CN103031123B - 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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- CN103031123B CN103031123B CN201110300423.1A CN201110300423A CN103031123B CN 103031123 B CN103031123 B CN 103031123B CN 201110300423 A CN201110300423 A CN 201110300423A CN 103031123 B CN103031123 B CN 103031123B
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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
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, crude oil that conventionally can extraction 30～40%, tertiary oil recovery, by intensified oil reduction measure, can make oil recovery factor further improve.How China's main oilfield, through once with after secondary recovery having entered high water-cut stage, improves oil recovery factor, develops to greatest extent remaining reserves, and tertiary oil recovery technology is ensureing to have brought into play very important effect aspect oilfield stable production high yield.In 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 profit mobility ratio, alleviates channelling phenomenon, improves sweep efficiency; Tensio-active agent and alkali reduce oil/water interfacial tension, increase capillary number, impel crude oil desorption and effectively dispersion on rock, realize the effective driving to irreducible oil, thereby improve recovery ratio.But in chemical combined flooding, the temperature resistant antisalt of polymkeric substance is a difficult problem for puzzlement high temperature and high salinity oil reservoir application always.
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, shutoff high permeability zone selectively, adjusts fluid entry profile, increases sweep efficiency, again because foaming agent itself is tensio-active agent, there is interfacial activity, reduce oil/water interfacial tension, 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.But, for high temperature, high salinity reservoirs was, because the compatibleness of independent negatively charged ion foaming agent and local water is poor, the calcium easily and in local water, the high valence ions such as magnesium form precipitation, work as Ca
2+, Mg
2+while exceeding 300 μ g/g, just lose oil displacement efficiency; And nonionic foaming agent exists cloud point, heat resistance is poor, and formation temperature is higher than cloud point, and tensio-active agent starts to separate out from water, has limited its application in tertiary oil recovery.And foam is a kind of thermodynamic unstable system, in the time adopting foam flooding, need again foam to retain the long as far as possible time on stratum.Therefore, the key problem of foam flooding is that development foaming power is strong, and good stability is good with 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 can only be applicable to the oil reservoir lower than 100 DEG C because the existence of sulfuric acid ester bond in host makes this system.
Summary of the invention
One of technical problem to be solved by this invention is the foaming agent poor heat stability existing in prior art, meets divalent ion precipitation, can not meet 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 DEG C of foams after aging 10 days bubble and substantially unconverted advantage of transformation period.Two of technical problem to be solved by this invention is to provide 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:
The polyoxyethylene alkylphenol ether benzene sulfonate of (1) 0.1～1 part;
The alkylbenzene sulfonate of (2) 0.1～1 parts;
The local water of (3) 90～100 parts;
Wherein polyoxyethylene alkylphenol ether benzene sulfonate (1), has following general molecular formula:
R in formula
1for C
1～C
20alkyl, M is any one metal ion or the ammonium being selected from 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;
Wherein alkylbenzene sulfonate (2), has following general molecular formula:
R in formula
2for C
8～C
20alkyl, M is any one metal ion being selected from basic metal.In technique scheme, M preferred version is sodium or the potassium ion in 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; 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; 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 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 foam flooding intensified oil reduction.
The preparation method of the foaming agent combination that can be used for tertiary oil recovery in the present invention, comprises the following steps:
(a) preparation of polyoxyethylene alkylphenol ether:
Be 85～160 DEG C by required proportioning in temperature of reaction by alkylphenol and oxyethane, pressure is less than under 0.60MPa gauge pressure condition, and the basic cpd of calcium is catalyzer, reacts to obtain 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, taking toluene as solvent, 40～100 DEG C of temperature of reaction, react 3～15 hours, after reaction finishes, obtain alkyl phenol polyoxyethylene benzylic ether through 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 DEG C of conditions by required proportioning in temperature of reaction, react 1～10 hour to obtain polyoxyethylene alkylphenol ether Phenylsulfonic acid, neutralize to obtain polyoxyethylene alkylphenol ether benzene sulfonate with alkali; 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 of aequum are evenly mixed, stirring at room temperature 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 technique scheme, (a) the temperature of reaction preferable range in step is 140～160 DEG C, and 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 step the 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 DEG C, and the reaction times is preferably 5～12 hours; (c) in step the mol ratio of alkyl phenol polyoxyethylene benzylic ether and the vitriol oil be preferably 1: 2～5, temperature of reaction preferable range is 40～70 DEG C, 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.
Polyoxyethylene alkylphenol ether benzene sulfonate prepared by the present invention, owing to containing aerobic ethene non-ionic group and azochlorosulfonate acid anion group in its molecular structure simultaneously, 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 applicable to reservoir temperature higher than 200 DEG C, 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 are mixed to form stable foam, be applied to Central Plains three factory site layer water bubble system shop experiments, 85 DEG C time, Roche foaming process is measured its foam volume and is greater than 400ml, its transformation period of foam sweep measurement is greater than 360s, and resistance factor is greater than 35.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of polyoxyethylene alkylphenol ether benzene sulfonate.
Polyoxyethylene alkylphenol ether benzene sulfonate prepared by the present invention can characterize by the following method: after synthetics is purified, application U.S. Nicolet-5700 spectrograph, adopts 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
-1place, for the flexible characteristic peak of methyl and methylene radical C-H on alkyl chain, is 1608.8cm in wave number
-1, 1511.6cm
-1, 828.6cm
-1place is for the Absorption Characteristics peak of phenyl ring, at wave number 1124.2cm
-1place is the absorption peak of C-O-C key, and this peak is owing to having connected due to ethoxy group, at wave number 1251cm
-1, 679.1cm
-1place is sulfonic characteristic peak on 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 this feature 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 applicable 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
Add 220 grams of (1 mole) nonyl phenols and 4.4 grams of calcium oxide catalysts to being equipped with in the reactor of condensing works, whipping appts and gas distributor, when logical nitrogen limit, limit is heated to 135 DEG C, add 20 grams of water, stirring reaction 1 hour.Remove after moisture content, be cooled to 80 DEG C, the sulfuric acid (20 (wt) %) that slowly drips 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 DEG C, open vacuum system, under high vacuum, dewater 2 hours, then use nitrogen purging 3～4 times, system temperature of reaction is adjusted to 150 DEG C and slowly passes into 396 grams of (9 moles) oxyethane, control pressure≤0.40MPa.After reaction finishes, use nitrogen purging system, cooling rear neutralization, dehydration, obtain 609 grams of nonylphenol Soxylat A 25-7s (n=9), molar yield 98.9%.(b) nonylphenol polyoxyethylene (n=9) benzylic ether is synthetic
The nonylphenol Soxylat A 25-7 (n=9) of step (a) synthesized 609 grams (0.989 mole) and 83.2 grams of (1.484 moles) potassium hydroxide, 137.6 grams of (1.088 moles) benzyl chlorine, 12.7 grams of (0.040 mole) Tetrabutyl amonium bromides, 700 milliliters of toluene are mixed in be furnished with mechanical stirring, in the four-hole boiling flask of 2000 milliliters of thermometer and reflux condensing tube, be heated to 80 DEG C of reactions 8 hours, obtain 617.9 grams of nonylphenol polyoxyethylene (n=9) benzylic ethers through aftertreatment, molar yield is 88.5%.(c) nonylphenol Soxylat A 25-7 (n=9) sodium sulfonate (x+y=1) is synthetic
By 617.9 grams of nonylphenol polyoxyethylene (n=9) benzylic ethers (0.875 mole) of step (b) synthesized, add in the reactor that reflux condensate device, thermometer, agitator are housed, be warming up to 45 DEG C, under stirring, slowly drip 175.0 grams of the vitriol oils (98wt%) (1.750 moles), in 1.0 hours, add, insulation reaction finishes reaction in 5 hours again, obtains yellow thick liquid be nonylphenol Soxylat A 25-7 (n=9) sodium sulfonate in sodium hydroxide with aftertreatment.
To synthetic nonylphenol Soxylat A 25-7 (n=9) sodium sulfonate, application U.S. Nicolet-5700 infrared spectrometer, adopts liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), there is the characteristic peak shown in Fig. 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%), Zhongyuan Oil Field local water, stir 30 minutes, obtain required foaming agent combination.Stratum, Zhongyuan Oil Field Analysis Results of Water Quality is in table 1.Under 85 DEG C of water bath condition, Roche 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 | 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]
The foaming agent combination of getting in [embodiment 1] packs in Pressure vessel, puts into baking oven and within aging 10 days, takes out at 150 DEG C, and under 85 DEG C of water bath condition, Roche method is measured aging rear said composition latherability and foam scanner and measured 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 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, be pressed into nitrogen with the speed of 9mL/min simultaneously, measure pressure difference of blocking 1.69MPa, calculate resistance factor 42.3.
[embodiment 4]
(a) Octylphenol polyoxyethylene ether (n=4) is synthetic
Add 206 grams of (1 mole) octyl phenols and 6.2 grams of calcium oxide catalysts to being equipped with in the reactor of condensing works, whipping appts and gas distributor, when logical nitrogen limit, limit is heated to 135 DEG C, add 28 grams of water, stirring reaction 1 hour.Remove after moisture content, be cooled to 80 DEG C, the sulfuric acid (20 (wt) %) that slowly drips 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 DEG C, open vacuum system, under high vacuum, dewater 2 hours, then use nitrogen purging 3～4 times, system temperature of reaction is adjusted to 160 DEG C and slowly passes into 176 grams of (4 moles) oxyethane, control pressure≤0.40MPa.After reaction finishes, use nitrogen purging system, cooling rear neutralization, dehydration, obtain 379 grams of Octylphenol polyoxyethylene ethers (n=4), molar yield 99.3%.(b) octyl phenol polyoxyethylene (n=4) benzylic ether is synthetic
The Octylphenol polyoxyethylene ether (n=4) of step (a) synthesized 379 grams (0.993 mole) and 83.8 grams of (1.494 moles) potassium hydroxide, 132.3 grams of (1.046 moles) benzyl chlorine, 32.2 grams of (0.10 mole) Tetrabutyl amonium bromides, 500 milliliters of toluene are mixed in be furnished with mechanical stirring, in the four-hole boiling flask of 2000 milliliters of thermometer and reflux condensing tube, be heated to 60 DEG C of reactions 12 hours, obtain 405.0 grams of octyl phenol polyoxyethylene (n=4) benzylic ethers through aftertreatment, molar yield is 86.4%.(c) Octylphenol polyoxyethylene ether (n=4) sodium disulfonate (x+y=2) is synthetic
By 405.0 grams grams of octyl phenol polyoxyethylene (n=4) benzylic ethers (0.858 mole) of step (b) synthesized, add in the reactor that reflux condensate device, thermometer, agitator are housed, be warming up to 70 DEG C, under stirring, slowly drip 343.2 grams of the vitriol oils (98wt%) (3.432 moles), in 2.0 hours, add, insulation reaction finishes reaction in 1 hour again, obtains yellow thick liquid be Octylphenol polyoxyethylene ether (n=4) sodium disulfonate in sodium hydroxide with aftertreatment.
To synthetic Octylphenol polyoxyethylene ether (n=4) sodium disulfonate, application U.S. Nicolet-5700 infrared spectrometer, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm-1), there is the characteristic peak shown in Fig. 1.(d) by percentage to the quality, get synthetic Octylphenol polyoxyethylene ether (n=4) sodium disulfonate X (wt%), Sodium dodecylbenzene sulfonate Y (w t%), Zhongyuan Oil Field local water, stir 40 minutes, obtain required foaming agent combination.Stratum, Zhongyuan Oil Field Analysis Results of Water Quality is in table 4.Under 90 DEG C of water bath condition, Roche 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 | 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]
The foaming agent combination of getting in [embodiment 4] packs in Pressure vessel, puts into baking oven and within aging 10 days, takes out at 150 DEG C, and under 90 DEG C of water bath condition, Roche method is measured aging rear said composition latherability and foam scanner and measured 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 of Zhongyuan Oil Field local water composition, carry out sealing characteristics evaluation experimental with the condition in [embodiment 3], mensuration pressure difference of blocking is 1.70MPa, calculates resistance factor 42.5.
[embodiment 7]
(a) dodecylbenzene phenol polyethenoxy ether (n=16) is synthetic
Add 262 grams of (1 mole) dodecyl phenols and 3.9 grams of calcium oxide catalysts to being equipped with in the reactor of condensing works, whipping appts and gas distributor, when logical nitrogen limit, limit is heated to 135 DEG C, add 18 grams of water, stirring reaction 1 hour.Remove after moisture content, be cooled to 80 DEG C, the sulfuric acid (20 (wt) %) that slowly drips 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 DEG C, open vacuum system, under high vacuum, dewater 2 hours, then use nitrogen purging 3～4 times, system temperature of reaction is adjusted to 150 DEG C and slowly passes into 704 grams of (16 moles) oxyethane, control pressure≤0.40MPa.After reaction finishes, use nitrogen purging system, cooling rear neutralization, dehydration, obtain 932 grams of dodecylbenzene phenol polyethenoxy ethers (n=16), molar yield 96.5%.
(b) dodecylbenzene phenol polyethenoxy (n=16) benzylic ether is synthetic
The dodecylbenzene phenol polyethenoxy ether (n=16) of step (a) synthesized 932 grams (0.965 mole) and 115.8 grams of (2.895 moles) sodium hydroxide, 158.7 grams of (1.255 moles) benzyl chlorine, 6.3 grams of (0.019 mole) Tetrabutyl amonium bromides, 1000 milliliters of toluene are mixed in be furnished with mechanical stirring, in the four-hole boiling flask of 5000 milliliters of thermometer and reflux condensing tube, be heated to 90 DEG C of reactions 5 hours, obtain 856.0 grams of dodecylbenzene phenol polyethenoxy (n=16) benzylic ethers through aftertreatment, molar yield is 84.0%.
(c) dodecylbenzene phenol polyethenoxy ether (n=16) sodium sulfonate (x+y=1) is synthetic
By 856.0 grams of dodecylbenzene phenol polyethenoxy (n=16) benzylic ethers (0.811 mole) of step (b) synthesized, add in the reactor that reflux condensate device, thermometer, agitator are housed, be warming up to 70 DEG C, under stirring, slowly drip 243.3 grams of the vitriol oils (98wt%) (2.433 moles), in 1.5 hours, add, insulation reaction finishes reaction in 1.5 hours again, obtains yellow thick liquid be dodecylbenzene phenol polyethenoxy ether (n=16) sodium sulfonate in sodium hydroxide with aftertreatment.
To synthetic dodecylbenzene phenol polyethenoxy ether (n=16) sodium sulfonate, application U.S. Nicolet-5700 infrared spectrometer, adopts liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), there is the characteristic peak shown in Fig. 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%), Zhongyuan Oil Field local water, stir 35 minutes, obtain required foaming agent combination.Stratum, Zhongyuan Oil Field Analysis Results of Water Quality is in table 1.Under 85 DEG C of water bath condition, Roche 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]
The foaming agent combination of getting in [embodiment 7] packs in Pressure vessel, puts into baking oven and within aging 10 days, takes out at 150 DEG C, and under 85 DEG C of water bath condition, Roche method is measured aging rear said composition latherability and foam scanner and measured 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 of Zhongyuan Oil Field local water composition, carry out sealing characteristics evaluation experimental with under [embodiment 3] experiment condition, mensuration pressure difference of blocking is 1.79MPa, calculates resistance factor 44.8.
[embodiment 10]
(a) dodecylbenzene phenol polyethenoxy ether (n=7) is synthetic
Add 262 grams of (1 mole) dodecyl phenols and 2.6 grams of calcium oxide catalysts to being equipped with in the reactor of condensing works, whipping appts and gas distributor, when logical nitrogen limit, limit is heated to 135 DEG C, add 11 grams of water, stirring reaction 1 hour.Remove after moisture content, be cooled to 80 DEG C, the sulfuric acid (20 (wt) %) that slowly drips 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 DEG C, open vacuum system, under high vacuum, dewater 2 hours, then use nitrogen purging 3～4 times, system temperature of reaction is adjusted to 140 DEG C and slowly passes into 308 grams of (7 moles) oxyethane, control pressure≤0.40MPa.After reaction finishes, use nitrogen purging system, cooling rear neutralization, dehydration, obtain 560 grams of dodecylbenzene phenol polyethenoxy ethers (n=7), molar yield 98.1%.
(b) dodecylbenzene phenol polyethenoxy (n=7) benzylic ether is synthetic
The dodecylbenzene phenol polyethenoxy ether (n=7) of step (a) synthesized 560 grams (0.981 mole) and 82.6 grams of (1.472 moles) potassium hydroxide, 148.9 grams of (1.177 moles) benzyl chlorine, 19.0 grams of (0.059 mole) Tetrabutyl amonium bromides, 600 milliliters of toluene are mixed in be furnished with mechanical stirring, in the four-hole boiling flask of 2000 milliliters of thermometer and reflux condensing tube, be heated to 75 DEG C of reactions 8 hours, obtain 566.5 grams of dodecylbenzene phenol polyethenoxy (n=7) benzylic ethers through aftertreatment, molar yield is 87.5%.
(c) dodecylbenzene phenol polyethenoxy ether (n=7) sodium disulfonate (x+y=2) is synthetic
By 566.5 grams of dodecylbenzene phenol polyethenoxy (n=7) benzylic ethers (0.858 mole) of step (b) synthesized, add in the reactor that reflux condensate device, thermometer, agitator are housed, be warming up to 70 DEG C, under stirring, slowly drip 429.2 grams of the vitriol oils (98wt%) (4.292 moles), in 2 hours, add, insulation reaction finishes reaction in 3 hours again, obtains yellow thick liquid be dodecylbenzene phenol polyethenoxy ether (n=7) sodium disulfonate in sodium hydroxide with aftertreatment.
To synthetic dodecylbenzene phenol polyethenoxy ether (n=7) sodium disulfonate, application U.S. Nicolet-5700 infrared spectrometer, adopts liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), there is the characteristic peak shown in Fig. 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, stir 30 minutes, obtain required foaming agent combination.Stratum, Zhongyuan Oil Field Analysis Results of Water Quality is in table 9.Under 85 DEG C of water bath condition, Roche 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 | 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]
The foaming agent combination of getting in [embodiment 10] packs in Pressure vessel, puts into baking oven and within aging 10 days, takes out at 150 DEG C, and under 85 DEG C of water bath condition, Roche method is measured aging rear said composition latherability and foam scanner and measured 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 of Zhongyuan Oil Field local water composition, carry out sealing characteristics evaluation experimental with under [embodiment 3] experiment condition, mensuration pressure difference of blocking is 1.85MPa, calculates resistance factor 46.3.
Claims (5)
1. can be used for a foaming agent combination for tertiary oil recovery, comprise following component in mass fraction:
The polyoxyethylene alkylphenol ether benzene sulfonate of (1) 0.1～1 part;
The alkylbenzene sulfonate of (2) 0.1～1 parts;
The local water of (3) 90～100 parts;
Wherein polyoxyethylene alkylphenol ether benzene sulfonate (1), has following general molecular formula:
R in formula
1for C
4～C
15alkyl, M is for being selected from sodium or potassium or ammonium, n is the adduction number of ethoxy group EO, its span is any one integer in 2～20, the number that x, y are sulfonic acid group, its span is any one integer in x+y=1 or 2;
Wherein alkylbenzene sulfonate (2), has following general molecular formula:
R in formula
2for C
10～C
18alkyl, M is for being selected from sodium or potassium.
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; R
1for C
8～C
12alkyl, R
2for C
12～C
16alkyl; N is any one integer in 4～16.
3. 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 is less than 100000mg/L, Ca
2++ Mg
2+be less than 5000mg/L, water type is Na
2sO
4type.
4. the foaming agent combination that can be used for tertiary oil recovery according to claim 3, is characterized in that the total mineralization of described local water is 40000～98000mg/L, Ca
2++ Mg
2+be 2000～4500mg/L, water type is Na
2sO
4type.
5. the foaming agent combination that can be used for tertiary oil recovery claimed in claim 1 is applied in foam flooding intensified oil reduction.
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| CN104277809B (en) * | 2013-07-09 | 2017-06-20 | 中国石油化工股份有限公司 | Displacement composition and preparation method thereof |
| CN103937481A (en) * | 2014-05-07 | 2014-07-23 | 中国石油化工股份有限公司河南油田分公司石油勘探开发研究院 | High-temperature-resistant and low-tension foam flooding agent and preparation method thereof |
| CN105038755A (en) * | 2015-06-17 | 2015-11-11 | 成都高普石油工程技术有限公司 | Technique for preparing foam flooding for petroleum extraction |
| CN106281286B (en) * | 2015-06-26 | 2020-02-21 | 中国石油化工股份有限公司 | Foaming agent and preparation method thereof |
| CN111087533B (en) * | 2018-10-23 | 2021-08-03 | 中国石油化工股份有限公司 | Polymer microemulsion system adopting anionic non-sulfonate type composite emulsifier, profile control and flooding system, preparation method and application thereof |
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