CN104877654A - Compound oil-displacing agent containing asymmetric di-long chain alkylmethyl carboxyl betaine and application thereof - Google Patents
Compound oil-displacing agent containing asymmetric di-long chain alkylmethyl carboxyl betaine and application thereof 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
- 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
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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
- 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
Abstract
The invention relates to a compound oil-displacing agent containing asymmetric di-long chain alkylmethyl carboxyl betaine and application thereof, and belongs to the technical field of chemical oil displacement. The asymmetric di-long chain alkylmethyl carboxyl betaine is prepared by adopting fatty acids with different chain lengths and monomethylamine as original raw materials by means of amide reduction and carboxymethylation, and a molecular formula of the asymmetric di-long chain alkylmethyl carboxyl betaine is abbreviated as Cm+nB, wherein m is not equal to n. Compared with the symmetric di-long chain alkylmethyl carboxyl betaine identical in main alkyl chain length, the asymmetric betaine basically maintains high surface activity of the symmetric betaine, but the water solubility of the product is remarkably improved, and the adsorption onto the surface of rock is obviously lowered. The interface tension between C7-C9 n-alkanes and Daqing formation water and between Daqing crude oil and Daqing formation water is respectively reduced to 10<-3>mN/m and 10<-2>mN/m by virtue of C18+6B single component; the asymmetric di-long chain alkylmethyl carboxyl betaine is compounded with a symmetric homologous series and a single-long-chain alkyl-dimethyl carboxyl betaine, the interface tension of Daqing crude oil/formation water is lowered to 10<-3>mN/m in a wide range of total concentration.
Description
Technical field
The present invention relates to a kind of composite oil-displacing agent for alkali-free binary combination flooding, wherein containing asymmetric double long-chain alkyl methyl carboxyl betaine surfactant, belong to chemical displacement of reservoir oil technical field.
Background technology
As everyone knows, the a lot of maturing field of China enters high water-cut stage successively, in filled drive Produced Liquid, water-content reaches more than 90%, face the Natural Attenuation of crude production rate, and on the other hand, still having the irreducible oil of about 60% not to be plucked out of, therefore after the filled drive stage, adopt tertiary oil recovery technology to improve recovery ratio further, is the only way of China's maturing field high and stable yields.
In the later stage in filled drive stage, irreducible oil is caught with the form of oil droplet in the hole of porous rock by circle, due to wicking action, is difficult to flow out under conventional waterflood pressure.Adopt chemical displacement of reservoir oil technology, such as, inject the aqueous solution containing tensio-active agent, when crude oil/water interface drops to 10 in the effect of tensio-active agent
-3during the mN/m order of magnitude, just can be overcome wicking action under conventional waterflood pressure by the oil droplet that circle is caught and flow out from porous medium.The so-called ultra low interfacial tension displacement of reservoir oil that Here it is, a kind of important tertiary oil recovery technology.
Since the eighties in last century, extensively carry out the research of alkali, surfactant and polymer (ASP) ternary composite driving technology both at home and abroad.Namely at injection water, except adding tensio-active agent, polymkeric substance and alkali is also added, such as caustic alkali NaOH.Add polymkeric substance to be intended to improve the viscosity injecting water, prevent displacing fluid from stratum, fingering occurring, improve the sweep efficiency of displacing fluid, and add alkali can by the organic acid and ester deter-mation class material saponification in crude oil, generate tensio-active agent, act synergistically with additional tensio-active agent, be conducive to reducing crude oil/local water interfacial tension, and make rock surface keep water-wet.The ternary composite driving of optimization of C/C composites can improve recovery ratio 18 ~ 28% further after filled drive.But field test in recent years shows, use highly basic can cause the corrosion and scaling of pipeline and equipment, degradation disadvantageous effect under zone permeability, stratum capillary channel blocking may be caused time serious, also significantly can reduce the thickening effectiveness of polymkeric substance simultaneously.Therefore replace with the surfactant and polymer of alkali-free (SP) binary combination flooding the new trend that ASP ternary composite driving becomes chemical displacement of reservoir oil technical development.
But under alkali-free condition, use ASP surfactant oil displacement mostly crude oil/local water interfacial tension can not be dropped to ultralow (<0.01mN/m), one of reason is that the lipophilicity of tensio-active agent is on the low side.Need to research and develop the higher tensio-active agent of lipophilicity for this reason.If still adopt the single-long-chain alkyl structure of conventional surfactants, then to Daqing crude oil, the alkyl chain length of applicable tensio-active agent will more than C
18, and in current market raw material, no matter derive from natural fats and oils or derive from petrochemicals, rarely have bulk raw material to match.In order to solve this difficult problem, researchist designs the tensio-active agent of double long-chain alkyl list hydrophilic group structure, the disclosed a kind of two dodecyl methyl carboxybetaine of such as CN101549266A, this compound has enough lipophilicities, by composite with hydrophilic surfactant active, the interfacial tension of Daqing crude oil/local water can be down to 10
-3the mN/m order of magnitude.But this product is water-soluble poor, and there is larger absorption on oil-sand surface.The present invention attempts to introduce unsymmetrical structure in double long-chain alkyl methyl carboxybetaine, even if two chain alkyls in molecule have different chain lengths, total and chain length keep certain.Result shows, this structure is conducive to improving the water-soluble of tensio-active agent, reduces the adsorption losses of tensio-active agent on oil-sand surface, can keep the high surface of symmetric form double long-chain alkyl methyl carboxybetaine simultaneously.
Summary of the invention
The object of the invention is to: propose a kind of composite oil-displacing agent, be applicable to the surfactant and polymer binary combination flooding of Daqing crude oil, wherein containing a kind of asymmetric double long-chain alkyl methyl carboxybetaine, by symmetric form double long-chain alkyl methyl carboxybetaine strong to itself and lipophilicity and water miscible single-long-chain alkyl dimethyl carboxybetaine composite, can Daqing crude oil/local water interfacial tension be down to ultralow, and adding of this asymmetric double long-chain alkyl methyl carboxybetaine significantly can improve the water-soluble of formula, reduce the adsorption losses of tensio-active agent on oil-sand surface.
Technical scheme of the present invention: a kind of composite oil-displacing agent containing asymmetric double long-chain alkyl methyl carboxybetaine, wherein asymmetric double long-chain alkyl methyl carboxybetaine has following general formula:
Be abbreviated as C
m+nb, wherein m ≠ n, 12≤m≤18,6≤n≤12, m+n=18 ~ 30 are best with m+n=22 ~ 26 especially.
Technical scheme of the present invention: a kind of composite oil-displacing agent containing asymmetric double long-chain alkyl methyl carboxybetaine, wherein second surface active agent composition is conventional single-long-chain alkyl dimethyl carboxybetaine, and its structural formula is:
Be abbreviated as C
yb, wherein y=12 ~ 18, they can be single compound or homologous mixture.
Technical scheme of the present invention: a kind of composite oil-displacing agent containing asymmetric double long-chain alkyl methyl carboxybetaine, wherein the 3rd surface active agent composition is symmetric form double long-chain alkyl methyl carboxybetaine, and its structural formula is:
Be abbreviated as C
12+12b.
The preparation method of described asymmetric double long-chain alkyl methyl carboxybetaine.The first step: with the saturated fatty acid of different alkyl chain length for initiator, first make acyl chlorides; Second step: use a kind of acyl chlorides, the acyl chlorides that normally alkyl chain is longer and Monomethylamine react, and generate N-methyl nitrosourea, through with lithium aluminium hydride reduction, generate N-chain alkyl-N-methyl secondary amine; 3rd step: by N-chain alkyl-N-methyl secondary amine and another acyl chloride reaction, forms N-chain alkyl-N-methyl nitrosourea, through with lithium aluminium hydride reduction, generates N, N-double long-chain alkyl-N-methyl tertiary amine; 4th step: N, N-double long-chain alkyl-N-methyl tertiary amine and sodium chloroacetate are reacted, namely obtains target product.Reaction formula is as follows:
R in formula
m=C
mh
2m+1, R
n=C
nh
2n+1.
The one application of the described composite oil-displacing agent containing asymmetric double long-chain alkyl methyl carboxybetaine, when m/n>=3, be significantly increased compared with the water-soluble and symmetric form double long-chain alkyl methyl carboxybetaine with same carbon atoms number of asymmetric double long-chain alkyl methyl carboxybetaine, such as, at 25 DEG C, C
18+6the solubleness of B in water compares C
12+12b improves more than 200 times.C
18+6b one-component therefore can be water-soluble, is 5mmol/L in concentration, adds 1000mg/L polyacrylamide in aqueous phase, under 45 DEG C of conditions, and can by C
7~ C
9normal paraffin/water interfacial tension is down to 10
-3the mN/m order of magnitude, is down to 10 by Daqing crude oil/local water interfacial tension
-2the mN/m order of magnitude.
The one application of the described composite oil-displacing agent containing asymmetric double long-chain alkyl methyl carboxybetaine, the SP for Daqing crude oil drives.In this composite oil-displacing agent, asymmetric molar fraction>=0.3 of double long-chain alkyl methyl carboxybetaine in total surfactant, second component C
ythe molar fraction of B in total surfactant is 0 ~ 0.5, three components C
12+12the molar fraction of B in total surfactant is 0 ~ 0.4, is zero when wherein second component is different with the molar fraction of three components.Composite oil-displacing agent is dissolved in grand celebration local water, tensio-active agent total concn is 0.25 ~ 7.5mmol/L, 1000mg/L polyacrylamide (molecular weight 2,500 ten thousand) is added in water, but do not add any alkali, inorganic salt and cosurfactant, at 45 DEG C, Daqing crude oil/local water interfacial tension can be down to 10
-3the mN/m order of magnitude.
Useful benefit of the present invention
Compared with the symmetric form double long-chain alkyl carboxybetaine identical with total alkyl chain length, asymmetrical type trimethyl-glycine maintains the high surface of symmetric form trimethyl-glycine substantially, but the water-soluble increase with alkyl chain length asymmetry and increasing, reduces with the increase of asymmetry at the saturated extent of adsorption on oil-sand surface.Therefore the present invention contains the composite oil-displacing agent of symmetric form double long-chain alkyl carboxybetaine, and it is water-soluble is significantly improved, and has obvious reduction in the adsorption losses on oil-sand surface.
Accompanying drawing explanation
Fig. 1 N-octadecyl-N-hexyl methyl carboxybetaine (C
18+6b) infrared spectrogram of purified product
Fig. 2 N-octadecyl-N-hexyl methyl carboxybetaine (C
18+6b) mass spectrum (positive charge pattern) of purified product
Fig. 3 N-octadecyl-N-hexyl methyl carboxybetaine (C
18+6b) nuclear magnetic spectrogram (400MHz, the CDCl of purified product
3)
Some C during Fig. 4 25 DEG C
m+nthe transmittance of B product water solution is with the change of concentration.
Some C during Fig. 5 25 DEG C
m+nthe surface tension of B product water solution is with the change of concentration.
C during Fig. 6 45 DEG C
18+6the interfacial tension of the B one-component aqueous solution and normal paraffin and Daqing crude oil.C
18+6b concentration 5mmol/L, containing 1000mg/L polyacrylamide (molecular weight 2,500 ten thousand) in aqueous phase.
Containing C during Fig. 7 45 DEG C
14+10the composite oil-displacing agent aqueous solution of B and the interfacial tension of Daqing crude oil.Grand celebration local water, containing 1000mg/L polyacrylamide (molecular weight 2,500 ten thousand) in aqueous phase, C in mixed surfactant
14+10the molar fraction of B is 0.6, and all the other are single-long-chain alkyl dimethyl carboxybetaine (C
16b), tensio-active agent total concn as For the illustrated example.
Containing C during Fig. 8 45 DEG C
18+6the composite oil-displacing agent aqueous solution of B and the interfacial tension of Daqing crude oil.Grand celebration local water, containing 1000mg/L polyacrylamide (molecular weight 2,500 ten thousand) in aqueous phase, C in mixed surfactant
18+6b molar fraction is 0.3, and all the other are symmetric form double long-chain alkyl methyl carboxybetaine C
12+12b and single-long-chain alkyl dimethyl carboxybetaine (C
16b), tensio-active agent total concn as For the illustrated example.
C during Fig. 9 45 DEG C
18+6the adsorption isothermal line of B on Daqing oil sand and and C thereof
12+12the comparison of B.
Embodiment
Experiment material: C
6to C
18lipid acid, sulfur oxychloride, sodium hydroxide, AR level reagent, Chemical Reagent Co., Ltd., Sinopharm Group; Lithium aluminium hydride, 97% (massfraction), aqueous methylamine solution, 40% (massfraction), Shanghai Jing Chun biochemical technology limited-liability company; Mono Chloro Acetic Acid, technical grade, two dodecyl methyl tertiary amine C
12+12a, technical grade, single-long-chain alkyl dimethyl carboxybetaine C
yb (y=12 ~ 18), technical grade, Solvay (Zhangjiagang) Precision Chemical Co., Ltd.; All the other reagent are all AR level, Chemical Reagent Co., Ltd., Sinopharm Group.
Embodiment 1:N-octadecyl-N-hexyl methyl tertiary amine (C
18+6a) preparation.With stearic acid (C
18) be initial feed, be called reactant A, react with sulfur oxychloride, sulfur oxychloride is called reactant B.A:B=1:1.4 in molar ratio, adds 0.5mol (142g) A, 1mL DMF (DMF), 50mL methylene dichloride, is heated to 55 DEG C in 500mL there-necked flask.Take 0.7mol (83.3g) B with beaker, be transferred to rapidly in 250mL constant pressure funnel, drop in there-necked flask.HCl and SO that reaction generates
2the sour gas 700mL 10%NaOH aqueous solution absorbs process.After B dropping terminates, be warming up to 65 DEG C, continue reaction 2h.After reaction terminates, with the vacuum pump using circulatory water B that (50-60 DEG C) extraction is remaining while hot and methylene dichloride, obtain intermediates stearyl chloride, be called intermediate C.Reaction equation is as follows:
In 1000mL there-necked flask, add 40% aqueous methylamine solution that 200mL refrigerates at-6 DEG C, be called reactant D, with ice-water bath control temperature at about 0 DEG C.C:D=1:5 in molar ratio, reacts by the first step to gained stearyl chloride and is transferred in 250mL constant pressure funnel, slowly drop in aqueous methylamine solution, generates white solid.After dropping terminates, continue reaction 2h.Obtain octadecyl N-methyl nitrosourea through water-washing desalting, ethyl alcohol recrystallization and drying after reaction terminates, finished product is solid, is called intermediate E, and from A to E, the comprehensive yield of two-step reaction is 85.8%.Reaction equation is as follows:
In 500mL there-necked flask, add 400mL tetrahydrofuran (THF) (THF), under room temperature, open magnetic agitation.0.4mol (15.182g) lithium aluminium hydride (AlLiH is accurately taken with beaker
4), join rapidly in there-necked flask, stir 5min, make it be dispersed in THF.Be warming up to 60 DEG C, in molar ratio E:(AlLiH
4)=1:1.3 takes in E to the 400mL beaker of a certain amount of drying, adds in there-necked flask with spoon in batches.Be warming up to 70 DEG C after feeding intake, under reflux temperature, continue reaction 2h.After reaction terminates, according to mass ratio (AlLiH
4): (H
2o): (15%NaOH): (Na
2sO
4)=1:1:2:2 adds rear three kinds of material cancellation reaction successively, then obtains N-octadecyl-N-methyl secondary amine through suction filtration desalination, drying, and be called intermediate F, yield is 84.5%, and reaction equation is:
In 250mL there-necked flask, take 0.1mol F, add 0.4mol triethylamine, 100mL methylene dichloride, stir at ice bath temperature.0.15mol by above-mentioned similar approach synthesis acyl chlorides (reactant G) is transferred in 250mL constant pressure funnel, is then added drop-wise in there-necked flask.Drip and terminate, continue reaction 2h.Desolventize through revolving steaming, water-washing desalting, acetone recrystallization, obtain N-octadecyl N-methyl hexanoyl amine, be called intermediate H, yield is 85.5%.Reaction equation is:
Use AlLiH as stated above
4reduction intermediate H, obtain N-octadecyl-N-hexyl methyl tertiary amine, be called intermediates I, yield is 80.4%, and reaction equation is:
Other asymmetric double long-chain alkyl methyl tertiary amine that total alkyl chain length is 20 ~ 30 can be prepared by similar method.
Embodiment 2:N-octadecyl-N-hexyl methyl carboxybetaine (C
18+6b) preparation.I:(Mono Chloro Acetic Acid in molar ratio)=1:1.1, in 250mL there-necked flask, add 0.05mol tertiary amine respectively and 10mL is dissolved with the chloroacetic aqueous solution of 0.055mol, vigorous stirring slowly raised temperature to 80 DEG C.According to mol ratio (Mono Chloro Acetic Acid): NaOH=1:1.1, aqueous solution 10mL being dissolved with 0.0605mol NaOH in 0.5 ~ 1h drops in there-necked flask.After dropwising, material is warming up to reflux temperature (100 DEG C) and continues reaction 10h.After reaction terminates, add the Mono Chloro Acetic Acid of 20% and the NaOH of respective numbers, continue reaction 4 hours, obtain target product (J).Yield is about 80%, and reaction formula is as follows:
The purifying of product: after completion of the reaction, adds appropriate NaOH (0.1mol/L) aqueous solution, the Amine from Tertiary Amine Hydrochloride that broken ring may be formed, stratification, removing water layer (saliferous).Collect upper strata, add silica gel chromatography separator column, elute unreacted free uncle amine with ethyl acetate solvent, then use ethyl acetate/methanol (volume ratio 1:1) mixed solvent to elute trimethyl-glycine, after drying, namely obtain target product N-octadecyl-N-hexyl methyl carboxybetaine C
18+6b (J).
Embodiment 3:N-octadecyl-N-hexyl methyl carboxybetaine (C
18+6b) structural characterization.To purified product (C
18+6b) structural characterization is carried out with infrared spectra, mass spectrum and nuclear-magnetism.
Fig. 1 is the infrared spectrogram of purified product (J).At 1643cm
-1place's absorption peak is the stretching vibration of C=O key, 1305cm
-1place's absorption peak is the stretching vibration of C – O, shows Cun – COO-group in structure.2927cm
-1and 2856cm
-1absorption peak is respectively the asymmetric of c h bond and symmetrical stretching vibration, 1469cm
-1and 1394cm
-1for the flexural vibration of c h bond, 727cm
-1for the flexural vibration of chain alkyl, match with two chain alkyl chain lengths in molecule.1076cm
-1and 885cm
-1locate stretching vibration and flexural vibration that more weak absorption band is respectively C-N key.
Fig. 2 is the mass spectrum of purified product (J).Under positive charge pattern, the strongest quasi-molecular ions (m/z=426.4) is a trimethyl-glycine molecular juction unification H
+, i.e. [M+H]
+, the last the second quasi-molecular ions (m/z=448.4) is a trimethyl-glycine molecular juction unification Na
+, i.e. [M+Na]
+, the molecular weight of product of both correspondences is 425.4, with target product C
18+6the molecular weight of B is consistent.M/z=851.9 and m/z=873.9 two quasi-molecular ions are respectively diploid in conjunction with a H
+with diploid in conjunction with a Na
+, i.e. [2M+H]
+[2M+Na]
+.All the other may be fragment peak.
Fig. 3 is the nuclear magnetic spectrum of purified product (J).δ＝0.84～0.92(t,6H,CH
3(CH
2)
17-,-(CH
2)
5CH
3),δ＝1.21～1.36(m,36H,CH
3(CH
2)
15(CH
2)
2-,-(CH
2)
2(CH
2)
3CH
3),δ＝1.62～1.72(m,4H,CH
3(CH
2)
15CH
2CH
2-,-CH
2CH
2(CH
2)
3CH
3),δ＝3.18～3.22(s,3H,-NCH
3),δ＝3.45～3.56(t,4H,CH
3(CH
2)
16CH
2-，-CH
2(CH
2)
4CH
3),δ＝3.74～3.77(s,2H,-CH
2COO
-)。H atom sum 55, coincide with molecular formula.
Water-soluble and the determination of surface activity of embodiment 4 asymmetric double long-chain alkyl methyl carboxybetaine
Some asymmetric double long-chain alkyl methyl carboxybetaine products are mixed with respectively the aqueous solution of a series of different concns, at 25 DEG C, measure transmittance T with spectrophotometer at 600nm wavelength place, take pure water as reference.Also measure symmetric form double long-chain alkyl methyl carboxybetaine C simultaneously
12+12the transmittance of B.Fig. 4 is the change of transmittance with concentration.At low concentrations visible, the transmittance of solution is close to 100%, and when concentration exceedes its solubleness, transmittance increases with concentration and declines, and make curve near tangent, tangent line and the concentration corresponding to horizontal intersection point can as solubleness.Visible, total when the carbon chain lengths of two alkyl chain lengths remains unchanged, solubleness increases with the asymmetry increase of chain alkyl chain length.Obtain C
12+12b, C
14+10b and C
16+8the solubleness (25 DEG C) of B is respectively 4.8 × 10
-5mol/L, 6.35 × 10
-5mol/L and 1.14 × 10
-4mol/L, and C
18+6b solution is until when concentration is 0.010mol/L, and transmittance is still 100%, i.e. C
18+6the solubleness of B is at least than C
12+12b improves 200 times.
Some asymmetric double long-chain alkyl methyl carboxybetaine products are mixed with respectively the aqueous solution of a series of different concns, at 25 DEG C, measure the surface tension of solution, also measure symmetric form double long-chain alkyl methyl carboxybetaine C simultaneously
12+12the surface tension of B solution.Fig. 5 is the change of surface tension with concentration, and from figure, curve can obtain micelle-forming concentration cmc, reduce capillary usefulness γ
cmc, saturated extent of adsorption Γ at air/water interface
∞, and saturated adsorption time molecular cross sectional area a at interface
∞, result is as shown in table 1.The visible increase along with chain alkyl chain length asymmetry, cmc remains on the same order of magnitude, γ
cmc, slightly increase, saturated extent of adsorption slightly declines, and molecular cross sectional area slightly rises.Namely asymmetric double long-chain alkyl methyl carboxybetaine maintains the high surface of symmetric form double long-chain alkyl methyl carboxybetaine substantially.
Embodiment 5: asymmetric double long-chain alkyl methyl carboxybetaine C
18+6b reduces separately normal paraffin/water and Daqing crude oil/local water interfacial tension.C
18+6b has excellent water-soluble, and be dissolved in grand celebration local water, concentration is 5mmol/L, and the total mineralization of water is 5535mg/L, wherein Ca
2+and Mg
2+ion total content is about 40mg/L, is also dissolved with the polyacrylamide (molecular weight 2,500 ten thousand) of 1000mg/L in water.At 45 DEG C, measure the interfacial tension to normal paraffin and Daqing crude oil with rotating liquid drop low interfacial tension instrument, result as shown in Figure 6.Visible C
18+6b separately can by C
7~ C
9normal paraffin/local water interfacial tension drops to ultralow (<0.01mN/m), to C
10above normal paraffin and Daqing crude oil, can be down to 10 by interfacial tension
-2the mN/m order of magnitude.The equivalent carbonatoms (EACN) of known Daqing crude oil is C
10, consistent with experimental configuration as seen from Figure 6.
Embodiment 6: composite oil-displacing agent is for reducing Daqing crude oil/local water interfacial tension.C
14+10b's is water-soluble relatively poor, by itself and water-soluble homologue C
16b is composite, wherein C
14+10the molar fraction of B in total surfactant is 0.6, is dissolved in grand celebration local water, is also dissolved with the polyacrylamide (molecular weight 2,500 ten thousand) of 1000mg/L in water.At 45 DEG C, measure the interfacial tension to Daqing crude oil with rotating liquid drop low interfacial tension instrument, result as shown in Figure 7.Daqing crude oil/local water interfacial tension can drop to ultralow (<0.01mN/m) by visible composite oil-displacing agent within the scope of the total surfactant concentration of 0.25mmol/L ~ 5.0mmol/L.
C
18+6b's is very well water-soluble, but will be down to ultralow by Daqing crude oil/local water interfacial tension, and lipophilicity shows slightly not enough.By C strong to itself and lipophilicity
12+12b and wetting ability homologue C
16b is composite, wherein C
18+6the molar fraction of B is 0.3, and at 45 DEG C, measure the interfacial tension to Daqing crude oil with rotating liquid drop low interfacial tension instrument, result as shown in Figure 8.Daqing crude oil/local water interfacial tension can drop to ultralow (<0.01mN/m) by visible composite oil-displacing agent within the scope of the total surfactant concentration of 2.5mmol/L ~ 7.5mmol/L.This composite oil-displacing agent has good water-soluble.
Embodiment 7: the adsorption losses of asymmetric double long-chain alkyl methyl carboxybetaine on Daqing oil sand.C
18+6b has well water-soluble, directly can measure its adsorption isothermal line in Daqing oil sand/water termination.Adopt Daqing oil sand, granular size is 60-100 order, and BET specific surface area is 3.5m
2/ g, oil-sand/surfactant soln (mass ratio) is 1/9, starting time 24 hours.The equilibrium concentration that standing separation goes out oil-sand rear surface promoting agent adopts liquid chromatography for measuring, also can measure by two-phase titration when concentration is higher.Measuring temperature is 45 DEG C.
First C is measured with liquid phase method
18+6the typical curve of B, the linear relationship of ie in solution concentration C and peak area A, result linear relationship is LogA=1.4853LogC+10.899 (C=1 × 10
-5~ 1 × 10
-3mol/L, R2=0.9910).Measure C on this basis
18+6the adsorption isothermal line of B on Daqing oil sand, as shown in Figure 9.Give symmetric form double long-chain alkyl methyl carboxybetaine C in Fig. 9 simultaneously
12+12the adsorption isothermal line of B, the equilibrium concentration liquid chromatography for measuring wherein under lower concentration.Due to C under high density
12+12b does not dissolve in water, by itself and C
12the adsorptive capacity of the rear each component of available liquid chromatography for measuring of B mixing and total adsorptive capacity, by C
12+12the molar fraction of B in total surfactant is increased to 0.8 from 0.5, obtains total saturated extent of adsorption and is almost constant, therefore using the average total saturated extent of adsorption of above-mentioned mixed system as C
12+12the saturated extent of adsorption of B, as shown by the broken line in fig. 9.So obtain C
18+6the saturated extent of adsorption of B on Daqing oil sand is 0.021mmol/g, and the saturated extent of adsorption recorded by two-phase titration is 0.022mmol/g, and both are consistent; C
12+12the saturated extent of adsorption of B is 0.030mmol/g, with C
12+12b compares, C
18+6the saturated extent of adsorption of B reduces 33%.
Some asymmetric double long-chain alkyl methyl carboxybetaine C of table 1
m+nthe surfactivity parameter (25 DEG C) of B (m+n=24) and with symmetric form double long-chain alkyl methyl carboxybetaine C
12+12the comparison of B.
Claims (5)
1., containing a composite oil-displacing agent for asymmetric double long-chain alkyl methyl carboxybetaine, wherein asymmetric double long-chain alkyl methyl carboxybetaine has following general formula:
Said structure general formula is abbreviated as C
m+nb, wherein m ≠ n, 12≤m≤18,6≤n≤12, m+n=18 ~ 30;
Asymmetric double long-chain alkyl methyl carboxybetaine C
m+nmolar fraction>=0.3 of B in oil-displacing agent total surfactant;
Second component that can contain in composite oil-displacing agent is single-long-chain alkyl dimethyl carboxybetaine, is abbreviated as C
yb, wherein y=12 ~ 18, single-long-chain alkyl dimethyl carboxybetaine can be single compound or homologous mixture, and the molar fraction in oil-displacing agent total surfactant is 0 ~ 0.5;
The 3rd component that composite oil-displacing agent can contain is symmetric form double long-chain alkyl methyl carboxybetaine C
12+12b, C
12+12the molar fraction of B in oil-displacing agent total surfactant is 0 ~ 0.4.
2. the application of the composite oil-displacing agent containing asymmetric double long-chain alkyl methyl carboxybetaine according to claim 1, this composite oil-displacing agent is applied to alkali-free binary combination flooding, i.e. surfactant and polymer binary combination flooding after the Daqing oil field water drive stage.
3. the application method of the composite oil-displacing agent containing asymmetric double long-chain alkyl methyl carboxybetaine according to claim 1 and 2 is, this composite oil-displacing agent is dissolved in grand celebration local water, tensio-active agent total concn is 7.5mmol/L, wherein second different with the molar fraction of three components time be zero, add 1000mg/L polyacrylamide (molecular weight 2,500 ten thousand) in aqueous phase, do not add any alkali, do not add any inorganic salt, do not add any cosurfactant, temperature is 45 DEG C; Use this composite oil-displacing agent under these conditions, in the scope that tensio-active agent total concn is 0.25 ~ 7.5mmol/L, Daqing crude oil/local water interfacial tension can be down to 10
-3the mN/m order of magnitude.
4. the one application of the composite oil-displacing agent containing asymmetric double long-chain alkyl methyl carboxybetaine according to claim 1, when m/n>=3, water-soluble the significantly improving of asymmetric double long-chain alkyl methyl carboxybetaine, C
18+6b one-component can be water-soluble, under concentration is add 1000mg/L polyacrylamide, 45 DEG C of conditions in 5mmol/L, aqueous phase, and can by C
7~ C
9normal paraffin/water interfacial tension is down to 10
-3the mN/m order of magnitude, is down to 10 by Daqing crude oil/local water interfacial tension
-2the mN/m order of magnitude.
5. the preparation method containing asymmetric double long-chain alkyl methyl carboxybetaine in the composite oil-displacing agent of asymmetric double long-chain alkyl methyl carboxybetaine according to Claims 1-4, with the saturated fatty acid of two kinds of different chain length for raw material, first make acyl chlorides respectively; Then react with a kind of acyl chlorides and Monomethylamine and generate N-methyl nitrosourea, through with lithium aluminium hydride reduction, generate N-chain alkyl-N-methyl secondary amine; Form N-chain alkyl-N-methyl nitrosourea with another acyl chloride reaction again, through with lithium aluminium hydride reduction, generate N, N-double long-chain alkyl-N-methyl tertiary amine; Last and sodium chloroacetate reacts, and generate target compound, reaction formula is as follows:
R in formula
m=C
mh
2m+1, R
n=C
nh
2n+1.
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