CN103897682B - Composition for improving recovery efficiency of tertiary recovery, and preparation method and use thereof - Google Patents
Composition for improving recovery efficiency of tertiary recovery, and preparation method and use thereof Download PDFInfo
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Abstract
The invention relates to a composition for improving the recovery efficiency of tertiary recovery, and a preparation method thereof. The problems of bad temperature and salt resistance and low oil displacement efficiency of polymer-containing oil displacement agents in the prior art are solved in the invention. The oil displacement composition for tertiary recovery comprises 0.01-5.0wt% of a temperature and salt resistance copolymer NWKY-PAN, 0.01-5.0wt% of a fatty alcohol polyoxyethylene ether carboxylate surfactant and 90.0-99.98wt% of injected water. The above technical scheme can well solve the problems, and the composition can be used in the tertiary recovery production of oilfields to improve the recovery efficiency.
Description
Technical field
The present invention relates to a kind of tertiary oil recovery improves recovery ratio compositionss and preparation method thereof and purposes.
Background technology
With the development of World Economics, the social required quantity of oil is continuously increased, and petroleum reserves is constantly reduced.Oil is made
Just becoming more and more valuable for non-renewable resource.Problems faced has one, and imbalance between supply and demand is projected, oil demand amount it is more big more
Greatly, new oil field is fewer and feweri；Two, it is also left in depleted reservoirs to have substantial oil.Primary oil recovery (POR) can produce 10～25% ground
Lower crude oil, secondary oil recovery (SOR) can produce 15～25% underground crude oils, i.e. primary oil recovery and secondary oil recovery only produces 25～50% ground
Lower crude oil.In order to ensure that oil is supplied steadily in the long term, meets human wants, it is necessary to which research and development improves oil recovery skill
Art, tertiary oil recovery (EOR) can make oil recovery factor improve 6～20% again by intensified oil reduction measure, even more many.
Domestic each elephant through once, secondary oil recovery, crude oil water content is continuously increased, and part elephant successively enters three
The secondary oil recovery stage.Polymer flooding is the main technique methods of tertiary oil recovery, and mechanism of oil displacement understands that technique is relatively easy, technology day
Become ripe, be one and effectively improve recovery efficiency technique measure.The mechanism of oil displacement of polymer mainly uses water-soluble polypropylene
The viscosity of amide molecule chain, improves the mobility ratio of displacing fluid, displacement efficiency and swept volume is improved, so as to reach raising recovery ratio
Purpose.
Because the tertiary oil recovery cycle is long, deep layer oil temperature is high, therefore, polymer used for tertiary oil recovery must have good increasing
Viscous, heatproof, salt-resistance, stable performance.And the partially hydrolyzed polyacrylamide (PHPA) for being used at present is under the conditions of high temperature and high salt, easily
Hydrolysis, so as to cause carboxyl-content to increase, polymer molecular chain curling, Efficient Adhesive Promotion is drastically reduced, in addition the high price in oil reservoir
Metal ion（Such as Ca2+、Mg2+）Easily precipitate partially hydrolyzed polyacrylamide (PHPA), so as to further reduce partial hydrolysiss
The Efficient Adhesive Promotion of polyacrylamide, thus be difficult to meet deep two, the demand of three class oil reservoir high temperature and high salinities.In recent years, state
The research of inside and outside Heat Resistant and Salt Tolerant Polymer used for tertiary oil recovery can be divided into two general orientation, i.e., ultrahigh molecular weight partially-hydrolyzed polyacrylamide
The chemical modification of amine and polyacrylamide.The chemical modification of polyacrylamide mostly introduce other monomers copolymerization by way of come
Carry out.
Patent CN 1814637A discloses a kind of preparation method of temperature-tolerant anti-salt polyacrylamide, introduces three kinds of heatproofs resistance to
Salt monomer and acrylamide copolymerization, have synthesized acrylamide/2- acrylamide-2-methylpro panesulfonic acids/methacrylic acid/diformazan
Base diallyl ammonium chloride quadripolymer, acrylamide/2- acrylamides and -2- methyl propane sulfonic acids/itaconic acid/acryloyl-oxy
The heat-resistant salt-resistant copolymer such as ethyl-trimethyl salmiac quadripolymer, the heatproof of the product that these polymer improve really is resistance to
Salt performance, but salinity can only be met and be less than under conditions of 65 DEG C less than 10000mg/L, temperature, it is impossible to meet higher temperature
With the application demand under the conditions of salinity.
Patent CN 1876751A discloses a kind of braided comb-shaped thickener for salt-resistant polymer, this thickening agent heat-resistant salt-resistant
Performance is better than comb shape heat-resistant salt-resistant thickening agent of copolymer, and molecular weight is relatively low, in grand celebration clear water（Total salinity 1000mg/
L, wherein calcium ions and magnesium ions 15mg/L）, grand celebration sewage（Total salinity 4000mg/L, wherein calcium ions and magnesium ions 60mg/L）, huge port sewage
（Total salinity 5024mg/L, wherein calcium ions and magnesium ions 60mg/L）In Efficient Adhesive Promotion better than plain polypropylene amide products and comb shape
Salt-resistant polymer industrial goods, are adapted to the requirement of the class oil reservoir tertiary oil recovery of grand celebration two, but still cannot meet 10000mg/L,
Ca2++Mg2+For the requirement of tertiary oil recovery in more than 200mg/L salinity oil reservoirs.
And in recent years, the research about ultra high molecular weight anion-type polyacrylamide is concentrated mainly on initiator system, gathers
Improvement of conjunction method and method for hydrolysis etc..Such as CN1865299, CN 1498908A, CN1746198, CN101157736A and
CN1240799 etc. is to have studied polymerization technique, cause technique and hydrolysis process etc., although by all means improve it is cloudy from
The molecular weight of subtype polyacrylamide or dissolution velocity aspect have larger improvement, but the less pass in terms of temperature-resistant anti-salt performance
Note, some techniques or method it is complex, commercial production or can be somewhat limited in tertiary oil recovery practical application.
In tertiary oil recovery at present, for a class oil reservoir（Temperature<70 DEG C, salinity<1×104mg/L）Polymer it is easy
Prepare, and meet two class oil reservoirs（70～80 DEG C of temperature, salinity 1～3 × 104）With three class oil reservoirs（Temperature>80 DEG C, salinity>
3×104）The polymer of requirement then seldom, be not price too higher position be unstable properties.So, for those high temperature and high salts
Harsh oil reservoir, we ought to seek a kind of with preferable hydrolytic stability, and have higher solution apparent viscosity in saline
Polymer.Polymer of high temperature and high salt and preparation method thereof, the binary of being just suitable for of the present invention is combined and its at three times
Application in oil recovery.
The content of the invention
One of the technical problem to be solved is that the polymer in prior art in the oil displacement agent containing polymer exists
Facile hydrolysiss under the conditions of high temperature and high salt, it is impossible to meet the low problem of tertiary oil recovery requirement, oil displacement efficiency, there is provided a kind of tertiary oil recovery is carried
High recovery rate compositionss, the method is used for the compositionss of the NWKY- PAN of copolymer containing temperature-resistant anti-salt in oil displacement process, has
Hydrolytic stability is good, the characteristics of oil displacement efficiency is high under the conditions of high temperature and high salt.
The two of the technical problem to be solved be to provide it is a kind of with solve the corresponding displacement of reservoir oil of one of technical problem
With the preparation method of compositionss.
The three of the technical problem to be solved be to provide it is a kind of with solve the corresponding displacement of reservoir oil of one of technical problem
With the purposes of compositionss.
In order to solve one of above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of tertiary oil recovery is improved and adopted
Yield compositionss, with composition weight percentages, including following components：
（1）0.01～5.0% temperature-resistant anti-salt copolymer NWKY-PAN；
（2）0.01～5.0% aliphatic alcohol polyethenoxy ether carboxylate surfactant；
（3）90.0～99.98% water；
Wherein（1）The general molecular formula of component temperature-resistant anti-salt copolymer NWKY-PAN is：
（Ⅰ）
In formula, p is-CH2- quantity, numerical value be 1 ~ 3, x, y, m are respectively acrylamide, hydrolyzed acrylamide, lactams
The construction unit molal quantity of class monomer, it is that 4 ~ 40, m is 1 ~ 45 that x is 95 ~ 15, y；The molecular weight of copolymer NWKY-PAN is 1200
～1,800 ten thousand.
In above-mentioned technical proposal, preferred technical scheme, wet concentration is from oilfield injection water；The total salinity of described injection water
It is 200～1800mg/L for 10000～38000mg/L, calcium ions and magnesium ions total concentration.Surfactant is selected from aliphatic alcohol polyethenoxy
Ether carboxylate type the moon-non-surface-active agent, general molecular formula is RO (CH2CH2O)nCH2COOM；In formula：R is C10～C20Alkyl,
Preferably C1,2～C18Alkyl；N for ethoxy group EO adduction number, any one integer in 2～8；M be selected from potassium,
Any one metal ion in sodium or lithium, preferred version is potassium or sodium.Preferred technical scheme, described injects the total of water
Salinity is 20000～30000mg/L, and calcium ions and magnesium ions total concentration is 400～1000mg/L.Preferred technical scheme, it is described
Surfactant be selected from aliphatic alcohol polyethenoxy ether carboxylate type the moon-non-surface-active agent, general molecular formula be RO (CH2CH2O)nCH2COOM；In formula：R is C12～C18Alkyl, n for ethoxy group EO adduction number, M is selected from potassium ion or sodium ion.More
Preferred technical scheme, R is C in described aliphatic alcohol polyethenoxy ether carboxylate14～C16Alkyl；N appointing in 3～7
Meaning integer；Metal ions M is selected from sodium ion.
To solve the two of above-mentioned technical problem, the technical solution adopted in the present invention is as follows：A kind of tertiary oil recovery is improved and adopted
The preparation method of yield compositionss, comprises the following steps：
a）First monomer, second comonomer are made into into the aqueous solution I that total mass concentration is 5 ~ 45w.t.%, wherein the first monomer
For acrylamide, second comonomer is lactams material；
b）Lead to nitrogen deoxidation in solution I, addition accounts for the composite initiation system of total monomer quality 0.001 ~ 3%, obtains molten
Liquid II；Wherein composite initiation system by weight percentage, including following components：(A) 15～85% oxidant；5 (B)～
75% reducing agent；(C) 10～80% tertiary amines functional monomer；Wherein oxidant is selected from potassium peroxydisulfate, Ammonium persulfate., mistake
One kind in sodium sulfate, the one kind of reducing agent in sodium sulfite, sodium thiosulfate, rongalite, tertiary amines feature list
Body is methacrylic acid N, N- dimethylaminoethyls or β-dimethylaminopropionitrile；
c）Lead to nitrogen deoxidation in solution II, at 5 ~ 20 DEG C, initiation reaction 15 ~ 180 minutes, then it is warmed up to 30 ~ 80 DEG C,
Continue isothermal reaction 2 ~ 16 hours, the colloidal product I for obtaining；
d）The alkali liquor that mass concentration is 1 ~ 30% is added in colloidal product I, 50 ~ 100 DEG C are warming up to, hydrolysis 0.5 ~ 3 is little
When, obtain colloidal product II；
e）After colloidal product II is dried, is crushed, being sieved, powder heat-resistant salt-resistant copolymer NWKY-PAN is obtained；
f）Heat-resistant salt-resistant copolymer NWKY-PAN, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate and injection water are uniformly mixed
Close, stir 1～3 hour, obtain required compositionss；With composition weight percentages, heat-resistant salt-resistant copolymer NWKY-PAN,
The proportioning of aliphatic alcohol polyethenoxy ether carboxylate and injection water is 0.01～3.0%: 0.01～5.0%: 92.0～99.98%.
In above-mentioned technical proposal, the preferred acrylamide of the monomer of preferred version first, the preferred N- vinyl pyrrolidines of second comonomer
One kind in ketone, N- vinyl caprolactams；The mol ratio preferred scope of the first monomer and second comonomer is 65 ~ 95: 5~35；It is single
The total mass fraction preferred scope of the first monomer and second comonomer is 15 ~ 35% in liquid solution；Composite initiation system concentration is preferably accounted for
Monomer mass fraction 0.003 ~ 1.5%；The preferred potassium peroxydisulfate of oxidant and Ammonium persulfate. in composite initiation system, reducing agent is preferred
Sodium sulfite, the preferred methacrylic acid N of tertiary amines function monomer, N- dimethylaminoethyls；Preferably 5 ~ 15 DEG C of initiation temperature, draws
Send out preferably 30 ~ 120 minutes time；Preferably 20 ~ 50 DEG C of polymerization temperature, polymerization reaction time preferably 4 ~ 18 hours；Alkali liquor is preferably
Sodium hydroxide solution, mass concentration preferably 5 ~ 15%, preferably 80 ~ 90 DEG C of hydrolysis temperature, hydrolysis time preferred scope 1 ~ 3 hour.
To solve the three of above-mentioned technical problem, the technical solution adopted in the present invention is as follows：
Above-mentioned tertiary oil recovery improves recovery ratio compositionss to be used to improve recovery ratio in tertiary oil production in oil field production.
Tertiary oil recovery prepared by the present invention improves the temperature-resistant anti-salt copolymer NWKY-PAN in recovery ratio compositionss, by
In from increase polymer chain rigidity and suppress polymer in amide group angle of facile hydrolysiss in high temperature and high salinity saline go out
Send out, by introducing the lactams monomer with circulus and acrylamide copolymerization in strand, on the one hand increase polymerization
Thing molecule chain rigidity, improves polymer stabilisation, on the other hand can suppress amide group hydrolysis, such monomer in polymer
Functional group by the functionalization with amide group, such as hydrogen bond action, amide group is formed and is protected, suppress amide groups
The hydrolysis of group, so as to improve the hydrolytic stability of polymer, and then improves the heat-resistant salt-resistant performance of polymer.The copolymer is in height
Under warm high salinity, hydrolytic stability is improved, due to adopting composite initiation system, obtained temperature-resistant anti-salt copolymer NWKY-PAN
Molecular weight>107, in salinity 20000mg/L or so is reached（Wherein calcium ions and magnesium ions concentration is more than 500mg/L）, temperature is up to 85 DEG C
Its Biao sees Nian Du≤21mPas in saline under the conditions of high temperature and high salinity, it is aging after viscosity retention ratio up to more than 80.5%,
With higher viscosity retention ratio, stronger resistant to hydrolysis ability is embodied, possess good heat-resistant salt-resistant performance.And the preparation side
Method technological process is relatively simple, is conducive to industrialized production.
After by purification of products, using U.S.'s Nicolet-380 FT-IR spectrogrphs, using KBr pressed disc methods infrared point is carried out
Analysis（4000 ~ 400cm of sweep limitss-1）.Apparent viscosity is measured by the type viscosity of BROOKFIELD III of Brookfield companies of the U.S.
Fixed, interfacial tension is determined by the TX500 types rotating interfacial tensimeter that Texas ,Usa university produces.
Using the present invention prepare heat-resistant salt-resistant copolymer NWKY-PAN, with consumption as 0.1～0.3wt% and 0.1～
The aliphatic alcohol polyethenoxy ether carboxylate surfactant of 0.4wt% forms displacement of reservoir oil compositionss, under the conditions of alkali-free, can be used for
The in-place oil and water of the oil field block of higher temperature and salinity, determines the oil displacement agent and simulates in the areas of Shengli Oil Field Sheng Tuo bis-
Solution apparent viscosity at 75 DEG C ~ 85 DEG C of water is more than the dynamic interface between 21mPa.s, with the area's crude oil of Shengli Oil Field Sheng Tuo bis-
Force value, up to 10-3～10-4The ultralow interfacial tension of mN/m, Jing physical modeling's displacement experiment Lab-evaluations are in high temperature, high salt oil
The oil displacement agent can be on the basis of water drive on Tibetan（Water drive improves oil recovery factor up to 40.6%）Oil recovery factor is improved up to 18.1%,
Achieve preferable technique effect.
Description of the drawings
Fig. 1 is the infrared spectrum of copolymer in embodiment 1, can be seen by Fig. 1,3453.4cm-1For NH2Characteristic peak,
1652.7 cm-1For the absworption peak of C=O on amide, 1401.6 cm-1For the absworption peak of the C-N of amide, 1293.6 cm-1For N-
The characteristic absorption peak of-C-N-in vinylpyrrolidone five-membered ring, contains acrylamide, N- ethylene pyrroles in infrared spectrum
The characteristic peak of two kinds of monomers of alkanone, it was demonstrated that products therefrom is strictly acrylamide, the copolymer of N- vinylpyrrolidones.Additionally,
1048 cm in figure-1Nearby occur in that the characteristic absorption peak of C-O-C, functions monomer methacrylic acid -2-（Dimethylamino）
Ethyl ester take part in polymerization, give copolymer with special construction feature.
Below by embodiment, the invention will be further elaborated.
Specific embodiment
【Embodiment 1】
In terms of parts by weight, 69.3 parts of acrylamide and 5.7 parts of N- vinylpyrrolidones are dissolved in 422 parts of water,
The mol ratio for making two kinds of monomers of acrylamide and N, N- DMAA is 95:5, total mass fraction is 15%；With 2
Part sodium hydroxide solution reconciles pH value to 8 ~ 10, pours monomer solution into reaction vessel, makes bath temperature for 5 DEG C, and logical nitrogen is removed
Oxygen 30 minutes；It is subsequently adding 0.003% composite initiation system：0.15% 0.23 part of potassium persulfate solution, 0.09% bisulfite
0.13 part of sodium solution, 0.6% methacrylic acid N, 0.3 part of N- dimethylaminoethyls；After reaction 30 minutes, 20 DEG C are warmed up to, are continued
After constant temperature polyreaction 4 hours, stopped reaction, by the colloidal product for obtaining, adds the sodium hydroxide solution that concentration is 5%
157.6g, at 80 DEG C, hydrolyzes 1 hour, is then vacuum dried, and crushes, that is, obtain temperature-resistant anti-salt copolymer NWKY-PAN, molecule
Amount 1.2 × 107, in salinity 20000mg/L or so is reached（Wherein calcium ions and magnesium ions concentration is more than 500mg/L）, temperature is up to 85 DEG C
In saline under the conditions of high temperature and high salinity it is aging after viscosity retention ratio be 80.5%.
By synthesized temperature-resistant anti-salt copolymer NWKY-PAN0.15wt%, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate
（n=4）The areas of 0.25wt% and 99.6wt% Shengli Oil Fields Sheng Tuo bis- victory injection water uniformly mixes, and is stirred at room temperature 1～3 hour, obtains
Required displacement of reservoir oil compositionss.In 85 DEG C of temperature, salinity 19334mg/L, Ca2++Mg2+In the water of 514mg/L, this group is measured
The apparent viscosity of compound is 21.2mPa.s；Formed between said composition and the area 0-141 well dewatered oils of Shengli Oil Field Sheng Tuo bis-
The ultralow interfacial tension of 0.0056mN/m.Apparent viscosity is measured by the type viscosity of BROOKFIELD III of Brookfield companies of the U.S.
Fixed, interfacial tension is determined by the TX500 types rotating interfacial tensimeter that Texas ,Usa university produces.
First with salinity 19334mg/L, Ca2++Mg2+By rock core, (length is 30 centimetres to the injection water of 514mg/L, a diameter of
2.5 centimetres, permeability is 1.5 microns2) saturation, the pore volume (PV) for determining rock core is 50.2%, then with Shengli Oil Field victory
The two area 0-141 wells dewatered oils that stick together carry out saturation, and under 85 DEG C of constant temperature oil displacement test is simulated：First water drive to aqueous 92%,
Measure water drive and improve oil recovery factor 40.6%, then the displacement of reservoir oil combination of tuberculosiss 0.3pv (rock pore volume) step (f) synthesis
After thing, water drive is measured and can improve again on the basis of water drive oil recovery factor 18.5% to aqueous 99%.
【Embodiment 2】
In terms of parts by weight, 85.2 parts of acrylamide and 89.8 parts of N- caprolactams are dissolved in into 293 parts of water
In, the mol ratio for making two kinds of monomers of acrylamide and N- caprolactams is 65:35, total mass fraction is 35%；With
2 parts of sodium hydroxide solutions reconcile pH value to 8 ~ 10, pour monomer solution into reaction vessel, make bath temperature for 15 DEG C, lead to nitrogen
Deoxygenation 30 minutes；It is subsequently adding 1.5% composite initiation system：3.15% 12.5 parts of potassium persulfate solution, 15.75% sulfurous
12.5 parts of sour hydrogen sodium solution, 5.25% methacrylic acid N, 5 parts of N- dimethylaminoethyls；After reaction 120 minutes, 50 DEG C are warmed up to,
Continue constant temperature polyreaction after 18 hours, stopped reaction, by the colloidal product for obtaining, adds the sodium hydroxide that concentration is 15%
Solution 71.3g, at 90 DEG C, hydrolyzes 3 hours, is then vacuum dried, and crushes, that is, obtain temperature-resistant anti-salt copolymer NWKY-PAN,
Molecular weight 1.1 × 107, in salinity 20000mg/L or so is reached（Wherein calcium ions and magnesium ions concentration is more than 500mg/L）, temperature is up to 85
DEG C high temperature and high salinity under the conditions of saline in it is aging after viscosity retention ratio be 86.9%.
By synthesized temperature-resistant anti-salt copolymer NWKY-PAN0.25wt%, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate
（n=4）The areas of 0.35wt% and 99.4wt% Shengli Oil Fields Sheng Tuo bis- victory injection water uniformly mixes, and is stirred at room temperature 1～3 hour, obtains
Required displacement of reservoir oil compositionss.In 75 DEG C of temperature, salinity 19334mg/L, Ca2++Mg2+In the water of 514mg/L, this group is measured
The apparent viscosity of compound is 28.7mPa.s；Formed between said composition and the area 0-141 well dewatered oils of Shengli Oil Field Sheng Tuo bis-
The ultralow interfacial tension of 0.0043mN/m.Apparent viscosity is measured by the type viscosity of BROOKFIELD III of Brookfield companies of the U.S.
Fixed, interfacial tension is determined by the TX500 types rotating interfacial tensimeter that Texas ,Usa university produces.
First with salinity 19334mg/L, Ca2++Mg2+By rock core, (length is 30 centimetres to the injection water of 514mg/L, a diameter of
2.5 centimetres, permeability is 1.5 microns2) saturation, the pore volume (PV) for determining rock core is 51.8%, then with Shengli Oil Field victory
The two area 0-141 wells dewatered oils that stick together carry out saturation, and under 75 DEG C of constant temperature oil displacement test is simulated：First water drive to aqueous 92%,
Measure water drive and improve oil recovery factor 40.7%, then the displacement of reservoir oil combination of tuberculosiss 0.3pv (rock pore volume) step (f) synthesis
After thing, water drive is measured and can improve again on the basis of water drive oil recovery factor 18.3% to aqueous 99%.
【Embodiment 3】
In terms of parts by weight, 123.2 parts of acrylamide and 26.8 parts of N- caprolactams are dissolved in into 340 parts of water
In, the mol ratio for making two kinds of monomers of acrylamide and N- caprolactams is 90:10, total mass fraction is 30%；With
2 parts of sodium hydroxide solutions reconcile pH value to 8 ~ 10, pour monomer solution into reaction vessel, make bath temperature for 10 DEG C, lead to nitrogen
Deoxygenation 30 minutes；It is subsequently adding 0.03% composite initiation system：0.76% 5 parts of potassium persulfate solution, 0.23% sodium sulfite
1 part of solution, 0.45% methacrylic acid N, 1 part of N- dimethylaminoethyls；After reaction 90 minutes, 25 DEG C are warmed up to, continue constant temperature and gather
After closing reaction 12 hours, stopped reaction, by the colloidal product for obtaining, adds the sodium hydroxide solution 157.6g that concentration is 10%,
At 90 DEG C, hydrolyze 3 hours, be then vacuum dried, crush, that is, obtain temperature-resistant anti-salt copolymer NWKY-PAN, molecular weight 1.7 ×
107, in salinity 20000mg/L or so is reached（Wherein calcium ions and magnesium ions concentration is more than 500mg/L）, temperature is up to 85 DEG C of the high ore deposit of high temperature
In saline under the conditions of change degree it is aging after viscosity retention ratio be 82.7%.
By synthesized temperature-resistant anti-salt copolymer NWKY-PAN0.35wt%, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate
（n=4）The areas of 0.25wt% and 99.4wt% Shengli Oil Fields Sheng Tuo bis- victory injection water uniformly mixes, and is stirred at room temperature 1～3 hour, obtains
Required displacement of reservoir oil compositionss.In 80 DEG C of temperature, salinity 19334mg/L, Ca2++Mg2+In the water of 514 mg/L, this is measured
The apparent viscosity of compositionss is 26.4mPa.s；Shape between said composition and the area 0-141 well dewatered oils of Shengli Oil Field Sheng Tuo bis-
Into the ultralow interfacial tension of 0.0050mN/m.Apparent viscosity by Brookfield companies of the U.S. the type viscometers of BROOKFIELD III
Determine, interfacial tension is determined by the TX500 types rotating interfacial tensimeter that Texas ,Usa university produces.
First with salinity 19334mg/L, Ca2++Mg2+By rock core, (length is 30 centimetres to the injection water of 514mg/L, a diameter of
2.5 centimetres, permeability is 1.5 microns2) saturation, the pore volume (PV) for determining rock core is 51.6%, then with Shengli Oil Field victory
The two area 0-141 wells dewatered oils that stick together carry out saturation, and under 80 DEG C of constant temperature oil displacement test is simulated：First water drive to aqueous 92%,
Measure water drive and improve oil recovery factor 40.4%, then the displacement of reservoir oil combination of tuberculosiss 0.3pv (rock pore volume) step (f) synthesis
After thing, water drive is measured and can improve again on the basis of water drive oil recovery factor 18.7% to aqueous 99%.
【Embodiment 4】
In terms of parts by weight, 49.3 parts of acrylamide and 25.7 parts of N- vinylpyrrolidones are dissolved in 420 parts of water,
The mol ratio for making two kinds of monomers of acrylamide and N- vinylpyrrolidones is 75:25, total mass fraction is 15%；With 2 parts of hydrogen
Sodium hydroxide solution reconciles pH value to 8 ~ 10, pours monomer solution into reaction vessel, makes bath temperature for 8 DEG C, leads to nitrogen deoxygenation 30
Minute；It is subsequently adding 0.15% composite initiation system：0.45% 1 part of potassium persulfate solution, 0.15% sodium sulfite solution
1.5 parts, 0.45% methacrylic acid N, 1 part of N- dimethylaminoethyls；After reaction 60 minutes, 30 DEG C are warmed up to, continue constant temperature polymerization
After reaction 8 hours, stopped reaction, by the colloidal product for obtaining, adds the sodium hydroxide solution 45.8g that concentration is 7.5%,
At 85 DEG C, hydrolyze 2 hours, be then vacuum dried, crush, that is, obtain temperature-resistant anti-salt copolymer NWKY-PAN, molecular weight 1.5 ×
107, in salinity 20000mg/L or so is reached（Wherein calcium ions and magnesium ions concentration is more than 500mg/L）, temperature is up to 85 DEG C of the high ore deposit of high temperature
In saline under the conditions of change degree it is aging after viscosity retention ratio be 83.4%.
By synthesized temperature-resistant anti-salt copolymer NWKY-PAN0.50wt%, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate
（n=4）The areas of 0.40wt% and 99.10wt% Shengli Oil Fields Sheng Tuo bis- victory injection water uniformly mixes, and is stirred at room temperature 1～3 hour, obtains
To required displacement of reservoir oil compositionss.In 78 DEG C of temperature, salinity 19334mg/L, Ca2++Mg2+In the water of 514mg/L, this is measured
The apparent viscosity of compositionss is 30.5mPa.s.；Shape between said composition and the area 0-141 well dewatered oils of Shengli Oil Field Sheng Tuo bis-
Into the ultralow interfacial tension of 0.0045mN/m.Apparent viscosity by Brookfield companies of the U.S. the type viscometers of BROOKFIELD III
Determine, interfacial tension is determined by the TX500 types rotating interfacial tensimeter that Texas ,Usa university produces.
First with salinity 19334mg/L, Ca2++Mg2+By rock core, (length is 30 centimetres to the injection water of 514mg/L, a diameter of
2.5 centimetres, permeability is 1.5 microns2) saturation, the pore volume (PV) for determining rock core is 51.2%, then with Shengli Oil Field victory
The two area 0-141 wells dewatered oils that stick together carry out saturation, and under 78 DEG C of constant temperature oil displacement test is simulated：First water drive to aqueous 92%,
Measure water drive and improve oil recovery factor 40.2%, then the displacement of reservoir oil combination of tuberculosiss 0.3pv (rock pore volume) step (f) synthesis
After thing, water drive is measured and can improve again on the basis of water drive oil recovery factor 18.8% to aqueous 99%.
【Embodiment 5】
In terms of parts by weight, 71.9 parts of acrylamide and 28.1 parts of N- vinylpyrrolidones are dissolved in 395 parts of water,
The mol ratio for making two kinds of monomers of acrylamide and N- vinylpyrrolidones is 75:25, total mass fraction is 20%；With 2 parts of hydrogen
Sodium hydroxide solution reconciles pH value to 8 ~ 10, pours monomer solution into reaction vessel, makes bath temperature for 12 DEG C, leads to nitrogen deoxygenation 30
Minute；It is subsequently adding 0.009% composite initiation system：0.27% 1 part of potassium persulfate solution, 0.54% sodium sulfite solution 1
Part, 0.27% methacrylic acid N, 1 part of N- dimethylaminoethyls；After reaction 75 minutes, 40 DEG C are warmed up to, continue constant temperature polymerization anti-
After answering 15 hours, stopped reaction, by the colloidal product for obtaining, adds the sodium hydroxide solution 156.0g that concentration is 7%, 85
At DEG C, hydrolyze 1.5 hours, be then vacuum dried, crush, that is, obtain temperature-resistant anti-salt copolymer NWKY-PAN, molecular weight 2.1 ×
107, in salinity 20000mg/L or so is reached（Wherein calcium ions and magnesium ions concentration is more than 500mg/L）, temperature is up to 85 DEG C of the high ore deposit of high temperature
In saline under the conditions of change degree it is aging after viscosity retention ratio be 84.2%.
By synthesized temperature-resistant anti-salt copolymer NWKY-PAN0.15wt%, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate
（n=4）The areas of 0.35wt% and 99.5wt% Shengli Oil Fields Sheng Tuo bis- victory injection water uniformly mixes, and is stirred at room temperature 1～3 hour, obtains
Required displacement of reservoir oil compositionss.In 83 DEG C of temperature, salinity 19334mg/L, Ca2++Mg2+In the water of 514mg/L, this group is measured
The apparent viscosity of compound is 21.8mPa.s.；Formed between said composition and the area 0-141 well dewatered oils of Shengli Oil Field Sheng Tuo bis-
The ultralow interfacial tension of 0.0055mN/m.Apparent viscosity is measured by the type viscosity of BROOKFIELD III of Brookfield companies of the U.S.
Fixed, interfacial tension is determined by the TX500 types rotating interfacial tensimeter that Texas ,Usa university produces.
First with salinity 19334mg/L, Ca2++Mg2+By rock core, (length is 30 centimetres to the injection water of 514mg/L, a diameter of
2.5 centimetres, permeability is 1.5 microns2) saturation, the pore volume (PV) for determining rock core is 50.8%, then with Shengli Oil Field victory
The two area 0-141 wells dewatered oils that stick together carry out saturation, and under 83 DEG C of constant temperature oil displacement test is simulated：First water drive to aqueous 92%,
Measure water drive and improve oil recovery factor 40.5%, then the displacement of reservoir oil combination of tuberculosiss 0.3pv (rock pore volume) step (f) synthesis
After thing, water drive is measured and can improve again on the basis of water drive oil recovery factor 18.6% to aqueous 99%.
【Comparative example 1】
Together【Embodiment 1】, with the super high molecular weight polyacrylamide of 0.15wt%, (viscosity-average molecular weight is 2500 to difference
Ten thousand) the above-mentioned Heat Resistant and Salt Tolerant Polymer NWKY-PAN of 0.15wt% are substituted, remaining is identical, and the apparent viscosity for measuring this compositions is
11.5mPa.s, forms the interface of 0.0537mN/m between said composition and the area 0-141 well dewatered oils of Shengli Oil Field Sheng Tuo bis-
Tension force.Apparent viscosity by Brookfield companies of the U.S. BROODFIELDType viscometer is determined, and interfacial tension is by U.S.'s moral
The TX500 type rotating interfacial tensimeters of Ke Sasi universities production.
Displacement composition obtained above is with same【Embodiment 1】Method carry out the displacement of reservoir oil, measure water drive and can improve crude oil and adopt
Yield 40.2%, can again improve oil recovery factor 11.9% on the basis of water drive after the above-mentioned displacement composition of tuberculosiss, the results are shown in Table 1 institute
Show.
【Comparative example 2】
Together【Embodiment 1】, it is fatty that difference substitutes 0.25wt% with the petroleum sodium sulfonate (Wuxi oil plant) of 0.25wt%
Polyoxyethylenated alcohol carboxylate, remaining is identical, and the apparent viscosity for measuring this compositions is 16.3mPa.s, said composition and triumph
The interfacial tension of 0.0667mN/m is formed between the area 0-141 well dewatered oils of oil field Sheng Tuo bis-.Apparent viscosity is by the U.S.
The BROODFIELD of Brookfield companiesType viscometer is determined, and interfacial tension is produced by Texas ,Usa university
TX500 type rotating interfacial tensimeters.
Displacement composition obtained above is with same【Embodiment 1】Method carry out the displacement of reservoir oil, measure water drive and can improve crude oil and adopt
Yield 40.5%, can again improve oil recovery factor 14.6% on the basis of water drive after the above-mentioned displacement composition of tuberculosiss, the results are shown in Table 1 institute
Show.
Table 1
Claims (7)
1. a kind of tertiary oil recovery improves recovery ratio compositionss, with composition weight percentages, including following components：
(1) 0.1～0.3% temperature-resistant anti-salt copolymer NWKY-PAN；
(2) 0.1～0.4% aliphatic alcohol polyethenoxy ether carboxylate surfactant；
(3) water of surplus；
The general molecular formula of wherein (1) component temperature-resistant anti-salt copolymer NWKY-PAN is：
In formula, x, y, m are respectively the construction unit molal quantitys of acrylamide, hydrolyzed acrylamide, N- vinylpyrrolidones, and x is
It is 1～45 that 95～15, y are 4～40, m；The molecular weight of copolymer NWKY-PAN is 1200～18,000,000；The temperature-resistant anti-salt is total to
The preparation method of polymers NWKY-PAN, comprises the following steps：
A) the first monomer, second comonomer are made into into the aqueous solution I that total mass concentration is 5～45w.t.%, wherein the first monomer is
Acrylamide, second comonomer is lactams material；
B) nitrogen deoxidation is led to in solution I, addition accounts for the composite initiation system of total monomer quality 0.001～3%, obtains solution
Ⅱ；Wherein composite initiation system by weight percentage, including following components：(A) 15～85% oxidant；(B) 5～75%
Reducing agent；(C) 10～80% tertiary amines functional monomer；Wherein oxidant is selected from potassium peroxydisulfate, Ammonium persulfate., persulfuric acid
One kind in sodium, reducing agent is selected from the one kind in sodium sulfite, sodium thiosulfate, rongalite, and tertiary amines functional monomer is
Methacrylic acid N, N- dimethylaminoethyl or β-dimethylaminopropionitrile；
C) nitrogen deoxidation is led to in solution II, at 5～20 DEG C, initiation reaction 15～180 minutes, then it is warmed up to 30～80 DEG C,
Continue isothermal reaction 2～16 hours, the colloidal product I for obtaining；
D) alkali liquor that mass concentration is 1～30% is added in colloidal product I, is warming up to 50～100 DEG C, hydrolysis 0.5～3 is little
When, obtain colloidal product II；
E) after colloidal product II being dried, crushed, being sieved, powder heat-resistant salt-resistant copolymer NWKY-PAN is obtained；
Wherein, the first monomer is acrylamide, and second comonomer is N- vinylpyrrolidones；First monomer and second comonomer mole
It is 65～95 than scope:5～35；
Described aliphatic alcohol polyethenoxy ether carboxylate surfactant is selected from aliphatic alcohol polyethenoxy ether carboxylate type the moon-Fei Biao
Face activating agent, general molecular formula is RO (CH2CH2O)nCH2COOM；In formula：R is C14～C16Alkyl, n is any in 3～7
Integer；M is any one metal ion in potassium, sodium or lithium.
2. tertiary oil recovery according to claim 1 improves recovery ratio compositionss, it is characterised in that wet concentration injects from oil field
Water；The total salinity of described injection water is 10000～38000mg/L, and calcium ions and magnesium ions total concentration is 200～1800mg/L.
3. tertiary oil recovery according to claim 2 improves recovery ratio compositionss, it is characterised in that described injection water
Total salinity is 20000～30000mg/L, and calcium ions and magnesium ions total concentration is 400～1000mg/L.
4. tertiary oil recovery according to claim 1 improves recovery ratio compositionss, it is characterised in that described M is selected from potassium
Ion or sodium ion.
5. tertiary oil recovery according to claim 1 improves recovery ratio compositionss, it is characterised in that described M selected from sodium from
Son.
6. the tertiary oil recovery described in claim 1 improves the preparation method of recovery ratio compositionss, comprises the following steps：
A) the first monomer, second comonomer are made into into the aqueous solution I that total mass concentration is 5～45wt%, wherein the first monomer is third
Acrylamide, second comonomer is N- vinylpyrrolidones；
B) nitrogen deoxidation is led to in solution I, addition accounts for the composite initiation system of total monomer quality 0.001～3%, obtains solution
Ⅱ；Wherein composite initiation system by weight percentage, including following components：(A) 15～85% oxidant；(B) 5～75%
Reducing agent；(C) 10～80% tertiary amines functional monomer；Wherein oxidant is selected from potassium peroxydisulfate, Ammonium persulfate., persulfuric acid
At least one in sodium, at least one of the reducing agent in sodium sulfite, sodium thiosulfate, rongalite, tertiary amines function
Property monomer be methacrylic acid N, N- dimethylaminoethyls or β-dimethylaminopropionitrile；
C) nitrogen deoxidation is led to in solution II, at 5～20 DEG C, initiation reaction 15～180 minutes, then it is warmed up to 30～80 DEG C,
Continue isothermal reaction 2～16 hours, the colloidal product I for obtaining；
D) alkali liquor that mass concentration is 1～30% is added in colloidal product I, is warming up to 50～100 DEG C, hydrolysis 0.5～6 is little
When, obtain colloidal product II；
E) after colloidal product II being dried, crushed, being sieved, powder heat-resistant salt-resistant copolymer NWKY-PAN is obtained；
F) heat-resistant salt-resistant copolymer NWKY-PAN, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate and injection water are uniformly mixed,
Stirring 1～3 hour, obtains required compositionss；With composition weight percentages, heat-resistant salt-resistant copolymer NWKY-PAN, fat
The proportioning of fat polyoxyethylenated alcohol carboxylate and injection water is 0.01～3.0%: 0.01～5.0%: 92.0～99.98%.
7. any one tertiary oil recovery described in Claims 1 to 5 improves recovery ratio compositionss for tertiary oil production in oil field life
The purposes of recovery ratio is improved in product.
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