CN106566509A - Three-component compound flooding composition and application thereof to high-temperature and high-salinity reservoir - Google Patents
Three-component compound flooding composition and application thereof to high-temperature and high-salinity reservoir Download PDFInfo
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- 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
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- 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
- C09K8/588—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 polymers
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- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
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Abstract
The invention provides a three-component compound flooding composition and an application thereof to a high-temperature and high-salinity reservoir. The composition is prepared from the following components in percentage by weight: 0.03-3.0% of an alkaline substance, 0.05-0.30% of a short and long-chain betaine surfactant, 0.05-0.30% of a polymer, and the balance of water, wherein the short and long-chain betaine surfactant has the following structure RN+R1R2X; and in the structure, R is linear or branched alkyl of C10-C24, R1 is linear alkyl of C2-C5, R2 is linear alkyl of C2-C5, and X is -CH2COO-, -CH2CH2SO3-, -CH2CH2CH2SO3-, or -CH2CHOHCH2SO3-. The invention furthermore provides the application of the three-component compound flooding composition to the high-temperature and high-salinity reservoir. According to the technical scheme provided by the composition and the application, the recovery efficiency can be effectively improved under the high-temperature and high-salinity condition, so that higher oil-flooding efficiency is obtained.
Description
Technical field
The present invention relates to a kind of ternary composite driving compositionss and its application in high temperature and high salt oil deposit, belong to oil exploitation
Technical field.
Background technology
With continually developing for oil field, Chinese land main force oil field enters high recovery percent of reserves, high water cut stage.Old filed is steady
Produce, volume increase becomes the important topic put in face of oil field development worker.Chemistry with polymer flooding, ternary composite driving as representative
Drive the stable yields that raising recovery efficiency technique is domestic crude oil and be made that significant contribution.In Daqing oil field, using heavy alkylbenzene sulfonate
The strong base ternary composite driving of surfactant（Sodium hydroxide/heavy alkylbenzene sulfonate/polymer）Technology has been enter into expanding chemical industry
The industry application stage；Using the Weak Base ASP Flood of petroleum sulfonate surfactant（Sodium carbonate/petroleum sulfonate/polymer）
The field test of technology also takes successfully and continues to expand scene applies scale.
With going deep into for domestic and international oil field development degree, high temperature and high salt oil deposit chemical flooding improves recovery ratio problem and refer to view
Come in thing schedule.Compared with conventional oil reservoir chemical combined flooding surfactant, high temperature and high salt oil deposit requires surface activity used
Agent has stronger heat resistance, anti-salt property and anti-divalent ion performance.Heavy alkylbenzene sulfonate, petroleum sulfonate etc. it is cloudy from
Although sub- surfactant heat resistance is good, salt resistant character and the poor-performing of resistance to calcium ions and magnesium ions, it is impossible to be applied to high temperature high
Salt oil deposit alkali-free binary combination flooding system.Fatty alcohol ether nonionic surfactant salt resistant character is good, but has cloud point resistance to
Warm nature can not be good, also cannot use in high temperature and high salt oil deposit.
Compared with other classes of surfactant, betaine type amphoteric surfac-tant has many excellent performances, such as pole
Good stability in hard water, salt tolerance, low toxicity, easily biological-degradable, moderate performance compatibility are good etc..Additionally, beet alkali surface activator
Also there is preferable chemical stability, good emulsibility, dispersibility and antistatic behaviour, some types also have sterilization and press down mould
Property, viscoelasticity etc., range of application is quite varied.
Compared with other classes of surfactant, betaine type amphoteric surfac-tant has many excellent performances, such as pole
Good stability in hard water, salt tolerance, low toxicity, easily biological-degradable, moderate performance compatibility are good etc..Due to existing in molecular structure simultaneously
Zwitterion, beet alkali surface activator molecule are arranged relatively closely, with stronger reduction oil-water interfaces in oil-water interfaces
The ability of power.And, betaine type amphoteric surfac-tant's salt resistant character, the superior of resistance to divalent ion.Conventional Long carbon chain two
Methyl betaine is long due to single hydrophobic chain, the poor use that have impact in chemical flooding of its dissolubility.Therefore, nearly more than ten year
It is domestic to have carried out substantial amounts of work in terms of displacement of reservoir oil garden beet alkaline surfactant development, have developed a series of glycine betaines
Type surfactant oil displacement.Aryl alkyl glycine betaine, octadecyl hexyl methyl as described in patent ZL201210056931.4
Carboxybetaine（Song Hongjuan, fine chemistry industry, 2015：32（6））Tie with Ju Beite with described in patent ZL200810238800.1
Alkyl polyoxyethylene ether glycine betaine of structure etc..These glycine betaines have the advantages that interface performance is good, oil displacement efficiency is high.But, virtue
Base alkyl betaine and octadecyl hexyl carboxybetaine preparation technology are more complicated；The alkyl polyoxy second of Ju Beite structures
The problems such as synthesis material used by alkene ether glycine betaine occupies shellfish Extra Old due to production technology and catalyst is difficult to obtain large-scale industry
Raw material.And, the single dose of the alkyl polyoxyethylene ether glycine betaine and octadecyl hexyl carboxybetaine of Ju Beite structures is difficult
To reach ultralow interfacial tension with crude oil.For example, cetyl Polyethylene oxide（3）Ether hydroxypropyl carboxybetaine need to add weak
The ultralow interfacial tension scope that could be reached with crude oil in the case of alkali sodium carbonate（10-3The mN/m orders of magnitude and following）.Octadecane
Base hexyl carboxybetaine need to be with hexadecyldimethyl benzyl ammonium carboxybetaine and double dodecyl methyl carboxybetaine compounding
Ultralow interfacial tension can be reached with crude oil.
The content of the invention
To solve above-mentioned technical problem, the invention provides a kind of ternary composite driving compositionss, ternary composite driving combination
Thing can effectively improve recovery ratio under the conditions of high temperature and high salt, obtain higher oil displacement efficiency.
To reach above-mentioned purpose, the invention provides a kind of ternary composite driving compositionss, by weight percentage, described group
Compound includes：
Alkaline matter 0.03-3.0%
Long short chain beet alkali surface activator 0.05-0.30%；
Polymer 0.05-0.30%；
Remaining is water；
The long short chain beet alkali surface activator has the structure shown in formula I
In the formula I, R is C10-C24Straight or branched alkyl；R1For C2-C5Straight chained alkyl；
R2For C2-C5Straight chained alkyl；X is-CH2COO-、-CH2CH2SO3 -、-CH2CH2CH2SO3 -Or-
CH2CHOHCH2SO3 -。
In above-mentioned ternary composite driving compositionss, wherein, the R includes the-C of straight or branched10H21、-C11H23、-
C12H25、-C13H27、-C14H29、-C15H31、-C16H33、-C18H37、-C20H41、-C22H45Or-C24H49；It is highly preferred that the R1Bag
Include-the C of straight chain2H5、-C3H7、-C4H9Or-C5H11；It is further preferred that the R2Including-the C of straight chain2H5、-C3H7、-C4H9
Or-C5H11。
In above-mentioned ternary composite driving compositionss, it is preferable that the long short chain beet alkali surface activator includes dodecane
Base diethyl hydroxypropyl sulfobetaines, the third sulfobetaines of dodecyl diamyl, myristyl ethyl pentyl group carboxybetaine,
Octadecyldimethylamine base hydroxypropyl sulfobetaines, cetyl dipropyl carboxybetaine, cetyl ethyl-butyl second sulfo group
Glycine betaine, octadecyl Diethlycarboxy glycine betaine, octadecyl dipropyl carboxybetaine or octadecyl dipropyl hydroxypropyl
Sulfobetaines.
In above-mentioned ternary composite driving compositionss, it is preferable that the long short chain beet alkali surface activator includes：
1. dodecyl diethyl hydroxypropyl sulfobetaines（As shown in Equation 1）
2. the third sulfobetaines of dodecyl diamyl（As shown in Equation 2）
3. myristyl ethyl pentyl group carboxybetaine（As shown in Equation 3）
4. octadecyldimethylamine base hydroxypropyl sulfobetaines（As shown in Equation 4）
5. cetyl dipropyl carboxybetaine（As shown in Equation 5）
6. cetyl ethyl-butyl second sulfobetaines（As shown in Equation 6）
7. octadecyl Diethlycarboxy glycine betaine（As shown in Equation 7）
8. octadecyl dipropyl carboxybetaine（As shown in Equation 8）
Or；9. octadecyl dipropyl hydroxypropyl sulfobetaines（As shown in Equation 9）.
In above-mentioned ternary composite driving compositionss, it is preferable that the R1And R2It is asynchronously-C2H5。
In above-mentioned ternary composite driving compositionss, it is preferable that the alkaline matter includes trimethylamine, triethylamine, ethylenediamine
One kind in four sodium sodium hydroxide of tetraacethyl, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium tetraborate, sodium phosphate or
Several combinations；It is highly preferred that the alkaline matter is sodium carbonate, sodium tetraborate or tetrasodium ethylenediamine tetraacetate.
In above-mentioned ternary composite driving compositionss, it is preferable that the percentage by weight of the alkaline matter is 0.05-0.20%；
More preferably 0.20%.
In above-mentioned ternary composite driving compositionss, it is preferable that the percentage by weight of the length beet alkali surface activator
For 0.10-0.30%；More preferably 0.20%.
In above-mentioned ternary composite driving compositionss, it is preferable that the percentage by weight of the polymer is 0.10-0.20%；More
Preferably 0.20%.
In above-mentioned ternary composite driving compositionss, it is preferable that the polymer includes that partially hydrolyzed polyacrylamide (PHPA) is polymerized
Thing, hydrophobic associated polymer or star-type polymer；It is highly preferred that the degree of hydrolysis of the partially hydrolyzed polyacrylamide (PHPA) polymer is
20%-30%, star-type polymer degree of hydrolysis are 1%-5%.
In above-mentioned ternary composite driving compositionss, the star-type polymer for being adopted can be Application No.
201010565501.6 Chinese invention patent application（It is entitled：A kind of preparation method of star-type polymer, the applying date is
On November 29th, 2010）In described star-type polymer, which is incorporated herein by reference in full.
In above-mentioned ternary composite driving compositionss, the hydrophobic associated polymer can be French Snf S. A. S.（SNF）It is raw
Polymer A N125 of product；Institute's partially hydrolyzed polyacrylamide (PHPA) can be the polymer MO4000 of Mitsubishi chemical conversion company production.
In above-mentioned ternary composite driving compositionss, it is preferable that the molecular weight of the polymer is 1200-3500 ten thousand.
In above-mentioned ternary composite driving compositionss, it is preferable that the water include oil field injected clear water, oil field injection sewage and
The combination of one or more in oil field extracted water；It is highly preferred that salinity >=the 10000mg/L of the water.
Present invention also offers application of the above-mentioned ternary composite driving compositionss in high temperature and high salt oil deposit, wherein, the height
Warm high salinity reservoir is primarily referred to as temperature >=70 DEG C, the oil reservoir of the salinity >=10000mg/L of water.
In above-mentioned application, it is preferable that the temperature of the oil reservoir is 70 DEG C -100 DEG C.
In above-mentioned application, it is preferable that bivalent ions content >=400mg/L in the high temperature and high salt oil deposit.
Present invention also offers a kind of method for preparing above-mentioned long short chain beet alkali surface activator, which includes following step
Suddenly：
It is C by organic salt and the total carbon number of alkyl3-C10Symmetrically or non-symmetrically double alkyl secondary amines press material amount ratio be 1:
(1-5) tertiary amine synthetic reaction is carried out, obtains intermediate tertiary amine；
It is 1 by the amount ratio that the intermediate tertiary amine and halogenated hydrocarbons press material:(0.5-2) quaterisation is carried out, length is obtained
Short chain beet alkali surface activator；Wherein,
The organic salt includes 3- chlorine-2-hydroxyl propanesulfonates, 2- sodium chloroacetates, 2- bromoethyls sodium sulfonate or 3- bromopropyls
Sodium sulfonate；
The halogenated hydrocarbons include chloralkane or brominated alkanes.
In above-mentioned preparation method, it is preferable that described pair of alkyl secondary amine includes that diethylamine, di-n-propylamine, ethyl pentyl group are secondary
Amine or two n-amylamines.
In above-mentioned preparation method, it is preferable that the carbon chain lengths of the halogenated hydrocarbons are C12-C18。
In above-mentioned preparation method, it is preferable that include the step of the tertiary amine synthetic reaction：The organic salt is made into water
Solution, is then added in described pair of alkyl secondary amine at a temperature of 5 DEG C -40 DEG C, and reaction 0.5h-4h is obtained at a temperature of 5 DEG C -80 DEG C
To mixed liquor, the mixed liquor is purified, the intermediate tertiary amine is obtained.
In above-mentioned preparation method, the concrete steps that the mixed liquor is purified are included：The mixed liquor is concentrated, is added
Ethanol, filtered while hot, then by the filtrate crystallisation for obtaining, washing sucking filtration, recrystallization, obtain the intermediate tertiary amine.
In above-mentioned preparation method, it is preferable that include the step of the quaterisation：By the intermediate tertiary amine and halogen
Be dissolved in n-butyl alcohol for alkane, then 10h-30h reacted at a temperature of 50 DEG C -130 DEG C, obtain crude product, by the crude product
Purification, obtains long short chain beet alkali surface activator.
In above-mentioned preparation method, the concrete steps that the crude product is purified are included：The crude product is added into acetic acid
Ethyl ester, filtered while hot, then by the filtrate for obtaining concentration, evaporate into dry, obtain long short chain beet alkali surface activator.
First prepare Long carbon chain tertiary amine intermediate, carry out that quaterisation is different again from the synthesis of conventional glycine betaine, the present invention is carried
For preparation method first with the double short chain tertiary amine intermediates of short chain secondary amine synthesis, then carry out quaterisation with long-chain halogenated alkane and obtain
To long short chain beet alkali surface activator.React with more typical synthesis material halogenated alkane, secondary amine as raw material, only with 2 steps
The betaine type amphoteric surfactant target product with branched structure is just prepared in reaction.The preparation method is easily achieved, easily
It is generalized to actual industrial production.Additionally, tying with aryl alkyl glycine betaine, octadecyl hexyl methyl carboxybetaine and Ju Beite
Alkyl polyoxyethylene ether glycine betaine of structure etc. is compared, and long short chain synthetic process for betaine as used in the present invention is simple, intermediate
With the high income of final product and under the conditions of alkali-free, interface performance is excellent.
Preferably, the preparation method of the long short chain beet alkali surface activator that the present invention is provided may comprise steps of：
Organic salt is made into aqueous solution, then the total carbon number of alkyl is added at a temperature of 5 DEG C -40 DEG C for C3-C10It is symmetrical or
In asymmetric pair of alkyl secondary amine, and at a temperature of 5 DEG C -80 DEG C, reaction 0.5h-4h obtains mixed liquor, and the mixed liquor is concentrated,
Ethanol, filtered while hot is added then by the filtrate crystallisation for obtaining, washing sucking filtration, recrystallization, to obtain the intermediate tertiary amine；
The intermediate tertiary amine and halogenated alkane are dissolved in n-butyl alcohol, then 10h- are reacted at a temperature of 50 DEG C -130 DEG C
30h, obtains crude product, ethyl acetate is added in the crude product, filtered while hot, then the filtrate for obtaining is concentrated, is waved
It is sent to dry, obtains long short chain beet alkali surface activator；
Wherein, the organic salt and the total carbon number of alkyl are C3-C10Symmetrically or non-symmetrically double alkyl secondary amines press the amount of material
Than for 1:(1-5)；
The amount ratio that the intermediate tertiary amine presses material with halogenated hydrocarbons is 1:(0.5-2)；
The organic salt includes 3- chlorine-2-hydroxyl propanesulfonates, 2- sodium chloroacetates, 2- bromoethyls sodium sulfonate or 3- bromopropyls
Sodium sulfonate；
Described pair of alkyl secondary amine includes any one in diethylamine, di-n-propylamine, ethyl pentyl group secondary amine or two n-amylamines；
The halogenated hydrocarbons include chloralkane or brominated alkanes, and the carbon chain lengths of the halogenated hydrocarbons are C12-C18。
Beneficial effects of the present invention：
Compared with traditional single straight chained alkyl dimethyl betaine isomerss, the ternary composite driving group that the present invention is provided
, using the long short chain glycine betaine with branched structure as surfactant, not only synthesis technique is simple, low cost, yield for compound
It is high, stable in properties, and with excellent three-component compound system interface performance, can significantly widen the oil reservoir of ternary composite driving technology
The scope of application；
Compared with conventional three-way drives compositionss, the ternary composite driving compositionss that the present invention is provided energy under the conditions of high temperature and high salt
Enough effectively improve recovery ratio, obtain higher oil displacement efficiency, therefore in high temperature and high salt oil deposit ternary oil displacement operation advantageously.
Specific embodiment
In order to be more clearly understood to the technical characteristic of the present invention, purpose and beneficial effect, now to skill of the invention
Art scheme carry out it is described further below, but it is not intended that to the present invention can practical range restriction.
Chemicals and equipment difference used in following examples is as described below：
1）Alkaline matter：Tetrasodium ethylenediamine tetraacetate
2）Surfactant：1. the third sulfobetaines of dodecyl diamyl（Code name：C18-5S）；2. octadecyldimethylamine
Base hydroxypropyl sulfobetaines（Code name：C14-3S）；3. octadecyl dipropyl carboxybetaine（Code name：C18-3C）；4. ten eight
Alkyl dimethyl hydroxypropyl sulfobetaines（For conventional linear dimethyl betaine, code name：C18-1S）；5. eicosyl dimethyl
Hydroxypropyl sulfobetaines（For conventional linear dimethyl betaine, code name：C20-1S）；Wherein,
1. -3. described surfactant is self-control, and preparation method is as described below：
1. the preparation process of the third sulfobetaine surfactant of dodecyl diamyl includes：
A, the aqueous solution of 3- bromopropyl sodium sulfonates is added in two n-amylamines at 10 DEG C, is then reacted at a temperature of 35 DEG C
3 hours, obtain mixed liquor；The mixed liquor concentration that this is obtained, is subsequently adding ethanol and is dissolved, and filters off insoluble white while hot solid
Body, and by the filtrate crystallisation by cooling for obtaining, sucking filtration, recrystallization, obtain intermediate tertiary amine 3-（N, N- diamyl amino）Propanesulfonate；
Wherein, the ratio of the amount of the material of the 3- bromopropyls sodium sulfonate and two n-amylamines is 1:1.5；
B, the intermediate tertiary amine 3- that step a is obtained（N, N- diamyl amino）Propanesulfonate and positive chlorinated dodecane are just dissolved in
In butanol, then react 25 hours at a temperature of 110 DEG C, obtain crude product, add ethyl acetate and dissolved, and take out while hot
Filter unreacted organic salt（3- bromopropyl sodium sulfonates）, subsequently by the filtrate for obtaining concentration, evaporate into dry, finally produced
Thing dodecyl the third sulfobetaine surfactant of diamyl；
Wherein, the intermediate tertiary amine 3-（N, N- diamyl amino）The amount of propanesulfonate and the material of positive chlorinated dodecane it
Than for 1:0.9.
2. the preparation process of octadecyldimethylamine base hydroxypropyl sulfobetaine surfactant includes：
A, the aqueous solution of 3- chlorine-2-hydroxyl propanesulfonates is added in di-n-propylamine at 5 DEG C, then at a temperature of 30 DEG C
Reaction 2.5 hours, obtains mixed liquor；The mixed liquor concentration that this is obtained, is subsequently adding ethanol and is dissolved, filter off while hot insoluble
White solid, and by the filtrate crystallisation by cooling for obtaining, sucking filtration, recrystallization, obtain intermediate tertiary amine 3-（N, N- dipropyl amino）-2-
Hydroxypropionate sodium；
Wherein, the 3- chlorine-2-hydroxyls propanesulfonate and the ratio of the amount of the material of di-n-propylamine are 1:3；
B, the intermediate tertiary amine 3- that step a is obtained（N, N- dipropyl amino）- 2- hydroxypropionate sodiums and positive bromo 14
Alkane is dissolved in n-butyl alcohol, is then reacted 24 hours at a temperature of 110 DEG C, is obtained crude product, add ethyl acetate and dissolved,
And sucking filtration removes unreacted organic salt while hot（3- chlorine-2-hydroxyl propanesulfonates）, subsequently the filtrate for obtaining is concentrated, is evaporated into
It is dry, obtain final product octadecyldimethylamine base hydroxypropyl sulfobetaine surfactant；
Wherein, the intermediate tertiary amine 3-（N, N- dipropyl amino）The thing of -2- hydroxypropionate sodiums and positive bromotetradecane
The ratio of the amount of matter is 1:0.9.
3. the preparation process of octadecyl dipropyl carboxyl betaine surfactant includes：
A, the aqueous solution of 2- sodium chloroacetates is added in di-n-propylamine at 8 DEG C, then at a temperature of 35 DEG C, reaction 3 is little
When, obtain mixed liquor；The mixed liquor concentration that this is obtained, is subsequently adding ethanol and is dissolved, filter off insoluble white solid while hot,
And by the filtrate crystallisation by cooling for obtaining, sucking filtration, recrystallization, obtain intermediate tertiary amine 3-（N, N- dipropyl amino）Sodium acetate；
Wherein, the 2- sodium chloroacetates and the ratio of the amount of the material of di-n-propylamine are 1:2.5；
B, the intermediate tertiary amine 3- that step a is obtained（N, N- dipropyl amino）Sodium acetate and positive chlorooctadecane are dissolved in positive fourth
In alcohol, then react 30 hours at a temperature of 120 DEG C, obtain crude product, add ethyl acetate and dissolved, and sucking filtration while hot
Remove unreacted organic salt（2- sodium chloroacetates）, subsequently by the filtrate for obtaining concentration, evaporate into dry, obtain final product 18
Alkyl dipropyl carboxyl betaine surfactant；
Wherein, the intermediate tertiary amine 3-（N, N- dipropyl amino）The ratio of sodium acetate and the amount of the material of positive chlorooctadecane
For 1:0.9.
3）Polymer：Star-type polymer（Code name：StarPam）, molecular weight is 12,470,000, and degree of hydrolysis is 3.28%；It is hydrophobic to form
Polymer A N125 is closed, molecular weight is 10,400,000, and degree of hydrolysis is 3.76%；Partially hydrolyzed polyacrylamide (PHPA) polymer MO4000, point
Son amount is 20,700,000, and degree of hydrolysis is 26.80%.
4）TX500C rotating interfacial tensimeters, for determining 2h interfacial tension stationary values at the formation temperature.
85 DEG C of the formation temperature of following examples high temperature high salinity reservoir, formation water salinity 117000mg/L.
Embodiment 1
The present embodiment has carried out solubility property test under the conditions of high temperature and high salt.Process of the test is as described below：
The quality of its solubility property is reflected using the critical micelle concentration of the surfactant for determining：Critical micelle concentration
More low then dissolubility is poorer, otherwise the more high then dissolubility of critical micelle concentration is better.
Under the conditions of 80 DEG C, series of surfactants solution is prepared with the stratum water of 20000mg/L, distinguished using piece method is hung
Determine octadecyldimethylamine base hydroxypropyl sulfobetaines and its isomerss routine dimethyl betaine（Hexadecyldimethylamine
Base hydroxypropyl sulfobetaines）Critical micelle concentration and contrasted.The results are shown in Table 1.
1 glycine betaine isomerss critical micelle concentration of table is contrasted
| Code name | Surfactant | Critical micelle concentration/(molL-1) |
| C14-3S | Octadecyldimethylamine base hydroxypropyl sulfobetaines | 2.18×10-5 |
| C18-1S | Octadecyldimethyl hydroxypropyl sulfobetaines | 1.59×10-6 |
As shown in Table 1, under the conditions of high temperature and high salt, long short chain beet alkali surface activator octadecyldimethylamine base hydroxypropyl sulphur
, compared with its isomerss octadecyldimethyl hydroxypropyl sulfobetaines, its critical micelle concentration is about big 1 for base glycine betaine
The order of magnitude.Above-mentioned experimental data shows：In high temperature and high salt oil deposit condition, long short chain beet alkali surface activator is sweet with its dimethyl
The isomerss of dish alkali are compared with bigger dissolubility such that it is able to meet the needs of practical application.
Embodiment 2
The present embodiment has carried out interfacial tension test under the conditions of high temperature and high salt.Test process is as described below：
Prepare ternary composite driving compositionss：
1.+0.05% octadecyl dipropyl carboxybetaine of 0.20% tetrasodium ethylenediamine tetraacetate（C18-3C）+ 0.10% star
Shape polymer；
2.+0.05% the third sulfobetaines of dodecyl diamyl of 0.20% tetrasodium ethylenediamine tetraacetate（C12-5S）+0.10%
Star polymer；
Three-component compound system solution is determined respectively 1. and 2. in high temperature and high salt oil deposit condition（85 DEG C of formation temperature, stratum water
Salinity 117000mg/L）The interfacial tension between crude oil, as a result as shown in table 2.
Interfacial tension between 2 three-component compound system of table and crude oil
| Sequence number | Three-component compound system | Interfacial tension, mN/m |
| 1 | 0.20%Na4EDTA+0.05%C18-3C+0.20%StarPam | 2.32×10-3 |
| 2 | 0.20%Na4EDTA+0.05%C12-5S+0.20%StarPam | 2.17×10-3 |
| 3 | 0.20%Na4EDTA+0.05%C20-1S+0.20%StarPam | N/A |
As shown in Table 2, under the conditions of high temperature and high salt oil deposit, the two long short chain beet alkali surface activators evaluated and star
The ternary composite driving compositionss of shape polymer composition can reach ultralow interfacial tension with crude oil, show excellent interface characteristics
Energy.And under same experiment condition, eicosyl dimethyl hydroxypropyl sulfobetaines（C20-1S）Dissolubility is too small and nothing
Method is normally prepared solution and determines interfacial tension.
Embodiment 3
The present embodiment has carried out interface performance test under the conditions of high temperature and high salt.Test process is as described below：
Prepare three-component compound system solution：
1.+0.05% octadecyldimethylamine base hydroxypropyl sulfobetaines of 0.20% tetrasodium ethylenediamine tetraacetate（C14-3S）+
0.20% star polymer；
2.+0.05% octadecyldimethyl hydroxypropyl sulfobetaines of 0.20% tetrasodium ethylenediamine tetraacetate（C18-1S, is normal
Rule straight chain dimethyl betaine）+ 0.20% star polymer；
In high temperature and high salt oil deposit condition（85 DEG C of formation temperature, formation water salinity 117000mg/L）Ternary is determined respectively
The compound system solution 1. and 2. interfacial tension between crude oil, as a result as shown in table 3.
Interfacial tension between 3 three-component compound system of table and crude oil
| Sequence number | Three-component compound system | Interfacial tension, mN/m |
| 1 | 0.20%Na4EDTA+0.05%C14-3S+0.20%StarPam | 4.53×10-3 |
| 2 | 0.20%Na4EDTA+0.05%C18-1S+0.20%StarPam | 6.41×10-2 |
As shown in Table 3, comprising octadecyldimethylamine base hydroxypropyl sulfobetaines（Long short chain betaine type amphoteric surfactant）
Three-component compound system and crude oil between equilibrium interfacial tension reach ultralow scope（10-3The mN/m orders of magnitude and following）；Phase therewith
Than balance circle between the three-component compound system comprising its isomerss octadecyldimethyl hydroxypropyl sulfobetaines and crude oil
Face tension force is only 10-2The mN/m orders of magnitude.
Embodiment 4
The present embodiment has carried out viscosity test.Test process is as described below：
1）Using the stratum water of salinity 117000mg/L as solvent, tri compound solution is prepared：
1.+0.20% octadecyldimethylamine base hydroxypropyl sulfo group of+0.20% star-type polymer of 0.20% tetrasodium ethylenediamine tetraacetate is sweet
Dish alkali（C14-3S）；
2.+0.20% polymer A N125+0.20% octadecyldimethylamine base hydroxypropyl sulfo group of 0.20% tetrasodium ethylenediamine tetraacetate
Glycine betaine（C14-3S）；
3.+0.20% polymer MO4000+0.20% octadecyldimethylamine base hydroxypropyl sulfo groups of 0.20% tetrasodium ethylenediamine tetraacetate
Glycine betaine（C14-3S）；
Wherein, the concrete physical and chemical index of each polymer is as shown in table 4.
2）Viscosity is tested：Using U.S.'s Brookfield LVDVII rotational viscometers, from 0# rotors, rotating speed is 6RPM,
Test temperature is 95 DEG C, and as shown in table 5, viscosity unit is mPas to experimental result.
4 polymer physical and chemical index of table
| Sequence number | Polymer | Molecular weight, ten thousand | Degree of hydrolysis, % | Solid content, % |
| 1 | Star-type polymer | 1247 | 3.28 | 90.56 |
| 2 | AN125 | 1040 | 3.76 | 85.12 |
| 3 | MO4000 | 2070 | 26.80 | 90.50 |
5 viscosity test result of table
From viscosity measurement result in table 5：The viscosity highest of the three-component compound system solution prepared with star-type polymer,
Illustrate under the experiment condition, the adhesion-promoting performance of star-type polymer is optimal.
Embodiment 5
The present embodiment has carried out core oil-displacement test with reference to petroleum industry standard SY/T 6424-2000.
The present embodiment is surveyed using core oil-displacement test and have rated the tri compound for high temperature and high salt oil deposit of the present invention
The oil displacement efficiency of compositionss is driven, and is contrasted with the ternary composition oil displacement efficiency comprising conventional dimethyl betaine（Knot
Fruit is as shown in table 6）.Wherein, the surfactant that ternary composition oil displacement experiment is used is that octadecyldimethyl hydroxyl sulfo group is sweet
Dish alkali, its percentage by weight are 0.20%；Ternary composite driving compositionss oil displacement experiment for high temperature and high salt oil deposit of the present invention
The surfactant for using is octadecyldimethylamine base hydroxypropyl sulfobetaines, and its percentage by weight is 0.20%.Two groups of rock cores drive
Polymer used by oil experiment is star-type polymer StarPam, and its percentage by weight is 0.20%；Two groups of core oil-displacement test institutes
Tetrasodium ethylenediamine tetraacetate is with alkaline matter, its percentage by weight is 0.20%.
5 ternary composite driving compositionss oil displacement efficiency evaluation result of table
Oil displacement experiment program is：Rock core vacuumizing saturation stratum water → measure water phase permeability → saturation crude oil makes irreducible water
→ carry out water drive to it is aqueous up to 98% → injection ternary composite driving compositionss drive slug → subsequently turn stratum water drive to aqueous up to 98%.
Experimental temperature is 90 DEG C, in displacement of reservoir oil compositionss, stratum water of the water for being adopted for salinity 117000mg/L.
As shown in Table 6：After water drive terminates, using conventional octadecyldimethyl hydroxypropyl sulfobetaines for high temperature
The ternary composite driving compositionss of high salinity reservoir improve recovery ratio 15.72%；Under basically identical experiment condition, using the present invention
The ternary composite driving compositionss comprising octadecyldimethylamine base hydroxypropyl sulfobetaines for providing improve recovery ratio and reach 20.89%.
It can be seen that, under the conditions of high temperature and high salt oil deposit, the ternary composite driving compositionss ratio comprising long short chain glycine betaine provided using the present invention
Higher oil displacement efficiency can be obtained using the ternary composite driving compositionss comprising conventional dimethyl betaine.Therefore, using this
The ternary composite driving compositionss comprising octadecyldimethylamine base hydroxypropyl sulfobetaines of bright offer carry out high temperature and high salt oil deposit three
First displacement of reservoir oil operation is advantageously.
Claims (10)
1. a kind of ternary composite driving compositionss, by weight percentage, the compositionss include：
Alkaline matter 0.03-3.0%
Long short chain beet alkali surface activator 0.05-0.30%；
Polymer 0.05-0.30%；
Remaining is water；
The long short chain beet alkali surface activator has the structure shown in formula I
RN+R1R2X formula I
In the formula I, R is C10-C24Straight or branched alkyl；R1For C2-C5Straight chained alkyl；
R2For C2-C5Straight chained alkyl；X is-CH2COO-、-CH2CH2SO3 -、-CH2CH2CH2SO3 -Or-CH2CHOHCH2SO3 -。
2. ternary composite driving compositionss according to claim 1, wherein, the R includes the-C of straight or branched10H21、-
C11H23、-C12H25、-C13H27、-C14H29、-C15H31、-C16H33、-C18H37、-C20H41、-C22H45Or-C24H49；
Preferably, the R1Including-the C of straight chain2H5、-C3H7、-C4H9Or-C5H11；
It is highly preferred that the R2Including-the C of straight chain2H5、-C3H7、-C4H9Or-C5H11。
3. ternary composite driving compositionss according to claim 1 and 2, wherein, the long short chain beet alkali surface activator
Including dodecyl diethyl hydroxypropyl sulfobetaines, the third sulfobetaines of dodecyl diamyl, myristyl ethyl pentyl group
Carboxybetaine, octadecyldimethylamine base hydroxypropyl sulfobetaines, cetyl dipropyl carboxybetaine, cetyl ethyl
Butyl second sulfobetaines, octadecyl Diethlycarboxy glycine betaine, octadecyl dipropyl carboxybetaine or octadecyl
Dipropyl hydroxypropyl sulfobetaines.
4. ternary composite driving compositionss according to claim 1 and 2, wherein, the R1And R2It is asynchronously-C2H5。
5. ternary composite driving compositionss according to claim 1 and 2, wherein, the alkaline matter includes trimethylamine, three second
In amine, tetrasodium ethylenediamine tetraacetate sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium tetraborate, sodium phosphate
The combination of one or more；
Preferably, the alkaline matter is sodium carbonate, sodium tetraborate or tetrasodium ethylenediamine tetraacetate.
6. ternary composite driving compositionss according to claim 1, wherein, in the composition,
The percentage by weight of the alkaline matter is 0.05-0.20%；Preferably 0.20%；
The percentage by weight of the length beet alkali surface activator is 0.10-0.30%；Preferably 0.20%；
The percentage by weight of the polymer is 0.10-0.20%；Preferably 0.20%.
7. ternary composite driving compositionss according to claim 1, wherein, the polymer includes partial hydrolysiss polyacrylamide
Amine polymer, hydrophobic associated polymer or star-type polymer；
Preferably, the degree of hydrolysis of the partially hydrolyzed polyacrylamide (PHPA) polymer is 20%-30%, the star-type polymer hydrolysis
Spend for 1%-5%；
It is highly preferred that the molecular weight of the polymer is 1200-3500 ten thousand.
8. application of the ternary composite driving compositionss described in any one of claim 1-7 in high temperature and high salt oil deposit, wherein, it is described
The property of high temperature and high salt oil deposit is as described below
Temperature >=70 DEG C of oil reservoir, the salinity >=10000mg/L of water.
9. application according to claim 8, wherein, the temperature of the oil reservoir is 70 DEG C -100 DEG C.
10. application according to claim 8 or claim 9, wherein, bivalent ions content in the high temperature and high salt oil deposit >=
400mg/L。
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