CN103740354A - 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 PDF

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CN103740354A
CN103740354A CN201210393062.4A CN201210393062A CN103740354A CN 103740354 A CN103740354 A CN 103740354A CN 201210393062 A CN201210393062 A CN 201210393062A CN 103740354 A CN103740354 A CN 103740354A
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surfactant composition
oil
active agent
anionic
oil recovery
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CN103740354B (en
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李应成
张卫东
沙鸥
沈之芹
邓舜
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/584Compositions 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

Be used for surfactant composition of tertiary oil recovery and preparation method thereof
Technical field
The present invention relates to a kind of surfactant composition for tertiary oil recovery and preparation method thereof.
Background technology
Along with the increase of world energy sources demand, the rational exploitation and utilization of oil has caused people's very big attention, and the produced quantity to oil and the requirement of production efficiency are also more and more higher.Realize the high-efficiency mining of hydrocarbon resources, for improving crude production rate, not only there is realistic meaning, have more important strategic importance.1/3 of the conventional general only extraction oil in-place of oil production method (once with secondary method), 2/3 the crude oil of also having an appointment is failed extraction, and the in the situation that of being therefore becoming tight in energy day, improving tar productivity has become the key subjects of oil production research.Tertiary oil recovery technology is a kind of method of effective raising tar productivity, can be divided into four large classes: the one, and heating power drives, and comprises steam flood, combustion in situ etc.; The 2nd, mixed phase drives, and comprises CO 2mixed phase, hydrocarbon mixed phase and other rare gas element mixed phases drive; The 3rd, chemical flooding; The 4th, microbe oil production, comprises that biological polymer, MICROBIAL SURFACTANT drive.Chemical flooding is the technology of extremely important in intensified oil reduction and extensive enforcement, comprises the multiple combination technology of polymer flooding, surfactant flooding, caustic waterflooding etc. and polymkeric substance, alkali, tensio-active agent.The effect of chemical flooding is the result of physical action and chemical action, and physical action refers to the effect that involves of displacing fluid, and chemical action refers to the microcosmic oil drive effect of displacing fluid.The core of chemical action is to reduce the interfacial tension of displacing fluid and crude oil.Tensio-active agent is owing to having oleophylic (hydrophobic) and hydrophilic (oleophobic) character concurrently, and when tensio-active agent is water-soluble, molecule is mainly distributed on water-oil interface, can significantly reduce oil water interfacial tension.The reduction of oil water interfacial tension means that surfactant system can overcome the force of cohesion between crude oil, and larger oil droplet is dispersed into little oil droplet, thereby improves the percent of pass of crude stream when pore throat.The oil displacement efficiency of tensio-active agent also shows the effect such as wettability of rock surface reversion, emulsification of crude oil, raising surface charge density and oil droplet coalescence that makes oleophylic, and this is the reason that tensio-active agent plays very important effect in chemical flooding technology.
Surface active agent for tertiary oil recovery adopts Recompounded multielement system mostly at present, comprises nonionic surface active agent and ionogenic surfactant simultaneously, in part formula, also adds the auxiliary agents such as alkali and alcohol.As the tensio-active agent that patent CN101024764A provides a kind of oil-field thick-oil well to use, this promoting agent is comprised of water, sheet alkali, ethanol, oleic acid, alkylphenol polyoxyethylene, Sodium dodecylbenzene sulfonate.For another example patent CN1458219A discloses a kind of pure binary ultra low interfacial tension of surfactant polymer combination flooding formula of tertiary oil recovery application, the tensio-active agent wherein using is sulfonated petro-leum or take sulfonated petro-leum as host, adds thinner and the complexed surfactant of other surfactant compound, the weight percent of its component is sulfonated petro-leum 50~100%, alkylsulfonate 0~50%, carboxylate salt 0~50%, alkylaryl sulphonate 0~35%, low-carbon alcohol 0~20%.And for example patent CN1394935 has invented a kind of chemical oil displacement agent, and it mainly comprises octyl group benzene sulfonic acid sodium salt anion surfactant, surfactant adjuvant, tensio-active agent synergistic agent, surface active agent solubilization agent.This oil-displacing agent can reduce the structural viscosity of viscous crude significantly, can reduce oil water interfacial tension simultaneously, thereby improves oil recovery factor.
But still there is more problem in above-mentioned surface active agent for tertiary oil recovery, be mainly that surfactant activity is poor, oil displacement efficiency is low, simultaneously because surfactant system is too complicated, thereby Produced Liquid breakdown of emulsion difficulty, sewage disposal difficulty is large; In addition because flooding system is containing mineral alkali, injury is brought in stratum and oil well, cause the problems such as etching apparatus and pipeline, and due to the seriously viscosity of reduction polymkeric substance of mineral alkali, for reaching required viscosity, have to greatly improve the working concentration of polymkeric substance, the comprehensive cost that makes to recover the oil improves; The high temperature resistance of tensio-active agent, high salt tolerance, anti-high salinity limited in one's ability.
As everyone knows, anion surfactant, as sulfonated petro-leum, petroleum carboxylate, alkylbenzene sulfonate etc. are widely used in tertiary oil recovery process at present, and cats product is easily adsorbed by stratum or produces precipitation because of it, therefore reduce the ability of oil water interfacial tension, be generally not used in tertiary oil recovery.While approaching equal proportion mixing due to cationic and anionic surfactant, its aqueous solution easily forms precipitation, thereby causes cationic and anionic surfactant mixed system not only in application, to become incompatibility, and correlation theory research also relatively lags behind.Research is in recent years found, the cationic and anionic surfactant mixed system aqueous solution has a lot of anomalous properties, as existed the interaction between strong electrostatic interaction and hydrophobicity carbochain in the aqueous solution due to cationic and anionic surfactant, promoted two kinds to be with the interionic association of different charged surface promoting agents, in solution, be easy to form micella, produce the surfactivity higher than single tensio-active agent.In addition, cationic and anionic surfactant mixed system can obviously reduce the absorption loss of cats product on rock core, thereby can significantly reduce the inherent defect of cats product.
Gong Yujun etc. (seeing volume the 1st phase Northwest University's journal (natural science edition) February the 30th in 2000,28~31) research thinks that cetyl trimethylammonium bromide (CTAB) and sodium lauryl sulphate (SDS) mixed system have solublization.In oil production process, utilize the solublization can " displacement of reservoir oil ", by under the oil wash sticking on the sandstone of rock stratum, thereby improve oil recovery.Huang Hongdu etc. (seeing oil and gas journal the 29th the 4th phase of volume of August in 2007,101~104) have studied the interfacial tension of the anion surfactants such as sulfonated petro-leum, petroleum carboxylate, alkylbenzene sulfonate and cetyl trimethylammonium bromide, alkali compound system and have drawn to draw a conclusion: adding of cats product improves the interfacial activity of petroleum carboxylate, alkylbenzene sulfonate, sulfonated petro-leum.
Above-mentioned result of study shows that yin, yang ionic surface active agent compound system has certain effect for reduction oil water interfacial tension, raising oil displacement efficiency.But the former result of study shows its interface performance and still have much room for improvement, the latter has still adopted alkali in system, thereby cannot avoid alkali to bring injury to stratum and oil well, the problems such as etching apparatus and pipeline and breakdown of emulsion difficulty.Above-mentioned system ratio is easier to generate precipitation in addition, is unfavorable for practical application.
For this reason, one aspect of the present invention absorbs has used for reference forefathers about yin, yang ionic surface active agent mixed system result of study, adopt on the other hand Anionic-nonionic tensio-active agent to replace traditional anion surfactant, the easy shortcoming such as precipitation while having overcome cationic anionic surfactant combination, has invented cats product and Anionic-nonionic surfactant composition for tertiary oil recovery process.
Summary of the invention
One of technical problem to be solved by this invention is that existing tensio-active agent oil displacement efficiency in tertiary oil recovery process is poor, simultaneously because flooding system contains mineral alkali, injury is brought in stratum and oil well, the problem of etching apparatus and pipeline and breakdown of emulsion difficulty, a kind of surfactant composition is provided, said composition has that interfacial activity is high, washing oil ability is strong, system is simple, can not bring injury to stratum and oil well, can etching apparatus and pipeline and can not cause the advantage of breakdown of emulsion difficulty.
Two of technical problem to be solved by this invention is to provide a kind of preparation method of the surfactant composition corresponding with technical solution problem one.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of surfactant composition for tertiary oil recovery and preparation method thereof, comprise cats product and Anionic-nonionic tensio-active agent, the mol ratio of described cats product and Anionic-nonionic tensio-active agent is 1: 0.01~1: 100, wherein cats product is selected from least one in quaternary ammonium salt or quaternary amine alkali, and Anionic-nonionic tensio-active agent is at least one in amidogen ether carboxylate salt or amidogen ether sulfonate;
The general molecular formula of amidogen ether carboxylate salt is:
Figure 418133DEST_PATH_IMAGE001
The general molecular formula of amidogen ether carboxylate salt is:
Figure 335273DEST_PATH_IMAGE002
In technique scheme, cats product preferred version is selected from least one in tetra-alkyl ammonium chloride or tetra-alkyl ammonium hydroxide; R preferred version is at least one in alkyl or aryl; R ' preferred version is any one in H, alkyl or aryl; " preferred version is C to R 1~C 5alkyl or substituted alkyl in any one; The oxyethyl group polymerization degree, propoxy-polymerization degree preferred version are any one integer or decimal in 0~20; Positively charged ion M preferred version is selected from Na, K, Mg, Ca or NH 4 +in any one; The mol ratio preferred version of cats product and Anionic-nonionic tensio-active agent is 1: 0.1~1: 10.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of preparation method of the surfactant composition for tertiary oil recovery, comprises the following steps:
A) organic amine, catalyzer and required oxyethane, propylene oxide are added to reactor, in 100~200 ℃ of reactions 1~20 hour; Then add sulfonated reagent or carboxylation reagent, wherein organic amine: the mol ratio of sulfonated reagent or carboxylation reagent is 1:1~4, in 50~200 ℃, continue reaction 1~20 hour, then add hydrochloric acid to be neutralized to pH<3, and carry out oily water separation, oil phase adds alkali lye to neutralize, and finally obtains aliphatic amine polyoxyethylene/polyoxypropylene ether carboxylate, sulfonate;
B) Anionic-nonionic tensio-active agent cats product and step a) being obtained is dissolved in the water respectively, then according to mol ratio, within 1: 0.1~1: 10, mixes, and obtains required composition.
In technique scheme, described catalyzer is any one in NaOH, KOH; Described sulfonated reagent is hydroxyl sulfoacid and salt, halogenosulfonic acid and salt thereof; Described carboxylation reagent is halogenated carboxylic acid and salt thereof.
Surfactant composition of the present invention is on the one hand due to strong electrostatic attraction effect between yin, yang ionic surface active agent opposite charges polar group, surfactant molecule adsorptive capacity on interface is increased, micelle-forming concentration significantly reduces, thereby has the incomparable high surface of single tensio-active agent; Due to the interfacial activity of surfactant composition superelevation, its aqueous solution can form ultra low interfacial tension with crude oil, thereby effectively overcomes the force of cohesion between crude oil, is conducive to former oil-out, and then significantly improves oil displacement efficiency simultaneously.Surfactant composition can change oil reservoir wettability of the surface on the other hand, as the cats product in composition by with the electronegative Interaction of substituents being adsorbed on solid surface, its desorption is got off, making glossy wet surface modification is intermediate wet or water-wet surface, reduce the work of adhesion of crude oil at solid surface, thereby be conducive to peeling off of crude oil.Yin, yang ionic surface active agent mixing solutions has solublization to crude oil simultaneously, can, further by under the former oil wash sticking on the sandstone of rock stratum, improve oil recovery factor.
In tertiary oil recovery process, adopt surfactant composition of the present invention, there is interfacial activity high: surfactant composition consumption is still can form 10 with underground crude oil under 0.01~0.05% condition -3~10 -4mN/m ultra low interfacial tension; Washing oil ability is strong: surfactant composition exceedes 40% to the washing oil rate of crude oil; Surfactant composition system is simple.Because flooding system is containing mineral alkali, thereby the problem of mineral alkali causes stratum while having avoided rig-site utilization injury, the corrosion that equipment is caused and the breakdown of emulsion difficulty that causes thus, good technique effect obtained.
Below by embodiment, the present invention is further elaborated.
 
Embodiment
[embodiment 1]
Lauryl amine, KOH are added to reactor according to mol ratio 1:2, stir 30 minutes, then add required oxyethane, propylene oxide, in 200 oc reaction 1 hour; Then according to lauryl amine and carboxylation reagent mol ratio 1:1, add Mono Chloro Acetic Acid, in 50 oc continues reaction and adds hydrochloric acid to be neutralized to pH<3 after 20 hours, stratification, and oil phase adds the 30%KOH aqueous solution to neutralize, and obtains Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent prepared by stearyl dimethyl benzyl ammonium chloride and the present invention is dissolved in the water respectively, stir 30 minutes, be mixed with 0.3% aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic tensio-active agent mol ratio mixes at 1: 0.1, obtain surfactant composition 1, its composition, structure are in Table 1.
 
[embodiment 2]
Adjacent phenylaniline, NaOH are added to reactor according to mol ratio 1:6, stir 30 minutes, then add required oxyethane, propylene oxide, in 100 oc reaction 20 hours; Then according to adjacent phenylaniline and sulfonated reagent mol ratio 1:4, add chlorsulfonic acid, in 120 oc continues reaction and adds hydrochloric acid to be neutralized to pH<3 after 14 hours, stratification, and oil phase adds the 30%NaOH aqueous solution to neutralize, and obtains Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent prepared by tetrabutylammonium chloride and the present invention is dissolved in the water respectively, stir 30 minutes, be mixed with 0.3% aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic tensio-active agent mol ratio mixes at 1: 0.5, obtain surfactant composition 2, its composition, structure are in Table 1.
 
[embodiment 3]
Hexahydroaniline, NaOH are added to reactor according to mol ratio 1:4, stir 30 minutes, then add required oxyethane, propylene oxide, in 160 oc reaction 2 hours; Then according to hexahydroaniline and sulfonated reagent mol ratio 1:2.5, add chlorine amyl group sodium sulfonate, in 120 oc continues reaction and adds hydrochloric acid to be neutralized to pH<3 after 14 hours, stratification, and oil phase adds the 30%NaOH aqueous solution to neutralize, and obtains Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent prepared by four octyl group ammonium chlorides and the present invention is dissolved in the water respectively, stir 30 minutes, be mixed with 0.3% aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic tensio-active agent mol ratio mixes at 1: 10, obtain surfactant composition 3, its composition, structure are in Table 1.
 
[embodiment 4]
To according to mol ratio 1:4, add reactor to amino-aniline, NaOH, stir 30 minutes, then add required oxyethane, propylene oxide, in 160 oc reaction 16 hours; Then according to amino-aniline and sulfonated reagent mol ratio 1:2.5 are added to 3-chlorine-2-hydroxyl propanesulfonate, in 180 oc continues reaction and adds hydrochloric acid to be neutralized to pH<3 after 18 hours, stratification, and oil phase adds the 30%NaOH aqueous solution to neutralize, and obtains Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent prepared by decyl triethyl ammonium hydroxide and the present invention is dissolved in the water respectively, stir 30 minutes, be mixed with 0.3% aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic tensio-active agent mol ratio mixes at 1: 6, obtain surfactant composition 4, its composition, structure are in Table 1.
 
[embodiment 5]
Hexadecylamine, NaOH are added to reactor according to mol ratio 1:2, stir 30 minutes, then add required oxyethane, propylene oxide, in 150 oc reaction 10 hours; Then according to hexadecylamine and carboxylation reagent mol ratio 1:1.5, add sodium chloroacetate, in 60 oc continues reaction and adds hydrochloric acid to be neutralized to pH<3 after 14 hours, stratification, and oil phase adds 10%Ca (HCO 3) 2the aqueous solution neutralizes, and obtains Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent prepared by phenyl trimethyl ammonium chloride and the present invention is dissolved in the water respectively, stir 30 minutes, be mixed with 0.3% aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic tensio-active agent mol ratio mixes at 1: 1.4, obtain surfactant composition 5, its composition, structure are in Table 1.
 
[embodiment 6]
Octadecylamine, NaOH are added to reactor according to mol ratio 1:2, stir 30 minutes, then add required oxyethane, propylene oxide, in 150 oc reaction 10 hours; Then according to octadecylamine and carboxylation reagent mol ratio 1:1.5, add sodium chloroacetate, in 70 oc continues reaction and adds hydrochloric acid to be neutralized to pH<3 after 12 hours, stratification, and oil phase adds 10%Mg (HCO 3) 2the aqueous solution neutralizes, and obtains Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent prepared by benzyltriethylammoinium chloride and the present invention is dissolved in the water respectively, stir 30 minutes, be mixed with 0.3% aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic tensio-active agent mol ratio mixes at 1: 1.8, obtain surfactant composition 6, its composition, structure are in Table 1.
 
[embodiment 7]
Oleyl amine, NaOH are added to reactor according to mol ratio 1:3, stir 30 minutes, then add required oxyethane, propylene oxide, in 150 oc reaction 10 hours; Then according to oleyl amine and sulfonated reagent mol ratio 1:3, add sodium isethionate, in 180 oc continues reaction and adds hydrochloric acid to be neutralized to pH<3 after 4 hours, stratification, and oil phase adds ammoniacal liquor to neutralize, and obtains Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent prepared by Dodecyl trimethyl ammonium chloride and the present invention is dissolved in the water respectively, stir 30 minutes, be mixed with 0.3% aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic tensio-active agent mol ratio mixes at 1: 2.5, obtain surfactant composition 7, its composition, structure are in Table 1.
 
[embodiment 8]
Octadecylamine, NaOH are added to reactor according to mol ratio 1:4, stir 30 minutes, then add required oxyethane, propylene oxide, in 140 oc reaction 12 hours; Then according to octadecylamine and sulfonated reagent mol ratio 1:3, add sodium isethionate, in 160 oc continues reaction and adds hydrochloric acid to be neutralized to pH<3 after 8 hours, stratification, and oil phase adds 10%Mg (HCO 3) 2the aqueous solution neutralizes, and obtains Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent prepared by palmityl trimethyl ammonium chloride and the present invention is dissolved in the water respectively, stir 30 minutes, be mixed with 0.3% aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic tensio-active agent mol ratio mixes at 1: 8, obtain surfactant composition 8, its composition, structure are in Table 1.
 
[embodiment 9]
Methylphenylamine, NaOH are added to reactor according to mol ratio 1:3, stir 30 minutes, then add required oxyethane, propylene oxide, in 150 oc reaction 10 hours; Then according to methylphenylamine and carboxylation reagent mol ratio 1:1.5, add sodium chloroacetate, in 80 oc continues reaction and adds hydrochloric acid to be neutralized to pH<3 after 8 hours, stratification, and oil phase adds the 30%NaOH aqueous solution to neutralize, and obtains Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent prepared by distearyl dimethyl ammonium chloride and the present invention is dissolved in the water respectively, stir 30 minutes, be mixed with 0.3% aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic tensio-active agent mol ratio mixes at 1: 4, obtain surfactant composition 9, its composition, structure are in Table 1.
 
[embodiment 10]
Hexahydroaniline, NaOH are added to reactor according to mol ratio 1:3, stir 30 minutes, then add required oxyethane, propylene oxide, in 160 oc reaction 10 hours; Then according to hexahydroaniline and carboxylation reagent mol ratio 1:1.5, add sodium chloroacetate, in 80 oc continues reaction and adds hydrochloric acid to be neutralized to pH<3 after 8 hours, stratification, and oil phase adds the 30%NaOH aqueous solution to neutralize, and obtains Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent prepared by etamon chloride and the present invention is dissolved in the water respectively, stir 30 minutes, be mixed with 0.3% aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic tensio-active agent mol ratio mixes at 1: 1.3, obtain surfactant composition 10, its composition, structure are in Table 1.
 
[embodiment 11]
0.30wt% surfactant composition prepared by embodiment 6 and 0.15wt% polyacrylamide (molecular weight 2,600 ten thousand) aqueous solution is even, obtains a kind of Polymer Used For Oil Displacement-surfactant complex.
Table 1 surfactant composition composition and structure
Figure 990377DEST_PATH_IMAGE004
The test of [embodiment 12] surfactant composition interface performance
With TX-500C rotation, drip interfacial tensimeter and measure surfactant oil displacement composition and Shuanghe Oil Field
Figure 576789DEST_PATH_IMAGE006
5-11 series of strata oil water interfacial tension.Surfactant composition consumption: 0.3%, measuring temperature is 81 oc, local water is NaHCO 3type, salinity is 7947mg/L, chloride ion content 2002 mg/L, Ca 2+content 20 mg/L, Mg 2+content 12.2 mg/L.
Table 2 surfactant composition and Shuan He oil field 5-11 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 surfactant composition of embodiment 1~10 preparation has good interface performance for Henan Oil Field.Embodiment 11 shows, after surfactant composition prepared by the present invention and polymkeric substance are composite, its interface performance is still good.
Surfactant composition prepared by embodiment 10 is mixed with different concns, respectively test and Shuanghe Oil Field
Figure 541651DEST_PATH_IMAGE006
5-11 series of strata oil water interfacial tension, the results are shown in Table 3.
Table 3 different concns surfactant composition 10 and Shuanghe Oil Field
Figure 114453DEST_PATH_IMAGE006
5-11 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 shows, surfactant composition of the present invention has very high interfacial activity for Henan Oil Field crude oil.
With TX-500C rotation, drip interfacial tensimeter and again measure surfactant composition prepared by embodiment 6 and the Zhongyuan Oil Field three factory's oil water interfacial tensions that recover the oil.Measuring temperature is 80 oc, formation water salinity is 79439mg/L, Ca 2+content 592 mg/L, Mg 2+content 2871mg/L, dosage of surfactant is 0.3%.Oil water interfacial tension is 0.002mN/m, shows that tensio-active agent of the present invention is not only for low mineralization oil reservoir, still has good interface performance for high temperature and high salt oil deposit simultaneously, has advantages of that the scope of application is wide.
The aptitude tests of [embodiment 13] surfactant composition washing oil
Get Shuanghe Oil Field
Figure 783332DEST_PATH_IMAGE006
5-11 series of strata oil-sand, according to oil: sand=1:4 (weight ratio) 81 oaging 7 days of C, stirs 5 minutes for every 2 hours; Then take out above-mentioned oil-sand 5g after aging, with 0.3% surfactant composition solution by oil-sand: solution=1:10 mixes, under reservoir temperature after aging 48 hours, with the crude oil in petroleum ether extraction solution, with 50ml colorimetric cylinder constant volume, spectrophotometer is in wavelength 430nm place's colorimetric analysis.Utilize typical curve gauging surface activator solution Crude Oil concentration.
Table 4 surfactant 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
The research of [embodiment 14] surfactant composition Oil Displacing Capacity
In length, be 30 centimetres, diameter is 2.5 centimetres, and rate of permeation is 1.5 microns 2rock core on carry out oil displacement test.First use Shuanghe Oil Field 5-11 series of strata local water is driven to moisture 92 %, and after the surfactant composition of metaideophone 0.3pv (rock pore volume), water drive, to moisture 100%, improve oil recovery factor and the results are shown in Table 5.
Table 5 surfactant 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) the 30th the 1st phase of volume of February in 2000, the methods such as 28~31 Gong Yu armies are mixed with mixed system (mol ratio 1:1.5) by cetyl trimethylammonium bromide (CTAB) and sodium lauryl sulphate (SDS), test respectively it when 0.3% consumption and Shuanghe Oil Field 5-11 series of strata crude oil oil water interfacial tension, washing oil rate and Oil Displacing Capacity, result is as follows:
Table 6 reference oil-displacing agent performance
Interfacial tension (MN/m) Washing oil rate % Improve recovery ratio %
0.03 45.6 2.8
[comparative example 2]
According to oil and gas journal the 29th the 4th phase of volume of August in 2007, Huang Hongdu etc. (101~104) method etc. are by 0.01% cetyl trimethylammonium bromide and 0.02% anion surfactant sulfonated petro-leum and 1.8%Na 2cO 3be mixed with mixed system, test respectively it when 0.3% consumption and Shuanghe Oil Field
Figure 520234DEST_PATH_IMAGE006
5-11 series of strata crude oil oil water interfacial tension, washing oil rate and Oil Displacing Capacity, result is as follows:
Table 7 reference oil-displacing agent performance
Interfacial tension (MN/m) Washing oil rate % Improve recovery ratio %
0.008 56.3 4.2

Claims (10)

1. the surfactant composition for tertiary oil recovery, comprise cats product and Anionic-nonionic tensio-active agent, the mol ratio of described cats product and Anionic-nonionic tensio-active agent is 1: 0.01~1: 100, wherein cats product is selected from least one in quaternary ammonium salt or quaternary amine alkali, and Anionic-nonionic tensio-active agent is at least one in amidogen ether carboxylate salt or amidogen ether sulfonate;
The general molecular formula of amidogen ether carboxylate salt is:
Figure 647987DEST_PATH_IMAGE001
The general molecular formula of amidogen ether sulfonate is:
Figure 592809DEST_PATH_IMAGE002
2. according to claim 1 for the surfactant composition of tertiary oil recovery, it is characterized in that described cats product is at least one in tetra-alkyl ammonium chloride or tetra-alkyl ammonium hydroxide.
3. according to claim 1 for the surfactant composition of tertiary oil recovery, it is characterized in that described R is any one in alkyl or aryl.
4. according to claim 1 for the surfactant composition of tertiary oil recovery, it is characterized in that described R ' is any one in H, alkyl or aryl.
5. according to claim 1 for the surfactant composition of tertiary oil recovery, it is characterized in that described R " is C 1~C 5alkyl or substituted alkyl in any one.
6. according to claim 1 for the surfactant composition of tertiary oil recovery, it is characterized in that the described oxyethyl group polymerization degree, the propoxy-polymerization degree are any one integer or the decimal in 0~20.
7. according to claim 1 for the surfactant composition of tertiary oil recovery, it is characterized in that in described Anionic-nonionic tensio-active agent, positively charged ion M is selected from Na, K, Mg, Ca or NH 4 +in any one.
8. according to claim 1 for the surfactant composition of tertiary oil recovery, it is characterized in that the mol ratio 1: 0.1~1: 10 of cats product and Anionic-nonionic tensio-active agent.
Described in claim 1 for the preparation method of the surfactant composition of tertiary oil recovery, comprise the following steps:
A) organic amine, catalyzer and required oxyethane, propylene oxide are added to reactor, in 100~200 ℃ of reactions 1~20 hour; Then add sulfonated reagent or carboxylation reagent, wherein organic amine: the mol ratio of sulfonated reagent or carboxylation reagent is 1:1~4, in 50~200 ℃, continue reaction 1~20 hour, then add hydrochloric acid to be neutralized to pH<3, and carry out oily water separation, oil phase adds alkali lye to neutralize, and finally obtains aliphatic amine polyoxyethylene/polyoxypropylene ether carboxylate, sulfonate;
B) Anionic-nonionic tensio-active agent cats product and step a) being obtained is dissolved in the water respectively, then according to mol ratio, within 1: 0.1~1: 10, mixes, and obtains required composition.
10. according to claim 9 for the preparation method of the surfactant composition of tertiary oil recovery, it is characterized in that described catalyzer is at least one in NaOH or KOH; Described sulfonated reagent is hydroxyl sulfoacid and salt, halogenosulfonic acid and salt thereof; Described carboxylation reagent is halogenated carboxylic acid and salt thereof.
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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014201854A1 (en) * 2013-06-17 2014-12-24 中国石油化工股份有限公司 Surfactant composition, and manufacturing method and application of same
CN105368430A (en) * 2014-08-27 2016-03-02 中国石油化工股份有限公司 Oil-displacing agent, preparing method of oil-displacing agent and intensified oil production method
CN105368431A (en) * 2014-08-27 2016-03-02 中国石油化工股份有限公司 Oil-displacing composition, preparing method of oil-displacing composition and intensified oil production method
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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
CN105642185A (en) * 2014-10-22 2016-06-08 中国石油化工股份有限公司 Anionic-cationic-nonionic surfactant, preparation method therefor and application of anionic-cationic-nonionic surfactant
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WO2022101081A1 (en) 2020-11-13 2022-05-19 Basf Se Method of mineral oil production from underground carbonate deposits
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4360061A (en) * 1980-04-03 1982-11-23 Exxon Research And Engineering Co. Oil recovery process using polymer microemulsion complexes
CN102516971A (en) * 2011-11-08 2012-06-27 西南石油大学 Block polyether zwitterionic heavy oil emulsified viscosity reducer and preparation method thereof
CN103666431A (en) * 2012-09-05 2014-03-26 中国石油化工股份有限公司 Surfactant composition and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4360061A (en) * 1980-04-03 1982-11-23 Exxon Research And Engineering Co. Oil recovery process using polymer microemulsion complexes
CN102516971A (en) * 2011-11-08 2012-06-27 西南石油大学 Block polyether zwitterionic heavy oil emulsified viscosity reducer and preparation method thereof
CN103666431A (en) * 2012-09-05 2014-03-26 中国石油化工股份有限公司 Surfactant composition and preparation method thereof

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