CN102373047B - Composition for improving recovery rate of oil field and preparation method thereof - Google Patents
Composition for improving recovery rate of oil field and preparation method thereof Download PDFInfo
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- 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
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- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
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Abstract
The invention relates to a composition for improving the recovery rate of an oil field and a preparation method thereof. In the invention, problems of bad heatproofness, bad salt resistance and low oil removal efficiency of an oil removal agent containing a polymer in the prior art are mainly solved. The oil removal composition for the tertiary oil recovery comprises 0.01-5.0 wt% of a heatproof salt-resistant copolymer KWKY-PAD (1), 0.01-5.0 wt% of a fatty alcohol polyoxyethylene ether carboxylate surfactant (2) and 90.0-99.98 wt% of injection water, wherein the molecular general formula of the heatproof salt resistant copolymer KWKY-PAD (1) is represented by a formula (I) shown in the specification, in the formula (I), R1 and R2 are C1-C16 alkyl, and x, y and m are molar numbers of constitutional units of monomers respectively; the molecular general formula of the fatty alcohol polyoxyethylene ether carboxylate surfactant (2) is RO(CH2CH2O)nCH2COOM, wherein R is C12-C18 alkyl, n is the addition number of ethyoxyl EO, and M is anyone selected from a potassium ion, a sodium ion or a lithium ion; and the injection water is selected from oil field injection water. Above technical scheme allows the problems to be well solved and can be applied to the production of the tertiary oil recovery of the oil field.
Description
Technical field
The present invention relates to a kind of composition and method of making the same that recovery ratio is improved in the oil field that is used for.
Background technology
Along with the development of world economy, the social demand amount of oil constantly increases, and prospective oil constantly reduces.Oil is just becoming more and more valuable as non-renewable resource.The problem that faces has one, and imbalance between supply and demand is outstanding, and the petroleum demand amount is big more big more, and find is fewer and feweri; Two, also left in the exhausted oil reservoir have a substantial oil.Primary oil recovery (POR) but extraction 10～25% underground crude oil, secondary oil recovery (SOR) but extraction 15～25% underground crude oil, 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, satisfy human wants that must research and development improve petroleum recovery technology, tertiary oil recovery (EOR) can make oil recovery factor improve 6～20% again by the intensified oil reduction measure, even more.
Domestic each elephant through once, secondary oil recovery, crude oil water content constantly increases, the part elephant successively enters tertiary phase.Polymer flooding is the main technique methods of tertiary oil recovery, and oil-displacement mechanism is clear, and technology is simple relatively, and technology reaches its maturity, and is one and effectively improves the recovery efficiency technique measure.The oil-displacement mechanism of polymkeric substance mainly is a viscosity of utilizing the water-soluble polyacrylamide molecular chain, improves the mobility ratio of displacing fluid, improves efficiency of displacement and swept volume, thereby reaches the purpose that improves recovery ratio.
Because the tertiary oil recovery cycle is long, deep layer oil temperature height, therefore, the used for tertiary oil recovery polymkeric substance must have good tackify, heatproof, salt resistance, stable performance.And present employed partially hydrolyzed polyacrylamide is under the high temperature and high salt condition, very easily hydrolysis, thus cause carboxyl-content to increase, polymer molecular chain curls, and the tackify effect sharply reduces, and the high volence metal ion in the oil reservoir is (as Ca in addition
2+, Mg
2+) partially hydrolyzed polyacrylamide is precipitated, thereby further reduced the tackify effect of partially hydrolyzed polyacrylamide, thereby be difficult to satisfy the demand of deep two, three class oil reservoir high temperature and high salinities.In recent years, the research of used for tertiary oil recovery temperature resistant antisalt polymkeric substance both at home and abroad 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, synthesized acrylamide/2-acrylamido-2-methyl propane sulfonic acid/methacrylic acid/dimethyl diallyl ammonium chloride tetrapolymer, acrylamide/2-acrylamide reaches-2-methyl propane sulfonic acid/methylene-succinic acid/heat-resistant salt-resistant multipolymers such as 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 satisfy salinity and be lower than 10000mg/L, temperature is lower than under 65 ℃ the condition, can not satisfy the application demand under higher temperature and the 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 is better than comb shape heat-resistant salt-resistant thickening agent of copolymer, and molecular weight is lower, at grand celebration clear water (total mineralization 1000mg/L, calcium ions and magnesium ions 15mg/L wherein), grand celebration sewage (total mineralization 4000mg/L, calcium ions and magnesium ions 60mg/L wherein), huge port sewage (total mineralization 5024mg/L, calcium ions and magnesium ions 60mg/L wherein) the tackify effect in is better than plain polypropylene acid amides product and comb shaped antisalt polymer industrial goods, the requirement of grand celebration two class oil reservoir tertiary oil recoveries can be adapted to, but still 10000mg/L can't be satisfied, Ca
2++ Mg
2+Requirement for tertiary oil recovery in the above salinity oil reservoir of 200mg/L.
And in recent years, the research of relevant ultra high molecular weight anion-type polyacrylamide mainly concentrates on the improvement of initiator system, polymerization process and method for hydrolysis etc.As CN1865299, CN 1498908A, CN1746198, CN101157736A and CN1240799 etc. all is to have studied polymerization technique, initiation technology and hydrolysis process etc., though aspect molecular weight that improves anion-polyacrylamide or the dissolution rate bigger improvement is being arranged by all means, but in the less concern of temperature resistant antisalt aspect of performance, some technology or method are comparatively complicated, industrial production or can be subjected to some restrictions in the tertiary oil recovery practical application.
At present in the tertiary oil recovery, at a class oil reservoir (temperature＜70 ℃, salinity＜1 * 10
4Mg/L) polymkeric substance prepares easily, and satisfies two class oil reservoirs (70～80 ℃ of temperature, salinity 1～3 * 10
4) and three class oil reservoirs (temperature＞80 ℃, salinity＞3 * 10
4) polymkeric substance that requires then seldom, be not price too the higher position be unstable properties.So at the harsh oil reservoir of those high temperature and high salts, we ought to seek a kind ofly have better stability to hydrolysis, and had the polymkeric substance of higher solution apparent viscosity in salt solution.Polymkeric substance that is suitable for high temperature and high salt just of the present invention and preparation method thereof, binary is compound and the application in tertiary oil recovery.
Summary of the invention
One of technical problem to be solved by this invention is the polymkeric substance facile hydrolysis under the high temperature and high salt condition that contains in the prior art in the oil-displacing agent of polymkeric substance, can not satisfy tertiary oil recovery requirement, problem that oil displacement efficiency is low, a kind of composition that is used to improve the tertiary oil recovery recovery ratio is provided, the composition that this method will contain temperature resistant antisalt multipolymer KWKY-PAD is used for oil displacement process, it is good to have stability to hydrolysis, the high characteristics of oil displacement efficiency under the high temperature and high salt condition.Two of technical problem to be solved by this invention provides one of a kind of and technical solution problem corresponding displacement of reservoir oil preparation of compositions method.
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 composition that is used for oil field raising recovery ratio comprises following component by weight percentage:
(1) 0.01～5.0% temperature resistant antisalt multipolymer KWKY-PAD;
(2) 0.01～5.0% aliphatic alcohol polyethenoxy ether carboxylate tensio-active agent;
(3) 90.0～99.98% injection water;
Wherein the general molecular formula of (1) component is:
In the formula, R
1, R
2Be C
1～C
16Alkyl, x, y, m are respectively the structural unit mole numbers of acrylamide, hydrolysis acrylamide, N-AAM; Molecular weight is 1200～1,800 ten thousand, reaching (wherein calcium ions and magnesium ions concentration is greater than 500mg/L), temperature about 20000mg/L in salinity reaches in the salt solution under the high temperature and high salinity condition more than 65 ℃, have good solubility, tackifying, and stability to hydrolysis improves, apparent viscosity 〉=21mPas, the viscosity retention ratio behind the high temperature ageing more than 65 ℃ is more than 70%.
For solve the problems of the technologies described above two, the technical solution adopted in the present invention is as follows: a kind of preparation of compositions method that can be used for improving the tertiary oil recovery recovery ratio may further comprise the steps:
A) first monomer, second monomer being made into total monomer quality concentration is 10～40% aqueous solution I;
B) in solution I, lead to nitrogen deoxidation 15～35 minutes, under 5～25 degree temperature, add the composite initiation system that accounts for monomer mass 0.001～3%, obtain solution II, wherein composite initiation system comprises following component by weight percentage: (A) 15～85% oxygenant; (B) 5～75% reductive agent; (C) 10～80% tertiary amines functional monomer.
C) in solution II, lead to nitrogen deoxidation 15～35 minutes, under 5～25 degree temperature, caused 15～90 minutes, be warmed up to 30～60 ℃ again, continue isothermal reaction 2～16 hours, the colloidal product I that obtains;
D) adding concentration in colloidal product I is 1～30% alkali lye, is warming up to 75～95 ℃, and hydrolysis is 0.5～3 hour under this temperature, obtains colloidal product II;
E) with colloidal product II drying, pulverize, sieve after, make Powdered heat-resistant salt-resistant multipolymer KWKY-PAD.
F) with the heat-resistant salt-resistant multipolymer KWKY-PAD of aequum, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate and injection water uniform mixing, stirring at room 1～3 hour, obtain required composition, by weight percentage, the proportioning of heat-resistant salt-resistant multipolymer KWKY-PAD, aliphatic alcohol polyethenoxy ether carboxylate and injection water is 0.01～3.0%: 0.01～5.0%: 92.0～99.98%.
In the technique scheme, the preferred acrylamide of first monomer, the preferred N,N-DMAA of second monomer, N, a kind of in the N-diethyl acrylamide; The total massfraction preferred 15～35% of first monomer and second monomer in the monomer solution; Composite initiation system concentration preferably accounts for monomer mass mark 0.003～1.5%; Preferred Potassium Persulphate of oxygenant and ammonium persulphate in the composite initiation system, the preferred sodium bisulfite of reductive agent, tertiary amines function monomer preferable methyl vinylformic acid N, N-dimethylaminoethyl; Preferred 5～15 ℃ of kick off temperature, preferred 30～60 minutes of initiation time; Preferred 30～50 ℃ of polymerization temperature, preferred 4～12 hours of polymerization reaction time; Alkali lye is preferably sodium hydroxide solution, and concentration is preferred 5～15%, preferred 80～90 ℃ of hydrolysis temperature, preferred 1～3 hour of hydrolysis time.
The present invention is prepared is used for improving the temperature resistant antisalt multipolymer KWKY-PAD of the composition of tertiary oil recovery recovery ratio; because the angle of amide group facile hydrolysis in high temperature and high salinity salt solution from suppress polymkeric substance; in molecular chain, introduce and make the stability-enhanced monomer that maybe can suppress amide group hydrolysis in the polymkeric substance of amide group; with the acrylamide copolymerization; interaction by this type of monomeric functional group and amide group; as hydrogen bond action etc.; amide group is formed protection; suppress the hydrolysis of amide group; thereby improve the stability to hydrolysis of polymkeric substance, and then improved the heat-resistant salt-resistant performance of polymkeric substance.This multipolymer is under high temperature and high salinity, and stability to hydrolysis improves, owing to adopt composite initiation system, the temperature resistant antisalt multipolymer KWKY-PAD molecular weight that makes can reach 10
7Reaching (wherein calcium ions and magnesium ions concentration is greater than 500mg/L), temperature about 20000mg/L in salinity reaches in the salt solution under the high temperature and high salinity condition more than 65 ℃, have good solubility, tackifying, and stability to hydrolysis improves, apparent viscosity 〉=21mPas, the viscosity retention ratio behind the high temperature ageing more than 65 ℃ is more than 70%.And this preparation method's technical process is comparatively easy, helps suitability for industrialized production.
Adopt the heat-resistant salt-resistant multipolymer KWKY-PAD of the present invention's preparation, with consumption is the aliphatic alcohol polyethenoxy ether carboxylate tensio-active agent formation displacement of reservoir oil composition of 0.1～0.3wt% and 0.1～0.4wt%, under the alkali-free condition, the in-place oil and the water that can be used for the oil field block of comparatively high temps and salinity, measured this oil-displacing agent and won solution apparent viscosity under 65 ℃ and 75 ℃ of the Tuo Er district Simulated Water at Shengli Oil Field, respectively greater than 21mPa.s and 15.6mPa.s, and Shengli Oil Field wins the dynamic interface tension value between the Tuo Er district crude oil, can reach 10
-3～10
-4The ultra low interfacial tension of mN/m, can on the water drive basis, can reach 17.8% by (water drive improves oil recovery factor and reaches 40.6%) raising oil recovery factor through the indoor evaluation of physical simulation displacement test at this oil-displacing agent on high temperature, the high salinity reservoir, obtain better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
The N,N-DMAA of 69.3 parts acrylamides and 5.7 parts is dissolved in 422 parts of water, and making the total massfraction of two kinds of monomers of acrylamide and N,N-DMAA 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; Add 0.003% composite initiation system then: 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 30 ℃, continue the constant temperature polyreaction after 4 hours, stopped reaction, with the colloidal product that obtains, adding concentration is 5% sodium hydroxide solution 157.6g, under 80 ℃, and hydrolysis 1 hour, vacuum-drying then, pulverize, promptly obtain heat-resistant salt-resistant multipolymer KWKY-PAD, molecular weight 1.2 * 10
7, reach (wherein calcium ions and magnesium ions concentration is greater than 500mg/L), temperature about 20000mg/L in salinity and reach that the viscosity retention ratio after aging is 71.2% in the salt solution under the high temperature and high salinity condition more than 65 ℃.
The synthetic heat-resistant salt-resistant multipolymer KWKY-PAD0.15wt% of institute, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate (n=4) 0.25wt% and 99.6wt% Shengli Oil Field are won Tuo Er district victory injection water uniform mixing, stirring at room 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 15.6mPa.s; Said composition and Shengli Oil Field win the ultra low interfacial tension that forms 0.0067mN/m between the Tuo Er district 0-141 well dewatered oil.Apparent viscosity is by the BROOKFIELDIII type viscometer determining of U.S. Brookfield company, and interfacial tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.
[embodiment 2]
With the N of 95 parts acrylamides and 80 parts, N-diethyl acrylamide is dissolved in 293 parts of water, makes acrylamide and N, and the total massfraction of two kinds of monomers of N-diethyl acrylamide 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; Add 1.5% composite initiation system then: 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 60 minutes, be warmed up to 50 ℃, continue the constant temperature polyreaction after 12 hours, stopped reaction, with the colloidal product that obtains, adding concentration is 15% sodium hydroxide solution 71.3g, under 90 ℃, and hydrolysis 3 hours, vacuum-drying then, pulverize, promptly obtain heat-resistant salt-resistant multipolymer KWKY-PAD, molecular weight 1.1 * 10
7, reach (wherein calcium ions and magnesium ions concentration is greater than 500mg/L), temperature about 20000mg/L in salinity and reach that the viscosity retention ratio after aging is 71.8% in the salt solution under the high temperature and high salinity condition more than 65 ℃.
The synthetic heat-resistant salt-resistant multipolymer KWKY-PAD0.25wt% of institute, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate (n=4) 0.35wt% and 99.4wt% Shengli Oil Field are won Tuo Er district victory injection water uniform mixing, stirring at room 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 17.9mPa.s.; Said composition and Shengli Oil Field win the ultra low interfacial tension that forms 0.0046mN/m between the Tuo Er district 0-141 well dewatered oil.Apparent viscosity is by the BROOKFIELDIII type viscometer determining of U.S. Brookfield company, and interfacial tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.
[embodiment 3]
The N,N-DMAA of 138.6 parts acrylamides and 11.4 parts is dissolved in 340 parts of water, and making the total massfraction of two kinds of monomers of acrylamide and N,N-DMAA 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 5 ℃, logical nitrogen deoxygenation 30 minutes; Add 0.03% composite initiation system then: 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 60 minutes, be warmed up to 30 ℃, continue the constant temperature polyreaction after 12 hours, stopped reaction, with the colloidal product that obtains, adding concentration is 10% sodium hydroxide solution 157.6g, under 90 ℃, and hydrolysis 3 hours, vacuum-drying then, pulverize, promptly obtain heat-resistant salt-resistant multipolymer KWKY-PAD, molecular weight 1.8 * 10
7, reach (wherein calcium ions and magnesium ions concentration is greater than 500mg/L), temperature about 20000mg/L in salinity and reach that the viscosity retention ratio after aging is 72.7% in the salt solution under the high temperature and high salinity condition more than 65 ℃.
The synthetic heat-resistant salt-resistant multipolymer KWKY-PAD0.35wt% of institute, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate (n=4) 0.25wt% and 99.4wt% Shengli Oil Field are won Tuo Er district victory injection water uniform mixing, stirring at room 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 18.6mPa.s; Said composition and Shengli Oil Field win the ultra low interfacial tension that forms 0.0070mN/m between the Tuo Er district 0-141 well dewatered oil.Apparent viscosity is by the BROOKFIELDIII type viscometer determining of U.S. Brookfield company, and interfacial tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.
[embodiment 4]
With the N of 40.7 parts acrylamides and 34.3 parts, N-diethyl acrylamide is dissolved in 420 parts of water, makes acrylamide and N, and the total massfraction of two kinds of monomers of N-diethyl acrylamide 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; Add 0.15% composite initiation system then: 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 30 minutes, be warmed up to 50 ℃, continue the constant temperature polyreaction after 4 hours, stopped reaction, with the colloidal product that obtains, adding concentration is 7.5% sodium hydroxide solution 45.8g, under 85 ℃, and hydrolysis 2 hours, vacuum-drying then, pulverize, promptly obtain heat-resistant salt-resistant multipolymer KWKY-PAD, molecular weight 1.3 * 10
7, reach (wherein calcium ions and magnesium ions concentration is greater than 500mg/L), temperature about 20000mg/L in salinity and reach that the viscosity retention ratio after aging is 70.6% in the salt solution under the high temperature and high salinity condition more than 65 ℃.
The synthetic heat-resistant salt-resistant multipolymer KWKY-PAD0.50wt% of institute, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate (n=4) 0.40wt% and 99.10wt% Shengli Oil Field are won Tuo Er district victory injection water uniform mixing, stirring at room 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 21mPa.s.; Said composition and Shengli Oil Field win the ultra low interfacial tension that forms 0.0050mN/m between the Tuo Er district 0-141 well dewatered oil.Apparent viscosity is by the BROOKFIELDIII type viscometer determining of U.S. Brookfield company, and interfacial tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.
[embodiment 5]
The N,N-DMAA of 78.4 parts acrylamides and 21.6 parts is dissolved in 395 parts of water, and making the total massfraction of two kinds of monomers of acrylamide and N,N-DMAA 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 10 ℃, logical nitrogen deoxygenation 30 minutes; Add 0.009% composite initiation system then: 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 45 minutes, be warmed up to 35 ℃, continue the constant temperature polyreaction after 8 hours, stopped reaction, with the colloidal product that obtains, adding concentration is 7% sodium hydroxide solution 156.0g, under 85 ℃, and hydrolysis 1.5 hours, vacuum-drying then, pulverize, promptly obtain heat-resistant salt-resistant multipolymer KWKY-PAD, molecular weight 1.9 * 10
7, reach (wherein calcium ions and magnesium ions concentration is greater than 500mg/L), temperature about 20000mg/L in salinity and reach that the viscosity retention ratio after aging is 73.2% in the salt solution under the high temperature and high salinity condition more than 65 ℃.
The synthetic heat-resistant salt-resistant multipolymer KWKY-PAD0.15wt% of institute, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate (n=4) 0.35wt% and 99.5wt% Shengli Oil Field are won Tuo Er district victory injection water uniform mixing, stirring at room 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 16.6mPa.s.; Said composition and Shengli Oil Field win the ultra low interfacial tension that forms 0.0055mN/m between the Tuo Er district 0-141 well dewatered oil.Apparent viscosity is by the BROOKFIELDIII type viscometer determining of U.S. Brookfield company, and interfacial tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.
[embodiment 6～10]
With [embodiment 1～5] synthetic heat-resistant salt-resistant multipolymer KWKY-PAD, with consumption is the aliphatic alcohol polyethenoxy ether carboxylate tensio-active agent formation displacement of reservoir oil composition of 0.1～0.3wt% and 0.1～0.4wt%, under the alkali-free condition, measured this oil-displacing agent and won solution apparent viscosity under 65 ℃ and 75 ℃ of the Tuo Er district Simulated Water at Shengli Oil Field, respectively greater than 21mPa.s and 15.6mPa.s, and Shengli Oil Field wins the dynamic interface tension value between the Tuo Er district crude oil, can reach 10
-3～10
-4The ultra low interfacial tension of mN/m; In length is 30 centimetres, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns
2Rock core on carry out the physical simulation displacement test, indoor evaluation this oil-displacing agent on high temperature, the high salinity reservoir can be on the water drive basis (water drive can improve oil recovery factor 40.1～40.8%) improve oil recovery factor and can reach 16.7～17.8%, the results are shown in Table shown in 1.Interfacial tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.
[comparative example 1]
With [embodiment 1], difference substitutes the above-mentioned temperature resistant antisalt polymkeric substance KWKY-PAD of 0.15wt% with the super high molecular weight polyacrylamide (viscosity-average molecular weight is 2,500 ten thousand) of 0.15wt%, all the other are identical, the apparent viscosity that records this composition is 11.5mPa.s, and said composition and Shengli Oil Field win the interfacial tension that forms 0.0623mN/m between the Tuo Er district 0-141 well dewatered oil.Apparent viscosity is by the BROODFIELDII type viscometer determining of U.S. Brookfield company, and interfacial tension is dripped interfacial tensimeter by the TX500 type rotation that Texas ,Usa university produces.
The above-mentioned displacement of reservoir oil composition that makes carries out the displacement of reservoir oil with the method with [embodiment 6], records water drive and can improve oil recovery factor 40.2%, can improve oil recovery factor 11.9% again on the water drive basis behind the above-mentioned displacement of reservoir oil composition of metaideophone, the results are shown in Table shown in 1.
[comparative example 2]
With [embodiment 1], difference substitutes the 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 14.4mPa.s, and said composition and Shengli Oil Field win the interfacial tension that forms 0.0712mN/m between the Tuo Er district 0-141 well dewatered oil.Apparent viscosity is by the BROODFIELDII type viscometer determining of U.S. Brookfield company, and interfacial tension is dripped interfacial tensimeter by the TX500 type rotation that Texas ,Usa university produces.
The above-mentioned displacement of reservoir oil composition that makes carries out the displacement of reservoir oil with the method with [embodiment 6], records water drive and can improve oil recovery factor 40.5%, can improve oil recovery factor 14.2% again on the water drive basis behind the above-mentioned displacement of reservoir oil composition of metaideophone, the results are shown in Table shown in 1.
Claims (5)
1. one kind is used for the composition that recovery ratio is improved in the oil field, comprises following component by weight percentage:
(1) 0.01～5.0% temperature resistant antisalt multipolymer KWKY-PAD;
(2) 0.01～5.0% aliphatic alcohol polyethenoxy ether carboxylate tensio-active agent;
(3) 90.0～99.98% injection water;
Wherein the general molecular formula of (1) component is:
In the formula, R
1, R
2Be C
1～C
16Alkyl, x, y, m are respectively the structural unit mole numbers of acrylamide, hydrolysis acrylamide, N～AAM; Molecular weight is 1200～1,800 ten thousand, reach about 20000mg/L in salinity, wherein calcium ions and magnesium ions concentration is greater than 500mg/L, temperature reaches in the salt solution under the high temperature and high salinity condition more than 65 ℃, have good solubility, tackifying, and stability to hydrolysis improves, apparent viscosity 〉=21mPas, and the viscosity retention ratio behind the high temperature ageing more than 65 ℃ is more than 70%.
2. the composition that is used for oil field raising recovery ratio according to claim 1, the total mineralization that it is characterized in that described injection water is 10000～30000mg/L, Ca
2++ Mg
2+Be 200～1000mg/L.
3. the composition that is used for oil field raising recovery ratio according to claim 1 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; The carbonatoms of R is 12～18 in the described aliphatic alcohol polyethenoxy ether carboxylate; N is the adduction number of ethoxy group EO, is selected from any one integer in 2～8; Metal ions M is selected from potassium, sodium or lithium.
4. the preparation of compositions method that is used for oil field raising recovery ratio according to claim 1 may further comprise the steps:
A) first monomer, second monomer being made into total monomer quality concentration is 10～45% aqueous solution I;
B) in solution I, lead to nitrogen deoxidation 15～35 minutes, under 5～25 degree temperature, add the composite initiation system that accounts for monomer mass 0.001～3%, obtain solution II, wherein composite initiation system comprises following component by weight percentage: (A) 15～85% oxygenant; (B) 5～75% reductive agent; (C) 10～80% tertiary amines functional monomer;
C) in solution II, lead to nitrogen deoxidation 15～35 minutes, under 5～25 degree temperature, caused 15～90 minutes, be warmed up to 30～60 ℃ again, continue isothermal reaction 2～16 hours, the colloidal product I that obtains;
D) adding concentration in colloidal product I is 1～30% alkali lye, is warming up to 75～95 ℃, and hydrolysis is 0.5～3 hour under this temperature, obtains colloidal product II;
E) with colloidal product II drying, pulverize, sieve after, make Powdered heat-resistant salt-resistant multipolymer KWKY-PAD;
F) with the heat-resistant salt-resistant multipolymer KWKY-PAD of aequum, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate and injection water uniform mixing, stirring at room 1～3 hour, obtain required composition, by weight percentage, the proportioning of heat-resistant salt-resistant multipolymer KWKY-PAD, aliphatic alcohol polyethenoxy ether carboxylate and injection water is 0.01～3.0%: 0.01～5.0%: 92.0～99.98%.
5. the preparation of compositions method that is used for oil field raising recovery ratio according to claim 4 is characterized in that first monomer is an acrylamide, and second monomer is the N-AAM.
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| CN103897682B (en) * | 2012-12-27 | 2017-04-19 | 中国石油化工股份有限公司 | Composition for improving recovery efficiency of tertiary recovery, and preparation method and use thereof |
| CN103967462B (en) * | 2013-02-05 | 2016-09-07 | 中国石油化工股份有限公司 | Use the flooding method of viscoelastic surfactant |
| CN104448128B (en) * | 2013-09-24 | 2017-05-10 | 中国石油化工股份有限公司 | Polymer mobility control agent suitable for high-temperature and high-salinity harsh reservoir and preparation method of polymer mobility control agent |
| CN104152130B (en) * | 2014-07-03 | 2016-12-07 | 西南石油大学 | AM/NaAA/NIDA hydrophobic associated polymer oil displacement agent and synthetic method thereof |
| EP3842407A1 (en) * | 2019-12-27 | 2021-06-30 | KAO CHEMICALS GmbH | Ether carboxylic acid composition |
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| CN101029224A (en) * | 2007-04-06 | 2007-09-05 | 山东大学 | Use of bi-alkyl carboxylate surface activator in triple oil recovery |
| CN101274974A (en) * | 2008-04-29 | 2008-10-01 | 成都理工大学 | Temperature-resistant water-soluble copolymer, preparation and use thereof |
| CN101293944A (en) * | 2008-04-03 | 2008-10-29 | 成都理工大学 | High adhesion-promotion salt resistant water-soluble copolymer, preparation method and application thereof |
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| CN101029224A (en) * | 2007-04-06 | 2007-09-05 | 山东大学 | Use of bi-alkyl carboxylate surface activator in triple oil recovery |
| CN101293944A (en) * | 2008-04-03 | 2008-10-29 | 成都理工大学 | High adhesion-promotion salt resistant water-soluble copolymer, preparation method and application thereof |
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