CN106590606A - Temperature and salt resisting low-tension foam and application thereof in foam plugging - Google Patents
Temperature and salt resisting low-tension foam and application thereof in foam plugging Download PDFInfo
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- CN106590606A CN106590606A CN201510682875.9A CN201510682875A CN106590606A CN 106590606 A CN106590606 A CN 106590606A CN 201510682875 A CN201510682875 A CN 201510682875A CN 106590606 A CN106590606 A CN 106590606A
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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
- C09K8/594—Compositions used in combination with injected gas, e.g. CO2 orcarbonated gas
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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
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
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Abstract
The invention relates to a low-tension foaming agent composition for tertiary oil recovery and application thereof in foam plugging. The problem that during current foam flooding, foaming agents cannot achieve good foam performance and low oil-water interfacial tension at the same time is mainly solved. Temperature and salt resisting low-tension foam comprises an aqueous solution of the temperature and salt resisting low-tension foaming agent composition and gas, wherein the volume ratio of the aqueous solution of the temperature and salt resisting low-tension foaming agent composition to the gas is 1:(0.5-20). According to the technical scheme, the temperature and salt resisting low-tension foaming agent composition comprises, by mass, 1 part of a polyether anion surfactant, 1-5 parts of alpha-olefin sulfonate and 0-10 parts of a zwitterionic surfactant, so that the problem is well solved. The low-tension foaming agent composition for tertiary oil recovery and the application thereof in foam plugging can be used for foam flooding in intensified oil production.
Description
Technical field
The invention belongs to field of oilfield chemistry, is related to high temperature and high salt oil deposit oil recovery foam flooding oil preparation, specifically one kind is used for
The low-tension foaming agent combination of tertiary oil recovery and its application in foam blocking.
Background technology
In recent years, China's main oilfield through once with secondary recovery after enter high water-cut stage, how to improve oil recovery factor,
Remaining reserves are developed to greatest extent, are the difficult problems that researcher faces.Research for many years has pointed out various intensified oil reductions
Technology, including physical method such as inject gas (gas drive, mixed phase drive), using heat energy (steam drives, hot water flooding)；Chemistry
Method such as polymer flooding, caustic waterflooding, surfactant flooding, alkali/Surfactant/Polymer combination flooding；Biological method is for example interior
Source and inoculating microbe drive also is exploring and is developing central.
Wherein, chemical flooding is domestic the most frequently used, most ripe intensified oil reduction method, by add surfactant reduce oil/
Water interfacial tension, increases capillary number, promotes crude oil to be desorbed from rock and effectively dispersion, realizes the effective driving to residual oil；
Addition polymer or glue increase the viscosity of driven water-replacing, reduce oil and water mobility ratio, alleviate channelling phenomenon, increase sweep efficiency, from
And improve recovery ratio.However, the heat and salt resistance of polymer always perplexs a difficult problem for high temperature and high salinity oil reservoir application, and
And, in postpolymer flood, how addition further improves recovery ratio, and what mode displacement the later stage adopts, by more next
More concerns.
Physical method recovers the oil and has been demonstrated that recovery ratio can be improved, and can produce certain economic benefit, but gas and steam are
The system lower than water density and viscosity, so by " fingering " or " channelling " caused by the anisotropism institute of oil reservoir generally existing
Phenomenon is inevitable, makes ultimate recovery unsatisfactory.
The method shared with physics using chemistry, by adding foam, makes gas and steam carry out in the form of aerated fluid
Displacement, can selectively block high permeability zone, increase sweep efficiency, adjust fluid entry profile.Why foam can be effectively
Control gas mobility, be because it in porosity medium during seepage flow with very unique seepage characteristic：Foam is in hole
In medium during seepage flow, its apparent viscosity is all more much higher than the viscosity of any phase in biphase (activated water and the gas) that constitutes it,
And raise with the increase of medium porosity (or permeability)；And foam is met water and is stablized, and meets oil rupture, is conducive in height
Infiltration band forms stable foam, produces closure.Therefore, foam can be regarded as " stifled very much not to block up little ", and " water blockoff is not blocked up
The intelligent control system of oil ".
If in consideration of it, chemical flooding can be combined with the advantage of foam flooding, being developed into low interfacial tension foam system, enter
And corresponding technology of reservoir sweep is developed, new raising recovery ratio method will be provided for old filed exploitation.
Although however, surfactant has the performance for lifting foam and the ability for reducing oil water interfacial tension simultaneously, receiving
To environmental factorss, including the impact of the factor such as gas phase composition, oil phase composition, temperature, salinity, additive so that it is existing
Conventional surfactant often shows the property runed counter to, i.e. foaminess in terms of lifting foaming properties and reducing interfacial tension
Foam reduction oil/water interfacial tension that can be good is limited, can only achieve several mN/m, according to the computing formula of capillary force,
The residual oil of oil reservoir can not effectively be cleaned up under this interfacial tension；And the spumescence that low-tension surfactant is formed
Can be again poor, it is difficult to form stable closure.Therefore, a kind of foaming capacity is developed by force, foam stability is good, with higher
Anti-salt property, foam flooding system compared with low interfacial tension can be reached with Reservoir Crude Oil, be instantly in the urgent need to.
Document CN101717627A discloses a kind of low-tension foam of raising high salinity reservoir oil recovery factor and its preparation
Method, wherein described foam host is Alkyl Dimethylamine second lactone, Dodecyl Polyoxyethylene Ether sulfuric ester sodium salt and coconut palm
Sub- Monoethanolamine Oleate, its heat resistance is not good, is only applicable to less than 60 DEG C of oil reservoir, and its compatibility with stratum water
Typically, the salinity being resistant to is only 100000mg/L, is not suitable for superelevation salt oil deposit.
Document CN102020981A discloses a kind of temperature-resistant anti-salt low-tension foam flooding oil preparation and preparation method thereof, wherein described
Foam host be alkanolamide and bipolarity surfactant, but its salinity highest being resistant to is also only 100000
Mg/L, and under equal conditions half foam life period only has 40min, and stability is relatively poor.
The content of the invention
One of the technical problem to be solved be in prior art be used for tertiary oil recovery foam interface tension force it is higher, bubble
A kind of bad problem of foam stability, there is provided temperature-resistant anti-salt low-tension foam for tertiary oil recovery.The foam stability is good,
Heatproof, salt resistant character are good, and the salinity being resistant to is up to 200000mg/L, and interfacial activity is strong, can be by crude oil/water circle
Face tension force is down to 10-2MN/m, improves recovery ratio effect is significant.
The two of the technical problem to be solved be to provide it is a kind of with solve the corresponding temperature-resistant anti-salt of one of technical problem
The preparation method of low-tension foam.
The three of the technical problem to be solved be to provide it is a kind of with solve the corresponding temperature-resistant anti-salt of one of technical problem
Application of the low-tension foam in foam blocking.
The two of the technical problem to be solved be to provide it is a kind of with solve the corresponding temperature-resistant anti-salt of one of technical problem
Application of the low-tension foam in intensified oil reduction.
In order to solve one of technical problem, the technical solution used in the present invention is as follows：A kind of temperature-resistant anti-salt low-tension foam, bag
Include following components：
(1) temperature-resistant anti-salt low-tension foaming agent combination aqueous solution；
(2) gas；
Wherein, temperature-resistant anti-salt low-tension foaming agent combination aqueous solution and the volume ratio of gas are 1:(0.5～20)；The heatproof
Salt resistance low-tension foaming agent combination, in terms of mass fraction, including following components：
(1) 1 part of polyethers anion surfactant；
(2) 1～5 parts of alkene sulfonate；
(3) 0～10 parts of zwitterionic surfactant；
Described polyethers anion surfactant, with following general molecular formula：
R1O-(CH2CH2O)m1-(CH(CH3)CH2O)n-(CH2CH2O)m2-R2Y, (1)；
R in formula1For C8～C30Aliphatic group or by C4～C20What the saturation of straight or branched and unsaturated alkyl replaced
Aryl, m1=0～30, n=1～50, m2=0～30, R2For C1～C5Alkylidene or hydroxyl substituted alkylene, Y is
COOM or SO3N, M and N are independently selected from hydrogen, alkali metal or by formula NR4(R5)(R6)(R7) shown in group at least
It is a kind of；R4、R5、R6、R7To be independently selected from H, (CH2)pOH or (CH2)qCH3In one kind, p=2～4, q=0～5
In any integer；
Described zwitterionic surfactant is selected from beet alkali surface activator；
In the temperature-resistant anti-salt low-tension foaming agent combination aqueous solution, with polyethers anion surfactant, a- alkene sulfonic acids
The total quality meter of salt, zwitterionic surfactant, the concentration of temperature-resistant anti-salt low-tension foaming agent combination is 0.05～1%.
In above-mentioned technical proposal, R in polyethers anion surfactant1Preferred version is C10～C18Alkyl；M1 is preferred
It is that 1～20, n preferred versions are 2～15 that scheme is 2～10, m2 preferred versions；R2Preferred version is C1～C3Alkylene
Base or hydroxyl replace propylidene；Y preferred versions are COOM, and M preferred versions are the sodium or potassium ion in alkali metal, more
Preferred version is selected from sodium.
In above-mentioned technical proposal, the alkene sulfonate is preferably a- alkene sulfonates, preferably with following general molecular formula：
R3- CH=CH-CH2-SO3K, (2)；
Wherein R3For C5～C30Alkyl, K is any one metal ion in alkali metal；Further preferably：K
Preferred version is sodium or potassium ion in alkali metal, and more preferably scheme is selected from sodium；R3Preferred version is selected from C8～C22's
Alkyl, more preferably scheme are selected from C14～C18Alkyl.
In above-mentioned technical proposal, the beet alkali surface activator is preferably dodecyldimethylammonium hydroxide inner salt, myristyl two
Methyl betaine, 3- sulfopropyl dodecyldimethylammonium hydroxide inner salts, 3- sulfopropyl dodecyldimethylamine base glycine betaines, 3- sulphurs third
Base Cetyl dimethyl betaine, at least one in cocamido propyl betaine；Further preferably scheme is dodecane
Base dimethyl betaine, 3- sulfopropyl dodecyldimethylammonium hydroxide inner salts, 3- sulfopropyl dodecyldimethylamine base glycine betaines, 3-
At least one in sulfopropyl Cetyl dimethyl betaine.
In above-mentioned technical proposal, in terms of mass fraction, the zwitterionic surfactant consumption is preferably greater than 0 part.
A kind of temperature-resistant anti-salt low-tension foam system surfactant in the present invention does not have particular/special requirement when preparing to water,
Can be deionized water, can also be the water containing inorganic mineral, and the water for containing inorganic mineral can be tap water, oil field
Stratum water or oilfield injection water.Suitable stratum water total salinity is 0～200000mg/L, and preferred version is
50000～200000mg/L, Ca2++Mg2+Concentration preferred version is 2000～8000mg/L, and water type is CaCl2Type.
In order to solve the two of above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of temperature-resistant anti-salt low-tension foam
The preparation method of agent compositionss, comprises the following steps：
(1) synthesis of polyethers anion surfactant
A, in the presence of base catalyst, R1O(CH2CH2O)m1H is obtained with aequum propylene oxide reaction
R1O(CH2CH2O)m1(CHCH3CH2O)nH；
B, in the presence of base catalyst, R1O(CH2CH2O)m1(CHCH3CH2O)nH and aequum reacting ethylene oxide
Obtain R1O(CH2CH2O)m1(CHCH3CH2O)n(CH2CH2O)m2H；
C, in the presence of alkali metal hydroxide or alkali metal alcoholates, product and XR that step b is obtained2Y in a solvent,
In 50～120 DEG C of reaction temperature, react 3～15 hours and generate anionic surfactant mixture containing polyethers；
D, in the anionic surfactant mixture containing polyethers that step c is obtained add acid adjust water phase pH=1～3, point
From obtaining organic faciess；
E, organic faciess purification is obtained into required polyethers anion surfactant；
(2) preparation of foaming agent combination
The desired amount of polyethers anion surfactant, a- alkene sulfonates, zwitterionic surfactant mix homogeneously are obtained
Temperature-resistant anti-salt low-tension foaming agent combination.
The key active ingredient of oil displacement agent of the present invention is the component (1), (2) and (3), and those skilled in the art know
Road, for the ease of transport and store or onsite application etc. from the aspect of, various supply forms can be adopted, such as it is water-free
Solid-state form, or aqueous solid-state form, or aqueous cream form, or aqueous solution form；Aqueous solution form bag
The form that concentrated solution is made into water is included, the foam form of live displacement of reservoir oil desired concn is directly made into；Wherein, to water without spy
It is different to require, can be deionized water, the water containing inorganic mineral is can also be, and the water for containing inorganic mineral can be originally
Water, oil field stratum water or oilfield injection water.
In order to solve the three of above-mentioned technical problem, the technical solution used in the present invention is as follows：One temperature-resistant anti-salt low-tension foam
Application of the compositionss in foam blocking, wherein the formation temperature of the application be 60～150 DEG C, formation water salinity be 0～
200000mg/L。
In above-mentioned technical proposal, the total salinity of described stratum simulation water is preferably greater than 50000mg/L, less than 200000
Mg/L, Ca2++Mg2+Concentration is less than 8000mg/L, and water type is CaCl2Type.In order to solve the four of above-mentioned technical problem, this
The technical scheme that invention is adopted is as follows：A kind of application of temperature-resistant anti-salt low-tension foaming agent combination in intensified oil reduction.
The foaming agent combination of the present invention has good compatibility, can also contain other inorganic agents commonly used in the art, such as
The oil recovery auxiliary agent such as surfactant, polymer, alkali.
The foaming agent combination of the present invention is applicable to reservoir temperature and is not higher than 150 DEG C, and salinity is less than 200000mg/L,
Ca2++Mg2+Oil reservoir of the concentration less than 8000mg/L.The foaming agent combination and nitrogen, air, carbon dioxide and natural
Gas is mixed to form stable foam, is applied to Zhongyuan Oil Field stratum water bubble system laboratory test, and Roche foam method is surveyed when 50 DEG C
Its foam volume is measured more than 300mL, the half-life is more than 20 more than 100min, resistance factor, and interfacial tension reaches 10-3mN/m；
Recovery ratio is reachable ..., achieves preferable technique effect.
Specific embodiment
In order to be better understood from the present invention, present disclosure, but present disclosure are expanded on further with reference to embodiments
It is not limited solely to the following examples.
【Embodiment 1】
The preparation of compositionss ZY-1, preparation process：
(1) lauryl alcohol polyoxypropylene (8) ether acetic acid (LAPO8CH2COOH synthesis) and preparation：
186.33 grams of (1 mole) n-dodecane alcohol, 5.61 grams of hydrogen are added in the 2L pressure reactors equipped with agitating device
Potassium oxide, when being heated to 80～90 DEG C, open vacuum system, under a high vacuum be dehydrated 1 hour, then with nitrogen displacement 3～
4 times, system reaction temperature is adjusted to into 150 DEG C and is slowly passed through 469.8 grams of (8.1 moles) expoxy propane, control pressure
≤0.60MPa.After reaction terminates, 90 DEG C are cooled to, low-boiling-point substance is removed in vacuum, neutralization, dehydration, obtain lauryl alcohol after cooling
642.2 grams of polyoxypropylene (8) ether, yield 98.8wt%.
325 grams of lauryl alcohol polyoxypropylene (8) ether (0.5 mole) and 112.2 grams of (2 moles) potassium hydroxide, 116.5
Gram (1 mole) sodium chloroacetate and 550 milliliters of toluene are mixed in and are furnished with the 2000 of mechanical agitation, thermometer and reflux condensing tube
In the reactor of milliliter, it is heated to 90 DEG C and reacts 6 hours.Cooling, with the acidifying of 25wt% sulphuric acid, divides and removes water and inorganic salt,
Solvent is evaporated off, 308.1 grams of lauryl alcohol polyoxypropylene (8) ether acetic acid product, Jing high performance liquid chromatography (HPLC) point is obtained
Analysis, lauryl alcohol polyoxypropylene (8) ether acetic acid (LAPO in product8CH2COOH) content is 94.62wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, lauryl alcohol polyoxypropylene (8) ether acetic acid obtained by synthesis in previous step is weighed
(LAPO8CH2COOH) 15.85 grams in reactor, add appropriate local originally water dissolution, then be added thereto to fit
The sodium hydroxide of amount adjusts pH to 8.6, and lauryl alcohol polyoxypropylene (8) ether acetic acid sodium is obtained after stirring and dissolving
(LAPO8CH2COONa)；10 grams of C is added thereto to again14～C16A- alkene sulfonic acid sodium (AOS14-16), 5
Gram 3- sulfopropyl dodecyldimethylammonium hydroxide inner salts, add enough local tap waters to 100 grams, be configured to 30wt%
Solution, be sufficiently stirred for 30min to being completely dissolved, obtain final product temperature-resistant anti-salt low-tension foaming agent combination ZY-1, produce
Product are faint yellow paste.
【Embodiment 2】
The preparation of compositionss ZY-2, preparation process：
(1) lauryl alcohol polyoxypropylene (8) ether acetic acid (LAPO8CH2COOH synthesis) and preparation：
186.33 grams of (1 mole) n-dodecane alcohol, 5.61 grams of hydrogen are added in the 2L pressure reactors equipped with agitating device
Potassium oxide, when being heated to 80～90 DEG C, open vacuum system, under a high vacuum be dehydrated 1 hour, then with nitrogen displacement 3～
4 times, system reaction temperature is adjusted to into 150 DEG C and is slowly passed through 469.8 grams of (8.1 moles) expoxy propane, control pressure
≤0.60MPa.After reaction terminates, 90 DEG C are cooled to, low-boiling-point substance is removed in vacuum, neutralization, dehydration, obtain lauryl alcohol after cooling
642.2 grams of polyoxypropylene (8) ether, yield 98.8wt%.
325 grams of lauryl alcohol polyoxypropylene (8) ether (0.5 mole) and 112.2 grams of (2 moles) potassium hydroxide, 116.5
Gram (1 mole) sodium chloroacetate and 550 milliliters of toluene are mixed in and are furnished with the 2000 of mechanical agitation, thermometer and reflux condensing tube
In the reactor of milliliter, it is heated to 90 DEG C and reacts 6 hours.Cooling, with the acidifying of 25wt% sulphuric acid, divides and removes water and inorganic salt,
Solvent is evaporated off, 308.1 grams of lauryl alcohol polyoxypropylene (8) ether acetic acid product, Jing high performance liquid chromatography (HPLC) point is obtained
Analysis, lauryl alcohol polyoxypropylene (8) ether acetic acid (LAPO in product8CH2COOH) content is 94.62wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, lauryl alcohol polyoxypropylene (8) ether acetic acid obtained by synthesis in previous step is weighed
(LAPO8CH2COOH) 11 grams in reactor, add appropriate local originally water dissolution, then be added thereto to appropriate
Sodium hydroxide adjust pH to 8.6, lauryl alcohol polyoxypropylene (8) ether acetic acid sodium is obtained after stirring and dissolving
(LAPO8CH2COONa)；9 grams of C is added thereto to again14～C16A- alkene sulfonic acid sodium (AOS14-16), 10
Gram 3- sulfopropyl dodecyldimethylamine base glycine betaines, add enough local tap waters to 100 grams, be configured to 30wt%
Solution, be sufficiently stirred for 30min to being completely dissolved, obtain final product temperature-resistant anti-salt low-tension foaming agent combination ZY-2, produce
Product are faint yellow paste.
【Embodiment 3】
The preparation of compositionss ZY-3, preparation process：
(1) lauryl alcohol Polyethylene oxide (3) polyoxypropylene (8) Polyethylene oxide (10) ether acetic acid (LAEO3PO8EO10CH2COOH)
Synthesis with prepare：
Add in the 2L pressure reactors equipped with agitating device 318 grams of (1 mole) lauryl alcohol Polyethylene oxide (3) ethers,
5.61 grams of potassium hydroxide, when being heated to 80～90 DEG C, open vacuum system, are dehydrated 1 hour under a high vacuum, then use nitrogen
Gas is replaced 3～4 times, system reaction temperature is adjusted to into 150 DEG C and is slowly passed through 469.8 grams of (8.1 moles) expoxy propane, is controlled
Pressing pressure≤0.60MPa, is adjusted to temperature 140 DEG C and is slowly passed through 444.4 grams (10.1 rub again after propylene oxide reaction terminates
You) oxirane, control pressure≤0.40MPa.After reaction terminates, 90 DEG C are cooled to, low-boiling-point substance is removed in vacuum, cooled down
Afterwards neutralization, dehydration, obtain 1270.6 grams of lauryl alcohol Polyethylene oxide (3) polyoxypropylene (8) Polyethylene oxide (10) ether, receive
Rate 98.0wt%.
427.7 grams of lauryl alcohol Polyethylene oxide (3) polyoxypropylene (8) Polyethylene oxide (10) ether (0.35 mole) and 112.2
Gram (2 moles) potassium hydroxide, 116.5 grams of (1 mole) sodium chloroacetates and 600 milliliters of toluene be mixed in be furnished with mechanical agitation,
In the reactor of 2000 milliliters of thermometer and reflux condensing tube, it is heated to 90 DEG C and reacts 6 hours.Cooling, with 25wt%
Sulphuric acid is acidified, and divides and removes water and inorganic salt, and solvent is evaporated off, and obtains lauryl alcohol Polyethylene oxide (3) polyoxypropylene (8) polyoxy second
506.7 grams of alkene (10) ether acetic acid product, Jing high performance liquid chromatography (HPLC) analysis, lauryl alcohol Polyethylene oxide (3) in product
Polyoxypropylene (8) Polyethylene oxide (10) ether acetic acid (LAEO3PO8EO10CH2COOH) content is 95.28wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, lauryl alcohol Polyethylene oxide (3) polyoxypropylene (8) polyoxy obtained by synthesis in previous step is weighed
Ethylene (10) ether acetic acid (LAEO3PO8EO10CH2COOH) 8 grams in reactor, add appropriate local tap water
Dissolve, then be added thereto to appropriate sodium hydroxide and obtain lauryl alcohol Polyethylene oxide (3) polyoxypropylene (8) Polyethylene oxide (10)
Ether acetic acid sodium (LAEO3PO8EO10CH2COONa)；11 grams of C is added thereto to again14～C16A- alkene sulfonic acid sodiums
(AOS14-16), 11 grams of 3- sulfopropyl dodecyldimethylamine base glycine betaines add enough local tap waters to 100
Gram, the solution of 30wt% is configured to, 30min is sufficiently stirred for being completely dissolved, obtain final product temperature-resistant anti-salt low-tension foam
Agent compositionss ZY-3, product is faint yellow paste.
【Embodiment 4】
The preparation of compositionss ZY-4, preparation process：
(1) lauryl alcohol Polyethylene oxide (3) polyoxypropylene (8) Polyethylene oxide (10) ether acetic acid (LAEO3PO8EO10CH2COOH)
Synthesis with prepare：
Add in the 2L pressure reactors equipped with agitating device 318 grams of (1 mole) lauryl alcohol Polyethylene oxide (3) ethers,
5.61 grams of potassium hydroxide, when being heated to 80～90 DEG C, open vacuum system, are dehydrated 1 hour under a high vacuum, then use nitrogen
Gas is replaced 3～4 times, system reaction temperature is adjusted to into 150 DEG C and is slowly passed through 469.8 grams of (8.1 moles) expoxy propane, is controlled
Pressing pressure≤0.60MPa, is adjusted to temperature 140 DEG C and is slowly passed through 444.4 grams (10.1 rub again after propylene oxide reaction terminates
You) oxirane, control pressure≤0.40MPa.After reaction terminates, 90 DEG C are cooled to, low-boiling-point substance is removed in vacuum, cooled down
Afterwards neutralization, dehydration, obtain 1270.6 grams of lauryl alcohol Polyethylene oxide (3) polyoxypropylene (8) Polyethylene oxide (10) ether, receive
Rate 98.0wt%.
427.7 grams of lauryl alcohol Polyethylene oxide (3) polyoxypropylene (8) Polyethylene oxide (10) ether (0.35 mole) and 112.2
Gram (2 moles) potassium hydroxide, 116.5 grams of (1 mole) sodium chloroacetates and 600 milliliters of toluene be mixed in be furnished with mechanical agitation,
In the reactor of 2000 milliliters of thermometer and reflux condensing tube, it is heated to 90 DEG C and reacts 6 hours.Cooling, with 25wt%
Sulphuric acid is acidified, and divides and removes water and inorganic salt, and solvent is evaporated off, and obtains lauryl alcohol Polyethylene oxide (3) polyoxypropylene (8) polyoxy second
506.7 grams of alkene (10) ether acetic acid product, Jing high performance liquid chromatography (HPLC) analysis, lauryl alcohol Polyethylene oxide (3) in product
Polyoxypropylene (8) Polyethylene oxide (10) ether acetic acid (LAEO3PO8EO10CH2COOH) content is 95.28wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, lauryl alcohol Polyethylene oxide (3) polyoxypropylene (8) polyoxy obtained by synthesis in previous step is weighed
Ethylene (10) ether acetic acid (LAEO3PO8EO10CH2COOH) 8 grams in reactor, add appropriate local tap water
Dissolve, then be added thereto to appropriate sodium hydroxide and obtain lauryl alcohol Polyethylene oxide (3) polyoxypropylene (8) Polyethylene oxide (10)
Ether acetic acid sodium (LAEO3PO8EO10CH2COONa)；8 grams of C is added thereto to again14～C18A- alkene sulfonic acid sodiums
(AOS14-18), 14 grams of 3- sulfopropyl dodecyldimethylamine base glycine betaines add enough local tap waters to 100
Gram, the solution of 30wt% is configured to, 30min is sufficiently stirred for being completely dissolved, obtain final product temperature-resistant anti-salt low-tension foam
Agent compositionss ZY-4, product is faint yellow paste.
【Embodiment 5】
Foam stability and oil water interfacial tension are tested：
The simulation water of different bivalent cations and total salinity is prepared respectively, and concrete composition is shown in Table 1.
A certain amount of foam ZY-1, ZY-2 are dissolved with simulation saline A, B of different salinities, 0.15wt% is configured to
Solution, determine under the concentration foam foaming properties, the results are shown in Table shown in 2.Foaming properties adopt Roche foam meter,
Method GB/T 7462-1994, under the conditions of temperature 50 C.
The oil water interfacial tension that foam under 0.15wt% concentration defends the crude oil of -95 blocks to Zhongyuan Oil Field is determined, be the results are shown in Table
Shown in 3, oil water interfacial tension measure defends the crude oil of -95 blocks with crude oil to Zhongyuan Oil Field.Interfacial tension uses TX-500C
Gamut interfacial tension measuring instrument, method SY/T5370-1999,73 DEG C of temperature, rotating speed 4500rpm.
【Embodiment 6】
Foam blocking and oil displacement experiment：The automatic core flooding test device of QY-C12 types produced using Jiangsu Huaan company, foam
Agent concentration：0.15wt%, injection mode：Mixing injection, temperature：73 DEG C, the foam envelope under different pressures, permeability
Stifled experiment.Using simulation core barrel, simulation core barrel outlet is determined, middle pressure tap, the pressure of outlet obtains pressure differential deltap P=PImport-POutlet, Δ P1=PImport-PMiddle pressure tap, Δ P2=PMiddle pressure tap-POutlet.Using mixing injection, preposition water drive is first carried out, reinjected
Sacrifice agent, then carries out foam flooding, is finally rearmounted water drive.Initial pressure difference Δ P is obtained during preposition water driveInitially=PImport-POutlet,
Pressure differential Δ P is obtained in foam floodingFoam=PImport-POutlet, it is calculated resistance factor δ=Δ PFoam/ΔPInitially。
Using foam in TDS-1 and TDS-2 mineralized waters, with prepared low-tension foam.
【Comparative example 1】
Contrast【Embodiment 1】、【Embodiment 2】, it is added without lauryl alcohol polyoxypropylene (8) ether acetic acid sodium
(LAPO8CH2COONa), a- alkene sulfonic acid sodium (AOS are only added14-16) and 3- sulfopropyl dodecyl dimethyls it is sweet
Dish alkali, a- alkene sulfonic acid sodium (AOS14-16) and 3- sulfopropyl dodecyldimethylamine base glycine betaines, it is prepared into foam combination
Thing B-1, B-2, with ZY-1, ZY-2 compare, together【Embodiment 7】Foaming properties and interface performance determination test are carried out,
And foam blocking and oil displacement experiment.
【Comparative example 2】
Contrast【Embodiment 3】、【Embodiment 4】, when prepared by foaming agent combination, only use lauryl alcohol Polyethylene oxide (3)
Polyoxypropylene (8) Polyethylene oxide (10) ether acetic acid sodium (LAEO3PO8EO6CH2) and a- alkene sulfonic acid sodiums COONa
(AOS14-16), lauryl alcohol Polyethylene oxide (3) polyoxypropylene (8) Polyethylene oxide (6) ether acetic acid sodium
(LAEO3PO8EO6CH2) and a- alkene sulfonic acid sodium (AOS COONa14-18) compounding, foaming agent combination B-3 is prepared into,
B-4, compares with ZY-3, ZY-4, together【Embodiment 7】Carry out foaming properties and interface performance determination test, and foam
Closure and oil displacement experiment.
【Comparative example 3】
Together【Embodiment 3】, difference is successively not reacted step by step with expoxy propane and oxirane,
But both are mixed into the reaction of later stepping row.469.8 grams of (8.1 moles) expoxy propane are slowly passed through at 140～150 DEG C
With 444.4 grams of (10.1 moles) ethylene oxide mixtures, control pressure≤0.60MPa, remaining is identical, obtain polyethers it is cloudy from
Sub- surfactant, and together【Embodiment 3】、【Embodiment 4】, be prepared into corresponding proportion foaming agent combination B-5,
B-6, compares with ZY-3, ZY-4, together【Embodiment 7】Carry out foaming properties and interface performance determination test the results are shown in Table 3,
Shown in 4.
【Comparative example 4】
The preparation of Comparative composition B-7, preparation process：
(1) lauryl alcohol Polyethylene oxide (9) polyoxypropylene (8) ether acetic acid (LAEO9PO8CH2COOH synthesis) and preparation：
Add in the 2L pressure reactors equipped with agitating device 582 grams of (1 mole) lauryl alcohol Polyethylene oxide (9) ethers,
5.61 grams of potassium hydroxide, when being heated to 80～90 DEG C, open vacuum system, are dehydrated 1 hour under a high vacuum, then use nitrogen
Gas is replaced 3～4 times, system reaction temperature is adjusted to into 150 DEG C and is slowly passed through 469.8 grams of (8.1 moles) expoxy propane, is controlled
Pressing pressure≤0.60MPa, after propylene oxide reaction terminates, is cooled to 90 DEG C, and low-boiling-point substance is removed in vacuum, neutralize after cooling,
Dehydration, obtains 1018.8.3 gram of lauryl alcohol Polyethylene oxide (9) polyoxypropylene (8) ether, yield 97.1wt%.
366.1 grams of lauryl alcohol Polyethylene oxide (9) polyoxypropylene (8) ether (0.35 mole) and 112.2 grams (2 moles)
Potassium hydroxide, 116.5 grams of (1 mole) sodium chloroacetates and 600 milliliters of toluene are mixed in and are furnished with mechanical agitation, thermometer and return
In the reactor of 2000 milliliters of stream condensing tube, it is heated to 90 DEG C and reacts 6 hours.Cooling, with the acidifying of 25wt% sulphuric acid,
Divide and remove water and inorganic salt, solvent is evaporated off, obtain lauryl alcohol Polyethylene oxide (9) polyoxypropylene (8) ether acetic acid product 436.2
Gram, Jing high performance liquid chromatography (HPLC) analysis, lauryl alcohol Polyethylene oxide (9) polyoxypropylene (8) ether acetic acid in product
(LAEO9PO8CH2COOH) content is 96.12wt%.
(2) preparation of foaming agent combination：
At normal temperatures and pressures, lauryl alcohol Polyethylene oxide (9) polyoxypropylene (8) the ether second obtained by synthesis in previous step is weighed
Acid (LAEO9PO8CH2COOH) 7.5 grams in reactor, add appropriate local originally water dissolution, then thereto plus
Enter appropriate sodium hydroxide and obtain lauryl alcohol Polyethylene oxide (3) polyoxypropylene (8) Polyethylene oxide (6) ether acetic acid sodium
(LAEO9PO8CH2COONa)；12 grams of C is added thereto to again14～C16A- alkene sulfonic acid sodium (AOS14-16),
10.5 grams of 3- sulfopropyl dodecyldimethylamine base glycine betaines, add enough local tap waters to 100 grams, are configured to
The solution of 30wt%, is sufficiently stirred for 30min to being completely dissolved, obtains final product temperature-resistant anti-salt low-tension foaming agent combination B-7,
Product is faint yellow paste.
The experiment crude oil of table 1
| Block | Defend -95 blocks in Zhongyuan Oil Field |
| Oil density | 0.87-0.89g/cm3 |
| Viscosity of crude | 15-46mP·s |
The salinity of the various simulation waters of table 2
| Simulation saline | Ca2+(mg/L) | Mg2+(mg/L) | TDS(mg/L) |
| TDS-1 | 2630 | 1360 | 120000 |
| TDS-2 | 5640 | 2420 | 200000 |
The foaming properties of the foam of table 3
The oil water interfacial tension performance of the comparative example foam agent of table 4
The mixing injection foam blocking experimental result of table 5
Table 6 alternately injects foam blocking experimental result
The oil displacement experiment experimental result of table 7
The each foam component table of table 8
Claims (9)
1. a kind of temperature-resistant anti-salt low-tension foam, including following components：
(1) temperature-resistant anti-salt low-tension foaming agent combination aqueous solution；
(2) gas；
Wherein, temperature-resistant anti-salt low-tension foaming agent combination aqueous solution and the volume ratio of gas are 1:(0.5～20)；The temperature-resistant anti-salt low-tension foaming agent combination, in terms of mass fraction, including following components：
(1) 1 part of polyethers anion surfactant；
(2) 1～5 parts of alkene sulfonate；
(3) 0～10 parts of zwitterionic surfactant；
Described polyethers anion surfactant, with following general molecular formula：
R1O-(CH2CH2O)m1-(CH(CH3)CH2O)n-(CH2CH2O)m2-R2Y, (1)；
R in formula1For C8～C30Aliphatic group or by C4～C20The aryl that the saturation of straight or branched and unsaturated alkyl replace, m1=0～30, n=1～50, m2=0～30, R2For C1～C5Alkylidene or hydroxyl substituted alkylene, Y be COOM or SO3N, M and N are independently selected from hydrogen, alkali metal or by formula NR4(R5)(R6)(R7) shown at least one in group；R4、R5、R6、R7To be independently selected from H, (CH2)pOH or (CH2)qCH3In one kind, any integer in p=2～4, q=0～5；
Described zwitterionic surfactant is selected from beet alkali surface activator.
2. temperature-resistant anti-salt low-tension foaming agent combination according to claim 1, it is characterised in that the R1For C12～C24Alkyl or by C8～C12Alkyl-substituted phenyl；M1=2～10, n=2～15, m2=1～20；R2For C1～C3Alkylidene or hydroxyl replace propylidene；P=2, q=0～1.
3. the temperature-resistant anti-salt low-tension foaming agent combination for tertiary oil recovery according to claim 1, it is characterised in that described alkene sulfonate has following general molecular formula：
R3- CH=CH-CH2-SO3K, (2)；
R in formula3For C5～C30Alkyl, K is any one metal ion in alkali metal.
4. temperature-resistant anti-salt low-tension foaming agent combination according to claim 1, it is characterized in that described zwitterionic surfactant is dodecyldimethylammonium hydroxide inner salt, dodecyldimethylamine base glycine betaine, 3- sulfopropyl dodecyldimethylammonium hydroxide inner salts, 3- sulfopropyl dodecyldimethylamine base glycine betaines, 3- sulfopropyl Cetyl dimethyl betaines, at least one in cocamido propyl betaine.
5. temperature-resistant anti-salt low-tension foaming agent combination according to claim 1, it is characterised in that in terms of mass fraction, zwitterionic surfactant consumption is more than 0 part.
6. a kind of preparation method of the arbitrary described temperature-resistant anti-salt low-tension foaming agent combination of Claims 1 to 5, comprises the following steps：
(1) synthesis of polyethers anion surfactant
A, in the presence of base catalyst, R1O(CH2CH2O)m1H obtains R with aequum propylene oxide reaction1O(CH2CH2O)m1(CHCH3CH2O)nH；
B, in the presence of base catalyst, R1O(CH2CH2O)m1(CHCH3CH2O)nH obtains R with aequum reacting ethylene oxide1O(CH2CH2O)m1(CHCH3CH2O)n(CH2CH2O)m2H；
C, in the presence of alkali metal hydroxide or alkali metal alcoholates, product and XR that step b is obtained2Y in a solvent, in 50～120 DEG C of reaction temperature, reacts 3～15 hours and generates anionic surfactant mixture containing polyethers；
D, in the anionic surfactant mixture containing polyethers that step c is obtained add acid adjust water phase pH=1～3, isolated organic faciess；
E, organic faciess purification is obtained into required polyethers anion surfactant.
(2) preparation of foaming agent combination
The desired amount of polyethers anion surfactant, alkene sulfonate, zwitterionic surfactant mix homogeneously are obtained into temperature-resistant anti-salt low-tension foaming agent combination.
7. application of the arbitrary described temperature-resistant anti-salt low-tension foam of a kind of Claims 1 to 5 in foam blocking, it is characterised in that the formation temperature of application is 60～150 DEG C, and formation water salinity is 0～200000mg/L.
8. application of the temperature-resistant anti-salt low-tension foam according to claim 7 in foam blocking, it is characterised in that the total salinity of described stratum simulation water is less than 200000mg/L, Ca2++Mg2+Concentration is less than 8000mg/L, and water type is CaCl2Type.
9. application of the temperature-resistant anti-salt low-tension foam described in a kind of Claims 1 to 5 in intensified oil reduction.
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