CN103740354B - A surfactant composition used for tertiary oil recovery and a preparation method thereof - Google Patents
A surfactant composition used for tertiary oil recovery and a preparation method thereof Download PDFInfo
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- 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
Abstract
The invention relates to a surfactant composition used for tertiary oil recovery and a preparation method thereof, mainly solving a problem of the low oil displacement efficiency of surfactants at present in tertiary oil recovery processes and problems of damage to stratums and oil wells, equipment and pipeline corrosion and difficult demulsification which are caused by inorganic bases in oil displacement systems. According to the technical scheme adopted by the surfactant composition and the preparation method, the surfactant composition comprises a cationic surfactant and an anionic-nonionic surfactant, wherein the cationic surfactant is at least one selected from a quaternary ammonium salt or a quaternary amine alkali, the anionic-nonionic surfactant is at least one of an amidogen ether carboxylate or an amidogen ether sulphonate, and the molar ratio of the cationic surfactant to the anionic-nonionic surfactant is 1:0.01-1:100. By the technical scheme, the problems are solved well and the surfactant composition can be used in enhanced oil recovery of an oil field.
Description
Technical field
The present invention relates to a kind of surface activator composition for tertiary oil recovery and preparation method thereof.
Background technology
With the increase of world energy sources demand, the rational exploitation and utilization of oil has caused the very big attention of people, to oil
Yield and production efficiency requirement also more and more higher.Realize the high-efficiency mining of petroleum resources, for raising crude output not
Only there is realistic meaning, with more important strategic importance.Conventional oil production method（Once with secondary method）Normally only produce former
The 1/3 of oily oil in place, the crude oil that there is also about 2/3 fails extraction, therefore in the case that energy day is becoming tight, improves tar productivity
The key subjects of oil exploitation research are become.Tertiary oil recovery technology is then a kind of effective method improving tar productivity, can divide
For four big class：One is that heating power drives, including steam drive, combustion in situ etc.；Two is that mixed phase drives, including CO2Mixed phase, hydrocarbon mixed phase and other
Noble gases mixed phase drives；Three is chemical flooding；Four is microbe oil production, drives including biopolymer, MICROBIAL SURFACTANT.Change
Learning drive is technology that is extremely important in intensified oil reduction and implementing on a large scale, including polymer flooding, surfactant flooding, caustic waterflooding etc.
And the multiple combination technology of polymer, alkali, surfactant.The effect of chemical flooding is the knot of physical action and chemical action
Really, physical action refers to the effect that involves of displacing fluid, and chemical action refers to the microcosmic oil drive effect of displacing fluid.Chemical action
Core is to reduce the interfacial tension of displacing fluid and crude oil.Surfactant is due to having oleophylic concurrently（Hydrophobic）With hydrophilic（Oleophobic）Property
Matter, when surfactant is dissolved in water, molecule is mainly distributed on oil-water interfaces, can significantly reduce oil water interfacial tension.Oil
The reduction of water interfacial tension means that surfactant system can overcome the cohesiveness between crude oil, and larger oil droplet is dispersed into little oil
Drip, thus improving crude oil to flow through percent of pass during pore throat.The oil displacement efficiency of surfactant is also manifested by making the rock table of oleophylic
Face wettability reversal, emulsification of crude oil, the raising effect such as surface charge density and oil droplet coalescence, this is surfactant in chemical flooding
The reason play very important effect in technology.
Surface active agent for tertiary oil recovery adopts Recompounded multielement system mostly at present, comprises non-ionic surfactant simultaneously
Agent and ionic surfactant, are additionally added the auxiliary agents such as alkali and alcohol in part formulation.As patent CN101024764A provides one
The surfactant of kind of oil-field thick-oil well, this activating agent be by water, piece alkali, ethanol, Oleic acid, alkylphenol polyoxyethylene, ten
Dialkyl benzene sulfonic acids sodium forms.For another example patent CN1458219A discloses a kind of surfactant polymer of tertiary oil recovery application
Pure binary ultralow interfacial tension combination flooding formula, used in it, surfactant is petroleum sulfonate or with petroleum sulfonate is
Host adds diluent and the complexed surfactant of other surfactant compound, and the percentage by weight of its component is mahogany acid
Salt 50～100%, alkylsulfonate 0～50%, carboxylate 0～50%, alkylaryl sulfonatess 0～35%, low-carbon alcohols 0～20%.Again
As patent CN1394935 has invented a kind of chemical oil displacement agent, it mainly includes sodium octylbenzene sulfonate anion surfactant, table
Face activity agent aid, surfactant synergist, surface active agent solubilization agent.This oil displacement agent can significantly reduce the knot of viscous crude
Structure viscosity, can reduce oil water interfacial tension simultaneously, thus improving oil recovery factor.
However, above-mentioned surface active agent for tertiary oil recovery still suffers from more problem, mainly surfactant activity is poor, drive
Oily efficiency is low, simultaneously because surfactant system is excessively complicated, thus Produced Liquid breakdown of emulsion is difficult, and sewage disposal difficulty is big；Separately
Outward because oil displacement system contains inorganic base, injury is brought to stratum and oil well, causes the problems such as etching apparatus and pipeline, and due to
Inorganic base can seriously reduce the viscosity of polymer, have to greatly improve the concentration of polymer for reaching required viscosity, make
Oil recovery integrated cost improves；The high temperature resistance of surfactant, high salt tolerance, anti-high salinity limited in one's ability.
It is known that anion surfactant, such as petroleum sulfonate, petroleum carboxylate, alkylbenzenesulfonate etc. are at present
During being widely used in tertiary oil recovery, and cationic surfactant is easily adsorbed or produced by stratum precipitation because of it, therefore fall
The ability of low oil water interfacial tension, is generally not used for tertiary oil recovery.Because cationic and anionic surfactant mixes close to equal proportion
During conjunction, its aqueous solution easily forms precipitation, thus lead to cationic and anionic surfactant mixed system not only to become in the application joining
5 taboos, and correlation theory research is also more delayed.Research in recent years finds, cationic and anionic surfactant mixed system
Aqueous solution has a lot of anomalous properties, such as because cationic and anionic surfactant has strong electrostatic interaction in aqueous
Interaction and between hydrophobic carbon chain, promotes two kinds of band difference interionic associations of charged surfactant, in the solution
It is readily formed micelle, the higher surface activity of the single surfactant of producing ratio.Additionally, cationic and anionic surfactant mixing
System can obviously reduce absorption loss on rock core for the cationic surfactant, thus cation surface activating can be significantly reduced
The inherent shortcoming of agent.
Gong Yujun etc.（See 2 months the 1st phases Northwest University's journal (natural science edition) of volume 30 in 2000,28～31）Research
Think cetyl trimethylammonium bromide（CTAB）With sodium lauryl sulphate（SDS）Mixed system has solubilization.In stone
In oily recovery process, using solubilization can " displacement of reservoir oil ", under the oil wash that will stick on the sandstone of rock stratum, thus improve oil adopting
Yield.Huang Hongdu etc.（See petroleum gas journal in August, 2007 the 4th phase of volume 29,101～104）Have studied petroleum sulfonate,
The anion surfactants such as petroleum carboxylate, alkylbenzenesulfonate and cetyl trimethylammonium bromide, alkali compound system
Interfacial tension simultaneously draws to draw a conclusion：The addition of cationic surfactant makes petroleum carboxylate, alkylbenzenesulfonate, oil sulphur
The interfacial activity of hydrochlorate is improved.
The studies above result shows anions and canons Surfactant Mixing Systems for reduction oil water interfacial tension, raising
Oil displacement efficiency has certain effect.But the former result of study shows that its interface performance still has much room for improvement, and the latter is in system
Still employ alkali, thus alkali cannot be avoided to bring injury, etching apparatus and pipeline and breakdown of emulsion difficulty etc. to ask on stratum and oil well
Topic.In addition above-mentioned system is easier to generate precipitation, is unfavorable for practical application.
For this reason, one aspect of the present invention absorbs has used for reference forefathers with regard to anions and canons Surfactants mixed system research knot
Really, on the other hand adopt Anionic-nonionic surfactant to replace traditional anion surfactant, overcome yin, yang
When ionic surface active agent compounds the shortcomings of easily precipitate, invented for tertiary oil recovery process cationic surfactant and
Anionic-nonionic surface activator composition.
Content of the invention
One of the technical problem to be solved is existing surfactant oil displacement efficiency during tertiary oil recovery
Difference, simultaneously because oil displacement system contains inorganic base, brings injury, etching apparatus and pipeline and breakdown of emulsion difficult to stratum and oil well
Problem, provides a kind of surface activator composition, and said composition has that interfacial activity is high, washing oil ability is strong, system simple, will not
Injury is brought to stratum and oil well, will not etching apparatus and pipeline and the advantage not resulting in breakdown of emulsion difficulty.
The two of the technical problem to be solved are to provide a kind of surface corresponding with solving technical problem one to live
The preparation method of property agent compositionss.
For solving one of above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of table for tertiary oil recovery
Face surfactant composition and preparation method thereof, including cationic surfactant and Anionic-nonionic surfactant, described
The mol ratio of cationic surfactant and Anionic-nonionic surfactant be 1: 0.01～1: 100, its cationic
Surfactant is selected from least one in quaternary ammonium salt or quaternary amine alkali, and Anionic-nonionic surfactant is amidogen ether carboxylate
Or at least one in amidogen ether sulfonate；
The general molecular formula of amidogen ether carboxylate is：
The general molecular formula of amidogen ether carboxylate is：
.
In technique scheme, cationic surfactant preferred version is selected from tetra-alkyl ammonium chloride or tetraalkyl hydrogen-oxygen
Change at least one in ammonium；R preferred version is at least one in alkyl or aryl；R preferred version is H, in alkyl or aryl
Any one；R " preferred version is C1～C5Alkyl or replace alkyl in any one；The ethyoxyl degree of polymerization, propoxyl group
Degree of polymerization preferred version is any one integer or decimal in 0～20；Cation M preferred version be selected from Na, K, Mg, Ca or
NH4 +In any one；Cationic surfactant with the mol ratio preferred version of Anionic-nonionic surfactant is
1: 0.1～1: 10.
For solving the two of above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of table for tertiary oil recovery
The preparation method of face surfactant composition, comprises the following steps：
A) organic amine, catalyst and required oxirane, expoxy propane are added reactor, react in 100～200 DEG C
1～20 hour；Then add sulfonated reagent or carboxylating reagent, wherein organic amine：The mol ratio of sulfonated reagent or carboxylating reagent is
1：1～4, continue reaction 1～20 hour in 50～200 DEG C, then add hydrochloric acid to be neutralized to pH<3, and carry out oil-water separation, oil
It is added to alkali liquor to be neutralized, finally obtain aliphatic amine polyoxyethylene/polyoxypropylene ether carboxylate, sulfonate；
B) the Anionic-nonionic surfactant obtaining cationic surfactant and step a) is dissolved separately in
In water, then according to mol ratio 1: 0.1～1: 10 mix homogeneously, obtain required compositionss.
In technique scheme, described catalyst is any one in NaOH, KOH；Described sulfonated reagent is hydroxyl
Base sulfonic acid and its salt, halogenosulfonic acid and its salt；Described carboxylating reagent is halogenated carboxylic acid and its salt.
The surface activator composition one side of the present invention due to anions and canons surfactant opposite charges polar group it
Between strong electrostatic attraction effect so that surfactant molecule increases in adsorbed on interfaces amount, critical micelle concentration significantly drops
Low, thus having the incomparable high surface of single surfactant；Simultaneously because surface activator composition superelevation
Interfacial activity, its aqueous solution can form ultralow interfacial tension with crude oil, thus effectively overcoming the cohesiveness between crude oil, is conducive to former
Oil-out, and then oil displacement efficiency is greatly improved.Another aspect surface activator composition can change the moistening on oil reservoir surface
Property, if the cationic surfactant in compositionss is by the electronegative Interaction of substituents on a solid surface with absorption,
Make it be desorbed, make glossy wet structure change into neutral wetting or water-wet surface, reduce the adhesion in the surface of solids for the crude oil
Work(, thus be conducive to the stripping of crude oil.Anions and canons surfactant mixed solution has solubilization to crude oil simultaneously, can
To wash down sticking to the crude oil on the sandstone of rock stratum further, improve oil recovery factor.
Adopt the surface activator composition of the present invention during tertiary oil recovery, there is interfacial activity high：Surfactant
Compositionss consumption be 0.01～0.05% under the conditions of remain to and underground crude oil formed 10-3～10-4MN/m ultralow interface open
Power；Washing oil ability is strong：Surface activator composition is to the washing oil rate of crude oil more than 40%；Surface activator composition system is simple.
Because oil displacement system does not contain inorganic base, thus avoid the injury that when scene is applied, inorganic base causes to stratum, equipment is caused
Corrosion and the difficult problem of the breakdown of emulsion that thus causes, achieve preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
【Embodiment 1】
By lauryl amine, KOH according to mol ratio 1：2 addition reactors, stir 30 minutes, then add required epoxy
Ethane, expoxy propane, in 200oC reacts 1 hour；Then according to lauryl amine and carboxylating reagent mol ratio 1：1 addition chloroethene
Acid, in 50oC adds hydrochloric acid to be neutralized to pH after continuing reaction 20 hours<3, stratification, oil phase adds 30%KOH aqueous solution to carry out
Neutralization, obtains Anionic-nonionic surfactant.
Will be molten respectively for the Anionic-nonionic surfactant of stearyl dimethyl benzyl ammonium chloride and present invention preparation
In Xie Yushui, stir 30 minutes, be configured to 0.3% aqueous solution, then by above-mentioned surfactant according to cation：Anion-non-
Ionic surface active agent mol ratio 1: 0.1 mix homogeneously, obtains surface activator composition 1, and its composition, structure are shown in Table 1.
【Embodiment 2】
By adjacent phenylaniline, NaOH according to mol ratio 1：6 addition reactors, stir 30 minutes, then add required ring
Oxidative ethane, expoxy propane, in 100oC reacts 20 hours；Then according to adjacent phenylaniline and sulfonated reagent mol ratio 1：4 addition chlorine
Sulfonic acid, in 120oC adds hydrochloric acid to be neutralized to pH after continuing reaction 14 hours<3, stratification, oil phase adds 30%NaOH aqueous solution
It is neutralized, obtain Anionic-nonionic surfactant.
The Anionic-nonionic surfactant of tetrabutylammonium chloride and present invention preparation is dissolved in water, stirs
Mix 30 minutes, be configured to 0.3% aqueous solution, then by above-mentioned surfactant according to cation：Live in Anionic-nonionic surface
Property agent mol ratio 1: 0.5 mix homogeneously, obtain surface activator composition 2, its composition, structure be shown in Table 1.
【Embodiment 3】
By cyclohexylamine, NaOH according to mol ratio 1：4 addition reactors, stir 30 minutes, then add required epoxy second
Alkane, expoxy propane, in 160oC reacts 2 hours；Then according to cyclohexylamine and sulfonated reagent mol ratio 1：2.5 addition chlorine amyl group sulphurs
Sour sodium, in 120oC adds hydrochloric acid to be neutralized to pH after continuing reaction 14 hours<3, stratification, oil phase adds 30%NaOH aqueous solution
It is neutralized, obtain Anionic-nonionic surfactant.
The Anionic-nonionic surfactant of four octyl group ammonium chloride and present invention preparation is dissolved in water, stirs
Mix 30 minutes, be configured to 0.3% aqueous solution, then by above-mentioned surfactant according to cation：Live in Anionic-nonionic surface
Property agent mol ratio 1: 10 mix homogeneously, obtain surface activator composition 3, its composition, structure be shown in Table 1.
【Embodiment 4】
Will be to amino-anilide, NaOH according to mol ratio 1：4 addition reactors, stir 30 minutes, then add required ring
Oxidative ethane, expoxy propane, in 160oC reacts 16 hours；Then according to amino-anilide and sulfonated reagent mol ratio 1：2.5 plus
Enter 3- chlorine-2-hydroxyl propanesulfonate, in 180oC adds hydrochloric acid to be neutralized to pH after continuing reaction 18 hours<3, stratification, oil phase
Add 30%NaOH aqueous solution to be neutralized, obtain Anionic-nonionic surfactant.
The Anionic-nonionic surfactant of decyl triethylammonium hydroxide and present invention preparation is dissolved separately in water
In, stir 30 minutes, be configured to 0.3% aqueous solution, then by above-mentioned surfactant according to cation：Anionic-nonionic table
Face activating agent mol ratio 1: 6 mix homogeneously, obtains surface activator composition 4, and its composition, structure are shown in Table 1.
【Embodiment 5】
By hexadecylamine, NaOH according to mol ratio 1：2 addition reactors, stir 30 minutes, then add required ring
Oxidative ethane, expoxy propane, in 150oC reacts 10 hours；Then according to hexadecylamine and carboxylating reagent mol ratio 1：1.5 adding
Sodium chloroacetate, in 60oC adds hydrochloric acid to be neutralized to pH after continuing reaction 14 hours<3, stratification, oil phase adds 10%Ca
(HCO3)2Aqueous solution is neutralized, and obtains Anionic-nonionic surfactant.
The Anionic-nonionic surfactant of phenyl trimethicone ammonium chloride and present invention preparation is dissolved separately in water
In, stir 30 minutes, be configured to 0.3% aqueous solution, then by above-mentioned surfactant according to cation：Anionic-nonionic table
Face activating agent mol ratio 1: 1.4 mix homogeneously, obtains surface activator composition 5, and its composition, structure are shown in Table 1.
【Embodiment 6】
By octadecylamine, NaOH according to mol ratio 1：2 addition reactors, stir 30 minutes, then add required ring
Oxidative ethane, expoxy propane, in 150oC reacts 10 hours；Then according to octadecylamine and carboxylating reagent mol ratio 1：1.5 adding
Sodium chloroacetate, in 70oC adds hydrochloric acid to be neutralized to pH after continuing reaction 12 hours<3, stratification, oil phase adds 10%Mg
(HCO3)2Aqueous solution is neutralized, and obtains Anionic-nonionic surfactant.
The Anionic-nonionic surfactant of benzyltriethylammoinium chloride and present invention preparation is dissolved separately in water
In, stir 30 minutes, be configured to 0.3% aqueous solution, then by above-mentioned surfactant according to cation：Anionic-nonionic table
Face activating agent mol ratio 1: 1.8 mix homogeneously, obtains surface activator composition 6, and its composition, structure are shown in Table 1.
【Embodiment 7】
By oleyl amine, NaOH according to mol ratio 1：3 addition reactors, stir 30 minutes, then add required oxirane,
Expoxy propane, in 150oC reacts 10 hours；Then according to oleyl amine and sulfonated reagent mol ratio 1：3 addition sodium isethionates, in
180oC adds hydrochloric acid to be neutralized to pH after continuing reaction 4 hours<3, stratification, oil phase adds ammonia to be neutralized, obtain cloudy from
Son-nonionic surfactant.
The Anionic-nonionic surfactant of Dodecyl trimethyl ammonium chloride and present invention preparation is dissolved separately in
In water, stir 30 minutes, be configured to 0.3% aqueous solution, then by above-mentioned surfactant according to cation：Anionic-nonionic
Surfactant molar ratio 1: 2.5 mix homogeneously, obtains surface activator composition 7, and its composition, structure are shown in Table 1.
【Embodiment 8】
By octadecylamine, NaOH according to mol ratio 1：4 addition reactors, stir 30 minutes, then add required ring
Oxidative ethane, expoxy propane, in 140oC reacts 12 hours；Then according to octadecylamine and sulfonated reagent mol ratio 1：3 addition hydroxyls
Ethylsulfonic acid sodium, in 160oC adds hydrochloric acid to be neutralized to pH after continuing reaction 8 hours<3, stratification, oil phase adds 10%Mg
(HCO3)2Aqueous solution is neutralized, and obtains Anionic-nonionic surfactant.
The Anionic-nonionic surfactant of hexadecyltrimethylammonium chloride and present invention preparation is dissolved separately in
In water, stir 30 minutes, be configured to 0.3% aqueous solution, then by above-mentioned surfactant according to cation：Anionic-nonionic
Surfactant molar ratio 1: 8 mix homogeneously, obtains surface activator composition 8, and its composition, structure are shown in Table 1.
【Embodiment 9】
By methylphenylamine, NaOH according to mol ratio 1：3 addition reactors, stir 30 minutes, then add required ring
Oxidative ethane, expoxy propane, in 150oC reacts 10 hours；Then according to methylphenylamine and carboxylating reagent mol ratio 1：1.5 adding
Sodium chloroacetate, in 80oC adds hydrochloric acid to be neutralized to pH after continuing reaction 8 hours<3, stratification, oil phase adds 30%NaOH water-soluble
Liquid is neutralized, and obtains Anionic-nonionic surfactant.
The Anionic-nonionic surfactant of dioctadecyl dimethyl ammonium chloride and present invention preparation is dissolved respectively
Yu Shuizhong, stirs 30 minutes, is configured to 0.3% aqueous solution, then by above-mentioned surfactant according to cation：Anion-non-from
Sub- surfactant molar ratio 1: 4 mix homogeneously, obtains surface activator composition 9, and its composition, structure are shown in Table 1.
【Embodiment 10】
By cyclohexylamine, NaOH according to mol ratio 1：3 addition reactors, stir 30 minutes, then add required epoxy second
Alkane, expoxy propane, in 160oC reacts 10 hours；Then according to cyclohexylamine and carboxylating reagent mol ratio 1：1.5 addition monoxones
Sodium, in 80oC adds hydrochloric acid to be neutralized to pH after continuing reaction 8 hours<3, stratification, oil phase adds 30%NaOH aqueous solution to carry out
Neutralization, obtains Anionic-nonionic surfactant.
The Anionic-nonionic surfactant of tetraethylammonium chloride and present invention preparation is dissolved in water, stirs
Mix 30 minutes, be configured to 0.3% aqueous solution, then by above-mentioned surfactant according to cation：Live in Anionic-nonionic surface
Property agent mol ratio 1: 1.3 mix homogeneously, obtain surface activator composition 10, its composition, structure be shown in Table 1.
【Embodiment 11】
The 0.30wt% surface activator composition that prepare embodiment 6 and 0.15wt% polyacrylamide (molecular weight 2600
Ten thousand) aqueous solution uniformly, obtains a kind of Polymer Used For Oil Displacement-surfactant complex.
Table 1 surface activator composition composition and structure
【Embodiment 12】Surface activator composition interface performance is tested
Measure surfactant oil displacement compositionss and Shuanghe Oil Field with TX-500C rotating interfacial tensimeter5-
11 series of strata oil water interfacial tensions.Surface activator composition consumption：0.3%, temperature of the measurement is 81oC, stratum water is NaHCO3Type,
Salinity is 7947mg/L, chloride ion content 2002 mg/L, Ca2+Content 20 mg/L, Mg2+Content 12.2 mg/L.
Table 2 surface activator composition and Shuan He oil field5-11 series of strata oil water interfacial tension
| Embodiment | Interfacial tension (mN/m) |
| 1 | 0.0086 |
| 2 | 0.0074 |
| 3 | 0.0068 |
| 4 | 0.0056 |
| 5 | 0.0020 |
| 6 | 0.0010 |
| 7 | 0.0042 |
| 8 | 0.0018 |
| 9 | 0.0008 |
| 10 | 0.0007 |
| 11 | 0.0052 |
As shown in Table 2, the surface activator composition of embodiment 1～10 preparation has good interface for Henan Oil Field
Performance.Embodiment 11 shows, after the surface activator composition of present invention preparation is compounded with polymer, its interface performance is still good
Good.
Surface activator composition prepared by embodiment 10 is configured to variable concentrations, respectively test and Shuanghe Oil Field5-11 series of strata oil water interfacial tension, the results are shown in Table 3.
Table 3 variable concentrations surface activator composition 10 and Shuanghe Oil Field5-11 series of strata oil water interfacial tension
| Dosage of surfactant (%) | 0.01 | 0.02 | 0.05 | 0.1 | 0.2 | 0.3 |
| Interfacial tension (MN/m) | 0.01 | 0.008 | 0.005 | 0.002 | 0.0009 | 0.0007 |
The above results show, surface activator composition of the present invention has very high oil-water interfaces for Henan Oil Field crude oil
Activity.
Measure surface activator composition and the Central Plains of embodiment 6 preparation with TX-500C rotating interfacial tensimeter again
Oil extraction in oil field three factory's oil water interfacial tension.Temperature of the measurement is 80oC, formation water salinity is 79439mg/L, Ca2+Content 592
Mg/L, Mg2+Content 2871mg/L, dosage of surfactant is 0.3%.Oil water interfacial tension is 0.002mN/m, shows the present invention
Surfactant not only for low mineralization oil reservoir, simultaneously for high temperature and high salt oil deposit, still there is good interface performance,
Have the advantages that the scope of application is wide.
【Embodiment 13】Surface activator composition washing oil aptitude tests
Take Shuanghe Oil Field5-11 series of strata oil-sand, according to oil：Sand=1：4 (weight ratios) are 81oAging 7 days of C, every 2 is little
When stir 5 minutes；Then take out above-mentioned aging after oil-sand 5g, press oil-sand with 0.3% surface activator composition solution：Molten
Liquid=1：10 mix homogeneously, after aging 48 hours under reservoir temperature, with the crude oil in petroleum ether extraction solution, use 50ml colorimetric
Pipe constant volume, spectrophotometer colorimetric analysiss at wavelength 430nm.Dense using standard curve gauging surface activator solution Crude Oil
Degree.
Table 4 surface activator composition washing oil result
| Embodiment | Washing oil rate % |
| 1 | 51.5 |
| 2 | 53.2 |
| 3 | 54.8 |
| 4 | 57.4 |
| 5 | 65.3 |
| 6 | 67.2 |
| 7 | 64.9 |
| 8 | 63.5 |
| 9 | 68.1 |
| 10 | 67.3 |
【Embodiment 14】Surface activator composition Oil Displacing Capacity is studied
It is 30 centimetres in length, a diameter of 2.5 centimetres, permeability is 1.5 microns2Rock core on carry out oil displacement test.First
Use Shuanghe Oil Field5-11 series of strata stratum water drive is to aqueous 92 %, the surface activity of tuberculosiss 0.3pv (rock pore volume)
After agent compositionss, water drive to aqueous 100%, improves oil recovery factor and the results are shown in Table 5.
Table 5 surface activator composition oil displacement test result
| Embodiment | Improve recovery ratio % |
| 1 | 4.8 |
| 2 | 5.1 |
| 3 | 5.3 |
| 4 | 5.5 |
| 5 | 7.2 |
| 6 | 8.3 |
| 7 | 6.8 |
| 8 | 7.5 |
| 9 | 7.1 |
| 10 | 7.8 |
【Comparative example 1】
According to Northwest University's journal (natural science edition) 2 months the 1st phases of volume 30 in 2000, the method such as 28～31 Gong Yu armies
Cetyl trimethylammonium bromide (CTAB) and sodium lauryl sulphate (SDS) are configured to mixed system (mol ratio 1：1.5),
Test it respectively in 0.3% consumption and Shuanghe Oil Field5-11 series of strata crude oil oil water interfacial tension, washing oil rate and the displacement of reservoir oil
Can, result is as follows：
Table 6 reference oil displacement agent performance
| Interfacial tension (MN/m) | Washing oil rate % | Improve recovery ratio % |
| 0.03 | 45.6 | 2.8 |
【Comparative example 2】
According to petroleum gas journal in August, 2007 the 4th phase of volume 29, Huang Hong degree etc. (101～104) method etc. will
0.01% cetyl trimethylammonium bromide and 0.02% anion surfactant petroleum sulfonate and 1.8%Na2CO3It is configured to mix
Fit system, tests it in 0.3% consumption and Shuanghe Oil Field respectively5-11 series of strata crude oil oil water interfacial tension, washing oil rate
And Oil Displacing Capacity, result is as follows：
Table 7 reference oil displacement agent performance
| Interfacial tension (MN/m) | Washing oil rate % | Improve recovery ratio % |
| 0.008 | 56.3 | 4.2 |
Claims (6)
1. a kind of surface activator composition for tertiary oil recovery, including cationic surfactant and Anionic-nonionic
Surfactant, described cationic surfactant is 1: 0.01～1 with the mol ratio of Anionic-nonionic surfactant
: 100, its cationic surfactant is selected from least one in quaternary ammonium salt or quaternary amine alkali, Anionic-nonionic surface activity
Agent is at least one in amidogen ether carboxylate or amidogen ether sulfonate；
The general molecular formula of amidogen ether carboxylate is：
The general molecular formula of amidogen ether sulfonate is：
Wherein, described R is any one in alkyl or aryl；R ' is H, any one in alkyl or aryl；R " is C1～C5
Alkyl or replace alkyl in any one；The described ethyoxyl degree of polymerization, the propoxyl group degree of polymerization are any one in 0～20
Integer or decimal.
2. it is used for the surface activator composition of tertiary oil recovery according to claim 1 it is characterised in that described cation form
Face activating agent is at least one in tetra-alkyl ammonium chloride or tetra-alkyl ammonium hydroxide.
3. be used for according to claim 1 the surface activator composition of tertiary oil recovery it is characterised in that described anion-non-
Ionic surface active agent cationic M is selected from Na, K, Mg, Ca or NH4 +In any one.
4. it is used for the surface activator composition of tertiary oil recovery according to claim 1 it is characterised in that cationic surface is lived
Property agent and Anionic-nonionic surfactant mol ratio 1: 0.1～1: 10.
5. it is used for the preparation method of the surface activator composition of tertiary oil recovery described in claim 1, comprise the following steps：
A) by organic amine, catalyst and required oxirane, expoxy propane add reactor, in 100～200 DEG C react 1～
20 hours；Then add sulfonated reagent or carboxylating reagent, wherein organic amine：The mol ratio of sulfonated reagent or carboxylating reagent is 1：1
～4, continue reaction 1～20 hour in 50～200 DEG C, then add hydrochloric acid to be neutralized to pH<3, and carry out oil-water separation, oil phase adds
Enter alkali liquor to be neutralized, finally obtain aliphatic amine polyoxyethylene/polyoxypropylene ether carboxylate, sulfonate；
B) the Anionic-nonionic surfactant obtaining cationic surfactant and step a) is dissolved in water,
Then according to mol ratio 1: 0.1～1: 10 mix homogeneously, obtain required compositionss.
6. the preparation method of surface activator composition being used for tertiary oil recovery according to claim 5 is it is characterised in that institute
The catalyst stated is at least one in NaOH or KOH；Described sulfonated reagent is hydroxyl sulfoacid and its salt, halogenosulfonic acid and its
Salt；Described carboxylating reagent is halogenated carboxylic acid and its salt.
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| CN105368431B (en) * | 2014-08-27 | 2019-01-01 | 中国石油化工股份有限公司 | Displacement composition and preparation method thereof and the method for intensified oil reduction |
| CN105441053B (en) * | 2014-08-27 | 2018-10-23 | 中国石油化工股份有限公司 | Surfactant for the sandstone oil reservoir displacement of reservoir oil |
| CN105368430B (en) * | 2014-08-27 | 2019-04-12 | 中国石油化工股份有限公司 | Oil displacement agent and preparation method thereof and the method for intensified oil reduction |
| CN105642185B (en) * | 2014-10-22 | 2018-07-31 | 中国石油化工股份有限公司 | A kind of anionic-cationic-nonionic surface active agent, its manufacturing method and its application |
| WO2016061712A1 (en) * | 2014-10-22 | 2016-04-28 | 中国石油化工股份有限公司 | Anionic-cationic-nonionic surfactant and manufacturing method and application thereof |
| CN106867494B (en) * | 2015-12-14 | 2020-10-16 | 中国石油化工股份有限公司 | Combined surfactant with strong crude oil solubilizing capability and low-cost preparation method |
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| CN112795002B (en) * | 2019-11-14 | 2022-04-01 | 中国石油化工股份有限公司 | Polyether anionic and nonionic surfactant containing heteroatom and preparation method thereof |
| CN113930227B (en) * | 2020-07-14 | 2023-05-02 | 中国石油化工股份有限公司 | Composition containing anionic-nonionic and cationic-nonionic surfactants, preparation method and application thereof |
| WO2022101081A1 (en) | 2020-11-13 | 2022-05-19 | Basf Se | Method of mineral oil production from underground carbonate deposits |
| CN113563858B (en) * | 2021-07-13 | 2022-08-19 | 黑龙江信维源化工有限公司 | Surfactant composition for oil displacement of high-temperature and high-salinity oil reservoir |
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