is opened, suitable rotational speed is selected, the formation whirlpool of the water in cup is preheated.
The polymer dry powder of amount of calculation is weighed, is uniformly sprinkled into along whirlpool wall, the mother liquor of the concentration to needed for being dissolved as is stirred.
3.2 prepare certain density target liquid
As needed, the mixing for taking appropriate polymer mother liquor and adding corresponding the species surfactant and alkali of amount of calculation is molten
The water of liquid, amount of calculation, 1h is stirred using vertical stirrer under appropriate rotating speed, the ternary system target liquid of concentration needed for being configured to
.
3.3 determination of solution viscosity
From Brookfield viscosimeters, a certain amount of ternary system target solution is taken to be fitted into Sheng sample cylinder, in required temperature
Degree is lower to be preheated.Choose to take the mean after appropriate rotor and rotating speed, measure 3,5,8min viscosity numbers and obtain target fluid viscosity
Value.
3.4 mechanical shearing retention rates
Appropriate ternary system target liquid is taken, solution viscosity (viscosity before shearing) is determined.Using waring agitators under I grades
Froth breaking is stood at normal temperatures after shearing 30s is stirred to the solution.Froth breaking takes clear liquid after finishing, and determines its viscosity (after shearing
Viscosity).Mechanical shearing retention rate is the ratio between viscosity and the preceding viscosity of shearing after shearing.
3.5 90 days aged viscosity retention rates
The ternary system target solution configured that viscosity (initial viscosity) will be determined is led to after nitrogen progress deoxygenation, packing
Into multiple ampoule bottles, simultaneously high temperature sintering sealing, ampoule bottle is positioned in the baking oven of relevant temperature, and one is taken out every certain number of days
Branch determines its viscosity, compares ternary system target solution viscosity B coefficent in 90 days, and solution glues when its viscosity retention ratio is 90 days
The ratio of degree and initial viscosity.
3.6 resistance coefficients are determined with residual resistance factor
The natural core or artificial core for having measured basic parameter are chosen, and is put it into core holding unit,
Plus appropriate ring pressure；Or the fill out sand tube for having measured basic parameter is chosen, it is put into the baking oven for rise to experimental temperature and adds
Heat.
Load intermediate receptacle after water used in experiment and the ternary system target solution prepared are filtered.Using essence
Close pump is first with appropriate flow velocity to rock core or fill out sand tube saturation water；After saturation water is finished, continue to be filled to pressure stability P1；With with
Water filling identical flow velocity injects ternary system target solution to pressure value stabilization P2, export the viscosity stabilization of efflux；Again finally
The steady P of pressure is filled to identical speed3。
Resistance coefficient is P2 and P1 ratio.
Residual resistance factor is P3 and P1 ratio.
3.7 improve recovery ratio degree
Heterogeneous reservoir oil displacement experiment can use artificial multilayer heterogeneous core, and sand tube, homogeneous people lithogenesis in parallel are filled out in parallel connection
The heart and natural core in parallel, below by taking the artificial side's core oil-displacement test in parallel for measuring parameters as an example：
Connect first after pipeline, setting oven temperature, saturation water operation is carried out to fill out sand tube using suitable flow rate.Wait to satisfy
After terminating with water, saturation crude oil or simulation oil operation are carried out, efflux is collected, the profit volume of outflow is recorded, treats saturated oils
Process closes fill out sand tube curing certain time immediately after terminating, be ready for water drive experiment.
When water drive is tested, rock core outlet is first opened, is discharged in model from oil spout untill no longer fuel-displaced, record is from oil spout
Volume, and it is deducted from saturation oil mass.By clamper outlet connection oil water separator, by constant speed pump into rock core according to
It is required that flow velocity carries out water filling, port of export efflux, and the liquid above and below certain time pressure of record, oil water separator are collected
Face, effluent volume, calculate instantaneous liquid outlet quantity, instantaneous moisture content, instantaneous oil yield, recovery ratio and injection pore volume times
Number；When instantaneous moisture content reaches the poly- condition of requirement metaideophone metaideophone ternary system immediately.
During metaideophone ternary system, stop water filling, ternary system is injected using desired flow velocity, and in exit collection liquid
Body.Pressure is read per 10min, liquid level, effluent volume above and below oil water separator, and record calculate instantaneous liquid outlet quantity,
Instantaneous moisture content, instantaneous oil yield, recovery ratio and injection pore volume multiple；When noting ternary system, when accumulative liquid outlet quantity reaches
During the ternary system injection rate of requirement of experiment, turn sequent water flooding immediately.
During sequent water flooding, stop injection ternary system, flow velocity water filling as requested collects liquid in the port of export；Per 10min
Liquid level, effluent volume above and below pressure of reading, oil water separator, and record calculates instantaneous liquid outlet quantity, instantaneous moisture content, wink
When oil yield, overall recovery factor and injection pore volume multiple；When displacement to oil-free or moisture content reaches requirement, terminate experiment.
Certain density demulsifier is added in oil water separator and is well mixed, stands to read after 24 h under experimental temperature and divides
From fluid value above and below device, and raising recovery ratio value (now overall recovery factor subtracts early stage waterflood recovery efficiency factor) now is calculated, with reality
Raising recovery ratio at the end of testing just compares, and amendment may caused recovery ratio error due to emulsification of crude oil.
Oil displacement system is evaluated according to this standard, it is 3~51mD to obtain evaluating heterogeneous reservoir permeability, and permeability extreme difference is
When 17, the performance test results of ternary built composite reservoir oil displacement system are shown in Table 18, and the composition of oil displacement system is shown in Table 17, and using molecular weight as
10000000 polyacrylamide is used as comparative example 9.
Experiment condition：
Temperature：82℃；TDS：75000mg/L；Calcium ions and magnesium ions：12000mg/L；Viscosity of crude：250mPa.s；Rock core is advised
Lattice：Two 4.5 × 4.5 × 30cm artificial cores in parallel；Injection rate 3m/d improves recovery ratio amplitude, moisture content 98% after water drive
When metaideophone poly- 0.3PV after continue water drive to moisture content 98%.
The composition of the oil displacement system of table 17
The performance test results of binary combination flooding oil displacement system when the permeability extreme difference of table 18 is 17
Oil displacement system is evaluated according to this standard, it is 452~504mD permeability extreme differences to obtain evaluating heterogeneous reservoir permeability
For 1.1 when, the performance test results of ternary built composite reservoir oil displacement system are shown in Table 20, and the composition of oil displacement system is shown in Table 19, and with molecule
The polyacrylamide for 18,000,000 is measured as comparative example 10.
Experiment condition：
Temperature：80℃；TDS：40000mg/L；Calcium ions and magnesium ions：3500mg/L；Viscosity of crude：500mPa.s；Rock core specification：
Two 4.5 × 4.5 × 30cm artificial cores in parallel；Injection rate 3m/d, improves recovery ratio amplitude after water drive, during moisture content 98%
Continue water drive after the poly- 0.3PV of metaideophone to moisture content 98%.
The composition of the oil displacement system of table 19
Ternary built composite reservoir oil displacement system the performance test results when the permeability extreme difference of table 20 is 1.1
Oil displacement system is evaluated according to this standard, it is 201~1042mD permeabilities pole to obtain evaluating heterogeneous reservoir permeability
When difference is 5.2, the performance test results of ternary built composite reservoir oil displacement system are shown in Table 22, and the composition of oil displacement system is shown in Table 21, and to divide
Son amount is used as comparative example 11 for 20,000,000 polyacrylamide.
Experiment condition：
Temperature：75℃；TDS：32000mg/L；Calcium ions and magnesium ions：2000mg/L；Viscosity of crude：900mPa.s；Rock core specification：
Two 4.5 × 4.5 × 30cm artificial cores in parallel；Injection rate 3m/d, improves recovery ratio amplitude after water drive, during moisture content 98%
Continue water drive after the poly- 0.3PV of metaideophone to moisture content 98%.
The composition of the oil displacement system of table 21
Ternary built composite reservoir oil displacement system the performance test results when the permeability extreme difference of table 22 is 5.2
Oil displacement system is evaluated according to this standard, it is 324~9947mD permeabilities pole to obtain evaluating heterogeneous reservoir permeability
When difference is 30.7, the performance test results of ternary built composite reservoir oil displacement system are shown in Table 24, and the composition of oil displacement system is shown in Table 23, and to divide
Son amount is used as comparative example 12 for 28,000,000 polyacrylamide.
Experiment condition：
Temperature：70℃；TDS：75000mg/L；Calcium ions and magnesium ions：18000mg/L；Viscosity of crude：2000mPa.s；Rock core is advised
Lattice：Two 4.5 × 4.5 × 30cm artificial cores in parallel；Injection rate 3m/d, improves recovery ratio amplitude, moisture content after water drive
Continue water drive when 98% after the poly- 0.3PV of metaideophone to moisture content 98%.
The composition of the oil displacement system of table 23
Ternary built composite reservoir oil displacement system the performance test results when the permeability extreme difference of table 24 is 30.7
Claims (9)
1. a kind of oil displacement system for heterogeneous reservoir, it is characterised in that including association polymer；The association polymer
Molecular weight is 103.6~4021.5 ten thousand；In mole percent, the association polymer by acrylamide, 0.11%~
9.96% hydrophobic monomer polymerize with 0~15.4% function monomer to be obtained；The concentration of association polymer in the oil displacement system
For 400~3500mg/L；
The hydrophobic monomer is selected from N- alkyl-substituted acrylamides and its derivative, alkyl acrylate, methacrylate
Ester, the alkyl acrylate of fluorine substitution, alkyl methacrylate, allyl alkyl quaternary ammonium salt, the acrylamide alkane of fluorine substitution
One or more in base sulfonic acid and its sulfonate, alkylphenol-polyethenoxy acrylate and acrylic acid polyxyethylated ester；
The function monomer is selected from sulfonic acid and its sulfonate derivatives containing end alkenyl and the heterocycle containing end alkenyl
One or more in derivative.
2. oil displacement system according to claim 1, it is characterised in that the N- alkyl-substituted acrylamides and its derivative
Thing, alkyl acrylate, alkyl methacrylate, allyl alkyl quaternary ammonium salt, acrylic acid alkyl sulfonic acid and its sulfonate, alkane
Base phenol polyethenoxy acrylate, acrylic acid polyxyethylated ester, the alkyl acrylate of fluorine substitution and the methyl of fluorine substitution
The carbon number of alkyl is each independently 4~40 in alkyl acrylate.
3. oil displacement system according to claim 1, it is characterised in that the function monomer is selected from 2- acrylamidos -2-
Methyl propane sulfonic acid and its sulfonate, vinyl sulfonic acid and its sulfonate, styrene sulfonic acid and its sulfonate and N- vinyl -2-
One or more in pyrrolidones.
4. oil displacement system according to claim 1, it is characterised in that also including surfactant；The surfactant
Quality be associtation polymer amount of substance 0.001%~0.76%.
5. oil displacement system according to claim 4, it is characterised in that the surfactant be petroleum-sulfonate it is cloudy from
Sub- surfactant, alkyl benzene sulfonate anion surfactant, alpha-alkene sulfonate anionoid surfactant, glycine betaine
Class both sexes surfactant, alkanolamide class non-ionic surfactant, non-ionic gemini surface active agent, anionic Shuangzi surface are lived
Property agent, alkylnaphthalene sulfonate, lignosulfonates, vegetable oil carboxylate, petroleum carboxylate, biological species surfactant with it is compound
One or more in surfactant.
6. oil displacement system according to claim 4, it is characterised in that also including alkaline matter；The matter of the alkaline matter
Measure as the 0.09%~2.1% of associtation polymer amount of substance.
7. oil displacement system according to claim 6, it is characterised in that the alkaline matter is NaOH, Na2CO3Have with amine
One or more in machine alkali.
8. oil displacement system according to claim 1, it is characterised in that the permeability extreme difference of the heterogeneous reservoir is 1.1
~30.7.
9. a kind of flooding method of heterogeneous reservoir, it is characterised in that using being used for described in claim 1~8 any one
The oil displacement system of heterogeneous reservoir carries out the displacement of reservoir oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710193004.XA CN106967406B (en) | 2017-03-28 | 2017-03-28 | Oil displacement system and method for heterogeneous oil reservoir |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710193004.XA CN106967406B (en) | 2017-03-28 | 2017-03-28 | Oil displacement system and method for heterogeneous oil reservoir |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106967406A true CN106967406A (en) | 2017-07-21 |
| CN106967406B CN106967406B (en) | 2020-08-11 |
Family
ID=59336119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710193004.XA Active CN106967406B (en) | 2017-03-28 | 2017-03-28 | Oil displacement system and method for heterogeneous oil reservoir |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106967406B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107936938A (en) * | 2017-12-05 | 2018-04-20 | 张晓静 | A kind of negative pressure on ground DP technology and its device |
| CN109838230A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | The quantitative evaluation method of oil reservoir Water Flooding Layer |
| CN110016324A (en) * | 2018-01-10 | 2019-07-16 | 中国石油化工股份有限公司 | A kind of high-temperature resistant water base drilling fluid extracting and cutting agent and preparation method thereof |
| CN112943192A (en) * | 2021-02-03 | 2021-06-11 | 中国石油天然气股份有限公司 | Mining method suitable for low-permeability conglomerate oil reservoir |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475667A (en) * | 2009-01-23 | 2009-07-08 | 成都理工大学 | Temperature-resistant salt-resistant efficient gel, and preparation and use thereof |
| CN101492515A (en) * | 2009-01-23 | 2009-07-29 | 成都理工大学 | Acrylic amide modified graft copolymer, preparation method and application thereof |
| CN104448127A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Polymer mobility control agent suitable for ultrahigh-salinity oil deposit and preparation method thereof |
| CN104448125A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Amphoteric hydrophobically-associating polymer and preparation method thereof |
| CN104694110A (en) * | 2015-02-02 | 2015-06-10 | 天津市浩宇助剂有限公司 | Hydrophobic association type oil-displacing agent |
| CN104892838A (en) * | 2015-06-12 | 2015-09-09 | 中国石油大学(华东) | Temperature-resistant anionic-nonionic amphoteric hydrophobically associating copolymer and preparation method thereof |
| CN105505364A (en) * | 2014-10-13 | 2016-04-20 | 中国石油化工股份有限公司 | Oil displacing agent for increasing oil recovery in high temperature high salt mid-low permeability oil reservoir, preparation method and applications thereof |
| CN105567208A (en) * | 2014-10-13 | 2016-05-11 | 中国石油化工股份有限公司 | Oil-displacement composition with improved injectivity, and preparation method and application thereof |
-
2017
- 2017-03-28 CN CN201710193004.XA patent/CN106967406B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475667A (en) * | 2009-01-23 | 2009-07-08 | 成都理工大学 | Temperature-resistant salt-resistant efficient gel, and preparation and use thereof |
| CN101492515A (en) * | 2009-01-23 | 2009-07-29 | 成都理工大学 | Acrylic amide modified graft copolymer, preparation method and application thereof |
| CN104448127A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Polymer mobility control agent suitable for ultrahigh-salinity oil deposit and preparation method thereof |
| CN104448125A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Amphoteric hydrophobically-associating polymer and preparation method thereof |
| CN105505364A (en) * | 2014-10-13 | 2016-04-20 | 中国石油化工股份有限公司 | Oil displacing agent for increasing oil recovery in high temperature high salt mid-low permeability oil reservoir, preparation method and applications thereof |
| CN105567208A (en) * | 2014-10-13 | 2016-05-11 | 中国石油化工股份有限公司 | Oil-displacement composition with improved injectivity, and preparation method and application thereof |
| CN104694110A (en) * | 2015-02-02 | 2015-06-10 | 天津市浩宇助剂有限公司 | Hydrophobic association type oil-displacing agent |
| CN104892838A (en) * | 2015-06-12 | 2015-09-09 | 中国石油大学(华东) | Temperature-resistant anionic-nonionic amphoteric hydrophobically associating copolymer and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 刘平德等: "疏水缔合AM/C_(10)AM/AMPS三元共聚物的合成与盐水溶液粘度性能", 《油田化学》 * |
| 李小瑞等: "氟碳型两性聚丙烯酰胺驱油剂的制备与性能", 《石油学报(石油加工)》 * |
| 王晨等: "长链疏水缔合聚丙烯酰胺的合成及其溶液性能与室内驱油效果", 《日用化学工业》 * |
| 雒贵明等: "耐温抗盐驱油共聚物的合成", 《精细石油化工》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109838230A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | The quantitative evaluation method of oil reservoir Water Flooding Layer |
| CN107936938A (en) * | 2017-12-05 | 2018-04-20 | 张晓静 | A kind of negative pressure on ground DP technology and its device |
| CN110016324A (en) * | 2018-01-10 | 2019-07-16 | 中国石油化工股份有限公司 | A kind of high-temperature resistant water base drilling fluid extracting and cutting agent and preparation method thereof |
| CN110016324B (en) * | 2018-01-10 | 2021-08-17 | 中国石油化工股份有限公司 | High-temperature-resistant water-based drilling fluid shear strength improving agent and preparation method thereof |
| CN112943192A (en) * | 2021-02-03 | 2021-06-11 | 中国石油天然气股份有限公司 | Mining method suitable for low-permeability conglomerate oil reservoir |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106967406B (en) | 2020-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Katende et al. | A critical review of low salinity water flooding: Mechanism, laboratory and field application | |
| Xiangguo et al. | Enhanced oil recovery mechanisms of polymer flooding in a heterogeneous oil reservoir | |
| CN103980873B (en) | A kind of three-phase froth composite oil-displacing system and application thereof | |
| Wang et al. | Sweep improvement options for the Daqing oil field | |
| CN102504794B (en) | Hydrophobically associating polymer and mixed surfactant binary compound oil displacement system | |
| CN106967406A (en) | A kind of oil displacement system and flooding method for heterogeneous reservoir | |
| CN104087275B (en) | A kind of high-temperature-resistant high-salt tiny gels granular profile control agent and its preparation method and application | |
| CN103254883B (en) | Oil-displacing agent and oil-displacing method for enhancing recovery ratio of high-temperature, high-salinity and high-hardness reservoir crude oil | |
| CN104650828B (en) | Reverse wetting agent and preparation method thereof and container horizon protective agent composition and for the drilling fluid of hyposmosis ultra-low permeability reservoir and application | |
| CN102618246A (en) | Composite foam flooding method suitable for oil field exploitation | |
| CN104178102A (en) | Cross-linkable high-temperature-resistant residue-free polybasic copolymerizable fracturing fluid and preparation method thereof | |
| CN106867488A (en) | One kind physical crosslinking gel-like profile control and water plugging system and its application | |
| CN102952533A (en) | Composite cross-linked polymer weak gel oil displacement agent and preparation method thereof | |
| CN105331348A (en) | Homogeneous-phase microemulsion oil-displacing agent applied to low-permeation oil field and preparation method of homogeneous-phase microemulsion oil-displacing agent | |
| CN106867497A (en) | A kind of oil displacement system and flooding method for low-permeability oil deposit | |
| Prince et al. | Investigation of anionic in place of cationic surfactants onto oil wet carbonate surfaces for improving recovery | |
| CN109321224B (en) | Monomer charge opposite association polymer composite oil displacement agent and alternate injection oil displacement method | |
| CN109135711B (en) | Monomer charge-oppositely-associated polymer composite oil displacement agent and single-plug oil displacement method | |
| CN103483497B (en) | A kind of physisorption type selective water shutoff agent and synthetic method thereof | |
| Chen et al. | Experimental Study on Fiber Balls for Bridging in Fractured-Vuggy Reservoir | |
| CN108147730A (en) | A kind of sandstone oil reservoir macropore blocks compound water shutoff agent and preparation method thereof | |
| CN103773348B (en) | Poly-table binary composite oil displacement agent and flooding method | |
| CN106609135A (en) | Salt-resistant nano-emulsion injection enhancement agent for oilfield water injection and preparation method thereof | |
| Zhao et al. | Development, performance evaluation and enhanced oil recovery regulations of a zwitterionic viscoelastic surfactant fracturing-flooding system | |
| CN106279526A (en) | A kind of gel micro-sphere system and preparation method thereof, gel micro-sphere dispersion, gel micro-sphere strengthening Polymer Flooding |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |