CN103031123A - Foaming agent composition for tertiary oil recovery and application thereof - Google Patents
Foaming agent composition for tertiary oil recovery and application thereof Download PDFInfo
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Abstract
The invention relates to a foaming agent composition for tertiary oil recovery and application thereof, mainly aiming at solving the problems that the thermal stability of the foaming agent is poor, the sedimentation occurs when the foaming agent meets divalent ions and the high-temperature and high-mineralization-degree stratum foaming flooding demand cannot be met in the existing foam flooding intensified oil recovery technique. By adopting the technical scheme for the foaming agent composition consisting of alkylphenol ethoxylate benzene sulfonate, alkylbenzene sulfonate and water and the application, the problems are better solved and the foaming agent composition can be used for foam flooding for tertiary oil recovery.
Description
Technical field
The present invention relates to a kind of foaming agent combination that can be used for tertiary oil recovery and uses thereof.
Background technology
The oil production process is divided primary oil recovery, secondary oil recovery and tertiary oil recovery.Once, secondary oil recovery is physical method and recovers the oil, but the common crude oil of extraction 30～40%, tertiary oil recovery can make oil recovery factor further improve by the intensified oil reduction measure.How China's main oilfield improves oil recovery factor through once with behind the secondary recovery having entered high water-cut stage, develops to greatest extent remaining reserves, and tertiary oil recovery technology is guaranteeing to have brought into play very important effect aspect the oilfield stable production high yield.In the tertiary oil recovery new technology, chemical combined flooding remains one of very promising method of tool.Its oil-displacement mechanism is mainly the viscosity of polymkeric substance or glue increase driven water-replacing, reduces the profit mobility ratio, alleviates the channelling phenomenon, improves sweep efficiency; Tensio-active agent and alkali reduce oil/water termination tension force, increase capillary number, impel crude oil desorption and effectively dispersion on rock, realize the effective driving to irreducible oil, thereby improve recovery ratio.Yet the temperature resistant antisalt of polymkeric substance is the difficult problem that puzzlement high temperature and high salinity oil reservoir is used always in the chemical combined flooding.
In order to improve the ability of shutoff most permeable zone, people find through a large amount of research, and foam has than polymkeric substance or glue and better enters and reduce the infiltrative ability of most permeable zone.Mix by adding foaming agent and gas, form with aerated fluid is carried out displacement, the shutoff high permeability zone is adjusted fluid entry profile selectively, increases sweep efficiency, again because foaming agent itself is tensio-active agent, have interfacial activity, reduce oil/water termination tension force, increase capillary number, can bring into play better effect, increase substantially recovery ratio.
Foaming agent in the market mainly contains two large classes: anionic foaming agent and non-ionic type foaming agent.Yet, for high temperature, high salinity reservoirs was because independent negatively charged ion foaming agent is relatively poor with the compatibleness of local water, easily with local water in calcium, the formation of the high price such as magnesium ion precipitates, and works as Ca
2+, Mg
2+Just lose oil displacement efficiency when surpassing 300 μ g/g; And there is cloud point in the nonionic foaming agent, and heat resistance is poor, and formation temperature is higher than cloud point, and tensio-active agent namely begins to separate out from water, has limited its application in tertiary oil recovery.And foam is a kind of thermodynamic unstable system, when adopting foam flooding, needs again foam to keep the long as far as possible time on the stratum.Therefore, the key problem of foam flooding is that the development foaming power is strong, and good stability is good with the local water compatibility, the foaming agent system of temperature resistance salt tolerant.
Document CN1648199A discloses a kind of foam formulation of the raising recovery ratio for conventional oil reservoir, wherein said whipping agent host is alkylpolyoxyethylene sulfuric ester sodium salt, but since in the host existence of sulfuric acid ester bond so that this system can only be applicable to be lower than 100 ℃ oil reservoir.
Summary of the invention
One of technical problem to be solved by this invention is the foaming agent poor heat stability that exists in the prior art, meets the divalent ion precipitation, can not satisfy the problem of high temperature and high salinity stratum foam flooding needs, and a kind of new foaming agent combination is provided.It is 40000～98000mg/L that said composition has in salinity, Ca
2++ Mg
2+Be clear under the local water condition of 2000～4500mg/L, 150 ℃ aging after 10 days foam bubble and substantially unconverted advantages of transformation period.Two of technical problem to be solved by this invention provides a kind of purposes of this foaming agent combination.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of foaming agent combination that can be used for tertiary oil recovery comprises following component in mass fraction:
(1) 0.1～1 part polyoxyethylene alkylphenol ether benzene sulfonate;
(2) 0.1～1 parts alkylbenzene sulfonate;
(3) 90～100 parts local water;
Polyoxyethylene alkylphenol ether benzene sulfonate (1) wherein has following general molecular formula:
R in the formula
1Be C
1～C
20Alkyl, M is any one metal ion or the ammonium that is selected from the basic metal, and n is the adduction number of ethoxy group EO, and its span is any one integer in 1～24, x, y are the number of sulfonic acid group, and its span is any one integer in x+y=1～5;
Alkylbenzene sulfonate (2) wherein has following general molecular formula:
R in the formula
2Be C
8～C
20Alkyl, M is any one metal ion that is selected from the basic metal.In the technique scheme, the M preferred version is sodium or the potassium ion in the basic metal, and more preferably scheme is for being selected from sodium; R
1Preferred version is for being selected from C
4～C
15Alkyl, more preferably scheme is for being selected from C
8～C
12Alkyl; R
2Preferred version is for being selected from C
10～C
18Alkyl, more preferably scheme is for being selected from C
12～C
16Alkyl; The n preferred version is any one integer in 2～20, and more preferably scheme is any one integer in 4～16; X+y=1 or 2; The local water total mineralization is preferably 40000～98000mg/L, and more preferably scheme is 55000～95000mg/L, Ca
2++ Mg
2+Be 2000～4500mg/L, more preferably scheme is 2500～4000mg/L, and the water type is Na
2SO
4Type.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of foaming agent combination is applied in the foam flooding intensified oil reduction.
The preparation method of the foaming agent combination that can be used for tertiary oil recovery among the present invention may further comprise the steps:
(a) preparation of polyoxyethylene alkylphenol ether:
Be 85～160 ℃ by required proportioning in temperature of reaction with alkylphenol and oxyethane, pressure is less than under the 0.60MPa gauge pressure condition, and the basic cpd of calcium is catalyzer, reacts to get polyoxyethylene alkylphenol ether; Wherein alkylphenol and oxyethane mol ratio are 1: 1～20, and catalyst levels is 0.5～5.0% of alkylphenol quality;
(b) preparation of alkyl phenol polyoxyethylene benzylic ether:
The synthetic polyoxyethylene alkylphenol ether of step (a) is pressed required proportioning and Benzyl Chloride, potassium hydroxide or sodium hydroxide and Tetrabutyl amonium bromide catalyst mix, take toluene as solvent, 40～100 ℃ of temperature of reaction, reacted 3～15 hours, reaction finishes to get the alkyl phenol polyoxyethylene benzylic ether by aftertreatment; Wherein the mol ratio of polyoxyethylene alkylphenol ether, Benzyl Chloride, potassium hydroxide or sodium hydroxide and Tetrabutyl amonium bromide is 1: 1～3: 1～4: 0.01～0.2.
(c) preparation of polyoxyethylene alkylphenol ether benzene sulfonate:
The alkyl phenol polyoxyethylene benzylic ether that step (b) is synthetic and the vitriol oil are under 30～80 ℃ of conditions by required proportioning in temperature of reaction, reacted 1～10 hour to get the polyoxyethylene alkylphenol ether Phenylsulfonic acid, with the alkali polyoxyethylene alkylphenol ether benzene sulfonate that neutralizes to get; Wherein the mol ratio of alkyl phenol polyoxyethylene benzylic ether and the vitriol oil is 1: 1～6.
(d) polyoxyethylene alkylphenol ether benzene sulfonate, alkylbenzene sulfonate and the water with aequum evenly mixes, and stirring at room 20～60 minutes obtains required foaming agent combination.In mass fraction, the proportioning of polyoxyethylene alkylphenol ether benzene sulfonate, alkylbenzene sulfonate and water is 0.1～1 part: 0.1～1 part: 90～100 parts.
In the technique scheme, (a) the temperature of reaction preferable range in the step is 140～160 ℃, and the pressure preferable range is 0.20～0.40MPa gauge pressure; The mol ratio of alkylphenol and oxyethane is preferably 1: 4～and 16, catalyst levels is preferably 1.0～3.0% of alkylphenol quality; (b) in the step mol ratio of polyoxyethylene alkylphenol ether, Benzyl Chloride, potassium hydroxide or sodium hydroxide and Tetrabutyl amonium bromide be preferably 1: 1～1.5: 1.5～3.0: 0.02～0.1, temperature of reaction is preferably 60～90 ℃, and the reaction times is preferably 5～12 hours; (c) in the step mol ratio of alkyl phenol polyoxyethylene benzylic ether and the vitriol oil be preferably 1: 2～5, the temperature of reaction preferable range is 40～70 ℃, the reaction times preferable range is 3～6 hours; (d) in mass fraction, the consumption preferable range of polyoxyethylene alkylphenol ether benzene sulfonate is 0.1～0.6 part, and alkylbenzene sulfonate consumption preferable range is 0.1～0.6 part, and the reaction times is preferably 30～40 minutes.
The polyoxyethylene alkylphenol ether benzene sulfonate of the present invention's preparation, owing to contain simultaneously aerobic ethene non-ionic group and azochlorosulfonate acid anion group in its molecular structure, make it have the strong and nonionic foam stability of negatively charged ion whipability concurrently by force and the advantage of anticalcium magnesium, and produce synergistic effect with the composite use of alkylbenzene sulfonate, can improve the anti-salt property of whole composition system.Foaming agent combination of the present invention is not higher than 200 ℃ applicable to reservoir temperature, and salinity is lower than 100000mg/L, and calcium ions and magnesium ions concentration is lower than the oil reservoir of 5000mg/L.This foaming agent combination and nitrogen, air, carbonic acid gas and Sweet natural gas mix the stable foam of formation, be applied to Central Plains three factory site layer water bubble system shop experiments, the Luo Shi foaming process is measured its foam volume greater than 400ml in the time of 85 ℃, its transformation period of foam sweep measurement, resistance factor was greater than 35 greater than 360s.
Description of drawings
Fig. 1 is the infrared spectrogram of polyoxyethylene alkylphenol ether benzene sulfonate.
The polyoxyethylene alkylphenol ether benzene sulfonate of the present invention's preparation can characterize by the following method: after synthetics is purified, use U.S. Nicolet-5700 spectrograph, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), determine the chemical structure of sample, to reach the Infrared Characterization to compound of the present invention.
As shown in Figure 1, at wave number 2959.2cm
-1The place is 1608.8cm for the flexible characteristic peak of methyl and methylene radical C-H on the alkyl chain in wave number
-1, 1511.6cm
-1, 828.6cm
-1The place is the Absorption Characteristics peak of phenyl ring, at wave number 1124.2cm
-1The place is that the absorption peak of C-O-C key, this peak are owing to having connected due to the ethoxy group, at wave number 1251cm
-1, 679.1cm
-1The place is sulfonic characteristic peak on the phenyl ring.
Embodiment
In actual design with in implementing, the present invention utilizes the good polyoxyethylene alkylphenol ether benzene sulfonate of salt resistant character can improve these characteristics of salt tolerance of alkylbenzene sulfonate, select a kind of polyoxyethylene alkylphenol ether benzene sulfonate and alkylbenzene sulfonate to carry out composite, adjust the salt resistant character of foaming agent combination by regulating compound proportion, to be fit to high salinity, especially contain the reservoir formation of high divalence calcium ions and magnesium ions.
Below by embodiment the present invention is further elaborated.
[embodiment 1]
(a) nonylphenol Soxylat A 25-7 (n=9) is synthetic
In the reactor that condensing works, whipping appts and gas distributor are housed, add 220 gram (1 mole) nonyl phenols and 4.4 gram calcium oxide catalysts, when logical nitrogen limit, limit is heated to 135 ℃, add 20 gram water, stirring reaction 1 hour.After removing moisture content, be cooled to 80 ℃, the sulfuric acid (20 (wt) %) that slowly drips the catalyst neutralisation theoretical amount makes the compound oxidizing calcium alkoxylating catalyst reaction solution system of high reactivity, highly selective, system temperature is heated to 80～90 ℃, open vacuum system, dehydration is 2 hours under high vacuum, then uses nitrogen purging 3～4 times, the system temperature of reaction is transferred to 150 ℃ slowly pass into 396 gram (9 moles) oxyethane, control pressure≤0.40MPa.Reaction is used the nitrogen purging system after finishing, and neutralization after the cooling, dehydration get nonylphenol Soxylat A 25-7 (n=9) 609 grams, molar yield 98.9%.(b) nonylphenol polyoxyethylene (n=9) benzylic ether is synthetic
Nonylphenol Soxylat A 25-7 (n=9) 609 grams (0.989 mole) that step (a) is synthesized and 83.2 gram (1.484 moles) potassium hydroxide, 137.6 gram (1.088 moles) benzyl chlorine, 12.7 gram (0.040 mole) Tetrabutyl amonium bromides, 700 milliliters of toluene be mixed in be furnished with mechanical stirring, in 2000 milliliters the four-hole boiling flask of thermometer and reflux condensing tube, be heated to 80 ℃ of reactions 8 hours, get nonylphenol polyoxyethylene (n=9) benzylic ether 617.9 grams through aftertreatment, molar yield is 88.5%.(c) nonylphenol Soxylat A 25-7 (n=9) sodium sulfonate (x+y=1) is synthetic
Nonylphenol polyoxyethylene (n=9) benzylic ether 617.9 that step (b) is synthesized restrains (0.875 mole), add and be equipped with in the reactor of reflux condensate device, thermometer, agitator, be warming up to 45 ℃, stir the lower vitriol oil (98wt%) 175.0 grams (1.750 moles) that slowly drip, 1.0 add in hour, insulation reaction finished reaction in 5 hours again, gets yellow thick liquid with aftertreatment and be nonylphenol Soxylat A 25-7 (n=9) sodium sulfonate in sodium hydroxide.
To synthetic nonylphenol Soxylat A 25-7 (n=9) sodium sulfonate, use U.S. Nicolet-5700 infrared spectrometer, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have characteristic peak shown in Figure 1.(d) by percentage to the quality, get synthetic nonylphenol Soxylat A 25-7 (n=9) sodium sulfonate X (wt%), Sodium dodecylbenzene sulfonate Y (wt%), the Zhongyuan Oil Field local water stirred 30 minutes, got required foaming agent combination.Stratum, Zhongyuan Oil Field Analysis Results of Water Quality sees Table 1.Under 85 ℃ of water bath condition, the Luo Shi method is measured said composition latherability and foam scanner and is measured its transformation period and the results are shown in Table 2.
Table 1
| Title | K ++Na + | Mg 2+ | Ca 2+ | Cl - | SO 4 2- | HCO 3 - | Total mineralization | The water type |
| Content (mg/L) | 24719 | 2871 | 592 | 37101 | 13939 | 217 | 79439 | Na 2SO 4 |
Table 2
| X(wt％) | 0.1 | 0.2 | 0.3 | 0.5 | 0.5 |
| Y(wt％) | 0.5 | 0.4 | 0.1 | 0.1 | 0.2 |
| Foam number (ml) | 360 | 400 | 450 | 480 | 500 |
| Transformation period (s) | 272 | 300 | 365 | 392 | 420 |
[embodiment 2]
Get foaming agent combination in [embodiment 1] and pack in the Pressure vessel, put into baking oven and took out in aging 10 days at 150 ℃, under 85 ℃ of water bath condition, the Luo Shi method measure aging after said composition latherability and foam scanner measure its transformation period and the results are shown in Table 3.
Table 3
| X(wt％) | 0.3 | 0.5 | 0.5 |
| Y(wt％) | 0.1 | 0.1 | 0.2 |
| Foam number (ml) | 430 | 460 | 480 |
| Transformation period (s) | 360 | 385 | 405 |
[embodiment 3]
Get foaming agent combination nonylphenol Soxylat A 25-7 (n=9) sodium sulfonate 0.5 (wt%) in [embodiment 1], Sodium dodecylbenzene sulfonate 0.1 (wt%) carries out the sealing characteristics evaluation experimental, quartz sand is filled and presented basket rate of permeation 4D, inject the foaming agent combination aqueous solution with 2mL/min speed to sandpipe, speed with 9mL/min is pressed into nitrogen simultaneously, measure pressure difference of blocking 1.69MPa, calculate resistance factor 42.3.
[embodiment 4]
(a) Octylphenol polyoxyethylene ether (n=4) is synthetic
In the reactor that condensing works, whipping appts and gas distributor are housed, add 206 gram (1 mole) octyl phenols and 6.2 gram calcium oxide catalysts, when logical nitrogen limit, limit is heated to 135 ℃, add 28 gram water, stirring reaction 1 hour.After removing moisture content, be cooled to 80 ℃, the sulfuric acid (20 (wt) %) that slowly drips the catalyst neutralisation theoretical amount makes the compound oxidizing calcium alkoxylating catalyst reaction solution system of high reactivity, highly selective, system temperature is heated to 80～90 ℃, open vacuum system, dehydration is 2 hours under high vacuum, then uses nitrogen purging 3～4 times, the system temperature of reaction is transferred to 160 ℃ slowly pass into 176 gram (4 moles) oxyethane, control pressure≤0.40MPa.Reaction is used the nitrogen purging system after finishing, and neutralization after the cooling, dehydration get Octylphenol polyoxyethylene ether (n=4) 379 grams, molar yield 99.3%.(b) octyl phenol polyoxyethylene (n=4) benzylic ether is synthetic
Octylphenol polyoxyethylene ether (n=4) 379 grams (0.993 mole) that step (a) is synthesized and 83.8 gram (1.494 moles) potassium hydroxide, 132.3 gram (1.046 moles) benzyl chlorine, 32.2 gram (0.10 mole) Tetrabutyl amonium bromides, 500 milliliters of toluene be mixed in be furnished with mechanical stirring, in 2000 milliliters the four-hole boiling flask of thermometer and reflux condensing tube, be heated to 60 ℃ of reactions 12 hours, get octyl phenol polyoxyethylene (n=4) benzylic ether 405.0 grams through aftertreatment, molar yield is 86.4%.(c) Octylphenol polyoxyethylene ether (n=4) sodium disulfonate (x+y=2) is synthetic
Octyl phenol polyoxyethylene (n=4) benzylic ether 405.0 grams that step (b) is synthesized restrain (0.858 mole), add and be equipped with in the reactor of reflux condensate device, thermometer, agitator, be warming up to 70 ℃, stir the lower vitriol oil (98wt%) 343.2 grams (3.432 moles) that slowly drip, 2.0 add in hour, insulation reaction finished reaction in 1 hour again, gets yellow thick liquid with aftertreatment and be Octylphenol polyoxyethylene ether (n=4) sodium disulfonate in sodium hydroxide.
To synthetic Octylphenol polyoxyethylene ether (n=4) sodium disulfonate, use U.S. Nicolet-5700 infrared spectrometer, (sweep limit 4000～400cm-1) has characteristic peak shown in Figure 1 to adopt liquid-film method to carry out Infrared spectroscopy.(d) by percentage to the quality, get synthetic Octylphenol polyoxyethylene ether (n=4) sodium disulfonate X (wt%), Sodium dodecylbenzene sulfonate Y (w t%), the Zhongyuan Oil Field local water stirred 40 minutes, got required foaming agent combination.Stratum, Zhongyuan Oil Field Analysis Results of Water Quality sees Table 4.Under 90 ℃ of water bath condition, the Luo Shi method is measured said composition latherability and foam scanner and is measured its transformation period and the results are shown in Table 5.
Table 4
| Title | K ++Na + | Mg 2+ | Ca 2+ | Cl - | SO 4 2- | HCO 3 - | Total mineralization | The water type |
| Content (mg/L) | 17846 | 2072 | 428 | 26783 | 10063 | 155 | 57347 | Na 2SO 4 |
Table 5
| X(wt％) | 0.1 | 0.2 | 0.3 | 0.5 | 0.5 |
| Y(wt％) | 0.5 | 0.4 | 0.15 | 0.1 | 0.2 |
| Foam number (ml) | 370 | 390 | 440 | 470 | 480 |
| Transformation period (s) | 270 | 338 | 445 | 452 | 505 |
[embodiment 5]
Get foaming agent combination in [embodiment 4] and pack in the Pressure vessel, put into baking oven and took out in aging 10 days at 150 ℃, under 90 ℃ of water bath condition, the Luo Shi method measure aging after said composition latherability and foam scanner measure its transformation period and the results are shown in Table 6.
Table 6
| X(wt％) | 0.3 | 0.5 | 0.5 |
| Y(wt％) | 0.15 | 0.1 | 0.2 |
| Foam number (ml) | 410 | 450 | 460 |
| Transformation period (s) | 415 | 440 | 485 |
[embodiment 6]
Get Octylphenol polyoxyethylene ether (n=4) sodium disulfonate 0.5 (wt%) in [embodiment 4], Sodium dodecylbenzene sulfonate 0.2 (wt%), the foaming agent combination that the Zhongyuan Oil Field local water forms, carry out the sealing characteristics evaluation experimental with the condition in [embodiment 3], the mensuration pressure difference of blocking is 1.70MPa, calculates resistance factor 42.5.
[embodiment 7]
(a) dodecylbenzene phenol polyethenoxy ether (n=16) is synthetic
In the reactor that condensing works, whipping appts and gas distributor are housed, add 262 gram (1 mole) dodecyl phenols and 3.9 gram calcium oxide catalysts, when logical nitrogen limit, limit is heated to 135 ℃, add 18 gram water, stirring reaction 1 hour.After removing moisture content, be cooled to 80 ℃, the sulfuric acid (20 (wt) %) that slowly drips the catalyst neutralisation theoretical amount makes the compound oxidizing calcium alkoxylating catalyst reaction solution system of high reactivity, highly selective, system temperature is heated to 80～90 ℃, open vacuum system, dehydration is 2 hours under high vacuum, then uses nitrogen purging 3～4 times, the system temperature of reaction is transferred to 150 ℃ slowly pass into 704 gram (16 moles) oxyethane, control pressure≤0.40MPa.Reaction is used the nitrogen purging system after finishing, and neutralization after the cooling, dehydration get dodecylbenzene phenol polyethenoxy ether (n=16) 932 grams, molar yield 96.5%.
(b) dodecylbenzene phenol polyethenoxy (n=16) benzylic ether is synthetic
Dodecylbenzene phenol polyethenoxy ether (n=16) 932 grams (0.965 mole) that step (a) is synthesized and 115.8 gram (2.895 moles) sodium hydroxide, 158.7 gram (1.255 moles) benzyl chlorine, 6.3 gram (0.019 mole) Tetrabutyl amonium bromides, 1000 milliliters of toluene be mixed in be furnished with mechanical stirring, in 5000 milliliters the four-hole boiling flask of thermometer and reflux condensing tube, be heated to 90 ℃ of reactions 5 hours, get dodecylbenzene phenol polyethenoxy (n=16) benzylic ether 856.0 grams through aftertreatment, molar yield is 84.0%.
(c) dodecylbenzene phenol polyethenoxy ether (n=16) sodium sulfonate (x+y=1) is synthetic
Dodecylbenzene phenol polyethenoxy (n=16) benzylic ether 856.0 that step (b) is synthesized restrains (0.811 mole), add and be equipped with in the reactor of reflux condensate device, thermometer, agitator, be warming up to 70 ℃, stir the lower vitriol oil (98wt%) 243.3 grams (2.433 moles) that slowly drip, 1.5 add in hour, insulation reaction finished reaction in 1.5 hours again, gets yellow thick liquid with aftertreatment and be dodecylbenzene phenol polyethenoxy ether (n=16) sodium sulfonate in sodium hydroxide.
To synthetic dodecylbenzene phenol polyethenoxy ether (n=16) sodium sulfonate, use U.S. Nicolet-5700 infrared spectrometer, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have characteristic peak shown in Figure 1.
(d) by percentage to the quality, get synthetic dodecylbenzene phenol polyethenoxy ether (n=16) sodium sulfonate X (wt%), tetradecyl benzene sulfonic acid sodium salt Y (wt%), the Zhongyuan Oil Field local water stirred 35 minutes, got required foaming agent combination.Stratum, Zhongyuan Oil Field Analysis Results of Water Quality sees Table 1.Under 85 ℃ of water bath condition, the Luo Shi method is measured this Foaming ability and foam scanner and is measured its transformation period and the results are shown in Table 7.
Table 7
| X(wt％) | 0.1 | 0.2 | 0.3 | 0.5 | 0.5 |
| Y(wt％) | 0.5 | 0.4 | 0.2 | 0.1 | 0.2 |
| Foam number (ml) | 390 | 410 | 450 | 480 | 500 |
| Transformation period (s) | 335 | 398 | 474 | 480 | 512 |
[embodiment 8]
Get foaming agent combination in [embodiment 7] and pack in the Pressure vessel, put into baking oven and took out in aging 10 days at 150 ℃, under 85 ℃ of water bath condition, the Luo Shi method measure aging after said composition latherability and foam scanner measure its transformation period and the results are shown in Table 8.
Table 8
| X(wt％) | 0.3 | 0.5 | 0.5 |
| Y(wt％) | 0.2 | 0.1 | 0.2 |
| Foam number (ml) | 440 | 460 | 490 |
| Transformation period (s) | 459 | 471 | 495 |
[embodiment 9]
Get dodecylbenzene phenol polyethenoxy ether (n=16) sodium sulfonate 0.5 (wt%) in [embodiment 7], tetradecyl benzene sulfonic acid sodium salt 0.2 (wt%), the foaming agent combination that the Zhongyuan Oil Field local water forms, carry out the sealing characteristics evaluation experimental with under [embodiment 3] experiment condition, the mensuration pressure difference of blocking is 1.79MPa, calculates resistance factor 44.8.
[embodiment 10]
(a) dodecylbenzene phenol polyethenoxy ether (n=7) is synthetic
In the reactor that condensing works, whipping appts and gas distributor are housed, add 262 gram (1 mole) dodecyl phenols and 2.6 gram calcium oxide catalysts, when logical nitrogen limit, limit is heated to 135 ℃, add 11 gram water, stirring reaction 1 hour.After removing moisture content, be cooled to 80 ℃, the sulfuric acid (20 (wt) %) that slowly drips the catalyst neutralisation theoretical amount makes the compound oxidizing calcium alkoxylating catalyst reaction solution system of high reactivity, highly selective, system temperature is heated to 80～90 ℃, open vacuum system, dehydration is 2 hours under high vacuum, then uses nitrogen purging 3～4 times, the system temperature of reaction is transferred to 140 ℃ slowly pass into 308 gram (7 moles) oxyethane, control pressure≤0.40MPa.Reaction is used the nitrogen purging system after finishing, and neutralization after the cooling, dehydration get dodecylbenzene phenol polyethenoxy ether (n=7) 560 grams, molar yield 98.1%.
(b) dodecylbenzene phenol polyethenoxy (n=7) benzylic ether is synthetic
Dodecylbenzene phenol polyethenoxy ether (n=7) 560 grams (0.981 mole) that step (a) is synthesized and 82.6 gram (1.472 moles) potassium hydroxide, 148.9 gram (1.177 moles) benzyl chlorine, 19.0 gram (0.059 mole) Tetrabutyl amonium bromides, 600 milliliters of toluene be mixed in be furnished with mechanical stirring, in 2000 milliliters the four-hole boiling flask of thermometer and reflux condensing tube, be heated to 75 ℃ of reactions 8 hours, get dodecylbenzene phenol polyethenoxy (n=7) benzylic ether 566.5 grams through aftertreatment, molar yield is 87.5%.
(c) dodecylbenzene phenol polyethenoxy ether (n=7) sodium disulfonate (x+y=2) is synthetic
Dodecylbenzene phenol polyethenoxy (n=7) benzylic ether 566.5 that step (b) is synthesized restrains (0.858 mole), add and be equipped with in the reactor of reflux condensate device, thermometer, agitator, be warming up to 70 ℃, stir the lower vitriol oil (98wt%) 429.2 grams (4.292 moles) that slowly drip, add in 2 hours, insulation reaction finished reaction in 3 hours again, gets yellow thick liquid with aftertreatment and be dodecylbenzene phenol polyethenoxy ether (n=7) sodium disulfonate in sodium hydroxide.
To synthetic dodecylbenzene phenol polyethenoxy ether (n=7) sodium disulfonate, use U.S. Nicolet-5700 infrared spectrometer, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have characteristic peak shown in Figure 1.
(d) by percentage to the quality, get synthetic dodecylbenzene phenol polyethenoxy ether (n=7) sodium disulfonate X (wt%), hexadecyl benzene sulfonic acid sodium salt Y (wt%), Zhongyuan Oil Field local water, stirred 30 minutes, and got required foaming agent combination.Stratum, Zhongyuan Oil Field Analysis Results of Water Quality sees Table 9.Under 85 ℃ of water bath condition, the Luo Shi method is measured this Foaming ability and foam scanner and is measured its transformation period and the results are shown in Table 10.
Table 9
| Title | K ++Na + | Mg 2+ | Ca 2+ | Cl - | SO 4 2- | HCO 3 - | Total mineralization | The water type |
| Content (mg/L) | 28553 | 3316 | 684 | 42855 | 16101 | 250 | 91759 | Na 2SO 4 |
Table 10
| X(wt％) | 0.1 | 0.2 | 0.3 | 0.5 | 0.5 |
| Y(wt％) | 0.5 | 0.4 | 0.2 | 0.1 | 0.2 |
| Foam number (ml) | 390 | 430 | 460 | 490 | 510 |
| Transformation period (s) | 335 | 393 | 480 | 485 | 515 |
[embodiment 11]
Get foaming agent combination in [embodiment 10] and pack in the Pressure vessel, put into baking oven and took out in aging 10 days at 150 ℃, under 85 ℃ of water bath condition, the Luo Shi method measure aging after said composition latherability and foam scanner measure its transformation period and the results are shown in Table 11.
Table 11
| X(wt％) | 0.3 | 0.5 | 0.5 |
| Y(wt％) | 0.2 | 0.1 | 0.2 |
| Foam number (m1) | 450 | 480 | 500 |
| Transformation period (s) | 458 | 460 | 496 |
[embodiment 12]
Get dodecylbenzene phenol polyethenoxy ether (n=7) sodium disulfonate 0.5 (wt%) in [embodiment 10], hexadecyl benzene sulfonic acid sodium salt 0.2 (wt%), the foaming agent combination that the Zhongyuan Oil Field local water forms, carry out the sealing characteristics evaluation experimental with under [embodiment 3] experiment condition, the mensuration pressure difference of blocking is 1.85MPa, calculates resistance factor 46.3.
Claims (8)
1. foaming agent combination that can be used for tertiary oil recovery comprises following component in mass fraction:
(1) 0.1～1 part polyoxyethylene alkylphenol ether benzene sulfonate;
(2) 0.1～1 parts alkylbenzene sulfonate;
(3) 90～100 parts local water;
Polyoxyethylene alkylphenol ether benzene sulfonate (1) wherein has following general molecular formula:
R in the formula
1Be C
1～C
20Alkyl, M is any one metal ion or the ammonium that is selected from the basic metal, and n is the adduction number of ethoxy group EO, and its span is any one integer in 1～24, x, y are the number of sulfonic acid group, and its span is any one integer in x+y=1～5;
Alkylbenzene sulfonate (2) wherein has following general molecular formula:
R in the formula
2Be C
8～C
20Alkyl, M is any one metal ion that is selected from the basic metal.
2. the foaming agent combination that can be used for tertiary oil recovery according to claim 1 is characterized in that described basic metal is sodium or potassium; R
1Be C
4～C
15Alkyl, R
2Be C
10～C
18Alkyl; N is any one integer in 2～20; X+y=1 or 2.
3. the foaming agent combination that can be used for tertiary oil recovery according to claim 2 is characterized in that described basic metal is sodium; R
1Be C
8～C
12Alkyl, R
2Be C
12～C
16Alkyl; N is any one integer in 4～16.
4. the foaming agent combination that can be used for tertiary oil recovery according to claim 1 is characterized in that in mass fraction, and polyoxyethylene alkylphenol ether benzene sulfonate consumption is 0.1～1 part.
5. the foaming agent combination that can be used for tertiary oil recovery according to claim 1 is characterized in that in mass fraction, and the consumption of alkylbenzene sulfonate is 0.1～1 part.
6. the foaming agent combination that can be used for tertiary oil recovery according to claim 1 is characterized in that the total mineralization of described local water less than 100000mg/L, Ca
2++ Mg
2+Less than 5000mg/L, the water type is Na
2SO
4Type.
7. the foaming agent combination that can be used for tertiary oil recovery according to claim 6, the total mineralization that it is characterized in that described local water is 40000～98000mg/L, Ca
2++ Mg
2+Be 2000～4500mg/L, the water type is Na
2SO
4Type.
8. the foaming agent combination that can be used for tertiary oil recovery claimed in claim 1 is applied in the foam flooding intensified oil reduction.
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