CN103540303B - Composite surfactant composition as well as preparation method thereof - Google Patents
Composite surfactant composition as well as preparation method thereof Download PDFInfo
- Publication number
- CN103540303B CN103540303B CN201210239959.1A CN201210239959A CN103540303B CN 103540303 B CN103540303 B CN 103540303B CN 201210239959 A CN201210239959 A CN 201210239959A CN 103540303 B CN103540303 B CN 103540303B
- Authority
- CN
- China
- Prior art keywords
- surfactant
- oil
- compositionss
- preparation
- anionic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a composite surfactant composition as well as a preparation method thereof, and mainly solves the problems that an existing surfactant is poor in oil driving efficiency during three times of oil extraction processes, meanwhile, an oil driving system contains inorganic alkaline, hurts the ground layer and an oil well, and corrodes equipment and pipelines, and demulsification is difficult. According to the composition and the preparation method, the surfactant composition comprises a cation surfactant and an anion-non-ion surfactant, wherein the cation surfactant is selected from any one of quaternary ammonium salt and quaternary amine alkali, the anion-non-ion surfactant is a surfactant containing ethoxy nonionic groups and carboxyl or sulfo anionic groups, and the mole ratio of the cation surfactant to the anion-non-ion surfactant is (1:0.01)-(1:100); by using the composition and the preparation method, the problems are solved well, and the composite surfactant composition as well as the preparation method thereof can be used in the process of three times of oil extraction in an oil field.
Description
Technical field
The present invention relates to a kind of compound surfactant compositionss 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
The shortcomings of ionic surface active agent easily precipitates when compounding, has invented the cation surface activating for improving oil recovery factor
Agent and Anionic-nonionic surfactant compound surfactant compositionss.
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 new compound surfactant compositionss, and said composition has that interfacial activity is high, washing oil ability is strong, body
System is simple, will not bring injury 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 compound surfactant
Compositionss and preparation method thereof, including cationic surfactant and Anionic-nonionic surfactant, described cation
Surfactant is 1: 0.01～1: 100 with the mol ratio of Anionic-nonionic surfactant, wherein cation surface activating
Agent is selected from least one in quaternary ammonium salt or quaternary amine alkali, and Anionic-nonionic surfactant molecule formula is：
Or
Wherein M is any one in alkali metal, alkaline-earth metal or ammonium ion, and R is H, C1～C20Alkyl, aryl,
COOM or SO3Any one in M, ethyoxyl polymerization degree n is any one integer or decimal in 1～40, and interval base R is
C1～C5Alkyl.
In technique scheme, described cationic surfactant preferred version is selected from tetra-alkyl ammonium chloride or tetraalkyl hydrogen
At least one in amine-oxides；Described Anionic-nonionic surfactant cationic M preferred version is selected from Na, K, Mg, Ca
Or NH4 +In any one；Described substituent R preferred version is H, C5～C15Alkyl, aryl, COOM or SO3Any in M
A kind of；Described ethyoxyl polymerization degree n preferred scope is any one integer or decimal in 1～20；Described cationic surface is lived
Property agent and Anionic-nonionic surfactant mol ratio preferred scope be 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 compound surfactant
The preparation method of compositionss, comprises the following steps：
A) by alkylphenol polyoxyethylene, catalyst according to mol ratio 1：1～5 addition reactor, in room temperature～100oC
Alkalization 1～10 hour, then adds sulfonated reagent or carboxylating reagent, wherein alkylphenol polyoxyethylene：Sulfonated reagent or carboxylation
The mol ratio of reagent is 1：1～4, it is warming up to 50～100oC continues reaction 1～20 hour, then adds hydrochloric acid to be neutralized to pH<3,
And carrying out oil-water separation, oil phase adds alkali liquor to be neutralized, and finally obtains alkylphenol polyoxyethylene sulfonate or alkyl phenol gathers
Oxygen ethylene ether carboxylate；
B) by cationic surfactant and the Anionic-nonionic surfactant that obtains according to step a) is molten respectively
In Xie Yushui, then obtain required compositionss according to mol ratio 1: 0.1～1: 10 mix homogeneously.
In technique scheme, described catalyst is selected from least one in NaOH or KOH；Described sulfonated reagent is
Hydroxyl sulfoacid and its salt or halogenosulfonic acid and its salt；Described carboxylating reagent is halogenated carboxylic acid and its salt.
The compound surfactant compositionss one side of the present invention is due to anions and canons surfactant opposite charges pole
Property base between strong electrostatic attraction effect so that surfactant molecule adsorbed on interfaces amount increase, critical micelle concentration
Significantly reduce, thus having the incomparable high surface of single surfactant；Simultaneously because compound surfactant
The interfacial activity of superelevation, its aqueous solution can form ultralow interfacial tension with crude oil, thus effectively overcoming the cohesiveness between crude oil, has
Beneficial to former oil-out, and then oil displacement efficiency is greatly improved.Another aspect compound surfactant compositionss can change oil
Cationic surfactant in the wettability of layer surface, such as compositionss is by the electronegative base on a solid surface with absorption
Group interacts so as to be desorbed, and makes glossy wet structure change into neutral wetting or water-wet surface, reduces crude oil in solid
The adhesion work on surface, thus be conducive to the stripping of crude oil.Anions and canons surfactant mixed solution has increasing to crude oil simultaneously
Molten effect, can wash down sticking to the crude oil on the sandstone of rock stratum further, improve oil recovery factor.
Adopt compound surfactant compositionss of the present invention during tertiary oil recovery, there is interfacial activity high：Compound
Surface activator composition consumption be 0.01～0.05% under the conditions of remain to and underground crude oil formed 10-3～10-4MN/m super
Low interfacial tension；Washing oil ability is strong：Compound surfactant compositionss are to the washing oil rate of crude oil more than 40%；Surfactant
Composition system is simple.Because system does not contain inorganic base, thus the injury that when avoiding scene application, inorganic base causes to stratum,
The corrosion that equipment is caused and the problem of the breakdown of emulsion difficulty thus causing, achieve preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
【Embodiment 1】
By alkylphenol polyoxyethylene, NaOH according to mol ratio 1：5 addition reactors, in 100oC alkalizes 1 hour, then
According to alkylphenol polyoxyethylene：Chloromethylsulfonic acid mol ratio 1：4 addition sulfonated reagents, are cooled to 50oIt is little that C continues reaction 20
When, then add hydrochloric acid to be neutralized to pH<3, stratification, oil phase adds 30%NaOH aqueous solution to be neutralized, and obtains alkyl phenol and gathers
Oxygen vinyl Ether sodium sulfonate.
Alkylphenol polyoxyethylene sulfonate surfactants by hexadecyltrimethylammonium chloride and present invention preparation
It is dissolved in water, stir 30 minutes, be configured to 0.3% aqueous solution, then by above-mentioned surfactant according to cation：Cloudy
Ion-nonionic surfactant mol ratio 1: 0.3 mix homogeneously, obtains compound surfactant compositionss 1, its composition,
Structure is shown in Table 1.
【Embodiment 2】
By alkylphenol polyoxyethylene, KOH according to mol ratio 1：1 addition reactor, alkalizes 10 hours in room temperature, then presses
According to alkylphenol polyoxyethylene：Sodium isethionate mol ratio 1：3 addition sulfonated reagents, are warming up to 70oC continues 10 hours, and
Hydrochloric acid is added to be neutralized to pH afterwards<3, and carry out oil-water separation, oil phase adds ammonia to be neutralized, and obtains alkylphenol polyoxyethylene
Ichthyodin.
By the alkylphenol polyoxyethylene sulfonic acid ammonium surfactant of benzyltriethylammoinium chloride and present invention preparation respectively
It is dissolved in the water, stir 30 minutes, be configured to 0.3% aqueous solution, then by above-mentioned surfactant according to cation：Anion-
Nonionic surfactant mol ratio 1: 0.1 mix homogeneously, obtains compound surfactant compositionss 2, and its composition, structure are shown in
Table 1.
【Embodiment 3】
By alkylphenol polyoxyethylene, KOH according to mol ratio 1：1.5 addition reactors, in 30oC alkalizes 8 hours, then
According to alkylphenol polyoxyethylene：Chlorine amyl group sodium sulfonate mol ratio 1：2 addition sulfonated reagents, are warming up to 60oC continues 15 hours,
Hydrochloric acid is then added to be neutralized to pH<3, and carry out oil-water separation, oil phase adds 10%Ca (HCO3)2Aqueous solution is neutralized, and obtains
Alkylphenol polyoxyethylene sulfoacid calcium.
Alkylphenol polyoxyethylene sulfoacid calcium surfactant by phenyl trimethicone ammonium chloride and according to present invention preparation
It is dissolved in water, stir 30 minutes, be configured to 0.3% aqueous solution, then by above-mentioned surfactant according to cation：Cloudy
Ion-nonionic surfactant mol ratio 1: 1.2 mix homogeneously, obtains compound surfactant 3, and its composition, structure are shown in
Table 1.
【Embodiment 4】
By alkylphenol polyoxyethylene, NaOH according to mol ratio 1：2 addition reactors, in 50oC alkalizes 6 hours, then presses
According to alkylphenol polyoxyethylene：3- chlorine-2-hydroxyl propanesulfonate mol ratio 1：2 addition sulfonated reagents, are warming up to 80oIt is little that C continues 8
When, then add hydrochloric acid to be neutralized to pH<3, and carry out oil-water separation, oil phase adds unsaturated carbonate hydrogen magnesium aqueous solution to be neutralized,
Obtain alkylphenol polyoxyethylene sulfonic acid magnesium.
Alkylphenol polyoxyethylene sulfonic acid magnesium table by stearyl dimethyl benzyl ammonium chloride and according to present invention preparation
Face activating agent is dissolved in water, and stirs 30 minutes, is configured to 0.3% aqueous solution, then by above-mentioned surfactant according to sun
Ion：Anionic-nonionic surfactant molar ratio 1: 2.0 mix homogeneously, obtains compound surfactant 4, its composition,
Structure is shown in Table 1.
【Embodiment 5】
By alkylphenol polyoxyethylene, NaOH according to mol ratio 1：3 addition reactors, in 60oC alkalizes 5 hours, then presses
According to alkylphenol polyoxyethylene：Monoxone mol ratio 1：1 addition carboxylating reagent, is warming up to 100oC continues 1 hour, then adds
Hydrochloric acid is neutralized to pH<3, and carry out oil-water separation, oil phase adds 30%NaOH aqueous solution to be neutralized, and obtains alkyl phenol polyoxy second
Alkene ether carboxylic acid sodium.
Alkylphenol polyoxyethylene carboxylic acid sodium surface activity by decyl triethylammonium hydroxide and according to present invention preparation
Agent is dissolved in water, and stirs 30 minutes, is configured to 0.3% aqueous solution, then by above-mentioned surfactant according to cation：
Anionic-nonionic surfactant molar ratio 1: 10 mix homogeneously, obtains compound surfactant 5, and its composition, structure are shown in
Table 1.
【Embodiment 6】
By alkylphenol polyoxyethylene, NaOH according to mol ratio 1：4 addition reactors, in 80oC alkalizes 2 hours, then presses
According to alkylphenol polyoxyethylene：Chloropropionic acid mol ratio 1：1.5 addition carboxylating reagent, are cooled to 50oC continue 18 hours, then plus
Enter hydrochloric acid and be neutralized to pH<3, and carry out oil-water separation, oil phase adds 10%Ca (HCO3)2It is neutralized, obtain alkyl phenol polyoxy second
Alkene ether calcium carboxylates.
Live by Dodecyl trimethyl ammonium chloride and according to the alkylphenol polyoxyethylene calcium carboxylates surface of present invention preparation
Property agent be dissolved in water, stir 30 minutes, be configured to 0.3% aqueous solution, then by above-mentioned surfactant according to sun from
Son：Anionic-nonionic surfactant molar ratio 1: 0.9 mix homogeneously, obtains compound surfactant 6, its composition, knot
Structure is shown in Table 1.
【Embodiment 7】
By alkylphenol polyoxyethylene, KOH according to mol ratio 1：1 addition reactor, alkalizes 10 hours in room temperature, then presses
According to alkylphenol polyoxyethylene：Sodium chloroacetate mol ratio 1：3 addition carboxylating reagent, are warming up to 80oC continues 8 hours, then adds
Hydrochloric acid is neutralized to pH<3, and carry out oil-water separation, oil phase adds 30%KOH aqueous solution to be neutralized, and obtains alkylphenol-polyethenoxy
Ether carboxylic acid potassium.
Alkylphenol polyoxyethylene carboxylic acid potassium surface by dioctadecyl dimethyl ammonium chloride and according to present invention preparation
Activating agent is dissolved in water, stir 30 minutes, be configured to 0.3% aqueous solution, then by above-mentioned surfactant according to sun from
Son：Anionic-nonionic surfactant molar ratio 1: 4 mix homogeneously, obtains compound surfactant 7, its composition, structure
It is shown in Table 1.
【Embodiment 8】
By alkylphenol polyoxyethylene, NaOH according to mol ratio 1：3 addition reactors, in 65oC alkalizes 2 hours, then presses
According to alkylphenol polyoxyethylene：Chloropropionic acid mol ratio 1：2 addition carboxylating reagent, are warming up to 75oC continues 9 hours, then adds salt
Acid is neutralized to pH<3, and carry out oil-water separation, oil phase adds 30%NaOH aqueous solution to be neutralized, and obtains alkylphenol-polyethenoxy
Ether carboxylic acid sodium.
Alkylphenol polyoxyethylene carboxyl acid natrium surfactant difference by four octyl group ammonium chloride and according to present invention preparation
It is dissolved in the water, stir 30 minutes, be configured to 0.3% aqueous solution, then by above-mentioned surfactant according to cation：Anion-
Nonionic surfactant mol ratio 1: 6 mix homogeneously, obtains compound surfactant 8, and its composition, structure are shown in Table 1.
【Embodiment 9】
The 0.30wt% compound surfactant that prepare embodiment 3 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 compound surfactant compositionss composition and structure
【Embodiment 10】Compound surfactant compositionss interface performance is tested
Measure compound surfactant compositionss and Shuanghe Oil Field with TX-500C rotating interfacial tensimeter5-
11 series of strata oil water interfacial tensions.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, compound surfactant compositionss consumption is 0.3%.
Table 2 compound surfactant compositionss and Shuan He oil field5-11 series of strata oil water interfacial tension
| Embodiment | Interfacial tension (mN/m) |
| 1 | 0.0080 |
| 2 | 0.0096 |
| 3 | 0.0004 |
| 4 | 0.0006 |
| 5 | 0.0068 |
| 6 | 0.0075 |
| 7 | 0.0011 |
| 8 | 0.0075 |
| 9 | 0.0062 |
As shown in Table 2, the compound surfactant of embodiment 1～8 preparation has good interface for Henan Oil Field
Performance.Embodiment 9 shows, after the surfactant of present invention preparation is compounded with polymer, its interface performance is still good.
Compound surfactant prepared by embodiment 3 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 3 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) | 0.009 | 0.007 | 0.004 | 0.002 | 0.0007 | 0.0004 |
The above results show, compound surfactant compositionss of the present invention have very high oil for Henan Oil Field crude oil
Water termination activity.
Measure compound surfactant and the Central Plains of embodiment 4 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 0.003mN/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 11】Compound surfactant compositionss 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% surfactant solution：Solution=1：
10 mix homogeneously, after aging 48 hours under reservoir temperature, with the crude oil in petroleum ether extraction solution, fixed with 50ml color comparison tube
Hold, spectrophotometer colorimetric analysiss at wavelength 430nm.Using standard curve gauging surface activator solution Central Plains oil concentration.
Table 4 compound surfactant compositionss washing oil result
| Embodiment | Washing oil rate % |
| 1 | 62.5 |
| 2 | 60.1 |
| 3 | 44.3 |
| 4 | 58.1 |
| 5 | 40.8 |
| 6 | 52.4 |
| 7 | 57.6 |
| 8 | 45.5 |
【Embodiment 12】Compound surfactant compositionss 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 compound table of tuberculosiss 0.3pv (rock pore volume)
After the surfactant composition of face, water drive to aqueous 100%, improves oil recovery factor and the results are shown in Table 5.
Table 5 compound surfactant compositionss oil displacement test result
| Surfactant sequence number | Improve recovery ratio % |
| 1 | 5.5 |
| 2 | 5.1 |
| 3 | 5.2 |
| 4 | 5.9 |
| 5 | 4.4 |
| 6 | 4.7 |
| 7 | 6.1 |
| 8 | 4.5 |
【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 compound surfactant compositionss, by cationic surfactant and Anionic-nonionic surfactant
Composition, described cationic surfactant is 1: 0.01～1: 100 with the mol ratio of Anionic-nonionic surfactant,
Its cationic surfactant is selected from least one in quaternary ammonium salt or quaternary ammonium base, and Anionic-nonionic surfactant divides
Sub- formula is：
Wherein M is any one in alkali metal ion, alkaline-earth metal ions or ammonium ion, and R is H, C1～C20Alkyl, virtue
Base, COOM or SO3Any one in M, R ' is C1～C5Alkyl, n is any one integer or decimal in 1～20.
2. according to claim 1 compound surfactant compositionss it is characterised in that described cationic surfactant
At least one in tetra-alkyl ammonium chloride or tetra-alkyl ammonium hydroxide.
3. according to claim 1 compound surfactant compositionss it is characterised in that described Anionic-nonionic surface
Activating agent cationic M is selected from Na+、K+、Mg2+、Ca2+Or NH4 +In any one.
4. according to claim 1 compound surfactant compositionss it is characterised in that described R be H, C5～C15Alkane
Base, aryl, COOM or SO3M.
5. the preparation method of compound surfactant compositionss described in claim 1, comprises the following steps：
A) by alkylphenol polyoxyethylene, catalyst according to mol ratio 1：1～5 addition reactor, in room temperature～100 DEG C alkalization 1
～10 hours, then add sulfonated reagent or carboxylating reagent, wherein alkylphenol polyoxyethylene：Sulfonated reagent or carboxylating reagent
Mol ratio is 1：1～4, it is warming up to 50～100 DEG C and continues reaction 1～20 hour, then add hydrochloric acid to be neutralized to pH<3, and carry out
Oil-water separation, oil phase adds alkali liquor to be neutralized, and finally obtains alkylphenol polyoxyethylene sulfonate or alkylphenol-polyethenoxy
Ether carboxylate；
B) by cationic surfactant and the Anionic-nonionic surfactant that obtains according to step a) is dissolved separately in
In water, then according to mol ratio 1: 0.1～1: 10 mix homogeneously, obtain required compositionss.
6. according to claim 5 the preparation method of compound surfactant compositionss it is characterised in that described catalysis
Agent is selected from least one in NaOH or KOH；Described sulfonated reagent is hydroxyl sulfoacid and its salt or halogenosulfonic acid and its salt；Institute
The carboxylating reagent stated is halogenated carboxylic acid and its salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210239959.1A CN103540303B (en) | 2012-07-12 | 2012-07-12 | Composite surfactant composition as well as preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210239959.1A CN103540303B (en) | 2012-07-12 | 2012-07-12 | Composite surfactant composition as well as preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103540303A CN103540303A (en) | 2014-01-29 |
| CN103540303B true CN103540303B (en) | 2017-02-15 |
Family
ID=49964183
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210239959.1A Active CN103540303B (en) | 2012-07-12 | 2012-07-12 | Composite surfactant composition as well as preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103540303B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10526528B2 (en) | 2014-08-12 | 2020-01-07 | China Petroleum & Chemical Corporation | Surfactant composition and preparation method therefor and application thereof |
| CN105482797B (en) * | 2014-10-10 | 2018-09-04 | 中国石油天然气股份有限公司 | A kind of organic composite alkali ternary composite driving finish and preparation method thereof |
| CN104963668B (en) * | 2015-06-29 | 2018-09-21 | 中国海洋石油集团有限公司 | A method of reducing oil field Polymer Used For Oil Displacement adsorbance |
| TW201728617A (en) * | 2015-10-09 | 2017-08-16 | 克萊瑞特國際股份有限公司 | Cashew nutshell liquid alkoxylate carboxylate as a new renewable surfactant composition for enhanced oil recovery applications |
| TW201728616A (en) * | 2015-10-09 | 2017-08-16 | 克萊瑞特國際股份有限公司 | Cashew nutshell liquid alkoxylate sulfate as a new renewable surfactant composition for enhanced oil recovery applications |
| CN111088005B (en) * | 2018-10-23 | 2022-10-11 | 中国石油化工股份有限公司 | Method for enhancing injection performance of surfactant composition for oil displacement, composition, preparation method and application thereof |
| CN112680206B (en) * | 2019-10-17 | 2022-11-04 | 中国石油化工股份有限公司 | Surfactant composition, and preparation method and application thereof |
| US11254855B2 (en) | 2019-11-14 | 2022-02-22 | Saudi Arabian Oil Company | Surfactant mixtures used during chemical enhanced oil recovery and methods of use thereof |
| CN111378063B (en) * | 2020-03-27 | 2023-07-07 | 国科广化韶关新材料研究院 | Ternary polymer amphoteric dispersant and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101056959A (en) * | 2004-11-15 | 2007-10-17 | 罗迪亚公司 | Viscoelastic surfactant fluids having enhanced shear recovery, rheology and stability performance |
| CN101310093A (en) * | 2005-11-16 | 2008-11-19 | 罗迪亚公司 | Methods for recovering oil from an oil reservoir |
| CN102161883A (en) * | 2011-01-28 | 2011-08-24 | 胜利油田胜利勘察设计研究院有限公司 | Composite chemical oil displacement agent for tertiary oil recovery in oil field |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1086184C (en) * | 1999-11-15 | 2002-06-12 | 广州绿色化学品研究中心 | 2-valence metal salt of alkylphenol polyoxyvinethene carboxylic acid and its preparing process |
| CN102234503A (en) * | 2010-04-21 | 2011-11-09 | 陈新阳 | Oil displacement agent |
| AR094914A1 (en) * | 2013-02-28 | 2015-09-09 | Univ Texas | PHENOL-ETOXYLATE CODISOLVENT TENSIOACTIVE COMPOSITION |
-
2012
- 2012-07-12 CN CN201210239959.1A patent/CN103540303B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101056959A (en) * | 2004-11-15 | 2007-10-17 | 罗迪亚公司 | Viscoelastic surfactant fluids having enhanced shear recovery, rheology and stability performance |
| CN101310093A (en) * | 2005-11-16 | 2008-11-19 | 罗迪亚公司 | Methods for recovering oil from an oil reservoir |
| CN102161883A (en) * | 2011-01-28 | 2011-08-24 | 胜利油田胜利勘察设计研究院有限公司 | Composite chemical oil displacement agent for tertiary oil recovery in oil field |
Non-Patent Citations (1)
| Title |
|---|
| 烷基酚聚氧乙烯醚羧酸盐的合成及其泡沫性能研究;王君等;《精细石油化工进展》;20080125;第09卷(第01期);第49页1.1节主要实验药品、1.2.1.2节合成步骤、1.2.2节产品纯化 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103540303A (en) | 2014-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103540304B (en) | Surfactant composition for intensified oil production and preparation method thereof | |
| CN103540303B (en) | Composite surfactant composition as well as preparation method thereof | |
| CN104232045B (en) | Composite surface active agent composition and preparation method and application thereof | |
| CN103740354B (en) | A surfactant composition used for tertiary oil recovery and a preparation method thereof | |
| CN104232044B (en) | Surface activator composition, preparation method and application for tertiary oil recovery | |
| CN103666431B (en) | Surfactant composition and preparation method thereof | |
| CN103666430B (en) | For the surfactant composition and preparation method thereof of intensified oil reduction | |
| CN103421480B (en) | Surfactant oil displacement composition and method of making the same | |
| CN103422840B (en) | Use the flooding method of anions and canons complexed surfactant | |
| CN103965854B (en) | Negative and positive system surfactant and preparation method available for low-permeability oil deposit | |
| CN104277814B (en) | Surfactant oil displacement composition, preparation method and application | |
| CN103965853A (en) | Combined surfactant and its preparation method | |
| CN103740357B (en) | Low-tension foaming agent combination and preparation method | |
| CN103540305B (en) | Surfactant composition for chemical displacement of reservoir oil and preparation method thereof | |
| CN103937481A (en) | High-temperature-resistant and low-tension foam flooding agent and preparation method thereof | |
| CN104277806B (en) | Displacement composition, its preparation method and its application | |
| CN106590606A (en) | Temperature and salt resisting low-tension foam and application thereof in foam plugging | |
| CN103540306B (en) | Three adopt surfactant composition and preparation method thereof | |
| CN104232047B (en) | Three using surface activator composition, preparation method and application | |
| CN107916098A (en) | Displacement of reservoir oil Surfactant Used in Viscoelastic Fracturing Fluids composition and its preparation method and application | |
| CN103773346B (en) | Surfactant composition for high-efficiency displacement and preparation method of composition | |
| CN104449630A (en) | Surfactant composition for oil recovery and preparation method of surfactant composition | |
| CN107828398A (en) | Efficient surfactant oil displacement composition and preparation method thereof | |
| CN106590578A (en) | Composite surfactant composition for medium-mineralization-degree reservoir oil displacement | |
| CN106590565B (en) | Middle low mineralization oil reservoir oil displacement compound surfactant composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |