CN106590565B - Middle low mineralization oil reservoir oil displacement compound surfactant composition - Google Patents
Middle low mineralization oil reservoir oil displacement compound surfactant composition Download PDFInfo
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Abstract
The present invention relates to a kind of composition of compound surfactant composition and application, mainly solve the problems, such as that surfactant oil displacement efficiency during middle low mineralization oil reservoir (6000~15000mg/L NaCl) tertiary oil recovery is poor.The present invention is by using compound surfactant composition, including anionic surfactant and cationic surfactant, the molar ratio of the anionic surfactant and cationic surfactant is 1:(0.01~100), wherein cationic surfactant is selected from least one of quaternary ammonium compound, anionic surfactant is indicated by following general molecular formula, wherein M is any one in ammonium ion or alkali metal ion, R H, C1~C22Fat-based or aromatic radical in the technical solution of any one preferably solve the problems, such as this, can be used for during middle low mineralization tertiary oil production in oil field.
Description
Technical field
The present invention relates to one kind to be suitable for middle low mineralization oil reservoir oil displacement compound surfactant composition.
Background technique
With the increase of world energy sources demand, the rational exploitation and utilization of petroleum has caused the very big attention of people, to petroleum
Yield and production efficiency requirement it is also higher and higher.The high-efficiency mining for realizing petroleum resources, for improving crude output not
Only there is realistic meaning, with more important strategic importance.The general only extraction of conventional oil production method (primary and secondary method) is former
The 1/3 of oily oil in place, there is also about 2/3 crude oil to fail to produce, therefore in the case where being becoming tight energy day, improves tar productivity
Have become the key subjects of oil exploitation research.Tertiary oil recovery technology is then a kind of effective method for improving tar productivity, can be divided
For four major class: first is that heating power drives, including steam drive, combustion in situ etc.；Second is that mixed phase drives, including CO2Mixed phase, hydrocarbon mixed phase and other
Inert gas mixed phase drives；Third is that chemical flooding；Fourth is that microbe oil production, including biopolymer, MICROBIAL SURFACTANT are driven.Change
Learning drive is technology, including polymer flooding, surfactant flooding, caustic waterflooding extremely important in intensified oil reduction and implement on a large scale etc.
And the multiple combinations technology of polymer, alkali, surfactant.The effect of chemical flooding is the knot of physical action and chemical action
Fruit, 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 both oleophylic (hydrophobic) and hydrophilic (oleophobic) property
Matter, when surfactant is dissolved in water, molecule is mainly distributed on oil-water interfaces, and oil water interfacial tension can be significantly reduced.Oil
The reduction of water interfacial tension means that surfactant system can overcome the cohesive force between crude oil, and larger oil droplet is dispersed into small oil
Drop, to improve percent of pass when crude oil flows through pore throat.The oil displacement efficiency of surfactant is also manifested by the rock table for making oleophylic
The effects of face wettability reversal, emulsification of crude oil, raising surface charge density and oil droplet are gathered simultaneously, this is surfactant in chemical flooding
Play the reason of very important in technology.
Surface active agent for tertiary oil recovery mostly uses greatly Recompounded multielement system at present, while including non-ionic surfactant
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 oil-field thick-oil well, which is by water, piece alkali, ethyl alcohol, oleic acid, alkyl phenol polyoxyethylene ether, ten
Dialkyl benzene sulfonic acids sodium composition.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 surfactant be petroleum sulfonate or with petroleum sulfonate be
Host agent adds the complexed surfactant of diluent and other surfactant compounds, and the weight percent of component is mahogany acid
Salt 50~100%, alkylsulfonate 0~50%, carboxylate 0~50%, alkylaryl sulfonates 0~35%, low-carbon alcohols 0~
20%.For another example patent CN1394935 has invented a kind of chemical oil displacement agent, mainly includes that sodium octylbenzene sulfonate anionic surface is living
Property agent, surfactant adjuvant, surfactant synergist, surface active agent solubilization agent.This oil displacement agent can be reduced significantly
The structural viscosity of viscous crude, while oil water interfacial tension can be reduced, to improve oil recovery factor.
However, above-mentioned surface active agent for tertiary oil recovery, there are still more problem, mainly surfactant activity is poor, drives
Oily low efficiency, simultaneously because surfactant system is excessively complicated, thus Produced Liquid demulsification is difficult, and sewage treatment difficulty is big；Separately
Outside since oil displacement system contains inorganic base, injury is brought to stratum and oil well, is caused the problems such as corroding equipment and pipeline, and due to
Inorganic base can seriously reduce the viscosity of polymer, and the viscosity to reach required is had to greatly improve the use concentration of polymer, made
Oil recovery overall cost improves；The resistant to high temperatures of surfactant, high salt tolerance, the ability of anti-high salinity are limited.
It is well known that anionic surfactant, such as petroleum sulfonate, petroleum carboxylate, alkylbenzene sulfonate are current
It is widely used in during tertiary oil recovery, and single cationic surfactant sinks because it is easily adsorbed or generated by stratum
It forms sediment, therefore the ability for reducing oil water interfacial tension is poor, is generally not used for tertiary oil recovery.Due to cationic and anionic surfactant close to etc.
Its aqueous solution precipitating easy to form when ratio mixes, not only in the application so as to cause cationic and anionic surfactant mixed system
As incompatibility, and lag is also compared in correlation theory research.In recent years the study found that cationic and anionic surfactant is mixed
Zoarium system aqueous solution has many anomalous properties, such as since there is strong quiet in aqueous solution for cationic and anionic surfactant
Interaction between electro ultrafiltration and hydrophobic carbon chain, promotes two kinds with the interionic association of different charged surfactants,
It is readily formed micella in solution, generates surface-active more higher than single surfactant.In addition, zwitterion surface-active
Agent mixed system can obviously reduce absorption loss of the cationic surfactant on rock core, so as to significantly reduce cation form
The inherent shortcoming of face activating agent.
Gong Yujun etc. (see 2 months 2000 the 1st phase Northwest University's journals (natural science edition) of volume 30,28~31) research is recognized
There is solubilization for cetyl trimethylammonium bromide (CTAB) and lauryl sodium sulfate (SDS) mixed system.In petroleum
In recovery process, using solubilization can " displacement of reservoir oil ", will be adhered under the oil wash on the sandstone of rock stratum, to improve oil recovery
Rate.Huang Hongdu etc. (see petroleum gas journal in August, 2007 the 4th phase of volume 29,101~104) has studied petroleum sulfonate, stone
The boundary of the anionic surfactants such as oily carboxylate, alkylbenzene sulfonate and cetyl trimethylammonium bromide, alkali compound system
Face tension is simultaneously concluded that the addition of cationic surfactant makes petroleum carboxylate, alkylbenzene sulfonate, mahogany acid
The interfacial activity of salt is improved.
The studies above the result shows that anions and canons Surfactant Mixing Systems for reduce oil water interfacial tension, improve
Oil displacement efficiency has a 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
Alkali is still used, injury is brought to stratum and oil well to not can avoid alkali, corrodes equipment and pipeline and demulsification difficulty etc. and asks
Topic.In addition above-mentioned system is easier to generate precipitating, is unfavorable for practical application.
For this purpose, forefathers have been used for reference in one aspect of the present invention absorption studies knot about anions and canons Surfactants mixed system
On the other hand fruit replaces traditional anion surface active using single alkyl diphenyl ether monosulfonate analog anion surfactants
Agent significantly improves the interfacial activity of Surfactant Mixing Systems, is suitable for middle low mineralization oil reservoir (6000~15000mg/
L ion concentration) three adopt technology, invented anionic surfactant for improving oil recovery factor and quaternary ammonium salt be compound
Type surface activator composition.
Summary of the invention
The first technical problem to be solved by the present invention is existing surfactant oil displacement efficiency during tertiary oil recovery
Difference brings injury to stratum and oil well simultaneously because oil displacement system contains inorganic base, corrodes equipment and pipeline and the difficulty that is demulsified
Problem provides a kind of new compound surfactant composition, and the composition is high with interfacial activity, washing oil ability is strong, body
System is simple, will not bring injury to stratum and oil well, will not corrode equipment and pipeline and not will cause the difficult advantage of demulsification.
It is living that the second technical problem to be solved by the present invention is to provide a kind of surface corresponding with technical problem one is solved
The preparation method of property agent composition.
Problem to be solved by this invention third is that surface activator composition is three times described in one of above-mentioned technical problem
Application in oil recovery.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: a kind of compound surfactant
Composition, including anionic surfactant and cationic surfactant, the anionic surfactant and cation
The molar ratio of surfactant is 1:(0.01~100), wherein cationic surfactant selects at least one in quaternary ammonium compound
Kind, anionic surfactant is indicated by following general molecular formula:
Or
Wherein M is any one in ammonium ion or alkali metal ion, R H, C1~C22Fat-based or aromatic radical in
Any one.
In above-mentioned technical proposal, the cationic surfactant is selected from least one of quaternary ammonium compound, can be
Quaternary ammonium compound surfactant commonly used in the art, such as quaternary ammonium salt, quaternary ammonium base, may be used to the present invention, as preferred
The cationic surfactant preferably is selected from least one of tetraalkyl quaternary ammonium compound, alkyl be saturated alkyl, alkylene,
Any one in aryl；Further preferably at least one of tetraalkyl quaternary ammonium salt.
In above-mentioned technical proposal, the total number of carbon atoms in the cationic surfactant molecule is preferably 4~60, into one
Step preferably 4~32.
In above-mentioned technical proposal, the tetraalkyl quaternary ammonium salt, more preferably from least one in molecular structure shown in formula (I)
Kind:
Wherein, R1、R2It is independently selected from C1~C22Alkyl, one of substituted hydrocarbon radical, R3、R4It is independently selected from C1~C5Rouge
Fat alkyl or substituted fatty hydrocarbon base；Y, which is selected from, makes molecule shown in formula (I) be in the anion of electroneutral, j_For the valence state of Y, 1/j Y
Number.
In above-mentioned technical proposal, as a preferred solution: R1、R2It is independently selected from C1~C22Alkyl, replace alkyl in one
Kind；R3、R4It is independently selected from C1~C5Alkyl or replace alkyl.
In above-mentioned technical proposal, as a preferred solution: Y is selected from halide ion, sulfate ion, nitrate ion, phosphoric acid
At least one of radical ion, polyanion etc., further preferably from halide ion, more preferably chloride ion or bromide ion.
In above-mentioned technical proposal, the substituted hydrocarbon radical, substituted fatty hydrocarbon base, replace alkyl in substituent group, can be
The common substituent group in field, such as hydroxyl, phenyl, halogen.
In above-mentioned technical proposal, cation M preferably is selected from any one in alkali metal in the anionic surfactant.
In above-mentioned technical proposal, the R is H, C1~C22Fat-based or aromatic radical in any one, wherein fat-based
Or aromatic radical can be saturated carbon chains, can also contain unsaturated carbon containing groups such as acyl group, carbonyl, ether, hydroxyls
Chain；Preferably R is preferably H, C1~C22Alkyl or substituted hydrocarbon radical；Substituent group can be the common substitution of chemical field
Base, such as hydroxyl, phenyl, halogen, further R are preferably H, C1~C22Alkyl, alkylene or aryl；Further R is excellent
It is selected as H, C8~C22Alkyl, alkylene or aryl.
The preferred model of molar ratio of cation quaternary ammonium salt described in above-mentioned technical proposal and Anionic-nonionic surfactant
It encloses for 1:(0.01~100).
To solve above-mentioned technical problem two, The technical solution adopted by the invention is as follows: described in one of above-mentioned technical problem
The preparation method of compound surfactant composition described in technical solution, comprising the following steps:
(1) anionic surfactant is dissolved in the water, obtains solution I；
(2) cation quaternary ammonium salt is dissolved in the water, obtains solution II；
(3) anionic surfactant and cation quaternary ammonium salt are dissolved in water, then according to molar ratio 1:
(0.01~100) it is uniformly mixed, obtains the surface activator composition.
To solve above-mentioned technical problem three, technical scheme is as follows: any one of one of technical problem technology
Application of the compound surfactant composition in tertiary oil recovery described in scheme.
In above-mentioned technical proposal, described application method those skilled in the art can be according to surfactant in the prior art
The method of drive is used, and has no particular/special requirement, such as but be not limited to the compound surfactant composition with water
It is contacted in the form injection reservoir formation of solution with underground crude oil, underground crude oil displacement is come out；Wherein, the compound surface
In surfactant composition aqueous solution, in terms of the quality total by cation quaternary ammonium salt and anionic surfactant, compound surface is living
Property agent composition concentration be 0.01~0.5%.
In above-mentioned technical proposal, the compound surfactant composition drives especially suitable for middle low mineralization oil reservoir
Oil, i.e. 6000~15000mg/L of salinity NaCl oil reservoir oil displacement.
Compound surfactant composition of the invention is on the one hand due to anions and canons quaternary ammonium salt opposite charges polar group
Between strong electrostatic attraction effect so that surfactant molecule increases in adsorbed on interfaces amount, critical micelle concentration is significant
It reduces, thus the high surface incomparable with single surfactant；Simultaneously because compound surfactant superelevation
Interfacial activity, aqueous solution can form ultralow interfacial tension with crude oil and be conducive to effectively overcome the cohesive force between crude oil
The outflow of crude oil, and then greatly improve oil displacement efficiency.Another aspect compound surfactant composition can change oil reservoir table
The wetability in face, as the cation quaternary ammonium salt in composition passes through the electronegative group phase interaction with absorption on a solid surface
With it is desorbed, so that glossy wet structure is changed into neutral wetting or water wetting surface, reduces crude oil in the viscous of the surface of solids
Attached function, to be conducive to the removing of crude oil.Anions and canons surfactant mixed solution has solubilization to crude oil simultaneously,
Further the crude oil being adhered on the sandstone of rock stratum can be washed down, improve oil recovery factor.
Compound surfactant composition of the present invention is used during tertiary oil recovery, has interfacial activity high: compound
Surface activator composition dosage remains to form 10 with underground crude oil under the conditions of being 0.01~0.05%wt-3~10-4MN/m's is super
Low interfacial tension；Surface activator composition system is simple.Since system is free of inorganic base, thus when avoiding field application without
Machine alkali injures caused by stratum, the corrosion caused by equipment and thus caused by the difficult problem of demulsification, achieve preferably
Technical effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1a]
Myristyl diphenyl oxide disulfonate and dodecyl diethylbenzyl chlorination ammonium surfactant are dissolved separately in
In water, stirs 30 minutes, 0.1%wt aqueous solution is configured to, then by above-mentioned surfactant according to anion: cationic quaternary ammonium
Salt molar ratio 1:5 is uniformly mixed, and obtains compound surfactant composition 1a.
[embodiment 2a]
Ten alkyl diphenyl ether sodium sulfonates are dissolved in water with cetyl trimethylammonium bromide surfactant, are stirred
It mixes 30 minutes, is configured to 0.1%wt aqueous solution, then by above-mentioned surfactant according to anion: cation quaternary ammonium salt mole
It is uniformly mixed than 1:0.8, obtains compound surfactant composition 2a.
[embodiment 3a]
Dodecyl diphenyl oxide sodium sulfonate and tetradecyltrimethylammonium bromide surfactant are dissolved in water,
Stirring 30 minutes, is configured to 0.1%wt aqueous solution, then by above-mentioned surfactant according to anion: cation quaternary ammonium salt rubs
You are uniformly mixed than 1:0.6, obtain compound surfactant composition 3a.
[embodiment 4a]
Hexadecyl diphenyloxide potassium sulfonate and eight alkyl trimethyl ammonium chloride surfactants are dissolved in water, stirred
It mixes 30 minutes, is configured to 0.1%wt aqueous solution, then by above-mentioned surfactant according to anion: cation quaternary ammonium salt mole
It is uniformly mixed than 1:0.5, obtains compound surfactant composition 4a.
[embodiment 5a]
Dodecyl diphenyl oxide sodium sulfonate and hexadecyltrimethylammonium chloride surfactant are dissolved in water,
Stirring 30 minutes, is configured to 0.1%wt aqueous solution, then by above-mentioned surfactant according to anion: cation quaternary ammonium salt rubs
You are uniformly mixed than 1:2, obtain compound surfactant composition 5a.
[embodiment 6a]
Octadecyl diphenyl oxide disulfonate and decyl trimethyl ammonium chloride surfactant are dissolved in water, stirred
It mixes 30 minutes, is configured to 0.1%wt aqueous solution, then by above-mentioned surfactant according to anion: cation quaternary ammonium salt mole
It is uniformly mixed than 1:1.2, obtains compound surfactant composition 6a.
[embodiment 7a]
Hexadecyl diphenyloxide sodium sulfonate and tetradecyl trimethyl ammonium chloride surfactant are dissolved in water,
Stirring 30 minutes, is configured to 0.1%wt aqueous solution, then by above-mentioned surfactant according to anion: cation quaternary ammonium salt rubs
You are uniformly mixed than 1:3.8, obtain compound surfactant composition 7a.
[embodiment 8a]
Ten alkyl diphenyl ether sodium sulfonates are dissolved in water with dodecyl trimethyl ammonium chloride surfactant, are stirred
It mixes 30 minutes, is configured to 0.1%wt aqueous solution, then by above-mentioned surfactant according to anion: cation quaternary ammonium salt mole
It is uniformly mixed than 1:0.4, obtains compound surfactant composition 8a.
The test of [embodiment 9a] compound surfactant composition interface performance
With TX-500C rotating interfacial tensimeter measurement compound surfactant composition and certain domestic oil field oil water circle
Face tension.Measuring temperature is 30~90 DEG C, and water salinity used is 6000~15000mg/L NaCl, oil density 0.9g/
Ml, viscosity 10.1mp.s.Compound surfactant composition dosage is 0.1%wt.
Table 1a compound surfactant composition oil water interfacial tension
By table 1a it is found that the compound surfactant of embodiment 1a~8a preparation has good interface performance,
6000~15000mg/L NaCl salinity can keep good interfacial activity.
The embodiment 6a compound surfactant prepared is configured to various concentration, at 60 DEG C, 10000mg/L NaCl
Under the conditions of salinity respectively test with the oil field oil water interfacial tension, the results are shown in Table 2a.
Table 2a various concentration surface activator composition 6a oil water interfacial tension
| Dosage of surfactant (%wt) | 0.01 | 0.02 | 0.05 | 0.1 | 0.2 | 0.3 |
| Interfacial tension (MN/m) | 0.0037 | 0.0031 | 0.0013 | 0.0014 | 0.0016 | 0.0024 |
The above results show that compound surfactant composition of the present invention has very high grease for the crude oil
Interfacial activity.
[embodiment 9a] compound surfactant composition solution rock core displacement test
Displacement test is carried out using natural core, rock core length is 5.48cm, diameter 2.51cm, permeability 7.2mD, hole
Degree 19.4%, crude oil saturation degree 58%.Water salinity used be 13000mg/L NaCl, 60 DEG C of experimental temperature.With surface-active
Agent composition 4a is displacing medium, the use of concentration is 0.1%wt, and displacement velocity 0.04mL/min, one time water drive injects 10PV,
Recovery ratio is 32%；It is subsequent that 10PV is injected using 0.1%wt surface activator composition 4a solution drive, improve recovery ratio 17%.
Show that compound surfactant composition of the present invention can significantly improve crude oil recovery ratio.
[comparative example 1b]
According to the 5th phase of volume 16 " Shanghai University's journal " in October, 2010, p437-442, the methods of Chen Jie are by dodecyl
Sodium sulphate is dissolved in water with cetyl trimethylammonium bromide surfactant, is stirred 30 minutes, is configured to 0.1%wt
Aqueous solution, then by above-mentioned surfactant according to anion: cation quaternary ammonium salt molar ratio 1:4 is uniformly mixed, and is obtained compound
Type surface activator composition 1b.
[comparative example 2b]
Ten alkyl diphenyl ether sulfonate surfactants are dissolved in the water, stirs 30 minutes, it is water-soluble to be configured to 0.1%wt
Liquid obtains surfactant solution 2b.
[comparative example 3b]
Dodecyl trimethyl ammonium bromide surfactant is dissolved in the water, stirs 30 minutes, is configured to 0.1%wt water
Solution obtains surfactant solution 3b.
The test of [comparative example 4b] compound surfactant composition interface performance
With TX-500C rotating interfacial tensimeter measurement compound surfactant composition and certain domestic oil field oil water circle
Face tension.Measuring temperature is 60 DEG C, and water salinity is 10000mg/L NaCl, oil density 0.9g/ml, and viscosity is
10.1mp.s.Compound surfactant composition dosage is 0.1%wt.
Table 1b compound surfactant composition oil water interfacial tension
| Sample | Interfacial tension (mN/m) |
| Embodiment 1a | 0.0046 |
| Comparative example 1b | 0.03 |
| Comparative example 2b | 0.87 |
| Comparative example 3b | 1.02 |
As shown in table 1b, embodiment 1a has the performance for more obviously reducing oil water interfacial tension than comparative example, and multiple
Mould assembly surfactant has higher interface efficiency than single surfactant.
[comparative example 5b] compound surfactant composition solution rock core displacement test
Displacement test is carried out using natural core, rock core length is 5.24cm, diameter 2.48cm, permeability 7.58mD, hole
Porosity 18.2%, crude oil saturation degree 61%.Water salinity used be 13000mg/L NaCl, 60 DEG C of experimental temperature.It is living with surface
Property agent composition 1b be displacing medium, the use of concentration is that 0.1%wt, displacement velocity 0.04mL/min, water drives are injected
10PV, recovery ratio 30%；It is subsequent that 10PV is injected using 0.1%wt surface activator composition 1b solution drive, improve recovery ratio
2.0%.Show that the compound surfactant composition 1b is unobvious to the crude oil recovery ratio improvement effect.
Claims (9)
1. a kind of application of compound surfactant composition in tertiary oil recovery, including anionic surfactant and sun from
The molar ratio of sub- surfactant, the anionic surfactant and cationic surfactant is 1:(0.01~100),
Wherein cationic surfactant is selected from least one of quaternary ammonium compound, and anionic surfactant is by following general molecular formula
It indicates:
Or
Wherein M is any one in ammonium ion or alkali metal ion, R H, C1~C22Fat-based or aromatic radical in appoint
It anticipates one kind.
2. application according to claim 1, it is characterised in that the cationic surfactant is selected from tetraalkyl quaternary ammonium
Close at least one of object.
3. application according to claim 2, it is characterised in that the cationic surfactant is selected from tetraalkyl quaternary ammonium salt
At least one of.
4. application according to claim 1, it is characterised in that the R is H, C1~C22Alkyl or substituted hydrocarbon radical.
5. application according to claim 4, it is characterised in that the R is H or C1~C22Alkyl, alkylene, aryl.
6. any application according to claim 1~5, it is characterised in that the carbon in the cationic surfactant molecule
Total atom number is 4~60.
7. application described in claim 1, it is characterised in that the preparation method of the compound surfactant composition, including
Following steps:
(1) anionic surfactant is dissolved in the water, obtains solution I；
(2) cation quaternary ammonium salt is dissolved in the water, obtains solution II；
(3) according to anionic surfactant and cation quaternary ammonium salt molar ratio 1:(0.01~100) solution I and solution II are mixed
It closes uniformly, obtains the surface activator composition.
8. application according to claim 1, it is characterised in that the compound surfactant composition is with aqueous solution
It is contacted in form injection reservoir formation with underground crude oil, underground crude oil displacement is come out.
9. application according to claim 8, it is characterised in that in the compound surfactant composition solution, with
Cation quaternary ammonium salt and the total quality meter of anionic surfactant, compound surfactant composition concentration is 0.01~
0.5%.
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