CN103897682A - 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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- CN103897682A CN103897682A CN201210575777.1A CN201210575777A CN103897682A CN 103897682 A CN103897682 A CN 103897682A CN 201210575777 A CN201210575777 A CN 201210575777A CN 103897682 A CN103897682 A CN 103897682A
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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 and improve recovery ratio composition and method of making the same and purposes.
Background technology
Along with the development of world economy, the social required quantity of oil constantly increases, and prospective oil constantly reduces.Oil is just becoming more and more valuable as non-renewable resource.The problem facing has one, and imbalance between supply and demand is outstanding, and petroleum demand amount is more larger, and find is fewer and feweri; Two, also left in exhausted oil reservoir have a substantial oil.Primary oil recovery (POR) can the underground crude oil of extraction 10～25%, and secondary oil recovery (SOR) can the underground crude oil of extraction 15～25%, i.e. a primary oil recovery and secondary oil recovery extraction 25～50% underground crude oil.In order to guarantee oil supply steady in a long-term, to meet human wants, must research and development improve petroleum recovery technology, tertiary oil recovery (EOR), by intensified oil reduction measure, can make oil recovery factor improve 6～20% again, even more.
Domestic each elephant through once, secondary oil recovery, crude oil water content constantly increases, part elephant successively enters tertiary phase.Polymer flooding is the main technique methods of tertiary oil recovery, and oil-displacement mechanism is clear, and technique is relatively simple, and technology reaches its maturity, and is one and effectively improves recovery efficiency technique measure.The oil-displacement mechanism of polymkeric substance is mainly the viscosity of utilizing water-soluble polyacrylamide molecular chain, improves the mobility ratio of displacing fluid, improves efficiency of displacement and swept volume, thereby reaches the object that improves recovery ratio.
Because the tertiary oil recovery cycle is long, deep layer oil temperature is high, and therefore, polymkeric substance used for tertiary oil recovery must have good tackify, heatproof, salt resistance, stable performance.And current used partially hydrolyzed polyacrylamide is under high temperature and high salt condition, be very easily hydrolyzed, thereby cause carboxyl-content to increase, polymer molecular chain is curling, and Efficient Adhesive Promotion sharply reduces, and the high volence metal ion in oil reservoir is (as Ca in addition
2+, Mg
2+) easily make partially hydrolyzed polyacrylamide precipitate, thereby further reduce the Efficient Adhesive Promotion of partially hydrolyzed polyacrylamide, thereby be difficult to meet the demand of deep two, three class oil reservoir high temperature and high salinities.In recent years, the research of domestic and international temperature resistant antisalt polymkeric substance used for tertiary oil recovery can be divided into two general orientation, i.e. the chemical modification of ultrahigh molecular weight partially-hydrolyzed polyacrylamide and polyacrylamide.The chemical modification of polyacrylamide is undertaken by the mode of introducing other monomer copolymerizations mostly.
Patent CN 1814637A discloses a kind of preparation method of temperature-tolerant anti-salt polyacrylamide, introduce three kinds of heat-resistant salt-resistant monomers and acrylamide copolymerization, synthesize acrylamide/2-acrylamide-2-methylpro panesulfonic acid/methacrylic acid/dimethyl diallyl ammonium chloride tetrapolymer, acrylamide/2-acrylamide and-the heat-resistant salt-resistant multipolymers such as 2-methyl propane sulfonic acid/methylene-succinic acid/acrylyl oxy-ethyl-trimethyl salmiac tetrapolymer, the heat-resistant salt-resistant performance of the product that these polymkeric substance have improved really, but can only meet salinity lower than 10000mg/L, temperature is lower than under the condition of 65 ℃, can not meet the application demand under higher temperature and salinity condition.
Patent CN 1876751A discloses a kind of braided comb-shaped thickener for salt-resistant polymer, this thickening material heat-resistant salt-resistant Performance Ratio comb shape heat-resistant salt-resistant thickening agent of copolymer will be got well, and molecular weight is lower, at grand celebration clear water (total mineralization 1000mg/L, wherein calcium ions and magnesium ions 15mg/L), grand celebration sewage (total mineralization 4000mg/L, wherein calcium ions and magnesium ions 60mg/L), huge port sewage (total mineralization 5024mg/L, wherein calcium ions and magnesium ions 60mg/L) in Efficient Adhesive Promotion be better than plain polypropylene acid amides product and comb shaped antisalt polymer industrial goods, can adapt to the requirement of grand celebration two class oil reservoir tertiary oil recoveries, but still cannot meet 10000mg/L, Ca
2++ Mg
2+for the requirement of tertiary oil recovery in the above salinity oil reservoir of 200mg/L.
And in recent years, mainly concentrate on improvement of initiator system, polymerization process and method for hydrolysis etc. about the research of ultra high molecular weight anion-type polyacrylamide.As CN1865299, CN 1498908A, CN1746198, CN101157736A and CN1240799 etc. have studied polymerization technique, initiation technique and hydrolysis process etc., although had larger improvement improving aspect the molecular weight of anion-polyacrylamide or dissolution rate by all means, but in the less concern of temperature resistant antisalt aspect of performance, some technique or method are comparatively complicated, industrial production or can be subject to some restrictions in tertiary oil recovery practical application.
In tertiary oil recovery at present, for class oil reservoir (temperature <70 ℃, salinity <1 × 10
4mg/L) polymkeric substance is easily prepared, and meets two class oil reservoirs (70～80 ℃ of temperature, salinity 1～3 × 10
4) and three class oil reservoir (temperature >80 ℃, salinity >3 × 10
4) require polymkeric substance little, be not price too higher position be unstable properties.So for the harsh oil reservoir of those high temperature and high salts, we ought to seek one and have better stability to hydrolysis, and had the polymkeric substance of higher solution apparent viscosity in salt solution.Compound and the application in tertiary oil recovery of polymkeric substance that is suitable for just high temperature and high salt of the present invention and preparation method thereof, binary.
Summary of the invention
One of technical problem to be solved by this invention is containing the polymkeric substance facile hydrolysis under high temperature and high salt condition in the oil-displacing agent of polymkeric substance in prior art, can not meet tertiary oil recovery requirement, problem that oil displacement efficiency is low, provide a kind of tertiary oil recovery to improve recovery ratio composition, the composition containing temperature resistant antisalt multipolymer NWKY-PAN is used for oil displacement process by the method, there is stability to hydrolysis good, the high feature of oil displacement efficiency under high temperature and high salt condition.
Two of technical problem to be solved by this invention is to provide the preparation method of a kind of displacement of reservoir oil corresponding with one of technical solution problem composition.
Three of technical problem to be solved by this invention is to provide the purposes of a kind of displacement of reservoir oil corresponding with one of technical solution problem composition.
In order one of to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of tertiary oil recovery improves recovery ratio composition, in composition weight per-cent, comprises following component:
(1) 0.01～5.0% temperature resistant antisalt multipolymer NWKY-PAN;
(2) 0.01～5.0% aliphatic alcohol polyethenoxy ether carboxylate tensio-active agent;
(3) 90.0～99.98% water;
Wherein the general molecular formula of (1) component temperature resistant antisalt multipolymer NWKY-PAN is:
In formula, p is-CH
2-quantity, numerical value is that 1 ~ 3, x, y, m are respectively the structural unit mole numbers of acrylamide, hydrolysis acrylamide, lactams monomer, x is that 95 ~ 15, y is that 4 ~ 40, m is 1 ~ 45; The molecular weight of multipolymer NWKY-PAN is 1200～1,800 ten thousand.
In technique scheme, preferred technical scheme, wet concentration is from oilfield injection water; The total mineralization of described injected water is that 10000～38000mg/L, calcium ions and magnesium ions total concn are 200～1800mg/L.Tensio-active agent is selected from aliphatic alcohol polyethenoxy ether carboxylate type the moon-nonsurfactant, and general molecular formula is RO (CH
2cH
2o)
ncH
2cOOM; In formula: R is C
10～C
20alkyl, be preferably C
1,2～C
18alkyl; N is the adduction number of ethoxy group EO, is selected from any one integer in 2～8; M is any one metal ion being selected from potassium, sodium or lithium, and preferred version is potassium or sodium.Preferred technical scheme, the total mineralization of described injected water is 20000～30000mg/L, calcium ions and magnesium ions total concn is 400～1000mg/L.Preferred technical scheme, described tensio-active agent is selected from aliphatic alcohol polyethenoxy ether carboxylate type the moon-nonsurfactant, and general molecular formula is RO (CH
2cH
2o)
ncH
2cOOM; In formula: R is C
12～C
18alkyl, n is the adduction number of ethoxy group EO, M is for being selected from potassium ion or sodium ion.Preferred technical scheme, in described aliphatic alcohol polyethenoxy ether carboxylate, R is C
14～C
16alkyl; N is selected from the arbitrary integer in 3～7; Metal ions M is selected from sodium ion.
For solve the problems of the technologies described above two, the technical solution adopted in the present invention is as follows: a kind of tertiary oil recovery improves the preparation method of recovery ratio composition, comprises the following steps:
A) the first monomer, the second monomer are made into the aqueous solution I that total mass concentration is 5 ~ 45w.t.%, wherein the first monomer is acrylamide, and the second monomer is lactams material;
B) in solution I, lead to nitrogen deoxidation, add the composite initiation system that accounts for total monomer quality 0.001 ~ 3%, obtain solution II; Wherein composite initiation system by weight percentage, comprises following component: (A) 15～85% oxygenant; (B) 5～75% reductive agent; (C) 10～80% tertiary amines functional monomer; Wherein oxygenant is selected from the one in Potassium Persulphate, ammonium persulphate, Sodium Persulfate, reductive agent is selected from the one in sodium bisulfite, Sulfothiorine, rongalite, tertiary amines functional monomer is methacrylic acid N, N-dimethylaminoethyl or β-dimethylaminopropionitrile;
C) in solution II, lead to nitrogen deoxidation, at 5 ~ 20 ℃, initiation reaction 15 ~ 180 minutes, then be warmed up to 30 ~ 80 ℃, continue isothermal reaction 2 ~ 16 hours, the colloidal product I obtaining;
D) be 1 ~ 30% alkali lye to adding mass concentration in colloidal product I, be warming up to 50 ~ 100 ℃, be hydrolyzed 0.5 ~ 3 hour, obtain colloidal product II;
E) after colloidal product II is dried, pulverizes, is sieved, make Powdered heat-resistant salt-resistant multipolymer NWKY-PAN;
F) heat-resistant salt-resistant multipolymer NWKY-PAN, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate and injected water are evenly mixed, stir 1～3 hour, obtain required composition; In composition weight per-cent, the proportioning of heat-resistant salt-resistant multipolymer NWKY-PAN, aliphatic alcohol polyethenoxy ether carboxylate and injected water is 0.01～3.0%: 0.01～5.0%: 92.0～99.98%.
In technique scheme, the preferred acrylamide of preferred version the first monomer, the one in the preferred N-V-Pyrol RC of the second monomer, N-ethene hexanolactam; The mol ratio preferable range of the first monomer and the second monomer is 65 ~ 95: 5 ~ 35; In monomer solution, the total massfraction preferable range of the first monomer and the second monomer is 15 ~ 35%; Composite initiation system concentration preferably accounts for monomer mass mark 0.003 ~ 1.5%; The preferred Potassium Persulphate of oxygenant and ammonium persulphate in composite initiation system, the preferred sodium bisulfite of reductive agent, tertiary amines function monomer preferable methyl vinylformic acid N, N-dimethylaminoethyl; Preferably 5 ~ 15 ℃ of kick off temperatures, preferably 30 ~ 120 minutes initiation time; Preferably 20 ~ 50 ℃ of polymerization temperatures, polymerization reaction time preferably 4 ~ 18 hours; Alkali lye is preferably sodium hydroxide solution, mass concentration preferably 5 ~ 15%, preferably 80 ~ 90 ℃ of hydrolysis temperatures, hydrolysis time preferable range 1 ~ 3 hour.
For solve the problems of the technologies described above three, the technical solution adopted in the present invention is as follows:
Above-mentioned tertiary oil recovery improves recovery ratio composition and produces and improve recovery ratio for tertiary oil production in oil field.
The prepared tertiary oil recovery of the present invention improves the temperature resistant antisalt multipolymer NWKY-PAN in composition for recovery ratio, due to the angle of amide group facile hydrolysis in high temperature and high salinity salt solution from increase polymer chain rigidity and inhibition polymkeric substance, by introduce lactams monomer and the acrylamide copolymerization with ring texture in molecular chain, increase on the one hand polymer molecule chain rigidity, polymer stabilizing is improved, can suppress on the other hand amide group hydrolysis in polymkeric substance, the functional group of this type of monomer by with the functionalization of amide group, as hydrogen bond action etc., amide group is formed to protection, suppress the hydrolysis of amide group, thereby improve the stability to hydrolysis of polymkeric substance, and then the heat-resistant salt-resistant performance of raising polymkeric substance.This multipolymer is under high temperature and high salinity, and stability to hydrolysis improves, owing to adopting composite initiation system, the temperature resistant antisalt multipolymer NWKY-PAN molecular weight >10 making
7reach its Biao in the salt solution under the high temperature and high salinity condition that about 20000mg/L (wherein calcium ions and magnesium ions concentration is greater than 500mg/L), temperature reach 85 ℃ in salinity and see Nian Du≤21mPas, viscosity retention ratio after aging reaches more than 80.5%, there is higher viscosity retention ratio, embody stronger resistant to hydrolysis ability, possess good heat-resistant salt-resistant performance.And this preparation method's technical process is comparatively easy, is conducive to suitability for industrialized production.
By after purification of products, application U.S. Nicolet-380 FT-IR spectrograph, utilizes KBr pressed disc method to carry out infrared analysis (sweep limit 4000 ~ 400cm
-1).Apparent viscosity is by the BROOKFIELD III type viscometer determining of Brookfield company of the U.S., and the TX500 type rotation interfacial tensimeter that interfacial tension is produced by Texas ,Usa university is measured.
The heat-resistant salt-resistant multipolymer NWKY-PAN that adopts the present invention to prepare, take consumption as 0.1～0.3wt% and the aliphatic alcohol polyethenoxy ether carboxylate tensio-active agent of 0.1～0.4wt% form displacement of reservoir oil composition, under alkali-free condition, can be used for in-place oil and the water of the oil field block of comparatively high temps and salinity, measure the solution apparent viscosity of this oil-displacing agent at 75 ℃ ~ 85 ℃ of Shengli Oil Field Sheng Tuo bis-district's Simulated Water and be greater than 21mPa.s, and the dynamic interface tension value between Shengli Oil Field Sheng Tuo bis-district's crude oil, can reach 10
-3～10
-4the ultra low interfacial tension of mN/m, can on water drive basis, can reach 18.1% by (water drive improves oil recovery factor and reaches 40.6%) raising oil recovery factor through physical simulation displacement test Lab-evaluation this oil-displacing agent on high temperature, high salinity reservoir, obtain good technique effect.
Accompanying drawing explanation
Fig. 1 is the infrared spectra of multipolymer in embodiment 1, by seeing in Fig. 1, and 3453.4cm
-1for NH
2characteristic peak, 1652.7 cm
-1for the absorption peak of C=O on acid amides, 1401.6 cm
-1for the absorption peak of the C-N of acid amides, 1293.6 cm
-1for in N-V-Pyrol RC five-ring-C-N-charateristic avsorption band, in infrared spectrum, comprised the characteristic peak of acrylamide, two kinds of monomers of N-V-Pyrol RC, prove that products therefrom is the multipolymer of acrylamide, N-V-Pyrol RC really.In addition 1048 cm in figure,
-1near there is the charateristic avsorption band of C-O-C, functions monomer methacrylic acid-2-(dimethylamino) ethyl ester participated in polymerization, gives multipolymer with special construction feature.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
In parts by weight, the N-V-Pyrol RC of the acrylamide of 69.3 parts and 5.7 parts is dissolved in 422 parts of water, making the mol ratio of acrylamide and two kinds of monomers of N,N-DMAA is 95: 5, total massfraction is 15%; Reconcile pH value to 8 ~ 10 with 2 parts of sodium hydroxide solutions, pour monomer solution into reaction vessel, making bath temperature is 5 ℃, logical nitrogen deoxygenation 30 minutes; Then add 0.003% composite initiation system: 0.23 part of 0.15% potassium persulfate solution, 0.09% 0.13 part of sodium sulfite solution, 0.6% methacrylic acid N, 0.3 part of N-dimethylaminoethyl; React after 30 minutes, be warmed up to 20 ℃, continue constant temperature polyreaction after 4 hours, stopped reaction, by the colloidal product obtaining, adding concentration is 5% sodium hydroxide solution 157.6g, at 80 ℃, is hydrolyzed 1 hour, then vacuum-drying, pulverize, obtain temperature resistant antisalt multipolymer NWKY-PAN, molecular weight 1.2 × 10
7, the viscosity retention ratio reaching after aging in the salt solution under the high temperature and high salinity condition that about 20000mg/L (wherein calcium ions and magnesium ions concentration is greater than 500mg/L), temperature reach 85 ℃ in salinity is 80.5%.
The temperature resistant antisalt multipolymer NWKY-PAN0.15wt% of synthesized, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate (n=4) 0.25wt% and 99.6wt% Shengli Oil Field Sheng Tuo bis-district's victory injected waters are evenly mixed, stirring at room temperature 1～3 hour, obtains required displacement of reservoir oil composition.At 85 ℃ of temperature, salinity 19334mg/L, Ca
2++ Mg
2+in the water of 514mg/L, the apparent viscosity that records this composition is 21.2mPa.s; Between said composition and Shengli Oil Field Sheng Tuo bis-district 0-141 well dewatered oils, form the ultra low interfacial tension of 0.0056mN/m.Apparent viscosity is by the BROOKFIELD III type viscometer determining of Brookfield company of the U.S., and the TX500 type rotation interfacial tensimeter that interfacial tension is produced by Texas ,Usa university is measured.
First with salinity 19334mg/L, Ca
2++ Mg
2+by rock core, (length is 30 centimetres to the injected water of 514mg/L, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns
2) saturated, the volume of voids (PV) of measuring rock core is 50.2%, then carry out saturated with Shengli Oil Field Sheng Tuo bis-district 0-141 well dewatered oils, under 85 ℃ of constant temperature, carry out imitation oil displacement experiment test: first water drive is to moisture 92%, record water drive and improve oil recovery factor 40.6%, the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (f) is with after composition again, and water drive, to moisture 99%, record on water drive basis and can improve oil recovery factor 18.5% again.
[embodiment 2]
In parts by weight, the N-caprolactam of the acrylamide of 85.2 parts and 89.8 parts is dissolved in 293 parts of water, making the mol ratio of acrylamide and two kinds of monomers of N-caprolactam is 65: 35, total massfraction is 35%; Reconcile pH value to 8 ~ 10 with 2 parts of sodium hydroxide solutions, pour monomer solution into reaction vessel, making bath temperature is 15 ℃, logical nitrogen deoxygenation 30 minutes; Then add 1.5% composite initiation system: 12.5 parts of 3.15% potassium persulfate solutions, 15.75% 12.5 parts of sodium sulfite solution, 5.25% methacrylic acid N, 5 parts of N-dimethylaminoethyls; React after 120 minutes, be warmed up to 50 ℃, continue constant temperature polyreaction after 18 hours, stopped reaction, by the colloidal product obtaining, adding concentration is 15% sodium hydroxide solution 71.3g, at 90 ℃, is hydrolyzed 3 hours, then vacuum-drying, pulverize, obtain temperature resistant antisalt multipolymer NWKY-PAN, molecular weight 1.1 × 10
7, the viscosity retention ratio reaching after aging in the salt solution under the high temperature and high salinity condition that about 20000mg/L (wherein calcium ions and magnesium ions concentration is greater than 500mg/L), temperature reach 85 ℃ in salinity is 86.9%.
The temperature resistant antisalt multipolymer NWKY-PAN0.25wt% of synthesized, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate (n=4) 0.35wt% and 99.4wt% Shengli Oil Field Sheng Tuo bis-district's victory injected waters are evenly mixed, stirring at room temperature 1～3 hour, obtains required displacement of reservoir oil composition.At 75 ℃ of temperature, salinity 19334mg/L, Ca
2++ Mg
2+in the water of 514mg/L, the apparent viscosity that records this composition is 28.7mPa.s; Between said composition and Shengli Oil Field Sheng Tuo bis-district 0-141 well dewatered oils, form the ultra low interfacial tension of 0.0043mN/m.Apparent viscosity is by the BROOKFIELD III type viscometer determining of Brookfield company of the U.S., and the TX500 type rotation interfacial tensimeter that interfacial tension is produced by Texas ,Usa university is measured.
First with salinity 19334mg/L, Ca
2++ Mg
2+by rock core, (length is 30 centimetres to the injected water of 514mg/L, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns
2) saturated, the volume of voids (PV) of measuring rock core is 51.8%, then carry out saturated with Shengli Oil Field Sheng Tuo bis-district 0-141 well dewatered oils, under 75 ℃ of constant temperature, carry out imitation oil displacement experiment test: first water drive is to moisture 92%, record water drive and improve oil recovery factor 40.7%, the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (f) is with after composition again, and water drive, to moisture 99%, record on water drive basis and can improve oil recovery factor 18.3% again.
[embodiment 3]
In parts by weight, the N-caprolactam of the acrylamide of 123.2 parts and 26.8 parts is dissolved in 340 parts of water, making the mol ratio of acrylamide and two kinds of monomers of N-caprolactam is 90: 10, total massfraction is 30%; Reconcile pH value to 8 ~ 10 with 2 parts of sodium hydroxide solutions, pour monomer solution into reaction vessel, making bath temperature is 10 ℃, logical nitrogen deoxygenation 30 minutes; Then add 0.03% composite initiation system: 5 parts of 0.76% potassium persulfate solutions, 0.23% 1 part of sodium sulfite solution, 0.45% methacrylic acid N, 1 part of N-dimethylaminoethyl; React after 90 minutes, be warmed up to 25 ℃, continue constant temperature polyreaction after 12 hours, stopped reaction, by the colloidal product obtaining, adding concentration is 10% sodium hydroxide solution 157.6g, at 90 ℃, is hydrolyzed 3 hours, then vacuum-drying, pulverize, obtain temperature resistant antisalt multipolymer NWKY-PAN, molecular weight 1.7 × 10
7, the viscosity retention ratio reaching after aging in the salt solution under the high temperature and high salinity condition that about 20000mg/L (wherein calcium ions and magnesium ions concentration is greater than 500mg/L), temperature reach 85 ℃ in salinity is 82.7%.
The temperature resistant antisalt multipolymer NWKY-PAN0.35wt% of synthesized, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate (n=4) 0.25wt% and 99.4wt% Shengli Oil Field Sheng Tuo bis-district's victory injected waters are evenly mixed, stirring at room temperature 1～3 hour, obtains required displacement of reservoir oil composition.At 80 ℃ of temperature, salinity 19334mg/L, Ca
2++ Mg
2+in the water of 514 mg/L, the apparent viscosity that records this composition is 26.4mPa.s; Between said composition and Shengli Oil Field Sheng Tuo bis-district 0-141 well dewatered oils, form the ultra low interfacial tension of 0.0050mN/m.Apparent viscosity is by the BROOKFIELD III type viscometer determining of Brookfield company of the U.S., and the TX500 type rotation interfacial tensimeter that interfacial tension is produced by Texas ,Usa university is measured.
First with salinity 19334mg/L, Ca
2++ Mg
2+by rock core, (length is 30 centimetres to the injected water of 514mg/L, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns
2) saturated, the volume of voids (PV) of measuring rock core is 51.6%, then carry out saturated with Shengli Oil Field Sheng Tuo bis-district 0-141 well dewatered oils, under 80 ℃ of constant temperature, carry out imitation oil displacement experiment test: first water drive is to moisture 92%, record water drive and improve oil recovery factor 40.4%, the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (f) is with after composition again, and water drive, to moisture 99%, record on water drive basis and can improve oil recovery factor 18.7% again.
[embodiment 4]
In parts by weight, the N-V-Pyrol RC of the acrylamide of 49.3 parts and 25.7 parts is dissolved in 420 parts of water, making the mol ratio of acrylamide and two kinds of monomers of N-V-Pyrol RC is 75: 25, total massfraction is 15%; Reconcile pH value to 8 ~ 10 with 2 parts of sodium hydroxide solutions, pour monomer solution into reaction vessel, making bath temperature is 8 ℃, logical nitrogen deoxygenation 30 minutes; Then add 0.15% composite initiation system: 1 part of 0.45% potassium persulfate solution, 0.15% 1.5 parts of sodium sulfite solution, 0.45% methacrylic acid N, 1 part of N-dimethylaminoethyl; React after 60 minutes, be warmed up to 30 ℃, continue constant temperature polyreaction after 8 hours, stopped reaction, by the colloidal product obtaining, adding concentration is 7.5% sodium hydroxide solution 45.8g, at 85 ℃, is hydrolyzed 2 hours, then vacuum-drying, pulverize, obtain temperature resistant antisalt multipolymer NWKY-PAN, molecular weight 1.5 × 10
7, the viscosity retention ratio reaching after aging in the salt solution under the high temperature and high salinity condition that about 20000mg/L (wherein calcium ions and magnesium ions concentration is greater than 500mg/L), temperature reach 85 ℃ in salinity is 83.4%.
The temperature resistant antisalt multipolymer NWKY-PAN0.50wt% of synthesized, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate (n=4) 0.40wt% and 99.10wt% Shengli Oil Field Sheng Tuo bis-district's victory injected waters are evenly mixed, stirring at room temperature 1～3 hour, obtains required displacement of reservoir oil composition.At 78 ℃ of temperature, salinity 19334mg/L, Ca
2++ Mg
2+in the water of 514mg/L, the apparent viscosity that records this composition is 30.5mPa.s.; Between said composition and Shengli Oil Field Sheng Tuo bis-district 0-141 well dewatered oils, form the ultra low interfacial tension of 0.0045mN/m.Apparent viscosity is by the BROOKFIELD III type viscometer determining of Brookfield company of the U.S., and the TX500 type rotation interfacial tensimeter that interfacial tension is produced by Texas ,Usa university is measured.
First with salinity 19334mg/L, Ca
2++ Mg
2+by rock core, (length is 30 centimetres to the injected water of 514mg/L, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns
2) saturated, the volume of voids (PV) of measuring rock core is 51.2%, then carry out saturated with Shengli Oil Field Sheng Tuo bis-district 0-141 well dewatered oils, under 78 ℃ of constant temperature, carry out imitation oil displacement experiment test: first water drive is to moisture 92%, record water drive and improve oil recovery factor 40.2%, the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (f) is with after composition again, and water drive, to moisture 99%, record on water drive basis and can improve oil recovery factor 18.8% again.
[embodiment 5]
In parts by weight, the N-V-Pyrol RC of the acrylamide of 71.9 parts and 28.1 parts is dissolved in 395 parts of water, making the mol ratio of acrylamide and two kinds of monomers of N-V-Pyrol RC is 75: 25, total massfraction is 20%; Reconcile pH value to 8 ~ 10 with 2 parts of sodium hydroxide solutions, pour monomer solution into reaction vessel, making bath temperature is 12 ℃, logical nitrogen deoxygenation 30 minutes; Then add 0.009% composite initiation system: 1 part of 0.27% potassium persulfate solution, 0.54% 1 part of sodium sulfite solution, 0.27% methacrylic acid N, 1 part of N-dimethylaminoethyl; React after 75 minutes, be warmed up to 40 ℃, continue constant temperature polyreaction after 15 hours, stopped reaction, by the colloidal product obtaining, adding concentration is 7% sodium hydroxide solution 156.0g, at 85 ℃, is hydrolyzed 1.5 hours, then vacuum-drying, pulverize, obtain temperature resistant antisalt multipolymer NWKY-PAN, molecular weight 2.1 × 10
7, the viscosity retention ratio reaching after aging in the salt solution under the high temperature and high salinity condition that about 20000mg/L (wherein calcium ions and magnesium ions concentration is greater than 500mg/L), temperature reach 85 ℃ in salinity is 84.2%.
The temperature resistant antisalt multipolymer NWKY-PAN0.15wt% of synthesized, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate (n=4) 0.35wt% and 99.5wt% Shengli Oil Field Sheng Tuo bis-district's victory injected waters are evenly mixed, stirring at room temperature 1～3 hour, obtains required displacement of reservoir oil composition.At 83 ℃ of temperature, salinity 19334mg/L, Ca
2++ Mg
2+in the water of 514mg/L, the apparent viscosity that records this composition is 21.8mPa.s.; Between said composition and Shengli Oil Field Sheng Tuo bis-district 0-141 well dewatered oils, form the ultra low interfacial tension of 0.0055mN/m.Apparent viscosity is by the BROOKFIELD III type viscometer determining of Brookfield company of the U.S., and the TX500 type rotation interfacial tensimeter that interfacial tension is produced by Texas ,Usa university is measured.
First with salinity 19334mg/L, Ca
2++ Mg
2+by rock core, (length is 30 centimetres to the injected water of 514mg/L, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns
2) saturated, the volume of voids (PV) of measuring rock core is 50.8%, then carry out saturated with Shengli Oil Field Sheng Tuo bis-district 0-141 well dewatered oils, under 83 ℃ of constant temperature, carry out imitation oil displacement experiment test: first water drive is to moisture 92%, record water drive and improve oil recovery factor 40.5%, the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (f) is with after composition again, and water drive, to moisture 99%, record on water drive basis and can improve oil recovery factor 18.6% again.
[comparative example 1]
With [embodiment 1], difference substitutes the above-mentioned temperature resistant antisalt polymkeric substance NWKY-PAN of 0.15wt% take the super high molecular weight polyacrylamide (viscosity-average molecular weight is as 2,500 ten thousand) of 0.15wt%, all the other are identical, the apparent viscosity that records this composition is 11.5mPa.s, forms the interfacial tension of 0.0537mN/m between said composition and Shengli Oil Field Sheng Tuo bis-district 0-141 well dewatered oils.Apparent viscosity is by the BROODFIELD of Brookfield company of the U.S.
type viscometer determining, interfacial tensimeter is dripped in the TX500 type rotation that interfacial tension is produced by Texas ,Usa university.
The above-mentioned displacement of reservoir oil composition making carries out the displacement of reservoir oil with the method with [embodiment 1], records water drive and can improve oil recovery factor 40.2%, after the above-mentioned displacement of reservoir oil composition of metaideophone, can on water drive basis, improve oil recovery factor 11.9% again, the results are shown in Table shown in 1.
[comparative example 2]
With [embodiment 1], difference substitutes 0.25wt% aliphatic alcohol polyethenoxy ether carboxylate with the petroleum sodium sulfonate (Wuxi refinery) of 0.25wt%, all the other are identical, the apparent viscosity that records this composition is 16.3mPa.s, forms the interfacial tension of 0.0667mN/m between said composition and Shengli Oil Field Sheng Tuo bis-district 0-141 well dewatered oils.Apparent viscosity is by the BROODFIELD of Brookfield company of the U.S.
type viscometer determining, interfacial tensimeter is dripped in the TX500 type rotation that interfacial tension is produced by Texas ,Usa university.
The above-mentioned displacement of reservoir oil composition making carries out the displacement of reservoir oil with the method with [embodiment 1], records water drive and can improve oil recovery factor 40.5%, after the above-mentioned displacement of reservoir oil composition of metaideophone, can on water drive basis, improve oil recovery factor 14.6% again, the results are shown in Table shown in 1.
Table 1
Claims (9)
1. tertiary oil recovery improves a recovery ratio composition, in composition weight per-cent, comprises following component:
(1) 0.01～5.0% temperature resistant antisalt multipolymer NWKY-PAN;
(2) 0.01～5.0% aliphatic alcohol polyethenoxy ether carboxylate tensio-active agent;
(3) 90.0～99.98% water;
Wherein the general molecular formula of (1) component temperature resistant antisalt multipolymer NWKY-PAN is:
In formula, p is-CH
2-quantity, numerical value is that 1 ~ 3, x, y, m are respectively the structural unit mole numbers of acrylamide, hydrolysis acrylamide, lactams monomer, x is that 95 ~ 15, y is that 4 ~ 40, m is 1 ~ 45; The molecular weight of multipolymer NWKY-PAN is 1200～1,800 ten thousand.
2. tertiary oil recovery according to claim 1 improves recovery ratio composition, it is characterized in that wet concentration is from oilfield injection water; The total mineralization of described injected water is 10000～38000mg/L, and calcium ions and magnesium ions total concn is 200～1800mg/L.
3. tertiary oil recovery according to claim 1 improves recovery ratio composition, it is characterized in that described aliphatic alcohol polyethenoxy ether carboxylate tensio-active agent is selected from aliphatic alcohol polyethenoxy ether carboxylate type the moon-nonsurfactant, general molecular formula is RO (CH
2cH
2o)
ncH
2cOOM; In formula: R is C
10～C
20alkyl, n is the adduction number of ethoxy group EO, M is any one metal ion being selected from potassium, sodium or lithium.
4. tertiary oil recovery according to claim 3 improves recovery ratio composition, it is characterized in that in described aliphatic alcohol polyethenoxy ether carboxylate, R is C
12～C
18alkyl; N is selected from the arbitrary integer in 2～8; Metal ions M is selected from potassium or sodium.
5. tertiary oil recovery according to claim 2 improves recovery ratio composition, it is characterized in that the total mineralization of described injected water is 20000～30000mg/L, and calcium ions and magnesium ions total concn is 400～1000mg/L.
6. tertiary oil recovery according to claim 3 improves recovery ratio composition, it is characterized in that described tensio-active agent is selected from aliphatic alcohol polyethenoxy ether carboxylate type the moon-nonsurfactant, and general molecular formula is RO (CH
2cH
2o)
ncH
2cOOM; In formula: R is C
12～C
18alkyl, n is the adduction number of ethoxy group EO, M is for being selected from potassium ion or sodium ion.
7. tertiary oil recovery according to claim 4 improves recovery ratio composition, it is characterized in that in described aliphatic alcohol polyethenoxy ether carboxylate, R is C
14～C
16alkyl; N is selected from the arbitrary integer in 3～7; Metal ions M is selected from sodium ion.
8. tertiary oil recovery claimed in claim 1 improves the preparation method of recovery ratio composition, comprises the following steps:
A) temperature resistant antisalt multipolymer NWKY-PAN, the second monomer are made into the aqueous solution I that total mass concentration is 5 ~ 45wt%, wherein the first monomer is acrylamide, and the second monomer is lactams material;
B) in solution I, lead to nitrogen deoxidation, add the composite initiation system that accounts for total monomer quality 0.001 ~ 3%, obtain solution II; Wherein composite initiation system by weight percentage, comprises following component: (A) 15～85% oxygenant; (B) 5～75% reductive agent; (C) 10～80% tertiary amines functional monomer; Wherein oxygenant is selected from least one in Potassium Persulphate, ammonium persulphate, Sodium Persulfate, reductive agent is selected from least one in sodium bisulfite, Sulfothiorine, rongalite, tertiary amines functional monomer is methacrylic acid N, N-dimethylaminoethyl or β-dimethylaminopropionitrile;
C) in solution II, lead to nitrogen deoxidation, at 5 ~ 20 ℃, initiation reaction 15 ~ 180 minutes, then be warmed up to 30 ~ 80 ℃, continue isothermal reaction 2 ~ 16 hours, the colloidal product I obtaining;
D) be 1 ~ 30% alkali lye to adding mass concentration in colloidal product I, be warming up to 50 ~ 100 ℃, be hydrolyzed 0.5 ~ 6 hour, obtain colloidal product II;
E) after colloidal product II is dried, pulverizes, is sieved, make Powdered heat-resistant salt-resistant multipolymer NWKY-PAN;
F) heat-resistant salt-resistant multipolymer NWKY-PAN, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate and injected water are evenly mixed, stir 1～3 hour, obtain required composition; In composition weight per-cent, the proportioning of heat-resistant salt-resistant multipolymer NWKY-PAN, aliphatic alcohol polyethenoxy ether carboxylate and injected water is 0.01～3.0%: 0.01～5.0%: 92.0～99.98%.
9. the tertiary oil recovery of any one described in claim 1 ~ 7 improves recovery ratio composition and improves recovery ratio for tertiary oil production in oil field production.
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| CN106368662A (en) * | 2015-07-23 | 2017-02-01 | 中国石油天然气股份有限公司 | Evaluation method for recovery ratio |
| CN106368662B (en) * | 2015-07-23 | 2019-04-09 | 中国石油天然气股份有限公司 | The evaluation method of recovery ratio |
| CN111117587A (en) * | 2019-12-17 | 2020-05-08 | 德仕能源科技集团股份有限公司 | Salt-resistant high-calcium-magnesium-resistant anionic-nonionic surfactant |
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