CN106590592A - Composite surfactant for improving crude oil recovery rate - Google Patents
Composite surfactant for improving crude oil recovery rate Download PDFInfo
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Abstract
The present invention relates to a composite surfactant capable of improving the crude oil recovery rate, and a preparation method thereof. In the prior art, the recovery rate is difficult to effectively improve through the composite oil displacement agent under the conditions of high temperature, high salt and high permeability oil reservoir. A purpose of the present invention is mainly to solve the problem in the prior art. The technical scheme of the present invention comprises the composite surfactant capable of substantially improving the crude oil recovery rate comprises, by mass, (1) 0.01-1.0 wt% of a hydroxyalkyl quaternary ammonium salt surfactant, and (2) 0.01-1.0 wt% of an alkylphenol polyetherate surfactant, wherein the molecule general formula of the hydroxyalkyl quaternary ammonium salt surfactant is represented by a formula (I), and the molecule general formula of the alkylphenol polyetherate surfactant is represented by a formula (II). With the technical scheme of the present invention, the problem in the prior art is well solved. The composite surfactant of the present invention can be used for the tertiary oil production of oilfield. The formulas (I) and (II) are defined in the specification.
Description
Technical field
The present invention relates to a kind of complexed surfactant for improving oil recovery factor.
Background technology
Oil is important irreproducibility strategic resource, and the world today increasingly increases for the demand of oil.Conventional oil recovery
Method is typically only capable of producing 1/3rd of oil in-place, and at present, most oil reservoirs have been enter into high water cut viscous heavy crude oil, produces
The trend that substantially tapers off is measured, continues larger using conventional water drive raising recovery ratio difficulty.Because formation temperature is high, water ore deposit is injected
Change degree and calcium ions and magnesium ions content are high, limit the development of the tertiary oil recovery mode such as polymer flooding.How water drive after recovery ratio is improved
It is current urgent need to solve the problem.
Surfactant flooding is when first three adopts one of main direction of studying for improving oil recovery factor.Surfactant can be effective
Oil water interfacial tension is reduced, changed reservoir wettability, solubilized crude oil, reduced Crude viscosity, played in tertiary oil recovery and focus on
Act on.Wherein zwitterion compound surfactant as a kind of new Surfactants mixed system, in many field tables
Property is revealed.There is strong electrostatic interaction between cationic and anionic surfactant, there is compound system lower
Critical micelle concentration, limit occupied area and more preferable interfacial activity, possess the ability for forming microemulsion well, are conducive to surpassing
The acquisition of low interfacial tension with it is stable.Meanwhile, the formation of zwitterion pair greatly strengthen the anti-suction of negative and positive compound surfactant
Attached, anticalcium magnesium ion ability, improves oil displacement efficiency of the system in high temperature and high salt oil deposit.
At present, using less during negative and positive compound surfactant is adopted three.Patent CN103773347A is reported containing aromatic ring
The complexed surfactant compositionss that alkyl polyoxyethylene ether anion surfactant is constituted with tetraalkyl ammonium salt, the combination
The thing interface performance good for Henan Oil Field has；Han Xia etc. (Acta PhySico-Chimica Sinica, 2012,28 (1), 146-153) leads to
Cross and the binary built system that alkyl ethoxy sulfonate is constituted with tetraalkyl amine bromide or bromide sixteen alkyls pyridine is ground
Study carefully, it was demonstrated that impact of the profit partition equilibrium of surfactant molecule to ultralow interfacial tension.These work have used tetraalkyl
/ aryl quat cationic surfactants, such surfactant dissolubility in concentrated water is poor, limits these
Application of the formula in high salinity reservoir.The present invention is compounded using hydroxyalkyl quaternary ammonium salt, compared with tetraalkyl ammonium salt, hydroxyl
Base is introduced into the dissolubility for optimizing surfactant in water, is conducive to the oil displacement agent allotment at the scene to use.
The content of the invention
One of the technical problem to be solved is compound oil displacement agent temperature-resistant anti-salt ability, concentration in prior art
The low problem of high, oil displacement efficiency, there is provided one kind can increase substantially recovery ratio under high temperature and high salt medium to high permeable reservoir condition
Complexed surfactant.Can be in wider concentration range, high temperature and high salt medium to high permeable rate oil reservoir with this complexed surfactant
Under the conditions of with crude oil formed 10-2～10-4The low interfacial tension of mN/m, so as to improve the oil displacement efficiency of oil displacement agent.
The two of the technical problem to be solved are the composite surfaces that one of above-mentioned technical problem is correspondingly improved recovery ratio
The preparation method of activating agent.
The three of the technical problem to be solved are the composite surfaces that one of above-mentioned technical problem is correspondingly improved recovery ratio
Application of the activating agent in oil extraction in oil field.
To solve one of above-mentioned technical problem, the technical solution used in the present invention is：A kind of complexed surfactant, with quality
Number meter, including following components：
(1) 0.01～1.0 part of hydroxyalkyl quaternary surfactant；
(2) 0.01～1.0 parts of alkyl phenol polyether acid salt surfactant；
Wherein, the general molecular formula of the hydroxyalkyl quaternary surfactant is shown in formula (I)：
The general molecular formula of the alkyl phenol polyether acid salt surfactant is shown in formula (II)：
In formula, R1For C1～C20Alkyl, R2、R3For C1～C4Alkyl, p is CH2The number of segment, selected from 1～6
In any one integer, X selected from making molecule shown in formula (I) in electroneutral anion, j falling for X valence state absolute values
Number；R4For C8～C16Fat-based；N is the sum that adds of ethoxy group, and n=5～8 count；M is that propoxyl group is rolled into a ball plus sum,
M=0～10；Q is CH2The number of segment, any one integer in 1～6；Y is selected from-COO—、-SO3 —In
It is at least one；Selected from making molecule shown in formula (II) in electroneutral cation, i is the inverse of M valence state absolute values to M.
In above-mentioned technical proposal, the X be preferably -1 valency anion when, the hydroxyalkyl quaternary surfactant point
Sub- formula is shown in formula (III)：
In above-mentioned technical proposal, when the M is preferably+1 valency cation, the alkyl phenol polyether acid salt surfactant
General molecular formula is shown in formula (IV)：
In above-mentioned technical proposal, described R1Preferably C1～C20Alkyl, R2、R3Preferably C1～C4Alkyl,
Further preferably R1For C12、C14、C16、C18Alkyl, R2、R3For methyl and ethyl.
In above-mentioned technical proposal, described p is any one integer in 1～6, more preferably 1,2,3.
In above-mentioned technical proposal, the X is preferably halide ion, more preferably-Cl—、-Br—、-I—In at least one
Kind.
In above-mentioned technical proposal, described R4For C8～C16Alkyl, more preferably C8、C9、C12、C15's
Alkyl.
In above-mentioned technical proposal, the quality of the alkyl phenol polyether acid salt surfactant and hydroxyalkyl quaternary surfactant
Proportioning is 10～1, more preferably 5～1.
In above-mentioned technical proposal, the M preferably be selected from ammonium ion or alkali metal ion at least one.
In above-mentioned technical proposal, the complexed surfactant for improving oil recovery factor in terms of mass fraction, also includes
98.0～99.98 parts of injection water.
In above-mentioned technical proposal, described injection water total salinity is preferably 100000～200000mg/L, Ca2++Mg2+It is preferred that
For 0～7000mg/L.
In above-mentioned technical proposal, the X—Preferably-Cl—。
In above-mentioned technical proposal, the m is preferably m=0～5.
To solve the two of above-mentioned technical problem, the technical solution used in the present invention is：A kind of composite table for improving oil recovery factor
The preparation method of face activating agent, comprises the following steps：
The preparation of (a) alkyl phenol Polyoxyalkylene ethers：
By required alkyl phenol and oxirane and/or expoxy propane in the presence of base catalyst and 85～160 DEG C of reaction temperature,
Pressure obtains the alkyl phenol Polyoxyalkylene ethers less than reaction is carried out under the conditions of 0.50MPa gauge pressures, and wherein catalyst amount is alkyl
1～3wt% of phenol quality；
The preparation of (b) alkyl phenol Polyoxyalkylene ethers hydrochlorate：
Alkyl phenol Polyoxyalkylene ethers and the sodium hydroxide that step (a) is synthesized at 45～75 DEG C after quaternization 2 hours, then with sulphur
Change reagent or carboxylating reagent reacts 2～15 hours at 70～90 DEG C, Jing is acidified, washes, removes solvent under reduced pressure after reaction terminates
Obtain the acid of alkyl phenol Polyoxyalkylene ethers.One kind wherein in solvent selected from ethanol, isopropanol, benzene；
C alkyl phenol Polyoxyalkylene ethers that () synthesizes step (b) are sour with appropriate sodium hydroxide, water mixing and stirring, consolidate
The alkyl phenol Polyoxyalkylene ethers hydrochlorate of 30～50wt% of content；
D () dissolves Alkyl Dimethylamine in a solvent, add potassium hydroxide that pH is adjusted to into 9～10.At 60～80 DEG C, press
Proportioning is slowly added to halogenated aliphatic alcohol, reacts 10～16 hours.Reaction steams solvent after terminating, and obtains product alkyl dimethyl
Hydroxyalkyl ammonium halide.One kind wherein in solvent selected from ethanol, isopropanol.
E () presses required proportioning, alkyl dimethyl hydroxyalkyl ammonium halide, the described alkyl phenol polyether hydrochlorate that step (a) is synthesized
Add in stainless steel with injection water, stirring obtains required complexed surfactant in 1～30 minute.
In above-mentioned technical proposal, step (e) is with total system quality percentages, the preferred model of alkyl phenol polyether carboxylate consumption
Enclose for 0.1～0.3wt%, the preferred scope of hydroxyalkyl quaternary surfactant is 0.02～0.15wt%.
To solve the three of above-mentioned technical problem, the technical solution used in the present invention is：A kind of composite table for improving oil recovery factor
Application of the face activating agent in oil extraction in oil field.
In above-mentioned technical proposal, the application process, those skilled in the art can be used according to prior art, for example
But it is not limited to contact complexed surfactant solution injection oil reservoir with underground crude oil, by underground crude oil body for out；Or
With other chemical agent for oil recovery compounding uses etc..
In above-mentioned technical proposal, the application process, with total system quality percentages, alkyl phenol polyether carboxylate consumption
Preferred scope be 0.1～0.3wt%, the preferred scope of hydroxyalkyl quaternary surfactant is 0.02～0.15wt%.
Anion-nonionic and cation complexed surfactant are present invention employs, anion-nonionic is answered with cationic surfactant
After matching somebody with somebody, the negatively charged hydrophilic group in anion-nonionic surfactant is positively charged hydrophilic with cationic surfactant
There is electrostatic attraction between base, can avoid conventional surfactant because caused by electrostatic repulsion between like charges interfacial film arrangement it is loose
The problems such as, and then strengthen built agent interfacial activity, improve oil displacement efficiency.Meanwhile, the interaction between zwitterion also strengthens
The anti-absorption of complexed surfactant, the ability of anticalcium magnesium ion so as to possess the possibility applied in high salinity reservoirs
Property.
Using the complexed surfactant of the improved recovery ratio of the present invention, can be used for formation temperature is 87 DEG C, and salinity is
17.7×104The In The Pucheng 2+3 blocks stratum water of mg/L and crude oil, with consumption as 0.1～0.3wt% alkylphenol-polyethenoxies
Ether carboxylate and 0.02～0.15wt% hydroxyalkyls ammonium halide form complexed surfactant oil displacement agent, determine the oil displacement agent water-soluble
Dynamical interfacial tension between liquid and In The Pucheng 2+3 block crude oil, up to 10-3～10-4The ultralow interfacial tension of mN/m,
Preferable technique effect is achieved, can be used to improve tertiary oil recovery recovery ratio.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
【Embodiment 1】
The preparation of (a) OPEO：
Octyl phenol 206 grams (1 moles) and 5 grams of potassium hydroxide are added into pressure reactor, is heated to being opened when 80～90 DEG C
Vacuum system, is dehydrated 1 hour under a high vacuum, substitutes nitrogen 3 times, system reaction temperature is adjusted to into 140 DEG C and is slowly passed through
268.4 grams of (6.1 moles) oxirane, control pressure≤0.50MPa.After reaction terminates, 90 DEG C are cooled to, vacuum is removed
Low-boiling-point substance is removed, neutralization, dehydration, obtain 456 grams of octyl phenol Polyethylene oxide (n=6) ether, yield 97% after cooling.
The preparation of (b) OPEO carboxylate：
456 grams of octyl phenol Polyethylene oxide (n=6) ether, 80 grams of the sodium hydroxide (2 moles) and 500 that step (a) is synthesized
Gram benzene adds reactor, and the reaction at 65 DEG C adds 140 grams of sodium chloroacetate (1.2 moles) after 3 hours, is warming up to 85 DEG C
Reaction 6 hours.Reaction cools the temperature to 65 DEG C after terminating, acidifying washing is removed under reduced pressure and obtain after solvent octyl phenol polyoxy second
Alkene ether carboxylic acid.
C OPEO carboxylic acid that () synthesizes step (b) and appropriate sodium hydroxide, water mixing and stirring, obtain
To pH=9～10, the OPEO carboxylate of solid content 30wt%.
D hexadecyldimethyl benzyl ammonium tertiary amine 269 grams (1 moles) and 800 grams of ethanol are added reactor by (), addition potassium hydroxide will
PH is adjusted to 9～10.At 60～80 DEG C, 102 grams of (1.1 moles) 3- chloropropyl alcohols are slowly added to by proportioning, are reacted 10～16 hours.
Reaction is evaporated off solvent and obtains 360 grams of hexadecyldimethyl benzyl ammonium hydroxyethyl ammonium chloride, yield 96% after terminating.
E OPEO (n=6) sodium acetate 0.1wt%, the hexadecane of step (d) synthesis that () synthesizes step (c)
The injection water of base dimethyl hydroxypropyl ammonium chloride 0.03wt% and 99.87wt% In The Pucheng Pu mono- is mixed, and is obtained the displacement of reservoir oil and is answered
Close surfactant.Interfacial tension at 87 DEG C, between the complexed surfactant and In The Pucheng 2+3 block dewatered oils
As shown in table 1 interfacial tension is determined by the TX500 types rotating interfacial tensimeter that Texas ,Usa university produces.
Table 1
【Embodiment 2】
The preparation of (a) NPE：
Nonyl phenol 220 grams (1 moles) and 5 grams of potassium hydroxide are added into pressure reactor, is heated to being opened when 80～90 DEG C
Vacuum system, is dehydrated 1 hour under a high vacuum, substitutes nitrogen 3 times, system reaction temperature is adjusted to into 140 DEG C and is slowly passed through
224.4 grams of (5.1 moles) oxirane, control pressure≤0.50MPa.After reaction terminates, 90 DEG C are cooled to, vacuum is removed
Low-boiling-point substance is removed, neutralization, dehydration, obtain 423 grams of Nonyl pheno (n=5) ether, yield 96% after cooling.
The preparation of (b) NPE carboxylate：
423 grams of Nonyl pheno (n=5) ether, 80 grams of the sodium hydroxide (2 moles) and 500 that step (a) is synthesized
Gram benzene adds reactor, and the reaction at 65 DEG C adds 140 grams of sodium chloroacetate (1.2 moles) after 3 hours, is warming up to 85 DEG C
Reaction 6 hours.Reaction cools the temperature to 65 DEG C after terminating, acidifying washing is removed under reduced pressure and obtain after solvent polyoxyethylene nonyl phenyl second
Alkene ether carboxylic acid.
C NPE carboxylic acid that () synthesizes step (b) and appropriate sodium hydroxide, water mixing and stirring, obtain
To pH=9～10, the NPE carboxylate of solid content 30wt%.
D octadecyldimethyl tertiary amine 297 grams (1 moles) and 800 grams of ethanol are added reactor by (), addition potassium hydroxide will
PH is adjusted to 9～10.At 60～80 DEG C, 88 grams of (1.1 moles) ethylene chlorhydrins are slowly added to by proportioning, are reacted 10～16 hours.
Reaction is evaporated off solvent and obtains 342 grams of octadecyldimethyl hydroxyethyl ammonium chloride, yield 96% after terminating.
E NPE (n=5) sodium acetate 0.1wt%, the octadecane of step (d) synthesis that () synthesizes step (c)
The injection water of base dimethyl hydroxyethyl ammonium chloride 0.02wt% and 99.88wt% In The Pucheng Pu mono- is mixed, and is obtained the displacement of reservoir oil and is answered
Close surfactant.Interfacial tension at 87 DEG C, between the complexed surfactant and In The Pucheng 2+3 block dewatered oils
As shown in table 2 interfacial tension is determined by the TX500 types rotating interfacial tensimeter that Texas ,Usa university produces.
Table 2
【Embodiment 3】
The preparation of (a) dodecyl phenol polyethenoxy ether：
Dodecylphenol 262 grams (1 moles) and 5 grams of potassium hydroxide are added into pressure reactor, when being heated to 80～90 DEG C
Vacuum system is opened, is dehydrated 1 hour under a high vacuum, substitute nitrogen 3 times, system reaction temperature is adjusted to into 140 DEG C slowly
It is passed through 356.4 grams of (8.1 moles) oxirane, control pressure≤0.50MPa.After reaction terminates, 90 DEG C are cooled to, very
Sky removes low-boiling-point substance, and neutralization, dehydration, obtain 589 grams of dodecyl phenol polyethenoxy (n=8) ether, yield 96% after cooling.
The preparation of (b) dodecylphenol polyethenoxy ether carboxylate：
By step (a) synthesize 589 grams of dodecyl phenol polyethenoxy (n=8) ether, 80 grams of sodium hydroxide (2 moles) and
600 grams of benzene add reactor, and after reacting 3 hours at 65 DEG C 140 grams of sodium chloroacetate (1.2 moles) is added, and are warming up to 85 DEG C
Reaction 6 hours.Reaction cools the temperature to 65 DEG C after terminating, acidifying washing, removes under reduced pressure and obtain after solvent dodecylphenol and gather
Oxygen vinyl Ether carboxylic acid.
C dodecyl phenol polyethenoxy ether carboxylic acid that () synthesizes step (b) and appropriate sodium hydroxide, water mixing and stirring,
Obtain the dodecylphenol polyethenoxy ether carboxylate of pH=9～10, solid content 30wt%.
D dodecyl phenol polyethenoxy ether (n=8) sodium acetate 1.0wt% that () synthesizes step (c), the ten of the synthesis of embodiment 1
The injection water of six alkyl dimethyl hydroxypropyl ammonium chloride 1.0wt% and 98.0wt% In The Pucheng Pu mono- is mixed, and obtains the displacement of reservoir oil
Complexed surfactant.At 87 DEG C, the interface between the complexed surfactant and In The Pucheng 2+3 block dewatered oils
Power interfacial tension as shown in table 3 is determined by the TX500 types rotating interfacial tensimeter that Texas ,Usa university produces.
Table 3
【Embodiment 4】
The preparation of (a) pentadecyl phenol polyethenoxy ether：
Pentadecyl phenol 304 grams (1 moles) and 5 grams of potassium hydroxide are added into pressure reactor, when being heated to 80～90 DEG C
Vacuum system is opened, is dehydrated 1 hour under a high vacuum, substitute nitrogen 3 times, system reaction temperature is adjusted to into 140 DEG C slowly
It is passed through 356.4 grams of (8.1 moles) oxirane, control pressure≤0.50MPa.After reaction terminates, 90 DEG C are cooled to, very
Sky removes low-boiling-point substance, and neutralization, dehydration, obtain 630 grams of pentadecyl phenol polyethenoxy (n=8) ether, yield 96% after cooling.
The preparation of (b) pentadecyl phenol polyethenoxy ether carboxylate：
By step (a) synthesize 630 grams of pentadecyl phenol polyethenoxy (n=8) ether, 80 grams of sodium hydroxide (2 moles) and
800 grams of benzene add reactor, and after reacting 3 hours at 65 DEG C 140 grams of sodium chloroacetate (1.2 moles) is added, and are warming up to 85 DEG C
Reaction 6 hours.Reaction cools the temperature to 65 DEG C after terminating, acidifying washing, removes under reduced pressure and obtain after solvent pentadecyl phenol and gather
Oxygen vinyl Ether carboxylic acid.
C pentadecyl phenol polyethenoxy ether carboxylic acid that () synthesizes step (b) and appropriate sodium hydroxide, water mixing and stirring,
Obtain the pentadecyl phenol polyethenoxy ether carboxylate of pH=9～10, solid content 30wt%.
D dodecyldimethylamine base tertiary amine 241 grams (1 moles) and 800 grams of ethanol are added reactor by (), add potassium hydroxide
PH is adjusted to into 9～10.At 60～80 DEG C, by proportioning 88 grams of (1.1 moles) ethylene chlorhydrins, reaction 10～16 are slowly added to
Hour.Reaction is evaporated off solvent and obtains 309 grams of dodecyldimethylamine base hydroxyethyl ammonium chloride, yield 96% after terminating.
E pentadecyl phenol polyethenoxy ether (n=8) sodium acetate 0.16wt% that () synthesizes step (c), the ten of step (d) synthesis
The injection water of tetraalkyl dimethyl hydroxypropyl ammonium chloride 0.08wt% and 99.76wt% In The Pucheng Pu mono- is mixed, and is driven
Oily complexed surfactant.Interface at 87 DEG C, between the complexed surfactant and In The Pucheng 2+3 block dewatered oils
Tension force interfacial tension as shown in table 4 is determined by the TX500 types rotating interfacial tensimeter that Texas ,Usa university produces.
Table 4
【Embodiment 5】
The preparation of (a) dodecyl phenol polyethenoxy ether：
Dodecylphenol 262 grams (1 moles) and 5 grams of potassium hydroxide are added into pressure reactor, when being heated to 80～90 DEG C
Vacuum system is opened, is dehydrated 1 hour under a high vacuum, substitute nitrogen 3 times, system reaction temperature is adjusted to into 140 DEG C slowly
It is passed through 268.4 grams of (6.1 moles) oxirane, control pressure≤0.50MPa.After reaction terminates, 90 DEG C are cooled to, very
Sky removes low-boiling-point substance, and neutralization, dehydration, obtain 511 grams of dodecyl phenol polyethenoxy (n=6) ether, yield 97% after cooling.
The preparation of (b) dodecylphenol polyethenoxy ether carboxylate：
By step (a) synthesize 511 grams of dodecyl phenol polyethenoxy (n=6) ether, 80 grams of sodium hydroxide (2 moles) and
500 grams of benzene add reactor, and after reacting 3 hours at 65 DEG C 140 grams of sodium chloroacetate (1.2 moles) is added, and are warming up to 85 DEG C
Reaction 6 hours.Reaction cools the temperature to 65 DEG C after terminating, acidifying washing, removes under reduced pressure and obtain after solvent dodecylphenol and gather
Oxygen vinyl Ether carboxylic acid.
C dodecyl phenol polyethenoxy ether carboxylic acid that () synthesizes step (b) and appropriate sodium hydroxide, water mixing and stirring,
Obtain the dodecylphenol polyethenoxy ether carboxylate of pH=9～10, solid content 30wt%.
D dodecyl phenol polyethenoxy ether (n=6) sodium acetate 0.03wt% that () synthesizes step (c), embodiment 1 synthesis
The injection water of hexadecyldimethyl benzyl ammonium hydroxypropyl ammonium chloride 0.01wt% and 99.96wt% In The Pucheng Pu mono- is mixed, and is obtained
Displacement of reservoir oil complexed surfactant.Boundary at 87 DEG C, between the complexed surfactant and In The Pucheng 2+3 block dewatered oils
Tension force interfacial tension as shown in table 5 in face is determined by the TX500 types rotating interfacial tensimeter that Texas ,Usa university produces.
Table 5
【Embodiment 6】
The preparation of (a) NPE：
Nonyl phenol 220 grams (1 moles) and 5 grams of potassium hydroxide are added into pressure reactor, is heated to being opened when 80～90 DEG C
Vacuum system, is dehydrated 1 hour under a high vacuum, substitutes nitrogen 3 times, system reaction temperature is adjusted to into 140 DEG C and is slowly passed through
179.8 grams of (3.1 moles) expoxy propane；312.4 grams of (7.1 moles) epoxies are slowly passed through after propylene oxide reaction terminates
Ethane, control pressure≤0.50MPa.After reaction terminates, 90 DEG C are cooled to, low-boiling-point substance is removed in vacuum, neutralize after cooling,
Dehydration, obtains 682 grams of nonyl phenol polyoxyethylene polyoxypropylene (n=7, m=3) ether, yield 97%.
The preparation of (b) NPE carboxylate：
682 grams of nonyl phenol polyoxyethylene polyoxypropylene (n=7, m=3) ether, 80 gram (2 of the sodium hydroxide that step (a) is synthesized
Mole) and 800 grams of benzene addition reactors, 140 grams of sodium chloroacetate (1.2 moles) is added after reacting 3 hours at 65 DEG C,
It is warming up to 85 DEG C to react 6 hours.Reaction cools the temperature to 65 DEG C after terminating, acidifying washing removed under reduced pressure and obtained after solvent
Nonyl phenol polyoxyethylene polyoxypropylene ether carboxylic acid.
C nonyl phenol polyoxyethylene polyoxypropylene ether carboxylic acid that () synthesizes step (b) is mixed with appropriate sodium hydroxide, water
Uniformly, the nonyl phenol polyoxyethylene polyoxypropylene ether carboxylate of pH=9～10, solid content 30wt% is obtained.
D cetyl diethyl tertiary amine 297 grams (1 moles) and 800 grams of ethanol are added reactor by (), addition potassium hydroxide will
PH is adjusted to 9～10.At 60～80 DEG C, 102 grams of (1.1 moles) 3- chloropropyl alcohols are slowly added to by proportioning, are reacted 10～16 hours.
Reaction is evaporated off solvent and obtains 386 grams of cetyl diethyl hydroxyethyl ammonium chloride, yield 96% after terminating.
D nonyl phenol polyoxyethylene polyoxypropylene ether (n=7, m=3) sodium acetate 0.06wt%, enforcement that () synthesizes step (c)
The injection water mixing of cetyl diethyl hydroxypropyl ammonium chloride 0.08wt% and 99.86wt% In The Pucheng Pu mono- of the synthesis of example 1
Stirring, obtains displacement of reservoir oil complexed surfactant.At 87 DEG C, the complexed surfactant is former with the dehydration of In The Pucheng 2+3 blocks
The TX500 types rotation drop interface that interfacial tension interfacial tension as shown in table 6 between oil is produced by Texas ,Usa university
Power instrument is determined.
Table 6
【Comparative example 1】
Amyl group phenol polyethenoxy ether (n=5) sodium acetate 0.1wt%, octadecyldimethyl hydroxyethyl ammonium chloride 0.02wt% and
The injection water of 99.88wt% In The Puchengs Pu mono- is mixed, and obtains displacement of reservoir oil complexed surfactant.At 87 DEG C, the composite table
Interfacial tension interfacial tension as shown in table 7 between face activating agent and In The Pucheng 2+3 block dewatered oils is by U.S. De Kesa
The TX500 types rotating interfacial tensimeter of this university's production is determined.
Table 7
【Comparative example 2】
Octadecyl phenol polyethenoxy ether (n=5) sodium acetate 0.1wt%, octadecyldimethyl hydroxyethyl ammonium chloride 0.02wt%
Mix with the injection water of 99.88wt% In The Puchengs Pu mono-, obtain displacement of reservoir oil complexed surfactant.At 87 DEG C, this is combined
Interfacial tension interfacial tension as shown in table 8 between surfactant and In The Pucheng 2+3 block dewatered oils is by U.S.'s moral gram
The TX500 types rotating interfacial tensimeter of Sa Si universities production is determined.
Table 8
【Comparative example 3】
NPE (n=5) sodium acetate 0.1wt%, octadecyl ammonium chloride 0.02wt% and 99.88wt% Central Plains
The injection water of Pu cities Pu mono- is mixed, and obtains displacement of reservoir oil complexed surfactant.At 87 DEG C, the complexed surfactant is with
What the interfacial tension interfacial tension as shown in table 8 between the 2+3 block dewatered oils of Yuan Pu cities was produced by Texas ,Usa university
TX500 types rotating interfacial tensimeter is determined.
Table 8
Claims (10)
1. a kind of complexed surfactant, in terms of mass fraction, including following components：
(1) 0.01～1.0 part of hydroxyalkyl quaternary surfactant；
(2) 0.01～1.0 parts of alkyl phenol polyether acid salt surfactant；
Wherein, the general molecular formula of the hydroxyalkyl quaternary surfactant is shown in formula (I)：
The general molecular formula of the alkyl phenol polyether acid salt surfactant is shown in formula (II)：
In formula, R1For C1～C20Alkyl, R2、R3For C1～C4Alkyl, p is CH2The number of segment, is selected from
Any one integer in 1～6, selected from making molecule shown in formula (I) in electroneutral anion, j is X valence state absolute values to X
Inverse；R4For C8～C16Fat-based；N is the sum that adds of ethoxy group, and n=5～8 count；M is adding for propoxyl group group
Sum, m=0～10；Q is CH2The number of segment, any one integer in 1～6；Y is selected from-COO—、-SO3 —In at least one；Selected from making molecule shown in formula (II) in electroneutral cation, i is the inverse of M valence state absolute values to M.
2. it is according to claim 1 improve oil recovery factor complexed surfactant, it is characterised in that described R1
For C12、C14、C16、C18Alkyl, R2、R3For methyl and ethyl.
3. it is according to claim 1 improve oil recovery factor complexed surfactant, it is characterised in that described p
For 1,2,3.
4. it is according to claim 1 improve oil recovery factor complexed surfactant, it is characterised in that described R4
For C8、C9、C12、C15Alkyl.
5. according to the complexed surfactant of raising oil recovery factor according to claim 1, it is characterised in that described
M=0～5.
6. according to the complexed surfactant of raising oil recovery factor according to claim 1, it is characterised in that the alkane
Base phenol polyethers acid salt surfactant is 10～1, preferably 5～1 with the quality proportioning of hydroxyalkyl quaternary surfactant.
7. according to the complexed surfactant of raising oil recovery factor according to claim 1, it is characterised in that described to carry
The complexed surfactant of high oil recovery factor, the injection water in terms of mass fraction, also including 98.0～99.98 parts.
8. it is according to claim 7 improve oil recovery factor complexed surfactant, it is characterised in that described note
Enter water 100000～200000mg/L of total salinity, Ca2++Mg2+For 0～7000mg/L.
9. the preparation method of the complexed surfactant of the arbitrary described raising oil recovery factor of claim 1～8 is as follows：
The preparation of (a) alkyl phenol Polyoxyalkylene ethers：
By required alkyl phenol and oxirane and/or expoxy propane in the presence of base catalyst and 85～160 DEG C of reaction temperature,
Pressure obtains the alkyl phenol Polyoxyalkylene ethers less than reaction is carried out under the conditions of 0.50MPa gauge pressures, and wherein catalyst amount is alkyl
1～3wt% of phenol quality；
The preparation of (b) alkyl phenol Polyoxyalkylene ethers hydrochlorate：
Alkyl phenol Polyoxyalkylene ethers and the sodium hydroxide that step (a) is synthesized at 45～75 DEG C after quaternization 2 hours, then with sulphur
Change reagent or carboxylating reagent react 2～15 hours at 70～90 DEG C, react Jing after terminating be acidified, wash, remove under reduced pressure it is molten
Agent obtains the acid of alkyl phenol Polyoxyalkylene ethers.One kind wherein in solvent selected from ethanol, isopropanol, benzene；
C alkyl phenol Polyoxyalkylene ethers that () synthesizes step (b) are sour with appropriate sodium hydroxide, water mixing and stirring, consolidate
The alkyl phenol Polyoxyalkylene ethers hydrochlorate of 30～50wt% of content；
D () dissolves Alkyl Dimethylamine in a solvent, add potassium hydroxide that pH is adjusted to into 9～10.At 60～80 DEG C,
Halogenated aliphatic alcohol is slowly added to by proportioning, is reacted 10～16 hours.Reaction steams solvent after terminating, and obtains product alkyl-dimethyl
Base hydroxyalkyl ammonium halide.One kind wherein in solvent selected from ethanol, isopropanol.
E () presses required proportioning, alkyl dimethyl hydroxyalkyl ammonium halide, the described alkyl phenol polyether hydrochlorate that step (a) is synthesized
Add in stainless steel with injection water, stirring obtains required complexed surfactant in 1～30 minute.
10. application of the complexed surfactant of the arbitrary described raising oil recovery factor of claim 1～8 in oil extraction in oil field.
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