CN103965852A - Composite oil displacement agent containing polymer and cationic/anionic surfactant, and oil displacement method - Google Patents
Composite oil displacement agent containing polymer and cationic/anionic surfactant, and oil displacement method Download PDFInfo
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- CN103965852A CN103965852A CN201310044451.0A CN201310044451A CN103965852A CN 103965852 A CN103965852 A CN 103965852A CN 201310044451 A CN201310044451 A CN 201310044451A CN 103965852 A CN103965852 A CN 103965852A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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Abstract
The invention relates to a composite oil displacement agent containing a polymer and a cationic/anionic surfactant, and an oil displacement method, and mainly solves a problem of bad oil displacement efficiency of composite oil displacement agents used in the prior art. The composite oil displacement agent containing a polymer and a cationic/anionic surfactant includes the cationic/anionic surfactant, the polymer and water; the cationic/anionic surfactant comprises an anionic surfactant and a cationic surfactant according to a molar ratio of (1-100):1; the anionic surfactant is anyone of sulfonate, carboxylate and phosphate; the cationic surfactant is a quaternary ammonium salt or quaternary ammonium alkali; the polymer is modified polyacrylamide obtained by copolymerizing two monomers of acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, and a molar ratio of the two monomers in the modified polyacrylamide is (1-4):1. The composite oil displacement agent solves the problem and can be used for enhanced oil displacement production of high temperature and low salinity oil reservoirs.
Description
Technical field
The present invention relates to compound oil displacement agent and flooding method containing polymkeric substance regulating YIN and YANG diagram of system surface-active agent.
Background technology
Chemical flooding is the main method of the strengthening displacement of reservoir oil.As an important technology in chemical flooding, the ASP Oil-Displacing Technology that polymkeric substance, tensio-active agent and alkali form has carried out some field tests in China and foreign countries, has obtained good oil displacement efficiency.But cause the adding of alkali easily causing in field test oil layer blocking, permeability plugging, and emulsification of crude oil is serious, Produced Liquid profit is difficult to separated.In the binary combination flooding formula that polymkeric substance and tensio-active agent form owing to not using alkali, effectively avoided the problems referred to above and drawn attention, but due to need not any alkali, interfacial tension between crude oil, water often cannot reach ultralow value, thereby affected oil displacement efficiency, therefore need to research and develop high-efficient oil-displacing agent.Known according to the formula Er=E υ Ed that improves oil recovery factor, Ed presentation surface surfactant flood improves oil recovery factor, and its mechanism of action is the interfacial tension reducing between profit; E υ represents that polymer flooding improves oil recovery factor, its mechanism of action is to increase sweep efficiency, the Main Function that reduces oil water interfacial tension in poly-table binary combination flooding is tensio-active agent, and the key of therefore developing high-efficient oil-displacing agent is exploitation and the equal good tensio-active agent of polymkeric substance compatibility and interface performance.
Surfactant for EOR has anion surfactant at present, as sulfonated petro-leum, alkylsulfonate, alkenyl sulphonate and sulfonated lignin etc.That uses cats product also has a report, as Chinese patent CN 1528853, CN 1817431, CN 1066137 etc. have reported that bisamide type is cationic in succession, fluorine-containing cationic type and containing pyridyl cation Gemini surfactant, but because positively charged ion has, absorption loss is large, high in cost of production shortcoming, has limited its use at Oil Field.The microemulsion flooding of foreign study report, as Kraft etc. has investigated at water-mineralizing degree under the condition up to 220 g/L, the microemulsion system phase of 5% Soxylat A 25-7 alkyl sodium carboxymethyl, transformation temperature (PIT) rule and interfacial tension, result shows, this tensio-active agent does not substantially decompose in 3 weeks at 95 ℃, adsorption losses 0.4 mg/g, and without obvious chromatographic separation, but because tensio-active agent usage quantity is large, cost is high, microemulsion flooding is restricted as oil-displacing agent.
The application of compound surfactant in the strengthening displacement of reservoir oil is mainly negatively charged ion and nonionic compound surfactant, in use often need to add additive alkali, to reach ultralow oil/water interfacial tension, but because non-ionic heat resistance is poor, often ineffective when high temperature.After different anions surfactant compound, as surfactant oil displacement, also there is report, as Chinese patent CN1458219A discloses a kind of Surfactant/Polymer binary ultra low interfacial tension combination flooding formula of strengthening displacement of reservoir oil application, use therein tensio-active agent is that sulfonated petro-leum or the sulfonated petro-leum of take add the complexed surfactant of thinner and other surfactant compound as host, the weight percent of its component is sulfonated petro-leum 50～100%, alkylsulfonate 0～50%, carboxylate salt 0～50%, alkylaryl sulphonate 0～35%, low-carbon alcohol 0～20%, this surface-active agent poor activity, oil displacement efficiency is low, surfactant system is too complicated.
Summary of the invention
One of technical problem to be solved by this invention is compound oil displacement agent poor problem of oil displacement efficiency in strengthening oil displacement process of using in prior art, and a kind of new compound oil displacement agent containing polymkeric substance regulating YIN and YANG diagram of system surface-active agent is provided.This oil-displacing agent is for oil displacement process, has advantages of alkali-free, corrosion-free and incrustation injury, working concentration is low, oil displacement efficiency is high under hot conditions.
Two of technical problem to be solved by this invention is to provide a kind of flooding method that adopts the described compound oil displacement agent of one of above-mentioned technical problem.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: the compound oil displacement agent containing polymkeric substance regulating YIN and YANG diagram of system surface-active agent, in mass fraction, comprises following component:
The negative and positive system tensio-active agent of (1) 0.01～5.0 part;
The polymkeric substance of (2) 0.01～3.0 parts;
The water of (3) 90.0～99.9 parts;
Described negative and positive system tensio-active agent by anion surfactant and quaternary ammonium cation tensio-active agent with mol ratio (1 ~ 100): 1 forms; Described anion surfactant is any one in sulfonate, carboxylate salt or phosphoric acid salt, and the lipophilic group in structure is C
8～C
30alkyl; Described cats product has C
8～C
30alkyl is connected with the nitrogen-atoms in described cats product structure, and described cats product is quaternary ammonium salt or quaternary amine alkali; Described polymkeric substance is modified polyacrylamide, by acrylamide (being called for short AM), two kinds of monomer copolymerizations of 2-acrylamide-2-methylpro panesulfonic acid (being called for short AMPS), formed, in modified polyacrylamide, two kinds of monomeric units mole is (1 ~ 4): 1, and viscosity-average molecular weight is 300 ~ 10,000,000.
The system of negative and positive described in technique scheme tensio-active agent by anion surfactant and cats product preferably with mol ratio (1.2 ~ 20): 1 forms.Described anion surfactant is preferably alkylbenzene sulfonate, C
12~ C
22sulfonated α-olefin, C
9~ C
17carboxylate salt, mahogany acid, petroleum carboxylate or sulfonated lignin in any one or mixture, the alkyl in described alkylbenzene sulfonate is preferably C
14~ C
22alkyl; Described cats product preferably has a C
10~ C
22alkyl and three C
1～C
4alkyl is connected with described nitrogen-atoms, more preferably has a C
10~ C
22alkyl is connected with described nitrogen-atoms with three methyl, or more preferably has a C
10~ C
22alkyl is connected with described nitrogen-atoms with three ethyls.The viscosity-average molecular weight of described modified polyacrylamide is preferably 500 ~ 9,000,000; Described compound oil displacement agent, in mass fraction, preferably includes 0.03～0.6 part, negative and positive system tensio-active agent; Described compound oil displacement agent, in mass fraction, preferably includes 0.05～0.2 part, polymkeric substance.
Described water can be deionized water, add water after inorganic salt (for example KCl, NaCl, inorganic salt are the preferred 1 ~ 15wt% of content in inorganic salt solution), containing the water of mineral substance, wherein the water containing mineral substance can be tap water, river, oil field stratum water, all can reach object of the present invention, but from environment protection and economic factors, consider, preferably oil field stratum water; The total mineralization of oil field stratum water is preferably 5000～15000 mg/litre, and further preferably water type is NaHCO
3type.
The oil-displacing agent adopting in flooding method of the present invention can also contain the oil recovery auxiliary agents such as the conventional polymkeric substance in this area (such as polyacrylamide etc.), foaming agent, small organic molecule (such as DMSO etc.), solid or liquid base (as sodium hydroxide, sodium carbonate, sodium bicarbonate, diethanolamine or trolamine).
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: the flooding method that adopts the described compound oil displacement agent of one of above-mentioned technical problem, described compound oil displacement agent is contacted with oil-bearing formation under 40 ~ 100 ℃ of displacement of reservoir oil temperature, total mineralization >1000 mg/litre oil field stratum water condition, by the mother oil displacement in described oil-bearing formation out.
In technique scheme, described displacement of reservoir oil temperature is preferably 60～90 ℃; The total mineralization of oil field stratum water is 1000～15000 mg/litre preferably, and more preferably total mineralization is 5000～15000 mg/litre; The preferred NaHCO of water type of oil field stratum water
3type.
Flooding method of the present invention, can also comprise the conventional water drive in this area, polymer flooding, poly-table alkali ternary composite driving, steam flood and foam flooding etc.
In technique scheme, after described compound oil displacement agent can adopt various ordinary methods to mix according to each component of aequum for the displacement of reservoir oil; But within the easier short period of time, obtain uniform oil-displacing agent meter, the preparation of compound oil displacement agent described in technique scheme preferably includes following steps:
(1) anion surfactant of aequum, cats product, water and low-carbon alcohol are added in mixing vessel, wherein low-carbon alcohol accounts for 5～70wt% of water and low-carbon alcohol gross weight by weight;
(2) being warming up to 40 ~ 100 ℃ stirs 1～4 hour;
(3) boil off low-carbon alcohol, obtain negative and positive system surfactant soln;
(4) negative and positive system surfactant soln step 3) being obtained and the polymkeric substance of aequum mix with water, stir 1～4 hour.
Described low-carbon alcohol is selected from C
1~ C
5fatty alcohol, preferably from methyl alcohol, ethanol, n-propyl alcohol or Virahol.
The inventive method adopts physical simulation displacement evaluation method to carry out effect assessment, and concrete evaluation method is:
Rock core constant temperature drying, to constant weight, is measured to the perm-plug method of rock core; With above-mentioned output water saturation rock core, calculate its volume of voids, at displacement of reservoir oil temperature, with crude oil saturated core, record the volume of saturated crude oil, speed with 0.2ml/min pumps into oil field stratum water, be driven to and moisturely reach 99%, calculate the recovery ratio that water drive improves crude oil, then after speed metaideophone 0.1 ~ 1PV (rock pore volume) compound oil displacement agent with 0.2ml/min, with the speed water drive of 0.2ml/min, to moisture 100%, calculate and on water drive basis, improve the percentage ratio of oil recovery factor.
In technique scheme, described modified polyacrylamide is formed by acrylamide, two kinds of monomer copolymerizations of 2-acrylamide-2-methylpro panesulfonic acid, can buy from market, also can make by conventional water solution polymerization process.No matter block copolymerization or random copolymerization, the product obtaining all can be used for the present invention and reaches object of the present invention.Modified polyacrylamide in the embodiment of the present invention, be by two kinds of monomers of acrylamide and 2-acrylamide-2-methylpro panesulfonic acid according to mol ratio (1 ~ 4): 1 take water after mixing obtains as solvent causes Raolical polymerizable with conventional free radical initiator.
The negative and positive system tensio-active agent that negatively charged ion prepared by the present invention and cats product form, due to negatively charged ion and cats product composite after, can present the advantages such as decline, solubilising effect of surface-active increase, micelle-forming concentration.This is to have strong electrostatic interaction because hydrophilic base in anion surfactant is ammonium ion positive charge in electronegativity and cats product, promoted two kinds to be with the interionic association of different charged surface promoting agents, and also has certain hydrophobic interaction between the hydrophobic group hydrocarbon chain of the two, impel different surfaces active agent molecule to take arrangement mode more closely, thereby in solution, be easy to form micella, produce than the higher surfactivity of single tensio-active agent and low micelle-forming concentration.Two tensio-active agents in negative and positive system tensio-active agent are ionic, and built agent also shows the feature of ionic surface active agent, i.e. good heat resistance.Therefore, this tensio-active agent had both had good heat-resisting property, there is again excellent interfacial activity, can solve the interfacial tension rising problem that progressively declines and cause because of surfactant concentration in Oil Field use procedure, make tensio-active agent in the migration process of down-hole, even if concentration is lower, still ultralow oil water interfacial tension can be kept, thereby oil displacement efficiency can be improved.In addition, because presenting more, formation core surface mixes wetting characteristic, contain oily wetted surface and water-wet surface simultaneously, negative and positive system tensio-active agent can effectively change the wettability of rock layer surface, particularly cats product is by the electronegative Interaction of substituents with being adsorbed on solid surface, can make glossy wet surface modification is intermediate wet or water-wet surface, reduce crude oil at the work of adhesion of solid surface, make crude oil be easy to peel off, improve displacement efficiency, be conducive to the raising of oil recovery factor.
In the embodiment of the present invention, the concentration of the negative and positive system tensio-active agent relating to while testing, all in test fluid containing the total amount of negatively charged ion in technique scheme and cats product component.
Adopt polymkeric substance regulating YIN and YANG diagram of system surface-active agent compound oil displacement agent of the present invention and flooding method, under alkali-free condition, can be used for the NaHCO of 60 ~ 90 ℃ of formation temperature, salinity 5000～20000 mg/litre
3husky 7 block local water and the crude oil of type Jiangsu oilfield, by percentage to the quality, consumption is that the above-mentioned modified polyacrylamide of 0.03～0.6wt% negative and positive system tensio-active agent and 0.05～0.2wt% forms oil-displacing agent composition, measured the apparent viscosity of this oil-displacing agent composition solution, and the dynamic interface tension value between the husky 7 block dewatered oils of Jiangsu oilfield can reach 10
-2～10
-4mN/m low interfacial tension, through physical simulation displacement test Lab-evaluation, this oil-displacing agent can improve oil recovery factor on water drive basis can reach 13.76%, has obtained good technique effect.
Accompanying drawing explanation
Fig. 1 is simulation core displacement test schema.
In Fig. 1,1 is constant-flux pump, and 2 is six-way valve, and 3 is intermediate receptacle, and 4 is pharmacy jar, and 5 is pressure pump, and 6 is six-way valve, and 7 is fill out sand tube, and 8 is graduated cylinder.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
(1) by octadecyl benzene sulfonic acid sodium salt and tetradecyl trimethyl ammonium chloride in molar ratio 5:1 add in reaction flask, take 40wt% aqueous ethanolic solution as solvent, be warming up to 70 ℃ and stir 2.5 hours to dissolving completely, ethanol is removed in underpressure distillation, obtain required negative and positive system tensio-active agent, wherein tensio-active agent total content is 45.1% by percentage to the quality.
(2) with husky 7 local waters of Jiangsu oilfield (TDS 15000mg/L) negative and positive system tensio-active agent and modified polyacrylamide (M=600 ten thousand) aqueous solution that respectively prepared by preparation steps (1), stir 3 hours, again both are mixed to get to a kind of poly-table compound oil displacement agent uniformly, the viscosity of mensuration system and with the oil water interfacial tension of husky 7 dewatered oils of Jiangsu oilfield, probe temperature is 83 ℃, is shown in Table 1.Apparent viscosity is by the BROODFIELD of U.S. Brookfield company
i type viscometer determining, the TX500 type rotation interfacial tensimeter that interfacial tension is produced by Texas ,Usa university is measured.
(3) by shale synthetic core constant temperature drying to constant weight, measure mean diameter and the rock core length of rock core, weigh rock core dry weight, measure the perm-plug method of rock core.With above-mentioned local water saturated core, test its volume of voids.With husky 7 block dewatered oil saturated cores, record the volume of saturated crude oil.At 83 ℃ of temperature, with husky 7 local waters, be driven to that Produced Liquid is moisture reaches 99%, calculate the recovery ratio that water drive improves crude oil, after the synthetic Surfactant/Polymer binary composite oil displacement agent of metaideophone 0.3pv (rock pore volume) step (2), water drive is to moisture 100%, calculating improves the percentage ratio of oil recovery factor on water drive basis, contrasts with the polymer phase of the identical PV of note simultaneously, is shown in Table 1.Rock core perm-plug method is measured with HKGP-3 type compact rock core gas permeability porosity measuring instrument, and the simulation core displacement test flow process of employing as shown in Figure 1.
Table 1
| Flooding system | 0.3wt%S1 | 0.1wt%P1 | 0.3%wtS1+0.1wt%P1 |
| Oil water interfacial tension/mN.m -1 | 6.32×10 -4 | / | 1.51×10 -3 |
| Viscosity/mPas | / | 3.51 | 4.13 |
| Improve recovery ratio/% | / | 9.18 | 14.76 |
Note: in table 1, P1 is modified polyacrylamide (AM/AMPS mol ratio=1.5:1, M=600 ten thousand); S1 is negative and positive system tensio-active agent prepared by step (1).
[embodiment 2]
(1) by petroleum sodium sulfonate and Tetradecyl Trimethyl Ammonium Bromide in molar ratio 8:1 add in reaction flask, take 20wt% methanol aqueous solution as solvent, be warming up to 50 ℃ and stir 3 hours to dissolving completely, methyl alcohol is removed in underpressure distillation, obtain required negative and positive system tensio-active agent, wherein tensio-active agent total content is 45.3% by percentage to the quality.
(2) with husky 7 local waters of Jiangsu oilfield (TDS 20000mg/L) negative and positive system tensio-active agent and modified polyacrylamide (M=900 ten thousand) aqueous solution that respectively prepared by preparation steps (1), stir 4 hours, all the other,, with [embodiment 1] (2), the results are shown in Table shown in 2.
(3) adopt 75 ℃ as displacement of reservoir oil temperature, all the other,, with [embodiment 1] (3), the results are shown in Table shown in 2.
Table 2
| Flooding system | 0.3wt%S2 | 0.07wt%P2 | 0.3%wtS1+0.07wt%P1 |
| Oil water interfacial tension/mN.m -1 | 1.32×10 -3 | / | 3.66×10 -3 |
| Viscosity/mPas | / | 3.22 | 3.67 |
| Improve recovery ratio/% | / | 9.01 | 12.86 |
Note: in table 2, P2 is modified polyacrylamide (AM/AMPS mol ratio=4:1, M=900 ten thousand); S2 is negative and positive system tensio-active agent prepared by step (1).
[embodiment 3]
(1) by alpha-olefin sodium sulfonate, (be commercially available C
16~ C
18alpha-olefin azochlorosulfonate acid sodium mixture) with Dodecyl trimethyl ammonium chloride in molar ratio 10:1 add in reaction flask, take 30wt% isopropanol water solution as solvent, be warming up to 60 ℃ and stir 3 hours to dissolving completely, Virahol is removed in underpressure distillation, obtain required negative and positive system tensio-active agent, wherein tensio-active agent total content is 50.9% by percentage to the quality.
(2) with husky 7 local waters of Jiangsu oilfield (TDS 10000mg/L) negative and positive system tensio-active agent and modified polyacrylamide (M=600 ten thousand) aqueous solution that respectively prepared by preparation steps (1), stir 2 hours, all the other,, with [embodiment 1] (2), the results are shown in Table shown in 3.
(3) adopt 90 ℃ as displacement of reservoir oil temperature, inject 0.2PV, all the other,, with [embodiment 1] (3), the results are shown in Table shown in 3.
Table 3
| Flooding system | 0.05wt%S3 | 0.2wt%P1 | 0.05wt%S3+0.2wt%P1 |
| Oil water interfacial tension/mN.m -1 | 4.32×10 -4 | / | 7.80×10 -4 |
| Viscosity/mPas | / | 5.12 | 5.28 |
| Improve recovery ratio/% | / | 11.21 | 13.97 |
Note: in table 3, P1 is modified polyacrylamide (AM/AMPS mol ratio=1.5:1, M=600 ten thousand); S3 is negative and positive system tensio-active agent prepared by step (1).
[embodiment 4]
(1) by sodium lignosulfonate and octadecyl trimethyl ammonium chloride in molar ratio 1.2:1 add in reaction flask, the 50wt% n-propyl alcohol aqueous solution of take is solvent, be warming up to 90 ℃ and stir 1.5 hours to dissolving completely, n-propyl alcohol is removed in underpressure distillation, obtain required negative and positive system tensio-active agent, wherein tensio-active agent total content is 42.5% by percentage to the quality.
(2) with husky 7 local waters of Jiangsu oilfield (TDS 10000mg/L) negative and positive system tensio-active agent and modified polyacrylamide (M=700 ten thousand) aqueous solution that respectively prepared by preparation steps (1), stir 3 hours, all the other,, with [embodiment 1] (2), the results are shown in Table shown in 4.
(3) adopt 85 ℃ as displacement of reservoir oil temperature, all the other,, with [embodiment 1] (3), the results are shown in Table shown in 4.
Table 4
| Flooding system | 0.2wt%S4 | 0.1wt%P3 | 0.2wt%S1+0.1wt%P3 |
| Oil water interfacial tension/mN.m -1 | 3.32×10 -4 | / | 5.69×10 -4 |
| Viscosity/mPas | / | 3.82 | 4.57 |
| Improve recovery ratio/% | / | 9.22 | 13.98 |
Note: in table 4, P3 is modified polyacrylamide (AM/AMPS mol ratio=2.5:1, M=700 ten thousand); S4 is negative and positive system tensio-active agent prepared by step (1).
[embodiment 5]
(1) by sodium laurate and Dodecyl trimethyl ammonium chloride in molar ratio 15:1 add in reaction flask, take 10wt% isopropanol water solution as solvent, be warming up to 80 ℃ and stir 2 hours to dissolving completely, Virahol is removed in underpressure distillation, obtain required negative and positive system tensio-active agent, wherein tensio-active agent total content is 40.8% by percentage to the quality.
(2) with husky 7 local waters of Jiangsu oilfield (TDS 5000mg/L) negative and positive system tensio-active agent and modified polyacrylamide (M=600 ten thousand) aqueous solution that respectively prepared by preparation steps (1), stir 2 hours, all the other,, with [embodiment 1] (2), the results are shown in Table shown in 5.
(3) inject 0.2PV, all the other,, with [embodiment 1] (3), the results are shown in Table shown in 5.
Table 5
| Flooding system | 0.1wt%S5 | 0.1wt%P1 | 0.1wt%S5+0.1wt%P1 |
| Oil water interfacial tension/mN.m -1 | 3.45×10 -3 | / | 5.11×10 -3 |
| Viscosity/mPas | / | 3.52 | 4.69 |
| Improve recovery ratio/% | / | 9.18 | 13.74 |
Note: in table 5, P1 is modified polyacrylamide (AM/AMPS mol ratio=1.5:1, M=600 ten thousand); S5 is negative and positive system tensio-active agent prepared by step (1).
[embodiment 6]
(1) by tetradecyl benzene sulfonic acid sodium salt and INCROQUAT TMC-80 in molar ratio 1.5:1 add in reaction flask, take 10wt% isopropanol water solution as solvent, be warming up to 80 ℃ and stir 2 hours to dissolving completely, Virahol is removed in underpressure distillation, obtain required negative and positive system tensio-active agent, wherein tensio-active agent total content is 45.6% by percentage to the quality.
(2) with husky 7 local waters of Jiangsu oilfield (TDS 15000mg/L) negative and positive system tensio-active agent and modified polyacrylamide (M=700 ten thousand) aqueous solution that respectively prepared by preparation steps (1), stir 3 hours, all the other,, with [embodiment 1] (2), the results are shown in Table shown in 6.
(3) adopt 65 ℃ as displacement of reservoir oil temperature, inject 0.4PV, all the other,, with [embodiment 1] (3), the results are shown in Table shown in 6.
Table 6
| Flooding system | 0.3wt%S6 | 0.1wt%P3 | 0.3%wtS6+0.1wt%P3 |
| Oil water interfacial tension/mN.m -1 | 7.98×10 -4 | / | 1.08×10 -3 |
| Viscosity/mPas | / | 3.82 | 5.11 |
| Improve recovery ratio/% | / | 9.24 | 13.96 |
Note: in table 6, P3 is modified polyacrylamide (AM/AMPS mol ratio=2.5:1, M=700 ten thousand); S6 is negative and positive system tensio-active agent prepared by step (1).
[embodiment 7]
(1) by alpha-olefin sodium sulfonate, (be commercially available C
14～C
16alpha-olefin azochlorosulfonate acid sodium mixture) with tetradecyl trimethyl ammonium chloride in molar ratio 20:1 add in reaction flask, take 40wt% aqueous ethanolic solution as solvent, be warming up to 70 ℃ and stir 3 hours to dissolving completely, ethanol is removed in underpressure distillation, obtain required negative and positive system tensio-active agent, wherein tensio-active agent total content is 42.3% by percentage to the quality.
(2) with husky 7 local waters of Jiangsu oilfield (TDS 10000mg/L) negative and positive system tensio-active agent and modified polyacrylamide (M=600 ten thousand) aqueous solution that respectively prepared by preparation steps (1), stir 2 hours, all the other,, with [embodiment 1] (2), the results are shown in Table shown in 7.
(3) adopt 85 ℃ as displacement of reservoir oil temperature, inject 0.1PV, all the other,, with [embodiment 1] (3), the results are shown in Table shown in 7.
Table 7
| Flooding system | 0.05wt%S7 | 0.2wt%P1 | 0.05wt%S7+0.2%P1 |
| Oil water interfacial tension/mN.m -1 | 5.32×10 -3 | / | 6.43×10 -3 |
| Viscosity/mPas | / | 5.12 | 5.36 |
| Improve recovery ratio/% | / | 11.21 | 13.55 |
Note: in table 7, P1 is modified polyacrylamide (AM/AMPS mol ratio=1.5:1, M=600 ten thousand); S7 is negative and positive system tensio-active agent prepared by step (1).
[embodiment 8]
(1) by sodium oleate and Tetradecyl Trimethyl Ammonium Bromide in molar ratio 12:1 add in reaction flask, the 20wt% n-propyl alcohol aqueous solution of take is solvent, be warming up to 60 ℃ and stir 3 hours to dissolving completely, n-propyl alcohol is removed in underpressure distillation, obtain required negative and positive system tensio-active agent, wherein tensio-active agent total content is 43.5% by percentage to the quality.
(2) with husky 7 local waters of Jiangsu oilfield (TDS 20000mg/L) negative and positive system tensio-active agent and modified polyacrylamide (M=900 ten thousand) aqueous solution that respectively prepared by preparation steps (1), stir 4 hours, all the other,, with [embodiment 1] (2), the results are shown in Table shown in 8.
(3) with [embodiment 1] (3), the results are shown in Table shown in 8.
Table 8
| Flooding system | 0.2wt%S8 | 0.1wt%P2 | 0.2wt%S8+0.1wt%P2 |
| Oil water interfacial tension/mN.m -1 | 1.32×10 -3 | / | 3.66×10 -3 |
| Viscosity/mPas | / | 4.64 | 5.55 |
| Improve recovery ratio/% | / | 10.53 | 14.26 |
Note: in table 8, P2 is modified polyacrylamide (AM/AMPS mol ratio=4:1, M=900 ten thousand); S8 is negative and positive system tensio-active agent prepared by step (1).
[embodiment 9]
Except by " mol ratio of octadecyl benzene sulfonic acid sodium salt and tetradecyl trimethyl ammonium chloride changes 1.05:1 into ", all the other,, with [embodiment 1], the results are shown in Table shown in 9.
Table 9
| Flooding system | 0.3wt%S9 | 0.1wt%P1 | 0.3%wtS9+0.1wt%P1 |
| Oil water interfacial tension/mN.m -1 | 4.32×10 -3 | / | 4.11×10 -3 |
| Viscosity/mPas | / | 3.51 | 3.69 |
| Improve recovery ratio/% | / | 9.18 | 11.91 |
Note: in table 9, P1 is modified polyacrylamide (AM/AMPS mol ratio=1.5:1, M=600 ten thousand); S9 is negative and positive system tensio-active agent prepared by step (1).
[embodiment 10]
Except by " mol ratio of octadecyl benzene sulfonic acid sodium salt and tetradecyl trimethyl ammonium chloride changes 30:1 into ", all the other,, with [embodiment 1], the results are shown in Table shown in 10.
Table 10
| Flooding system | 0.3wt%S10 | 0.1wt%P1 | 0.3%wtS10+0.1wt%P1 |
| Oil water interfacial tension/mN.m -1 | 1.25×10 -2 | / | 2.36×10 -2 |
| Viscosity/mPas | / | 3.51 | 3.96 |
| Improve recovery ratio/% | / | 9.18 | 11.89 |
Note: in table 10, P1 is modified polyacrylamide (AM/AMPS mol ratio=1.5:1, M=600 ten thousand); S10 is negative and positive system tensio-active agent prepared by step (1).
From embodiment 1 to embodiment 10, can find out, be all can reach object of the present invention in 1 ~ 100: 1 scope in the mol ratio of anion surfactant and cats product, but within the scope of 1.2 ~ 20:1, have better technique effect.
[comparative example 1]
Except substituting with " polyacrylamide (M=600 ten thousand) " " modified polyacrylamide P1(AM/AMPS mol ratio=1.5:1, M=600 ten thousand) ", all the other,, with [embodiment 1], the results are shown in Table shown in 11.
Table 11
| Flooding system | 0.3wt%S1 | 0.1wt%P4 | 0.3%wtS1+0.1wt%P4 |
| Oil water interfacial tension/mN.m -1 | 3.25×10 -2 | / | 5.36×10 -2 |
| Viscosity/mPas | / | 3.05 | 3.16 |
| Improve recovery ratio/% | / | 6.11 | 9.87 |
Note: P4 is polyacrylamide (M=600 ten thousand); S1 is negative and positive system tensio-active agent prepared by step (1).
[comparative example 2]
Except substituting with " polyacrylamide (M=900 ten thousand) " " modified polyacrylamide P2(AM/AMPS mol ratio=4:1, M=900 ten thousand) ", all the other,, with [embodiment 2], the results are shown in Table shown in 12.
Table 12
| Flooding system | 0.3wt%S2 | 0.07wt%P5 | 0.3%wtS1+0.07wt%P5 |
| Oil water interfacial tension/mN.m -1 | 1.32×10 -3 | / | 3.66×10 -3 |
| Viscosity/mPas | / | 3.11 | 3.27 |
| Improve recovery ratio/% | / | 6.32 | 9.60 |
Note: P5 is polyacrylamide (M=900 ten thousand); S2 is negative and positive system tensio-active agent prepared by step (1).
[comparative example 3]
Except substitute " the negative and positive system tensio-active agent that octadecyl benzene sulfonic acid sodium salt and tetradecyl trimethyl ammonium chloride form " with " octadecyl benzene sulfonic acid sodium salt ", all the other,, with [embodiment 1], the results are shown in Table shown in 13.
Table 13
| Flooding system | 0.3wt%S11 | 0.1wt%P1 | 0.3%wtS11+0.1wt%P1 |
| Oil water interfacial tension/mN.m -1 | 7.19×10 -2 | / | 7.67×10 -2 |
| Viscosity/mPas | / | 3.51 | 3.82 |
| Improve recovery ratio/% | / | 9.18 | 10.76 |
Note: P1 is modified polyacrylamide (AM/AMPS mol ratio=1.5:1, M=600 ten thousand); S11 is octadecyl benzene sulfonic acid sodium salt.
[comparative example 4]
Except take, " alpha-olefin sodium sulfonate (is commercially available C
16~ C
18alpha-olefin azochlorosulfonate acid sodium mixture) " substitute that " alpha-olefin sodium sulfonate (is commercially available C
16 ~ 18alpha-olefin azochlorosulfonate acid sodium mixture) the negative and positive system tensio-active agent forming with Dodecyl trimethyl ammonium chloride ", all the other,, with [embodiment 3], the results are shown in Table shown in 14.
Table 14
| Flooding system | 0.05wt%S12 | 0.2wt%P1 | 0.05wt%S12+0.2wt%P1 |
| Oil water interfacial tension/mN.m -1 | 7.98×10 -2 | / | 1.02.×10 -1 |
| Viscosity/mPas | / | 5.12 | 5.14 |
| Improve recovery ratio/% | / | 11.21 | 11.84 |
Note: P1 is modified polyacrylamide (AM/AMPS mol ratio=1.5:1, M=600 ten thousand); S12 is alpha-olefin sodium sulfonate (C
16 ~ 18).
Claims (10)
1. containing the compound oil displacement agent of polymkeric substance regulating YIN and YANG diagram of system surface-active agent, in mass fraction, comprise following component:
The negative and positive system tensio-active agent of (1) 0.01～5.0 part;
The polymkeric substance of (2) 0.01～3.0 parts;
The water of (3) 90.0～99.9 parts;
Described negative and positive system tensio-active agent by anion surfactant and quaternary ammonium cation tensio-active agent with mol ratio (1 ~ 100): 1 forms; Described anion surfactant is any one in sulfonate, carboxylate salt or phosphoric acid salt, and the lipophilic group in structure is C
8～C
30alkyl; Described cats product has C
8～C
30alkyl is connected with the nitrogen-atoms in described cats product structure, and described cats product is quaternary ammonium salt or quaternary amine alkali; Described polymkeric substance is modified polyacrylamide, by acrylamide, two kinds of monomer copolymerizations of 2-acrylamide-2-methylpro panesulfonic acid, is formed, and in modified polyacrylamide, the mol ratio of two kinds of monomeric units is (1 ~ 4): 1, and viscosity-average molecular weight is 300 ~ 10,000,000.
2. compound oil displacement agent according to claim 1, it is characterized in that described negative and positive system tensio-active agent by anion surfactant and cats product with mol ratio (1.2 ~ 20): 1 forms.
3. compound oil displacement agent according to claim 1, is characterized in that described anion surfactant is alkylbenzene sulfonate, C
12~ C
22sulfonated α-olefin, C
9~ C
17any one in carboxylate salt, mahogany acid, petroleum carboxylate or sulfonated lignin or mixture, the alkyl in described alkylbenzene sulfonate is C
14~ C
22alkyl; Described cats product has a C
10~ C
22alkyl and three C
1～C
4alkyl is connected with described nitrogen-atoms.
4. compound oil displacement agent according to claim 3, is characterized in that described cats product has a C
10~ C
22alkyl is connected with described nitrogen-atoms with three methyl, or has a C
10~ C
22alkyl is connected with described nitrogen-atoms with three ethyls.
5. compound oil displacement agent according to claim 1, the viscosity-average molecular weight that it is characterized in that described modified polyacrylamide is 500 ~ 9,000,000.
6. compound oil displacement agent according to claim 1, is characterized in that described compound oil displacement agent, in mass fraction, comprises 0.03～0.6 part, negative and positive system tensio-active agent.
7. compound oil displacement agent according to claim 1, is characterized in that described compound oil displacement agent, in mass fraction, comprises 0.05～0.2 part, polymkeric substance.
8. adopt according to the flooding method of compound oil displacement agent described in any one in claim 1 to 8, described compound oil displacement agent is contacted with oil-bearing formation under 40 ~ 100 ℃ of displacement of reservoir oil temperature, total mineralization >1000 mg/litre oil field stratum water condition, by the mother oil displacement in described oil-bearing formation out.
9. flooding method according to claim 8, is characterized in that described displacement of reservoir oil temperature is 60～90 ℃.
10. flooding method according to claim 8, is characterized in that described oil field stratum water, and total mineralization is 5000～15000 mg/litre.
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