CN106590598A - Oil-displacing composition and preparation method thereof - Google Patents
Oil-displacing composition and preparation method thereof Download PDFInfo
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- 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 an oil-displacing composition and a preparation method thereof. The problem that in the prior art, oil-displacing compositions are low in oil-displacing efficiency is mainly solved. The oil-displacing composition comprises the following components including, by mass, (1) 1 part of surface active agent and (2) more than 0 part and no more than 50 parts of polymers, wherein the surface active agent is a mixture formed by a non-ionic surface active agent shown in the formula (I) and anionic surface active agents shown in the formula (II) and the formula (III) with the mass ratio being (0.01-5):1:(0.1-5); R1, R2 and R3 represent C4-C40 aliphatic groups or aryl groups replaced with C4-C30 linear chain or branched chain saturated and unsaturated alkyls; and by adopting the technical scheme, the problem is well solved, and the technical scheme can be used for the oilfield oil-displacing composition and intensified oil production.
Description
Technical field
The present invention relates to a kind of displacement composition and preparation method thereof.
Background technology
Recovery efficiency technique is improved, i.e., foreign countries are often referred to reinforcing (EOR) and improve (IOR) recovery efficiency technique can be summarized as
Six aspects such as improving ecology, chemical flooding, heavy crude heat extraction, gas drive, microbe oil production and Physical oil recovery.At present, enter
The raising recovery efficiency technique of mining site scale application concentrates on thermal recovery, gas drive and chemical flooding three major types, wherein chemical flooding yield
5.18 × 104m3/ more than d, accounts for the 14.7% of world's EOR total outputs.Chemical flooding is by additionization in aqueous solution
Learn agent, change injection fluid physicochemical properties and rheological property and with the interaction characteristic of reservoir rock and improve
A kind of enhancements of recovery ratio, in China fast development is able to, and it is continental deposit heterogeneous body that its main cause is China's reservoir
Property is stronger, and terrestrial origin of petroleum Crude viscosity is higher, more suitable for chemical flooding in EOR methods.
Surfactant flooding technology is exactly added to surfactant in injection water, is improved by reducing oil water interfacial tension
Washing oil ability improves recovery ratio method come the one kind for improving oil displacement efficiency.Polymer displacement of reservoir oil tech is a kind of important raising oil
The method of recovery ratio, compared with general water drive, polymer displacement of reservoir oil is mainly to increase the viscosity of water phase, controls the stream of oil displacement system
Degree ratio, plays a part of to expand swept volume, and for surfactant, cost is relatively low.The addition of alkali is mainly dropped
Low surfactant adsorption amount, increases the interfacial activity of surfactant.As the important technology in chemical flooding, surface
Bioactivator activity water drive, micellar solution flooding and microemulsion drive the binary complex oil displacing skill that technology, polymeric surfactant are formed
The ASP Oil-Displacing Technology that art and polymeric surfactant alkali are formed has carried out some field tests in China and foreign countries, achieves
Good oil displacement efficiency.Daqing oil field in 2002 has been carried out note activated water increasing injection and has been tested in Periphery Low Permeability Oilfield, and 2003
Year carries out note In Surfactant Solution Flood test in Periphery Low Permeability Oilfield and loudspeaker, Sa, Fructus Pruni oil field Untabulated reservoirs, its objective is to make profit
Interfacial tension is substantially reduced, and reduces the effect on alternate surface, and the oil film that oil clot or stripping are sticked is detained in activation, dispersion, by
The increase of flowing porosity, improves the flowing permeability of oil reservoir, reduces startup pressure, improves floood conformance volume and drive
The effect of oily efficiency.It was verified that active water drive can increase substantially the oil recovery factor for having put into development block, and
The reserves that making a part can not employ under the conditions of current economic technology effectively put into exploitation.To 1994 since, Daqing oil
5 ternary composite driving tests have been carried out in field using the heavy alkylbenzene sulfonate of external import, carry again on the basis of waterflood recovery efficiency factor
High oil recovery factor 20%, and specify that ternary composite driving is the tertiary oil recovery dominant technology after polymer flooding according to this.Oil field
After ternary composite driving guide's field test is successful, it is contemplated that the difficult problem of fouling and breakdown of emulsion, binary combination flooding is taken
Technology path, using petroleum sulfonate surfactant with Shengli crude as Material synthesis as host, non-ionic surface is lived
Property is adjuvant, can be issued to ultralow interfacial tension in alkali-free condition, and has carried out ore deposit in the area southwest of Gu Dong seven in 2003
Pilot test, improve recovery ratio can 12%, solve fouling and breakdown of emulsion hardly possible problem.
In the technology of reservoir sweep implemented above, the use of high active surfactant is one of key factor, but domestic being applied to drives
Oily kinds of surfactants is few, properties of product stability is poor, universality is not strong.The screening of domestic surfactant oil displacement
It reduces the ability of oil water interfacial tension to Main Basiss, and it is external select surfactant oil displacement and cosurfactant according to
According to the phase behavior for being oil displacement system and crude oil：(1) big middle phase micro-emulsified is formed；(2) there is high solubilising under optimal salinity
Parameter；(3) can not there is the sticky phase such as layered liquid crystal.1973, Healy and Reed studied microemulsion body with three-phase diagram first
System, the work of Jing Healy, Reed, Nelson, Pope, Huh after this, establish the associating of oil displacement efficiency and phase behaviour,
The association of solubilization parameter and interfacial tension.Although phase behavior is the research carried out based on the dense surfactant flooding such as microemulsion flooding,
But theoretical system is more complete, so the screening of external efficient surfactant oil displacement system is still based on this.
The species of surfactant used is most with anionic in tertiary oil recovery research, next to that nonionic and amphion
Type, using it is minimum be cationic.Patent US3927716, US4018281 of Mobil Oil Corporation, US4216097
Report in succession using caustic flooding, surfactant or caustic flooding and the knot using the zwitterionic surfactant displacement of reservoir oil
Really, the zwitterionic surfactant for adopting for different chain length carboxylic acid or sulfonate type beet alkali surface activator, in Zong Kuang
Change 62000～160000mg/L, in the simulation saline of 1500～18000mg/L of calcium ions and magnesium ions, to Texas Southern crude oil
Interfacial tension is up to 10-1～10-4mN/m.Patent US4370243 of Mobil Oil Corporation is reported using oil-soluble alcohol, sulphur
The oil displacement system of sour glycine betaine and quaternary ammonium salt composition, the system can both play a part of surfactant, may also function as mobility control
The effect of preparation, wherein quaternary ammonium salt are the cationic surfactant of lipophilic group carbochain a length of 16～20, using the ten of 2wt%
Eight alkyl dihydroxy ethyl propyl sulfonic acid betaine salts and 1.0% hexanol are former after injection 1.9PV as displacement composition
Oil 100% can be displaced, but surfactant adsorption loss is larger reaches 6mg/g, add price relative on this basis
2.0% cheap tetraethylammonium bromide is as sacrifice agent reducing surfactant adsorption amount.Texas ,Usa university Shen
Patent US8211837 please, it was recently reported that using cheap and simple linear alcohol at high temperature catalytic dimerization reaction obtain be branched
Sulfuric acid esterification is carried out after long carbon alcohol, with expoxy propane, ethylene oxide polymerization, is lived relative to expensive sulfonate type surface
Property agent, low cost has synthesized big hydrophilic group polyethers sulfate surfactant, due to the presence of big hydrophilic group, so that
In the basic conditions high temperature stability performance is excellent for the sulfate surfactant, 0.3% branched-chain alcoho polyethers sulfate
(C32- 7PO-6EO sulfate) with 0.3% internal olefin sulphonates (C20～24IOS) saline solution is in 85 DEG C and equal amount
Crude oil mixing, its solubilization parameter be 14.The surfactant that foreign study is used because usage amount is big, high cost, as
Displacement composition receives in actual applications certain restriction.Also having been reported that using cationic surfactant, such as China
Patent CN 1528853, CN 1817431, CN 1066137 etc. report in succession bisamide type cationic, it is fluorine-containing sun from
Subtype and cation Gemini surfactant containing pyridine radicals, but because cation has the shortcomings that absorption is lost big, high cost,
Limit its use in Oil Field.
In the technology of reservoir sweep implemented above, the use of Heat Resistant and Salt Tolerant Polymer is another key factor.Early stage is usually used in strengthening stone
The industrial products of the polymer flooding of oil exploitation (EOR) only have partially hydrolyzed polyacrylamide (PHPA) (HPAM), and it depends on height
The repulsive interaction of ion and highly polar side base on molecular weight and polymer molecular chain reaches adhesion-promoting effect.But, high molecular
Polymer is when by larger stretching and shear stress, it is easy to mechanical degradation occurs and viscosity is lost, in low-permeability rock stratum
It is particularly evident during middle injection of polymer.Cation in aqueous solution, especially divalent ion, the ion in meeting shielded polymer
Group, crimps polymer molecular chain, and hydrodynamic volume reduces even precipitation, so that adhesion-promoting is substantially reduced.It is local
When layer reservoir temperature is higher (93 DEG C of ＞), the facile hydrolysiss in high temperature aqueous solution of the amide groups in polyacrylamide (PAM) make
The salt-resistance of polymer solution drastically declines.In recent years, about temperature-resistant and anti-salt type polyacrylamide research mainly by poly-
Introduce big side base on compound main chain or rigid side base improve the heat stability of polymer, introduce the monomer that suppresses hydrolysis or to salt not
Sensitive monomer carries out copolymerization to improve the hydrolysis and anti-salt property of polymer, or the heat resistance and salt tolerance for passing through hydrophobic group
To improve the temperature-resistant anti-salt performance of polymer.
China's chemical displacement of reservoir oil technology is relatively advanced, and live process matched therewith is perfect, carries out chemical displacement of reservoir oil technology in oil reservoirs such as middle and high infiltrations
Applied research exploitation it is significant.Therefore, for the sandstone oil reservoir of high temperature and high salt, one kind has been invented in formation temperature
Lower Stability Analysis of Structures, and 10 can be formed with crude oil-2～10-4MN/m low interfacial tensions, effectively improve the displacement of reservoir oil group of oil recovery factor
Compound system.The preparation method of exactly this displacement composition of the present invention and its application in intensified oil reduction.
The content of the invention
One of the technical problem to be solved is the problem of displacement composition oil displacement efficiency difference in prior art, there is provided one
Plant new displacement composition.The displacement composition will contain the aqueous solution of surfactant, or surfactant and polymer
Aqueous solution as displacement composition be used for oil displacement process in, with temperature-resistant anti-salt performance it is good, under high temperature superelevation salt harsh conditions
The high advantage of oil displacement efficiency.
The two of the technical problem to be solved are to provide a kind of preparation of the displacement composition of one of solution technical problem
Method.
In order to solve one of above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of displacement composition is with mass parts
Number meter, including following components：
1) 1 part of surfactant；
2) 0～50 part and more than 0 part of polymer；
The surfactant is anion nonionic surfactant, including the nonionic surfactant shown in formula (1)
With the anion surfactant shown in formula (2), the anion surfactant shown in (3), wherein shown in formula (1)
Nonionic surfactant, anion surfactant, the anion surfactant shown in (3) shown in formula (2)
Mass ratio be (0.01～5)：1：(0.1～5)；
R1And R2And R3It is independently chosen from C4～C40Aliphatic group or by C4～C30The saturation of straight or branched and insatiable hunger
The aryl replaced with alkyl；M1, m2, m3 and m4 are independently selected from 0～50, but m1 and m2, m3 and m4 can not
It is simultaneously 0；N1 and n2 are independently selected from 0～100, but n1 and n2 can not be simultaneously 0；R1, r2, r3 and r4 are independently selected
From 0～50, but r1 and r2, r3 and r4 can not be simultaneously 0；S1 and s2 are independently selected from 0～100, but s1 and s2 can not
It is simultaneously 0；P1, p2, p3 and p4 are independently selected from 0～50, but p1 and p2, p3 and p4 can not be simultaneously 0；Q1 and
Q2 is independently selected from 0～100, but q1 and q2 can not be simultaneously 0；Z1And Z2And Z3Respectively-R01Y1,-R02Y2、
- R03Y3；R01And R02And R03Selected from C1～C5Alkylidene or hydroxyl substituted alkylene, Y1And Y2And Y3It is selected from
SO3M or COOW, M and W are independently selected from hydrogen, alkali metal or by formula NR4(R5)(R6)(R7) shown in group, R4、
R5、R6、R7To be independently selected from H, (CH2)pOH or (CH2)q CH3, in any integer, q=0～5 in p=2～4
Any integer.
The anionic surface shown in nonionic surfactant, formula (2) in above-mentioned technical proposal, shown in the formula (1)
The mass ratio of the anion surfactant shown in activating agent, (3) is preferably (0.03～3)：1：(1～3).
In above-mentioned technical proposal, the preferably R1Or R2Or R3In at least one be C6～C20Alkyl or by C8～C16
Alkyl-substituted phenyl.
In above-mentioned technical proposal, preferred p=2, q=0～1.
In above-mentioned technical proposal, preferred m1+m2=2～10, m3+m4=2～20, n1+n2=5～40；And/or r1+r2=2～
10, r3+r4=2～20, s1+s2=5～40 and/or p1+p2=2～10, p3+p4=2～20, q1+q2=5～40.
The key of anion nonionic phenotype oil displacement surfactant of the present invention be active princlple be shown in formula (1) it is non-from
The anion surfactant shown in anion surfactant and formula (3) shown in sub- surfactant and formula (2), its
In, shown in formula (2) for single parent's head base anion surfactant, shown in formula (3) for parents' head base anion
Surfactant；One skilled in the art will appreciate that for the ease of transport and store or onsite application etc. from the aspect of, can adopt
With various supply forms, such as water-free solid-state form, or aqueous solid-state form, or aqueous cream form,
Or aqueous solution form；Aqueous solution form includes being made into the form of concentrated solution with water, is directly made into live displacement of reservoir oil desired concn
Solution form, for example in mass key active ingredient content be the solution of 0.005～0.6wt% be that the live displacement of reservoir oil is more suitable
Form；Wherein, there is no particular/special requirement to water, can be deionized water, can also be the water containing inorganic mineral, and contain
The water of inorganic mineral can be tap water, oil field stratum water or oilfield injection water.
The moon non-mixed oil displacement surfactant of the invention, can be by the nonionic surfactant and described single parent's head
Base anion surfactant and described parents' head base anion surfactant are obtained by mixing in required ratio, preferably
With two acquisitions of one of following two technical schemes for solving technical problem or technical scheme.
In above-mentioned technical proposal, the polymer, without strict restriction, can be various use well-known to those skilled in the art
In the polymer of oil extraction in oil field, those skilled in the art can be selected according to prior art, for example but not limited selected from Huang
Virgin rubber, hydroxymethyl cellulose, hydroxyethyl cellulose, anion-polyacrylamide, modified polyacrylamide, hydrophobic association
At least one in polymer, polymer microballoon.
In above-mentioned technical proposal, the modified polyacrylamide and hydrophobic associated polymer are preferably by acrylamide, temperature-resistant anti-salt
Monomer or hydrophobic monomer copolymerization are formed, temperature-resistant anti-salt monomer or hydrophobic monomer can be it is well-known to those skilled in the art containing
Big side base or rigid side base monomer (as styrene sulfonic acid, N- alkyl maleimides, acrylamido chain alkyl sulfonic acid,
Chain alkyl allyl dimethyl base ammonium halide, 3- acrylamidos -3 Methylbutanoic acid etc.), the monomer containing resistance to salt groups is (such as 2-
Acrylamide-2-methylpro panesulfonic acid), the monomer (such as N- alkyl acrylamides) containing hydrolysis group, containing acyl can be suppressed
At least one in monomer (such as N- vinylpyrrolidones), the monomer containing hydrophobic group of the group of amido hydrolysis, heatproof
Salt resistance monomer is preferably 2- acrylamide-2-methylpro panesulfonic acids, and hydrophobic monomer is preferably 2- acrylamido dodecyl sulphurs
Acid.
In above-mentioned technical proposal, in described modified polyacrylamide acrylamide and temperature-resistant anti-salt monomer mole preferably than for
(0.1～40): 1, more preferably (0.1～20): 1；In hydrophobic associated polymer acrylamide and temperature-resistant anti-salt monomer with
The mol ratio of hydrophobic monomer is 1：(0.1～40)：(0.001～0.05), more preferably 1: (0.1～20): (0.001～0.01).
In above-mentioned technical proposal, described modified polyacrylamide is preferably by acrylamide, 2- acrylamido -2- methyl-prop sulphurs
Sour copolymerization is formed, and acrylamide is preferably (0.1～40) with 2- acrylamide-2-methylpro panesulfonic acids mol ratio: 1, it is more excellent
Elect as (0.1～20): 1；The preferred acrylamide of hydrophobic associated polymer, 2- acrylamide-2-methylpro panesulfonic acids and 2- third
Acrylamide base dodecyl sodium sulfonate copolymerization is formed, acrylamide, 2- acrylamide-2-methylpro panesulfonic acids and 2- acrylamidos
Dodecyl sodium sulfonate mol ratio is preferably 1：(0.1～40)：(0.001～0.05), more preferably 1: (0.1～20):
(0.001～0.01).
In above-mentioned technical proposal, the viscosity-average molecular weight of described modified polyacrylamide is preferably 800～25,000,000, more preferably
For 1000～20,000,000, the viscosity-average molecular weight of hydrophobic associated polymer is preferably 1000～25,000,000, more preferably 1200～2200
Ten thousand.
In above-mentioned technical proposal, the mass ratio of surfactant and polymer is preferably 1 in the displacement composition: (0～2).
To solve the two of above-mentioned technical problem, one of the technical solution adopted in the present invention is as follows：One of above-mentioned technical problem institute
The preparation method of the displacement composition stated, comprises the following steps：
A, in the presence of base catalyst, R1NH2Successively with aequum oxirane, expoxy propane, reacting ethylene oxide
Obtain R1N((CH2CH2O)m1(CHCH3CH2O)n1(CH2CH2O)m3H)((CH2CH2O)m2)(CHCH3CH2O)n2
(CH2CH2O)m4H)；
B, the product that step a is obtained and X1R01Y01And alkali metal hydroxide or alkali metal alcoholates are with mol ratio 1:(1～2):
(1～4) in a solvent, obtains containing the nonionic table shown in formula (1) for 3～15 hours in 50～120 DEG C of reactions of reaction temperature
Single parent's head base anion surfactant and the parents' head base anion described in formula (5) described in face activating agent and (4)
Surfactant mixture；
Wherein, Z01For-R02Y01；Y01Selected from SO3M1Or COOW1, M1And W1For alkali metal, X1Selected from chlorine,
Bromine or iodine.
C, based on the mass fraction, the surfactant mixture that step b is obtained and the polymer mixed are uniform,
Obtain described displacement composition.
R in above-mentioned technical proposal, described in step b1N((CH2CH2O)m1(CHCH3CH2O)n1(CH2CH2O)m3H)
((CH2CH2O)m2)(CHCH3CH2O)n2(CH2CH2O)m4H):X1R01Y01:Alkali metal hydroxide or alkali metal alcohol
The mol ratio of salt is preferably 1:(1～2):(1～3).
In above-mentioned technical proposal, the solvent described in step b preferably is selected from C3～C8Ketone and C6～C9Aromatic hydrocarbons at least one,
For example by acetone, butanone, pentanone, the material group that constitutes from benzene, toluene or dimethylbenzene, trimethylbenzene, ethylbenzene and diethylbenzene
At least one.
In above-mentioned technical proposal, the optional alkali metal hydroxide (such as sodium hydroxide or potassium hydroxide) of the base catalyst,
Alkali metal alcoholates (such as Feldalat NM, Feldalat KM, Sodium ethylate, potassium ethoxide).
As long as having carried out the reaction of step b, those skilled in the art only can need to distill removal solvent without complicated separation,
The described cloudy non-mixed oil displacement surfactant of saliferous and excesses of basic catalysts is obtained.In order to obtain not saliferous and
The product containing formula (1) and formula (4) and formula (5) of excesses of basic catalysts, need not pay creative labor after step b
Dynamic those skilled in the art can implement.
For example, in order to obtain not saliferous and excesses of basic catalysts by formula (1) nonionic surfactant and formula (4)
Shown single parent's head base anion surfactant and parents' head base anion surfactant shown in formula (6) it is cloudy immiscible
Mould assembly oil displacement surfactant, works as M1Or W1For H when product, step d and step e can be further included：
D, in the reactant mixture that step b is obtained add acid adjust water phase pH=1～3, isolated organic faciess；
E, the organic faciess being concentrated to give obtain required product.
Again for example, in order to obtain not saliferous and excesses of basic catalysts by formula (1) nonionic surfactant and formula
(4) the moon of the base of single parent's head shown in anion surfactant and parents' head base anion surfactant shown in formula (6)
Non-mixed oil displacement surfactant works as M1Or W1For alkali metal or by formula NR4(R5)(R6)(R7) shown in group product,
Can on the basis of step d with required alkali metal or formula NR4(R5)(R6)(R7) shown in the neutralization of group corresponding alkali, then
Remove solvent described in organic faciess.
Required alkali metal or formula NR described in above-mentioned technical proposal4(R5)(R6)(R7) shown in the corresponding alkali of group, such as with alkali
The corresponding alkali of metal is selected from alkali metal hydroxide, alkali carbonate, alkali metal hydrogencarbonate, alkali metal oxide or alkali
Metal alkoxide etc., with NR4(R5)(R6)(R7) the corresponding alkali of the group selected from ammonia, ethanolamine, diethanolamine, triethanolamine,
Triethylamine, quaternary ammonium base etc..
X1R01Y01Example have but be not limited to chloroacetic alkali metal salt (such as sodium chloroacetate), 3- chlorine-2-hydroxyl propane sulfonic acid
Alkali metal salt, 2- ethyl chloride sulfonic acid alkali metal salts etc..
In order to solve the two of above-mentioned technical problem, the two of technical scheme are as follows：The drive of one of above-mentioned technical problem
The preparation method of fluid composition, comprises the following steps：
B product that () obtains one of above-mentioned technical proposal step a and the sultone of 1,3- third and alkali metal hydroxide or alkali
Metal alkoxide is with mol ratio 1:(1～2):(1～4) in a solvent, obtains for 3～15 hours in 50～120 DEG C of reactions of reaction temperature
Containing single parent's head base anion surfactant and formula (7) described in the nonionic surfactant shown in formula (1) and formula (6)
Described parents' head base anionic surfactant mixture；
Wherein Z '01For-CH2CH2CH2SO3M2；M2For alkali metal.
C () based on the mass fraction, the surfactant mixture that step (b) is obtained is equal with the polymer mixed
It is even, obtain described displacement composition.
R in above-mentioned technical proposal, described in step (b)1N((CH2CH2O)m1(CHCH3CH2O)n1(CH2CH2O)m3H)
((CH2CH2O)m2)(CHCH3CH2O)n2(CH2CH2O)m4H):The sultone of 1,3- third:Alkali metal hydroxide or alkali gold
The mol ratio of category alkoxide is preferably 1:(1～2):(1～4).
R in above-mentioned technical proposal, described in step b1N((CH2CH2O)m1(CHCH3CH2O)n1(CH2CH2O)m3H)
((CH2CH2O)m2)(CHCH3CH2O)n2(CH2CH2O)m4H):The sultone of 1,3- third:Alkali metal hydroxide or alkali gold
The mol ratio of category alkoxide is preferably 1:(1～2):(1～3).
In above-mentioned technical proposal, the solvent described in step (b) preferably is selected from C3～C8Ketone and C6～C9Aromatic hydrocarbons at least
One kind, such as by acetone, butanone, pentanone, the thing that constitutes from benzene, toluene or dimethylbenzene, trimethylbenzene, ethylbenzene and diethylbenzene
At least one in matter group.
As long as having carried out the reaction of step (b), those skilled in the art only can need to distill removal without complicated separation
Solvent, you can obtain the described cloudy non-mixed oil displacement surfactant of saliferous and excesses of basic catalysts.In order to obtain not
Need not pay after the product containing formula (1) and formula (6) and formula (7) of saliferous and excesses of basic catalysts, step (b)
Creative work those skilled in the art can implement.
For example, in order to obtain not saliferous and excesses of basic catalysts by formula (1) nonionic surfactant and formula (6)
Shown single parent's head base anion surfactant and parents' head base anion surfactant shown in formula (7) it is cloudy immiscible
Mould assembly oil displacement surfactant, works as M1Or W1For H when product, step (d) and step (e) can be further included：
D () adds acid to adjust pH=1～3 of water phase, isolated organic faciess in the reactant mixture that step (b) is obtained；
E organic faciess that () is concentrated to give obtain required product.
Again for example, in order to obtain not saliferous and excesses of basic catalysts by formula (1) nonionic surfactant and formula
(6) the moon of the base of single parent's head shown in anion surfactant and parents' head base anion surfactant shown in formula (7)
Non-mixed oil displacement surfactant works as M1Or W1For alkali metal or by formula NR4(R5)(R6)(R7) shown in group product,
Can on the basis of step (d) with required alkali metal or formula NR4(R5)(R6)(R7) shown in the neutralization of group corresponding alkali,
Then solvent described in organic faciess is removed.
Required alkali metal or formula NR described in above-mentioned technical proposal4(R5)(R6)(R7) shown in the corresponding alkali of group, such as with alkali
The corresponding alkali of metal is selected from alkali metal hydroxide, alkali carbonate, alkali metal hydrogencarbonate, alkali metal oxide or alkali
Metal alkoxide etc., with formula NR4(R5)(R6)(R7) the corresponding alkali of the group is selected from ammonia, ethanolamine, diethanolamine, three ethanol
Amine, triethylamine, quaternary ammonium base etc..
In above-mentioned technical proposal, the modified polyacrylamide is by two kinds of acrylamide, 2- acrylamide-2-methylpro panesulfonic acids
Monomer is formed using water solution polymerization process, can be buied from market, it is also possible to which free-radical polymerized by routine is obtained.No matter
Block copolymerization or random copolymerization, the product for obtaining is used equally to the present invention and reaches the purpose of the present invention.The embodiment of the present invention
In modified polyacrylamide, be according to mol ratio by acrylamide and two kinds of monomers of 2- acrylamide-2-methylpro panesulfonic acids
(0.5～5): is obtained with water after 1 mixing as solvent conventional radical initiators cause Raolical polymerizable.
In above-mentioned technical proposal, the hydrophobic associated polymer is by acrylamide, 2- acrylamide-2-methylpro panesulfonic acids and 2-
Three kinds of monomers of acrylamido dodecyl sodium sulfonate are formed using water solution polymerization process, can be buied from market, it is also possible to pass through
Conventional is free-radical polymerized prepared.No matter block copolymerization or random copolymerization, the product for obtaining is used equally to the present invention and reaches
The purpose of the present invention.Hydrophobic associated polymer in the embodiment of the present invention, is by acrylamide, 2- acrylamido -2- methyl
Three kinds of monomers of propane sulfonic acid and 2- acrylamidos dodecyl sodium sulfonate are according to mol ratio 1: (0.5～5): (0.001～0.01) mixes
Obtained as solvent conventional radical initiators cause Raolical polymerizable with water afterwards.
The key active ingredient of displacement composition of the present invention is the component (1), one skilled in the art will appreciate that in order to just
In transport and store or onsite application etc. from the aspect of, can adopt various supply forms, such as water-free solid-state form,
Or aqueous solid-state form, or aqueous cream form, or aqueous solution form；Aqueous solution form includes being made into water
The form of concentrated solution, is directly made into the displacement composition form of live displacement of reservoir oil desired concn；Wherein, there is no particular/special requirement 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.
Displacement composition of the present invention has good compatibility, can also contain other inorganic agents commonly used in the art, such as foam
The oil recovery auxiliary agents such as agent, small organic molecule (such as isopropanol, ethylene glycol monobutyl ether, DMSO etc.).
In above-mentioned technical proposal, the displacement composition obtained in step c or (c) can be using various conventional mixing sides
Method is mixed to get according to aequum each component, for obtaining displacement composition displacement of reservoir oil group according to desired concn water dissolution during the displacement of reservoir oil
Compound is used for the displacement of reservoir oil；Can be according to the concentration of required displacement composition, each component in the displacement composition being dissolved respectively
Yu Shuizhong obtains displacement composition for the displacement of reservoir oil.In preparation water used can be tap water, river, sea water, oil field stratum
Water；Preferred water is：Simulation oil field stratum water, total salinity is preferably 50000～250000 for mg/litre.
In the present invention, the anion surfactant shown in nonionic surfactant and formula (2) shown in the formula (1),
(3) EO, PO segment in the anion surfactant shown in is EO-PO-EO arrangements, and the present inventor is surprised
It was found that, other structures are identical and identical EO numbers and PO numbers under conditions of, the compositionss obtained using this kind of arrangement mode
Oil displacement efficiency be much better than EO-PO arrangement or PO-EO arrangement.
The present invention carries out effect assessment using physical modeling's displacement evaluation methodology, and concrete evaluation methodology is：
By rock core constant temperature drying to constant weight, the perm-plug method of rock core is determined；With above-mentioned simulation oil field stratum water saturation rock core,
Its pore volume is calculated, at a temperature of the displacement of reservoir oil, with crude oil saturated core, the volume of saturation crude oil is recorded, then with 0.1ml/min
Speed pump into stratum water, be driven to aqueous up to 100%, the recovery ratio that water drive improves crude oil is calculated, then with 0.1ml/min
Speed 0.1～1PV of tuberculosiss (rock pore volume) steps c or (c) displacement composition for obtaining, with the speed of 0.1ml/min
Degree water drive calculates the percent that oil recovery factor is improved on the basis of water drive to aqueous 100%.
In the present patent application file, it is related to the dosage of surfactant or concentration, with the nonionic table shown in formula (1)
The parents' head Ji Yin described in single parent's head base anion surfactant and formula (3) described in face activating agent and formula (2) from
The total amount meter of sub- surfactant.
Using displacement composition and preparation method thereof of the present invention, can be used for 75～95 DEG C of formation temperature, salinity 50000～
The simulation oil field stratum water of 250000 mg/litres and crude oil, by percentage to the quality, consumption is 0.005～0.6wt% mixture tables
Face activating agent and 0～0.3wt% above-mentioned modified polyacrylamide or hydrophobic associated polymer forms displacement composition, determines
Dynamical interfacial tension value between the apparent viscosity of the displacement composition aqueous solution, with oil field dewatered oil is up to 10-2~
10-4MN/m, Jing physical modeling's displacement experiment Lab-evaluation, the displacement composition can improve oil recovery factor on the basis of water drive
Up to 19.75%, preferable technique effect is achieved.
Description of the drawings
It is de- to oil field with the variable concentrations surfactant S-1～S-3 aqueous solutions for simulating saline A preparations when Fig. 1 a are 85 DEG C
The interfacial tension figure of water crude oil.
Fig. 1 b are the simulation saline B solution (95 DEG C) of variable concentrations S-1, S-4 and S-5, the simulation saline A of S-5 is molten
Interfacial tension figure of the liquid (85 DEG C) to oil field dewatered oil.
Fig. 1 c are simulation saline solution A (85 DEG C), the simulation saline B solution (95 DEG C) of S-6 of variable concentrations S-6～S-8
Interfacial tension figure to oil field dewatered oil.
Fig. 2 is simulation core displacement experiment flow chart.Wherein, 1 is constant-flux pump, and 2 is six-way valve, and 3 is intermediate receptacle, 4
For pharmacy jar, 5 is compression pump, and 6 is six-way valve, and 7 is fill out sand tube, and 8 is graduated cylinder.
Fig. 3 a are the saline A aqueous solutions of 0.15wt%P1,0.3wt%S-1+0.15wt%P1 in 85 DEG C of aging different times
Viscosity figure afterwards.
Fig. 3 b are the saline A aqueous solutions of 0.1wt%P2,0.3wt%S-1+0.1wt%P2 after 85 DEG C of aging different times
Viscosity figure.
Fig. 3 c are the saline A aqueous solutions of 0.08wt%P2,0.3wt%S-1+0.08wt%P2 in 75 DEG C of aging different times
Viscosity figure afterwards.
Fig. 3 d are 0.12wt%P2,0.3wt%S-1+0.12wt%P2 saline A aqueous solutions after 95 DEG C of aging different times
Viscosity figure.
Fig. 4 a are the saline A aqueous solutions of 0.3wt%S-1,0.3wt%S-1+0.15wt%P1 in 85 DEG C of aging different times
Afterwards to the interfacial tension figure of oil field dewatered oil.
Fig. 4 b are the saline A aqueous solutions of 0.3wt%S-1,0.3wt%S-1+0.1wt%P2 after 85 DEG C of aging different times
Interfacial tension figure to oil field dewatered oil.
Fig. 4 c are the saline A aqueous solutions of 0.3wt%S-1,0.3wt%S-1+0.08wt%P2 in 75 DEG C of aging different times
Afterwards to the interfacial tension figure of oil field dewatered oil.
Fig. 4 d are 0.3wt%S-1,0.3wt%S-1+0.12wt%P2 saline A aqueous solutions after 95 DEG C of aging different times
Interfacial tension figure to oil field dewatered oil.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
【Embodiment 1】
A, the anion nonionic surfactant structural formula for preparing are as follows, wherein, (1) Z1=H, Z2=H, it is non-from
Sub- surfactant；(2)Z1=H, Z2=CH2COONa, single parent's head base anion surfactant；(3)Z1=Z2=
CH2COONa, parents' head base anion surfactant；m1+m2=4, n1+n2=35, m3+m4=3.
261 grams of (1 mole) dodecyl polyanilines, 5.2 grams of hydrogen-oxygens are added in the 5L pressure reactors equipped with agitating device
Change sodium and 13.1 grams of Anhydrous potassium carbonates, when being heated to 80～90 DEG C, open vacuum system, be dehydrated 1 hour under a high vacuum,
Then with nitrogen displacement 3～4 times, system reaction temperature is adjusted to into 110 DEG C and is slowly passed through 178.2 grams of (4.05 moles) epoxy second
Alkane, control pressure≤0.50MPa after reacting ethylene oxide terminates, is slowly passed through 2053.2 grams (35.4 moles) in 150 DEG C
Temperature is adjusted to 140 DEG C and is slowly passed through 134.2 by expoxy propane, control pressure≤0.60MPa again after propylene oxide reaction terminates
Gram (3.05 moles) oxirane.After reaction terminates, 90 DEG C are cooled to, low-boiling-point substance is removed in vacuum, neutralization, dehydration after cooling,
Obtain 2515.8 grams of dodecyl polyaniline Polyethylene oxide (4) polyoxypropylene (35) Polyethylene oxide (3) ether, yield 96.8%.
1299.5 grams of dodecyl polyaniline Polyethylene oxide (4) polyoxypropylene (35) Polyethylene oxide (3) ether (0.5 mole)
Mix with 24 grams of (0.6 mole) sodium hydroxide, 58.3 grams of (0.5 mole) sodium chloroacetates and 1000 milliliters of toluene/benzene (v/v=1)
Together in 5000 milliliters that are furnished with mechanical agitation, thermometer and reflux condensing tube of four-hole boiling flasks, back flow reaction 7 is warming up to
Hour.Cooling, takes 50 grams of homogeneous reaction liquid with the acidifying of 20wt% hydrochloric acid, divides and removes water and inorganic salt, and solvent is evaporated off, and obtains
Mixture Jing high performance liquid chromatography (HPLC) analysis, dodecyl polyaniline Polyethylene oxide (4) polyoxypropylene (35) gather
Oxygen ethylene (3) ether and dodecyl polyaniline Polyethylene oxide (4) polyoxypropylene (35) Polyethylene oxide (3) ether acetic acid and ten
The mass percent of dialkyl aniline Polyethylene oxide (4) polyoxypropylene (35) Polyethylene oxide (3) ether oxalic acid is 49.2:20.0:
30.8.Remaining untreated reactant liquor distillation removes solvent, adds water mix homogeneously to obtain the mixed of sodium chloride-containing and sodium hydroxide
Close surfactant S-1.
B, the oil field simulated formation water for preparing different bivalent cations and total salinity respectively, concrete composition is shown in Table 1.
The S-1 surfactants prepared with oil field simulated formation water A difference preparation steps a and modified polyacrylamide (P1, copolymerization
AM/AMPS mol ratio=1/1, ten thousand) aqueous solution, the stirring 3 hours of viscosity-average molecular weight 1450, then both are mixed to get into one
Uniform poly- table binary system displacement composition is planted, system viscosity and oil water interfacial tension is determined, and compared with S-1 and P1
Compared with being shown in Table 2.With the S-1 aqueous solutions that oil field simulated formation water A and B prepare variable concentrations, its oil-water interfaces is determined
Tension force, as shown in Figure 1.Oil field dewatered oil viscosity is 2.5mPa.s, and test temperature is 85 DEG C, and apparent viscosity is by the U.S.
The BROODFIELD type IIIs viscosimeter of Brookfield companies is determined, and interfacial tension is produced by Texas ,Usa university
TX500 types rotating interfacial tensimeter determine.
C, by artificial core constant temperature drying to constant weight, measure the average diameter and rock core length of rock core, weigh rock core dry weight, survey
Determine the perm-plug method of rock core.With oil field simulated formation water A saturated cores, its pore volume is tested.With oil field dewatered oil
Saturated core, records the volume of saturation crude oil.At a temperature of 85 DEG C, contained to Produced Liquid with oil field simulated formation water A water drives
Water calculates the recovery ratio that water drive improves crude oil, the poly- table two of tuberculosiss 0.3pv (rock pore volume) step b synthesis up to 100%
After first system displacement composition, water drive to aqueous 100% calculates the percent that oil recovery factor is improved on the basis of water drive,
Simultaneously the single displacement composition of PV identical with note compares, and is shown in Table 2.Rock core perm-plug method HKGP-3 types
Compact rock core gas permeability porosity measuring instrument is determined, and the simulation core displacement experiment flow process of employing is as shown in Figure 2.
【Embodiment 2】
It is a, same【Embodiment 1】, difference is that all reactant liquors are acidified, are washed, are evaporated off by reaction after terminating
After solvent, the mixture for obtaining is mixed with water, with the pH=12 of the sodium hydrate aqueous solution regulation system of 30wt%, obtained
Required mixed surfactant S-2.
B, the S-2 prepared with oil field simulated formation water A difference preparation steps a and modified polyacrylamide (P1, copolymerization
AM/AMPS mol ratio=1/1, ten thousand) aqueous solution, the stirring 4 hours of viscosity-average molecular weight 1450, remaining is same【Embodiment 1】
B, the results are shown in Table shown in 3.The oil water interfacial tension of the S-2 aqueous solutions of variable concentrations, as shown in Figure 1.
It is c, same【Embodiment 1】C carries out laboratory simulation flooding test, the results are shown in Table shown in 3.
【Embodiment 3】
A, the anion nonionic surfactant structural formula for preparing are as follows, wherein, (1) Z1=H, Z2=H, it is non-from
Sub- surfactant；(2)Z1=H, Z2=CH2COOH.HN(CH2CH2OH)2, the work of single parent's head base anionic surface
Property agent；(3)Z1=Z2=CH2COOH.HN(CH2CH2OH)2, parents' head base anion surfactant；m1+m2=4,
n1+n2=35, m3+m4=3.
Together【Embodiment 2】, difference is to be adjusted with the sodium hydrate aqueous solution that 95% diethanolamine substitutes 30wt%
The pH=12 of section system, obtains required mixed surfactant S-3.
B, the S-3 prepared with oil field simulated formation water A difference preparation steps a and modified polyacrylamide (P1, copolymerization
AM/AMPS mol ratio=1/1, ten thousand) aqueous solution, the stirring 4 hours of viscosity-average molecular weight 1450, remaining is same【Embodiment 1】
B, the results are shown in Table shown in 4.The oil water interfacial tension of the S-3 aqueous solutions of variable concentrations, as shown in Figure 1.
It is c, same【Embodiment 1】C carries out laboratory simulation flooding test, the results are shown in Table shown in 4.
【Embodiment 4】
A, the anion nonionic surfactant structural formula for preparing are as follows, wherein, (1) Z1=H, Z2=H, it is non-from
Sub- surfactant；(2)Z1=H, Z2=CH2CH2CH2SO3Na, single parent's head base anion surfactant；(3)
Z1=Z2=CH2CH2CH2SO3Na, parents' head base anion surfactant；m1+m2=3, n1+n2=10, m3+m4=3.
325 grams of (1 mole) two lauryl amines, 9.7 grams of potassium hydroxide are added in the 2L pressure reactors equipped with agitating device,
Together【Embodiment 1】Eliminating water and nitrogen displacement are carried out, system reaction temperature is adjusted to into 120 DEG C and is slowly passed through 134.2 gram (3.05
Mole) oxirane, temperature is adjusted to 130 DEG C and is slowly passed through by control pressure≤0.60MPa again after reacting ethylene oxide terminates
585.8 grams of (10.1 moles) expoxy propane, control pressure≤0.60MPa is again adjusted to temperature after propylene oxide reaction terminates
140 DEG C are slowly passed through 134.2 grams of (3.05 moles) oxirane.After reaction terminates, 90 DEG C are cooled to, low-boiling-point substance are removed in vacuum,
Neutralization, dehydration, obtain two lauryl amine Polyethylene oxide (3) polyoxypropylene (10) Polyethylene oxide (3) ethers 1126.2 after cooling
Gram, yield 96.3%.
Two 584.5 grams of lauryl amine Polyethylene oxide (3) polyoxypropylene (10) Polyethylene oxide (3) ethers (0.5 mole) and 81.0
Gram (1.5 moles) Feldalat NM, 122 grams of (1.0 moles) sultone of 1,3- third and 800 milliliters of Ketocyclopentane be mixed in be furnished with mechanical agitation,
In the four-hole boiling flask of 5000 milliliters of thermometer and reflux condensing tube, back flow reaction is warming up to after adding 5 hours.Cooling,
With 30wt% phosphoric acids, divide and remove water and inorganic salt, solvent is evaporated off, mixture Jing high performance liquid chromatography (HPLC) for obtaining
Analysis, two lauryl amine Polyethylene oxide (3) polyoxypropylene (10) Polyethylene oxide (3) ethers and two lauryl amine Polyethylene oxide (3)
Polyoxypropylene (10) Polyethylene oxide (3) ether propane sulfonic acid and two lauryl amine Polyethylene oxide (3) polyoxypropylene (10) polyoxy second
The mass percent of the propane sulfonic acid of alkene (3) ether two is 1.2:27.8:71.0.Product is mixed with water, with 15% sodium hydroxide
The pH=13 of aqueous solution regulation system, obtains required mixed surfactant S-4.
B, the S-4 prepared with oil field simulated formation water B difference preparation steps a and hydrophobic associated polymer (P2, copolymerization
AM/AMPS/2- acrylamidos dodecyl sodium sulfonate mol ratio=1/0.5/0.002, the ten thousand) aqueous solution of viscosity-average molecular weight 1800,
Stirring 4 hours, remaining is same【Embodiment 1】B, the results are shown in Table shown in 5.The oil-water interfaces of the S-4 aqueous solutions of variable concentrations
Tension force, as shown in Figure 1.
It is c, same【Embodiment 1】C carries out laboratory simulation flooding test, and it is 95 DEG C that difference is displacement of reservoir oil temperature, is as a result seen
Shown in table 5.
【Embodiment 5】
It is a, same【Embodiment 4】A, difference is that the inventory of Feldalat NM is changed to into 1.25mol, the sultone of 1,3- third
Inventory is changed to 0.8mol, mixture Jing high performance liquid chromatography (HPLC) analysis for obtaining, two lauryl amine Polyethylene oxide (3)
Polyoxypropylene (10) Polyethylene oxide (3) ether and two lauryl amine Polyethylene oxide (3) polyoxypropylene (10) Polyethylene oxide (3)
The quality percentage of ether propane sulfonic acid and the propane sulfonic acid of two lauryl amine Polyethylene oxide (3) polyoxypropylene (10) Polyethylene oxide (3) ether two
Than for 17.6:29.2:53.2.Product is mixed with water, with the pH=13 of 15% sodium hydrate aqueous solution regulation system, is obtained
To required mixed surfactant S-5.
It is b, same【Embodiment 4】B, the results are shown in Table shown in 5.The oil water interfacial tension of the S-5 aqueous solutions of variable concentrations, is shown in
Shown in Fig. 1.
It is c, same【Embodiment 4】C carries out laboratory simulation flooding test, the results are shown in Table shown in 6.
【Embodiment 6】
A, the anion nonionic surfactant structural formula for preparing are as follows, wherein, (1) Z1=H, Z2=H, it is non-from
Sub- surfactant；(2)Z1=H, Z2=CH2CH2SO3Na, single parent's head base anion surfactant；(3)Z1=
Z2=CH2CH2SO3Na, parents' head base anion surfactant；m1+m2=6, n1+n2=25, m3+m4=15.
199 grams of (1 mole) tridecyl amines, 4.8 grams of potassium hydroxide are added in the 2L pressure reactors equipped with agitating device,
Together【Embodiment 1】Eliminating water and nitrogen displacement are carried out, system reaction temperature is adjusted to into 110 DEG C and is slowly passed through 266.2 gram (6.05
Mole) oxirane, control pressure≤0.60MPa after reacting ethylene oxide terminates, in 130 DEG C 1467.4 is slowly passed through
Temperature is adjusted to 140 DEG C by gram (25.3 moles) expoxy propane, control pressure≤0.60MPa again after propylene oxide reaction terminates
Slowly it is passed through 668.8 grams of (15.2 moles) oxirane.After reaction terminates, together【Embodiment 1】Post processing, obtains tridecyl amine and gathers
2421.2 grams of oxygen ethylene (6) polyoxypropylene (25) Polyethylene oxide (15) ether, yield 94.1%.
1286.5 grams of tridecyl amine Polyethylene oxide (6) polyoxypropylene (25) Polyethylene oxide (15) ether (0.5 mole) with 50 grams
(1.25 moles) sodium hydroxide, 83.3 grams of (0.5 mole) 2- ethyl chloride sodium sulfonates and 800 milliliters of toluene are mixed in be furnished with machinery and stirs
Mix, in 5000 milliliters of thermometer and reflux condensing tube of four-hole boiling flask, be heated to back flow reaction 6 hours.Cooling, takes
50 grams of homogeneous reaction liquid are divided and are removed water and inorganic salt with the acidifying of 35wt% sulphuric acid, and solvent is evaporated off, and the mixture Jing for obtaining is efficient
Liquid chromatograph (HPLC) is analyzed, tridecyl amine Polyethylene oxide (6) polyoxypropylene (25) Polyethylene oxide (15) ether and 13
Amine Polyethylene oxide (6) polyoxypropylene (25) Polyethylene oxide (15) ether ethyl sulfonic acid and tridecyl amine Polyethylene oxide (6) polyoxy third
The ethyl sulfonic acid mass percent of alkene (25) Polyethylene oxide (15) ether two is 48.5:25.1:26.4.Remaining untreated reactant liquor
Distillation removes solvent, adds water mix homogeneously to obtain the mixed surfactant S-6 of sodium chloride-containing and sodium hydroxide.
B, the S-6 prepared with oil field simulated formation water A difference preparation steps a and modified polyacrylamide (P1, copolymerization
AM/AMPS mol ratio=1/1, ten thousand) aqueous solution, the stirring 4 hours of viscosity-average molecular weight 1450, remaining is same【Embodiment 1】
B, the results are shown in Table shown in 6.The oil water interfacial tension of the S-6 aqueous solutions of variable concentrations, as shown in Figure 1.
It is c, same【Embodiment 1】C carries out laboratory simulation flooding test, the results are shown in Table shown in 7.
【Embodiment 7】
It is a, same【Embodiment 6】A, difference is that all reactant liquors are acidified, are washed, are steamed by reaction after terminating
After except solvent, the mixture for obtaining is mixed with water, with the pH=13 of the sodium hydrate aqueous solution regulation system of 30wt%, obtained
To required mixed surfactant S-7.
It is b, same【Embodiment 6】B, the results are shown in Table shown in 7.The oil water interfacial tension of the S-7 aqueous solutions of variable concentrations, is shown in
Shown in Fig. 1.
It is c, same【Embodiment 1】C carries out laboratory simulation flooding test, the results are shown in Table shown in 8.
【Embodiment 8】
A, the anion nonionic surfactant structural formula for preparing are as follows, wherein, (1) Z1=H, Z2=H is non-
Ionic surface active agent；(2)Z1=H, Z2=CH2CH2SO3H.N(CH2CH3)3, the work of single parent's head base anionic surface
Property agent；(3)Z1=Z2=CH2CH2SO3H.N(CH2CH3)3, parents' head base anion surfactant；m1+m2=6,
n1+n2=25, m3+m4=15.
Together【Embodiment 7】, difference is to adjust body with the sodium hydrate aqueous solution that 90% triethylamine amine substitutes 30wt%
The pH=13 of system, obtains required mixed surfactant S-8.
It is b, same【Embodiment 6】B, the results are shown in Table shown in 8.The oil water interfacial tension of the S-8 aqueous solutions of variable concentrations, is shown in
Shown in Fig. 1.
It is c, same【Embodiment 1】C carries out laboratory simulation flooding test, the results are shown in Table shown in 9.
【Embodiment 9】
Together【Embodiment 1】, difference is that polymer adopts hydrophobic associated polymer (P2, copolymerization AM/AMPS/2-
Acrylamido dodecyl sodium sulfonate mol ratio=1/0.5/0.002, viscosity-average molecular weight 1,800 ten thousand), displacement of reservoir oil temperature be 85 DEG C,
75 DEG C and 95 DEG C, the results are shown in Table shown in 10～12.
【Embodiment 10】
Will【Embodiment 1】With【Embodiment 9】The poly- table binary system displacement composition for preparing loads in 50 milliliters of ampoule bottles,
Vacuum goes to be put in baking oven after sealing carries out heat stabilization test, and contrasts with the polymer phase of same concentrations, sees figure
Shown in 3a～d；After determining different ageing times, oil-water interfaces of the poly- table binary system displacement composition to oil field dewatered oil
Power, and compare with the surfactant of same concentrations, as shown in Fig. 4 a～d.
【Comparative example 1】
A certain amount of contrast surfactant is dissolved with simulation the saline A or B of different salinities, contrast surface is determined and is lived
Property oil water interfacial tension of the agent solution to dewatered oil, and the surfactant prepared with corresponding embodiment compared with, as a result see
Shown in table 13, wherein the concentration of surfactant is 0.1wt%.
In table 13, S-9 is dodecyl polyaniline Polyethylene oxide (4) polyoxypropylene (35) Polyethylene oxide (3) ether；S-10
For two lauryl amine Polyethylene oxide (3) polyoxypropylene (10) Polyethylene oxide (3) ethers；S-11 is tridecyl amine Polyethylene oxide (6)
Polyoxypropylene (25) Polyethylene oxide (15) ether.
【Comparative example 2】
Together【Embodiment 1】、【Embodiment 4】With【Embodiment 6】, difference is, expoxy propane and epoxy second
Alkane is not successively reacted step by step, but oxirane and expoxy propane are pre-mixed into latter step by the amount needed for polymerization
Reacted, remaining is identical, obtained mixed surfactant S-12～S-14.Determine its interface to oil field dewatered oil
Power, the results are shown in Table shown in 14, and wherein the concentration of surfactant is 0.1wt%.
【Comparative example 3】
Together【Embodiment 2】, difference is that the consumption of sodium chloroacetate is changed to 349.5 grams of (3 moles), use of sodium hydroxide
Amount is changed to 100 grams (2.5 moles), and remaining is identical, and product Jing (HPLC) analyses obtained after solvent, detergent alkylate is evaporated off
Amine Polyethylene oxide (4) polyoxypropylene (35) Polyethylene oxide (3) ether oxalic acid and dodecyl polyaniline Polyethylene oxide (4)
The mass ratio of polyoxypropylene (35) Polyethylene oxide (3) ether is 1:0.013.Sodium hydroxide with concentration as 30wt% is adjusted
The pH=12 of system, obtains surfactant S-15 after mix homogeneously.Its oil water interfacial tension to dewatered oil is determined, and
Compared with S-2, the concentration of surfactant is 0.1wt%, be the results are shown in Table shown in 14.
【Comparative example 4】
Together【Embodiment 1】, difference is that (viscosity-average molecular weight is 2500 with high molecular wt. anionic polyacrylamide P3
Ten thousand) modified polyacrylamide P1 is substituted, remaining is identical, as a result as shown in 15.
Table 1
| Simulation saline | Ca2+(mg/L) | Mg2+(mg/L) | TDS(mg/L) |
| A | 1500 | 525 | 75000 |
| B | 5000 | 1500 | 255000 |
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
Table 8
Table 9
(the displacement of reservoir oil temperature of table 10：85℃)
(the displacement of reservoir oil temperature of table 11：75℃)
(the displacement of reservoir oil temperature of table 12：95℃)
Table 13
| Surfactant | Saline | Temperature (DEG C) | IFT(mN/m) |
| S-1 | A | 85 | 0.00077 |
| S-2 | A | 85 | 0.00053 |
| S-3 | A | 85 | 0.00112 |
| S-9 | A | 85 | 2.3455 |
| S-4 | B | 95 | 0.00129 |
| S-10 | B | 95 | 3.5512 |
| S-5 | A | 85 | 0.00071 |
| S-10 | A | 85 | 2.7796 |
| S-6 | A | 85 | 0.00056 |
| S-7 | A | 85 | 0.00087 |
| S-8 | A | 85 | 0.00145 |
| S-11 | A | 85 | 1.04522 |
Table 14
| Surfactant | Saline | Temperature (DEG C) | IFT(mN/m) |
| S-1 | A | 85 | 0.00077 |
| S-12 | A | 85 | 0.00898 |
| S-4 | B | 95 | 0.00129 |
| S-13 | B | 95 | 0.01255 |
| S-6 | A | 85 | 0.00056 |
| S-14 | A | 85 | 0.00733 |
| S-2 | A | 85 | 0.00053 |
| S-15 | A | 85 | 3.7764 |
Table 15
Claims (10)
1. a kind of displacement composition, in terms of mass fraction, including following components：
1) 1 part of surfactant；
2) 0～50 part and more than 0 part of polymer；
The surfactant is anion nonionic surfactant, including the anion surfactant shown in the nonionic surfactant shown in formula (1) and formula (2), the anion surfactant shown in (3), the anion surfactant shown in nonionic surfactant, formula (2) wherein shown in formula (1), the mass ratio of the anion surfactant shown in (3) are (0.01～5)：1：(0.1～5)；
R1And R2And R3It is independently chosen from C4～C40Aliphatic group or by C4～C30The aryl that the saturation of straight or branched and unsaturated alkyl replace；M1, m2, m3 and m4 are independently selected from 0～50, but m1 and m2, m3 and m4 can not be simultaneously 0；N1 and n2 are independently selected from 0～100, but n1 and n2 can not be simultaneously 0；R1, r2, r3 and r4 are independently selected from 0～50, but r1 and r2, r3 and r4 can not be simultaneously 0；S1 and s2 are independently selected from 0～100, but s1 and s2 can not be simultaneously 0；P1, p2, p3 and p4 are independently selected from 0～50, but p1 and p2, p3 and p4 can not be simultaneously 0；Q1 and q2 are independently selected from 0～100, but q1 and q2 can not be simultaneously 0；Z1And Z2And Z3Respectively-R01Y1,-R02Y2,-R03Y3；R01And R02And R03Selected from C1～C5Alkylidene or hydroxyl substituted alkylene, Y1And Y2And Y3Selected from SO3M or COOW, M and W are independently selected from hydrogen, alkali metal or by formula NR4(R5)(R6)(R7) shown in group, R4、R5、R6、R7To be independently selected from H, (CH2)pOH or (CH2)qCH3, any integer in any integer, q=0～5 in p=2～4.
2. displacement composition according to claim 1, it is characterised in that the R1Or R2Or R3In at least one be C6～C20Alkyl or by C8～C16Alkyl-substituted phenyl.
3. displacement composition according to claim 1, it is characterised in that the p=2, q=0～1；M1+m2=2～10, m3+m4=2～20, n1+n2=5～40；And/or r1+r2=2～10, r3+r4=2～20, s1+s2=5～40 and/or p1+p2=2～10, p3+p4=2～20, q1+q2=5～40.
4. displacement composition according to claim 1, it is characterised in that the polymer is at least one in xanthan gum, hydroxymethyl cellulose, hydroxyethyl cellulose, anion-polyacrylamide, modified polyacrylamide, hydrophobic associated polymer, polymer microballoon.
5. displacement composition according to claim 4, it is characterized in that the modified polyacrylamide is formed by acrylamide, temperature-resistant anti-salt monomer copolymerization, acrylamide is (0.1～40) with the mol ratio of temperature-resistant anti-salt monomer: 1, hydrophobic associated polymer is formed by acrylamide, temperature-resistant anti-salt monomer and hydrophobic monomer copolymerization, and the mol ratio of acrylamide, temperature-resistant anti-salt monomer and hydrophobic monomer is 1：(0.1～40)：(0.001～0.05).
6. displacement composition according to claim 5, it is characterised in that the viscosity-average molecular weight of the modified polyacrylamide is 800～25,000,000, the viscosity-average molecular weight of hydrophobic associated polymer is 1000～25,000,000.
7. the preparation method of the arbitrary described displacement composition of claim 1～6, comprises the following steps：
A, in the presence of base catalyst, R1NH2Obtain R with aequum oxirane, expoxy propane, reacting ethylene oxide successively1N((CH2CH2O)m1(CHCH3CH2O)n1(CH2CH2O)m3H)((CH2CH2O)m2)(CHCH3CH2O)n2(CH2CH2O)m4H)；
B, the product that step a is obtained and X1R01Y01And alkali metal hydroxide or alkali metal alcoholates are with mol ratio 1:(1～2):(1～4) in a solvent, in 50～120 DEG C of reactions of reaction temperature the single parent's head base anion surfactant and the parents' head base anionic surfactant mixture described in formula (5) containing the nonionic surfactant shown in formula (1) and described in (4) is obtained for 3～15 hours；
Wherein, Z01For-R02Y01；Y01Selected from SO3M1Or COOW1, M1And W1For alkali metal, X1Selected from chlorine, bromine or iodine.
C, based on the mass fraction, the surfactant mixture that step b is obtained and the polymer mixed are uniform, obtain described displacement composition.
8. the preparation method of displacement composition according to claim 7, is characterized in that the R described in step b1N((CH2CH2O)m1(CHCH3CH2O)n1(CH2CH2O)m3H)((CH2CH2O)m2)(CHCH3CH2O)n2(CH2CH2O)m4H):X1R01Y01:The mol ratio of alkali metal hydroxide or alkali metal alcoholates is 1:(1～2):(1～3).
9. a kind of preparation method of the arbitrary described displacement composition of claim 1～6, comprises the following steps：
B product that () obtains claim 7 step a and the sultone of 1,3- third and alkali metal hydroxide or alkali metal alcoholates are with mol ratio 1:(1～2):(1～4) in a solvent, in 50～120 DEG C of reactions of reaction temperature the parents' head base anionic surfactant mixture described in single parent's head base anion surfactant and formula (7) containing the nonionic surfactant shown in formula (1) and described in formula (6) is obtained for 3～15 hours；
Wherein Z '01For-CH2CH2CH2SO3M2；M2For alkali metal.
C () based on the mass fraction, the surfactant mixture that step (b) is obtained is uniform with the polymer mixed, obtain described displacement composition.
10. the preparation method of displacement composition according to claim 9, is characterized in that the R described in step (b)1N((CH2CH2O)m1(CHCH3CH2O)n1(CH2CH2O)m3H)((CH2CH2O)m2)(CHCH3CH2O)n2(CH2CH2O)m4H):The sultone of 1,3- third:The mol ratio of alkali metal hydroxide or alkali metal alcoholates is 1:(1～2):(1～3).
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