CN112251209B - Surfactant for efficiently improving recovery efficiency and preparation method thereof - Google Patents
Surfactant for efficiently improving recovery efficiency and preparation method thereof Download PDFInfo
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- 238000011084 recovery Methods 0.000 title claims abstract description 99
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 88
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 48
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 44
- 239000011734 sodium Substances 0.000 claims abstract description 44
- -1 sodium alkyl benzene Chemical class 0.000 claims abstract description 41
- 229940077388 benzenesulfonate Drugs 0.000 claims abstract description 38
- MXXDSLLVYZMTFA-UHFFFAOYSA-N octadecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 MXXDSLLVYZMTFA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229940077386 sodium benzenesulfonate Drugs 0.000 claims abstract description 25
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims abstract description 25
- 239000011780 sodium chloride Substances 0.000 claims abstract description 24
- IMCAQSSWXZDVKX-UHFFFAOYSA-N C(C1=CC=CC=C1)S(=O)(=O)OCCCCCCCCCCCCCCCCCC.[Na] Chemical compound C(C1=CC=CC=C1)S(=O)(=O)OCCCCCCCCCCCCCCCCCC.[Na] IMCAQSSWXZDVKX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 239000003921 oil Substances 0.000 abstract description 90
- 238000006073 displacement reaction Methods 0.000 abstract description 37
- 239000010779 crude oil Substances 0.000 abstract description 14
- 150000001875 compounds Chemical class 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 9
- 239000003513 alkali Substances 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 31
- 239000000203 mixture Substances 0.000 description 28
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 18
- 238000012360 testing method Methods 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 description 9
- 239000002131 composite material Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- 150000004996 alkyl benzenes Chemical class 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011435 rock Substances 0.000 description 4
- HEBRGEBJCIKEKX-UHFFFAOYSA-M sodium;2-hexadecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HEBRGEBJCIKEKX-UHFFFAOYSA-M 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011206 ternary composite Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003876 biosurfactant Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000008398 formation water Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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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
-
- 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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
-
- 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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mining & Mineral Resources (AREA)
- Geology (AREA)
- Physics & Mathematics (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Fluid Mechanics (AREA)
- Environmental & Geological Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of chemical oil displacement for improving the recovery ratio of crude oil, and particularly relates to a surfactant for efficiently improving the recovery ratio and a preparation method thereof, wherein the surfactant comprises 10-16 wt.% of sodium alkyl benzene sulfonate, 10-18 wt.% of sodium benzene sulfonate, 15-25 wt.% of industrial sodium chloride and the balance of water, and the content of each component is calculated by the total weight of the surfactant for efficiently improving the recovery ratio; the sodium alkyl benzene sulfonate is a combination of sodium octadecyl benzene sulfonate and sodium octadecyl toluene sulfonate. The surfactant for efficiently improving the recovery efficiency can reduce the oil-water interfacial tension to 1.0 multiplied by 10‑4The compound oil displacement system formed by compounding the compound oil displacement system with alkali and/or polyacrylamide has the advantages of effectively improving the oil displacement efficiency and further improving the crude oil recovery ratio by more than 45 percent compared with water drive.
Description
Technical Field
The invention belongs to the field of chemical oil displacement for improving the recovery ratio of crude oil, and particularly relates to a surfactant for efficiently improving the recovery ratio and a preparation method thereof.
Background
With the continuous progress of oil production, many areas of the world have entered the high water and extra high water phases of development. In order to increase the recovery rate of old oil fields and increase the recoverable reserves, tertiary oil recovery is often used to increase the recovery rate of crude oil after water flooding, which is also called Enhanced Oil Recovery (EOR) method, and generally refers to that after secondary oil recovery, the properties of oil, gas, water and rock are improved by injecting chemicals, heat, miscible solvents and other substances, so as to recover more oil.
Four major technological lines of tertiary oil recovery, namely chemical flooding, gas flooding, thermal flooding and microbial oil recovery, have now been developed around the world. Wherein the chemical flooding comprises polymer flooding, surfactant flooding, alkali water flooding and composite flooding technologies.
According to the existing analysis of potential for improving the oil recovery ratio in China, the water injection development of oil fields is suitable for covering geological reserves of chemical flooding methods by more than 60 hundred million tons, increasing the recoverable reserves by 9 hundred million tons and accounting for 76 percent of the potential of various methods for improving the oil recovery ratio, so that the method is the main attack direction of the research on improving the oil recovery ratio in China. In order to improve the existing oil field recovery ratio, the development of tertiary oil recovery technology is imperative. The oil displacement technology using the surface active agent as the main agent is the main technology of tertiary oil recovery in oil fields, and the oil displacement and precipitation effects are obvious. At present, the industrial application is gradually realized in large-scale oil fields such as Daqing oil fields and the like, and the method has better market prospect.
After an oil field enters a high water cut period, residual oil is trapped in the pores of reservoir rocks in a discontinuous oil film, and two main forces acting on oil droplets are viscous force and capillary force. If a proper surfactant system is used, the interfacial tension between oil and water is reduced, and the resistance caused by the deformation of oil droplets when residual oil moves is reduced, so that the oil displacement efficiency is improved.
The existing surfactants for efficiently improving the recovery ratio mainly comprise petroleum sulfonate, sodium alkyl benzene sulfonate, petroleum hydroxy acid salt, biosurfactant and the like, and all enter a pilot test stage to different degrees, so that the effect of improving the recovery ratio by 15-20% is achieved. But the production process and the production process of the respective surfactants are comprehensively considered, the production cost of the surfactants is higher, which is the root cause of the low tide of the international complex oil displacement technology; in the practical application process, the surfactant is influenced by the properties of crude oil in a reservoir, the temperature of the reservoir, the porosity, the permeability, the wetting characteristic and the like, the improvement effect of the surfactant on the oil recovery ratio is sometimes not obvious, and the surfactant is unstable in performance and easy to lose efficacy particularly at high temperature (above 70 ℃). Only by researching a surfactant and an oil displacement system which are cheap and efficient, the composite oil displacement technology can be fundamentally popularized and applied in a large scale. Therefore, the oil displacement agent which is efficient, cheap, stable in quality, reliable in process and free of pollution has wide market prospect in the aspect of synthesis and production of the surfactant.
For example, chinese patent CN111334276A discloses an oil displacement agent suitable for high-temperature low-salt oil reservoirs, which is a composite system of hydrophobic alkylbenzene sulfonate surfactant and hydrophilic sulfonate surfactant, and the weight ratio of the two is (90-30): (10-70); the oil displacement agent can form an oil displacement system together with a polymer and an oil displacement additive, so that a good effect of improving the recovery ratio by more than 30% of OOIP (oil-out-of-oil-water) compared with water displacement can be realized, but the oil displacement agent is completely composed of a surfactant, so that the production cost and the final use cost are overhigh, and the large-scale popularization and application are not facilitated.
For example, the anionic/nonionic surfactant oil displacement agent disclosed in Chinese patent CN104673263A is composed of fatty alcohol polyoxyethylene ether MOA and alkylbenzene sulfonate in a mass ratio of 1: 9-9: 1; the oil displacement agent can form a ternary composite oil displacement agent together with a polymer and alkali. The oil displacement agent can reduce the crude oil-water interfacial tension of a victory oil field to be ultra-low, but the oil displacement agent is composed of all surfactants, so that the production cost and the final use cost are overhigh, and the performance of reducing the oil-water interfacial tension and the oil displacement efficiency are still to be further improved.
Disclosure of Invention
Therefore, the technical problem to be solved by the present invention is to provide a method for reducing the oil-water interfacial tension to 1.0 × 10 with good universality and low production cost-4The surfactant for high-efficiency enhanced recovery is lower than mN/m and can enhance the recovery of crude oil by at least 45 percent compared with water drive.
As a result of earnest and diligent studies to solve the above problems, the present inventors have found that a surfactant for high efficiency enhanced oil recovery having a specific composition can reduce the oil-water interfacial tension to 1.0X 10-4The compound oil displacement system formed by compounding the compound oil displacement system with sodium carbonate and/or polyacrylamide has the advantages of effectively improving the oil displacement efficiency and further improving the crude oil recovery ratio by more than 45 percent compared with water drive.
The technical scheme of the invention is as follows:
the surfactant for high efficiency enhanced recovery consists of the following components:
10-16 wt.% of sodium alkyl benzene sulfonate, 10-18 wt.% of sodium benzene sulfonate, 15-25 wt.% of industrial sodium chloride and the balance of water, wherein the content of each component is calculated by the total weight of the surfactant for efficiently improving the recovery ratio; the sodium alkyl benzene sulfonate is a combination of sodium octadecyl benzene sulfonate and sodium octadecyl toluene sulfonate.
Wherein, the mass ratio of the sodium octadecyl benzene sulfonate to the sodium octadecyl toluene sulfonate is preferably 1: 3-3: 1, most preferably in a mass ratio of 1: 2.
the content of the sodium alkyl benzene sulfonate is more preferably 12-15 wt.%, and most preferably 13 wt.%.
The content of the sodium benzenesulfonate is more preferably 12-16 wt.%, and most preferably 14 wt.%.
The content of the industrial sodium chloride is more preferably 18-22 wt.%, and most preferably 20 wt.%.
The preparation method of the surfactant for high-efficiency enhanced oil recovery comprises the following steps:
1) preparing a material A: mixing and stirring sodium octadecyl benzene sulfonate and sodium octadecyl toluene sulfonate according to a metering ratio, then adding sodium benzene sulfonate, and continuously stirring for a certain time to obtain a material A;
2) preparing a material B: according to the metering ratio, firstly adding water, then adding industrial sodium chloride, and stirring for a certain time to obtain a material B;
3) mixing: and mixing the material B with the material A, and stirring for a certain time.
In the step 1), preferably, sodium octadecyl benzene sulfonate and sodium octadecyl toluene sulfonate are mixed and stirred for 10-15 minutes, sodium benzene sulfonate is added, and stirring is continued for 10-15 minutes to obtain the material A.
In the step 2), industrial sodium chloride is preferably added and then stirred for 10-15 minutes.
In the step 3), stirring is preferably carried out for 15 to 30 minutes.
The inventor of the application finds that the preparation process can obviously reduce the interfacial tension of oil and water compared with a one-step method of directly mixing all raw materials. Although the mechanism is not currently particularly clear, it may be associated with the pretreatment step of the raw materials (i.e. the separate preparation of materials A and B) effectively improving the properties of the micelles or microemulsions formed by mixing.
The invention also provides application of the surfactant for high-efficiency enhanced oil recovery in enhancing oil reservoir recovery.
When in use, the surfactant for efficiently improving the recovery efficiency can form a binary or ternary compound oil displacement system with alkali and/or polyacrylamide. Firstly, the surfactant for efficiently improving the recovery efficiency is utilized to reduce the oil-water interfacial tension, reduce rock stratum adsorption and improve the oil displacement efficiency; secondly, reducing the fluidity of the flooding phase by utilizing polyacrylamide, expanding sweep and profile control, and thirdly, changing the charge property of the rock surface by utilizing sodium carbonate, protecting expensive surfactant and polyacrylamide and reducing the loss of the surfactant and the polyacrylamide in the stratum; meanwhile, sodium carbonate can also react with acid components in crude oil to generate substances with surface activity in situ, so that the interfacial tension can be further reduced. The synergistic effect of the surfactant for efficiently improving the recovery ratio and sodium carbonate and/or polyacrylamide can realize the great improvement of the recovery ratio of an oil reservoir.
The molecular weight of the polyacrylamide is 1200-2500 ten thousand, preferably 1800-2000 ten thousand.
The polyacrylamide is preferably partially hydrolyzed polyacrylamide, the hydrolysis degree of the polyacrylamide is 15-30, and the most preferable hydrolysis degree is 20-25.
The present inventors have found that the formation of ultra low interfacial tension between surfactant and oil water is one of the requirements for surfactant flooding in order for surfactant flooding to be successful. And in the case of a monomolecular surfactant layer at the oil-water interface, the conditions for forming the ultra-low interfacial tension are as follows: the affinity of the lipophilic group of the surfactant for oil molecules is as much as possible equal to the affinity of the hydrophilic group for water molecules. Otherwise, the surfactant is pulled into a liquid phase with strong affinity, is easily dissolved in a water phase or an oil phase, and is difficult to be enriched on an oil-water interface. Therefore, the water solubility or oil solubility of surfactants suitable as oil displacing agents should be relatively moderate, but not unbalanced.
Compared with the prior art, the invention has the beneficial effects that:
1. the surfactant for high efficiency and increasing recovery efficiency and crude oil can form ultralow interfacial tension (oil-water interfacial tension can be reduced to 1.0 x 10)-4mN/m toNext), for example, twelve-point interfacial tensions at 0.1 wt.%, 0.2 wt.%, 0.3 wt.% and sodium carbonate concentrations of 0.6 wt.%, 0.8 wt.%, 1.0 wt.%, 1.2 wt.% for high efficiency enhanced oil recovery are all 1.0 × 10-4mN/m or less.
2. The surfactant for efficiently improving the recovery efficiency can effectively improve the oil displacement efficiency and can improve the recovery efficiency of crude oil by more than 45 percent compared with water drive.
3. The surfactant for efficiently improving the recovery efficiency can adopt the combination of sodium octadecyl benzene sulfonate and sodium octadecyl toluene sulfonate as the sodium alkyl benzene sulfonate component, thereby effectively utilizing the synergistic effect of the sodium alkyl benzene sulfonate and the sodium octadecyl toluene sulfonate and reducing the oil-water interfacial tension to 1.0 multiplied by 10-4The recovery ratio of crude oil is improved by more than 54 percent even the highest value below mN/m compared with water drive.
4. The surfactant for efficiently improving the recovery efficiency can form a binary or ternary compound oil displacement system with sodium carbonate and/or polyacrylamide, and effectively improves the recovery efficiency of crude oil.
5. The surfactant for efficiently improving the recovery ratio has a simple preparation process, and the preparation process is environment-friendly and does not cause environmental pollution.
6. The surfactant for efficiently improving the recovery efficiency has the advantages of easily available raw materials and wide sources, and can ensure that the production cost and the use cost of the product are extremely low.
Additional advantages will be set forth in part in the description which follows and in part will be obvious from the description, or may be learned by practice of the invention. The following advantages are realized and attained, particularly in light of the chemical compositions, methods, and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive.
Supplemental definition
The materials, compounds, compositions and components of the present invention may be used in, or may be used in combination with, the methods and compositions of the present invention, or may be used in the practice of the methods and in the preparation of the compositions, or as products resulting from the methods. It is to be understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each and every collective combination and permutation of these compounds may not be explicitly made, each is specifically contemplated and described herein. For example, if an extraction aid component is disclosed and discussed, and a number of alternative solid state forms of that component are discussed, each and every combination and permutation of the possible reference aid components and solid state forms is specifically contemplated unless specifically indicated to the contrary. This concept applies to all aspects of the invention, including but not limited to steps in methods of making and using the disclosed compositions. Thus, if there are a plurality of additional steps that can be performed it is understood that each of these additional steps can be performed by any specific embodiment or combination of embodiments of the disclosed methods, and that each such combination is specifically contemplated and should be considered disclosed.
In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined to have the following meanings:
it must be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include both one and more than one (i.e., two, including two) unless the context clearly dictates otherwise. Thus, for example, reference to "a base" can include a single base, or a mixture of two or more bases, and the like.
Unless otherwise indicated, the numerical ranges in this disclosure are approximate and thus may include values outside of the stated ranges. The numerical ranges may be stated herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the numerical ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
Reference in the specification and concluding claims to parts by weight of a particular element or component in a composition or article refers to the weight relationship between that element or component and any other elements or components in the composition or article, expressed as parts by weight. Thus, in a composition comprising 2 parts by weight of component X and 5 parts by weight of component Y, X and Y are present in a weight ratio of 2:5 and are present in this ratio regardless of whether additional components are included in the composition.
Unless specifically indicated to the contrary, or implied by the context or customary practice in the art, all parts and percentages referred to herein are by weight and the weight percentages of a component are based on the total weight of the composition or product in which it is included.
References to "comprising," "including," "having," and similar terms in this specification are not intended to exclude the presence of any optional components, steps or procedures, whether or not any optional components, steps or procedures are specifically disclosed. For the avoidance of any doubt, unless stated to the contrary, all methods claimed through use of the term "comprising" may include one or more additional steps, apparatus parts or components and/or materials. In contrast, the term "consisting of … …" excludes any component, step, or procedure not specifically recited or recited. Unless otherwise specified, the term "or" refers to the listed members individually as well as in any combination.
Furthermore, the contents of any referenced patent or non-patent document in this application are incorporated by reference in their entirety, especially with respect to definitions disclosed in the art (where not inconsistent with any definitions specifically provided herein) and general knowledge.
Detailed Description
The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices, and/or methods described and claimed herein are made and evaluated, and are intended to be purely exemplary and are not intended to limit the scope of what applicants regard as their invention. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for. Unless otherwise indicated, parts are parts by weight, temperatures are in degrees Celsius or at ambient temperature, and pressures are at or near atmospheric. There are many variations and combinations of reaction conditions (e.g., component concentrations, desired solvents, solvent mixtures, temperatures, pressures, and other reaction ranges) and conditions that can be used to optimize the purity and yield of the product obtained by the process. Only reasonable routine experimentation will be required to optimize such process conditions.
In addition, the instruments, reagents, materials and the like referred to in the following examples are conventional instruments, reagents, materials and the like in the prior art and are commercially available in a normal way unless otherwise specified. The experimental methods, detection methods and the like referred to in the following examples are conventional experimental methods, detection methods and the like in the prior art unless otherwise specified.
Example 1:
the surfactant for efficiently improving the recovery ratio comprises the following components: 10 wt.% of sodium alkyl benzene sulfonate, 10 wt.% of sodium benzene sulfonate, 15 wt.% of industrial sodium chloride and the balance of water, wherein the content of each component is calculated by the total weight of the surfactant for efficiently improving the recovery ratio; the mass ratio of the sodium alkyl benzene sulfonate to the sodium octadecyl benzene sulfonate is 1: 1 in combination.
The preparation process comprises the following steps:
1) preparing a material A: mixing and stirring sodium octadecyl benzene sulfonate and sodium octadecyl toluene sulfonate for 15 minutes according to a metering ratio, then adding sodium benzene sulfonate, and continuously stirring for 15 minutes to obtain a material A;
2) preparing a material B: according to the metering ratio, firstly adding water, then adding industrial sodium chloride, and stirring for 15 minutes to obtain a material B;
3) mixing: and mixing the material B with the material A, and stirring for 30 minutes.
Example 2
The surfactant for efficiently improving the recovery ratio comprises the following components: 16 wt.% of sodium alkyl benzene sulfonate, 18 wt.% of sodium benzene sulfonate, 25 wt.% of industrial sodium chloride and the balance of water, wherein the content of each component is calculated by the total weight of the surfactant for efficiently improving the recovery ratio; the mass ratio of the sodium alkyl benzene sulfonate to the sodium octadecyl benzene sulfonate is 1: 1 in combination.
The preparation method is the same as example 1.
Example 3
The surfactant for efficiently improving the recovery ratio comprises the following components: 13 wt.% of sodium alkyl benzene sulfonate, 14 wt.% of sodium benzene sulfonate, 20 wt.% of industrial sodium chloride and the balance of water, wherein the content of each component is calculated by the total weight of the surfactant for efficiently improving the recovery ratio; the mass ratio of the sodium alkyl benzene sulfonate to the sodium octadecyl benzene sulfonate is 1: 1 in combination.
The preparation method is the same as example 1.
Example 4
The surfactant for efficiently improving the recovery ratio comprises the following components: 13 wt.% of sodium alkyl benzene sulfonate, 14 wt.% of sodium benzene sulfonate, 20 wt.% of industrial sodium chloride and the balance of water, wherein the content of each component is calculated by the total weight of the surfactant for efficiently improving the recovery ratio; the mass ratio of the sodium alkyl benzene sulfonate to the sodium octadecyl benzene sulfonate is 1: 2 in combination.
The preparation method is the same as example 1.
Comparative example 1
The surfactant for efficiently improving the recovery ratio comprises the following components: 8 wt.% of sodium alkyl benzene sulfonate, 9 wt.% of sodium benzene sulfonate, 20 wt.% of industrial sodium chloride and the balance of water, wherein the content of each component is calculated by the total weight of the surfactant for efficiently improving the recovery ratio; the mass ratio of the sodium alkyl benzene sulfonate to the sodium octadecyl benzene sulfonate is 1: 2 in combination.
The preparation method is the same as example 1.
Comparative example 2
The surfactant for efficiently improving the recovery ratio comprises the following components: 17 wt.% of sodium alkyl benzene sulfonate, 20 wt.% of sodium benzenesulfonate, 20 wt.% of industrial sodium chloride and the balance of water, wherein the content of each component is calculated by the total weight of the surfactant for efficiently improving the recovery ratio; the mass ratio of the sodium alkyl benzene sulfonate to the sodium octadecyl benzene sulfonate is 1: 2 in combination.
The preparation method is the same as example 1.
Comparative example 3
The surfactant for efficiently improving the recovery ratio comprises the following components: 27 wt.% of sodium alkyl benzene sulfonate, 20 wt.% of industrial sodium chloride and the balance of water, wherein the content of each component is calculated by the total weight of the surfactant for efficiently improving the recovery ratio; the mass ratio of the sodium alkyl benzene sulfonate to the sodium octadecyl benzene sulfonate is 1: 2 in combination.
The preparation method is basically the same as that of example 1, and the step of adding sodium benzenesulfonate is omitted.
Comparative example 4
The surfactant for efficiently improving the recovery ratio comprises the following components: 27 wt% of sodium benzenesulfonate, 20 wt% of industrial sodium chloride and the balance of water, wherein the content of each component is based on the total weight of the surfactant for efficiently improving the recovery ratio.
The preparation method is basically the same as that of the example 1, and the step of adding sodium alkyl benzene sulfonate is omitted.
Comparative example 5
The surfactant for efficiently improving the recovery ratio comprises the following components: 13 wt.% of sodium alkyl benzene sulfonate, 14 wt.% of sodium benzene sulfonate and the balance of water, wherein the content of each component is calculated by the total weight of the surfactant for efficiently improving the recovery ratio; the mass ratio of the sodium alkyl benzene sulfonate to the sodium octadecyl benzene sulfonate is 1: 2 in combination.
The preparation method is basically the same as that of example 1, and the step of adding industrial sodium chloride is omitted.
Comparative example 6
The surfactant for efficiently improving the recovery ratio comprises the following components: 13 wt.% of sodium alkyl benzene sulfonate, 14 wt.% of sodium benzene sulfonate, 20 wt.% of industrial sodium chloride and the balance of water, wherein the content of each component is calculated by the total weight of the surfactant for efficiently improving the recovery ratio; the sodium alkyl benzene sulfonate is only sodium octadecyl benzene sulfonate.
The preparation method is basically the same as that of example 1, and the step of preparing the sodium alkyl benzene sulfonate mixture is omitted.
Comparative example 7
The surfactant for efficiently improving the recovery ratio comprises the following components: 13 wt.% of sodium alkyl benzene sulfonate, 14 wt.% of sodium benzene sulfonate, 20 wt.% of industrial sodium chloride and the balance of water, wherein the content of each component is calculated by the total weight of the surfactant for efficiently improving the recovery ratio; the sodium alkyl benzene sulfonate is only sodium octadecyl toluene sulfonate.
The preparation method is basically the same as that of example 1, and the step of preparing the sodium alkyl benzene sulfonate mixture is omitted.
Comparative example 8
The composition and preparation method of the surfactant for high-efficiency enhanced recovery are basically the same as those of the example 4, and the differences are only that: the sodium octadecyl benzene sulfonate is replaced by sodium hexadecylbenzene sulfonate, namely the mass ratio of the sodium octadecyl benzene sulfonate to the sodium hexadecylbenzene sulfonate is 1: 2 in combination.
Comparative example 9
The composition and preparation method of the surfactant for high-efficiency enhanced recovery are basically the same as those of the example 4, and the differences are only that: replacing sodium octadecyl benzene sulfonate with sodium hexadecylbenzene sulfonate, namely, the mass ratio of the sodium alkyl benzene sulfonate to the sodium octadecyl toluene sulfonate is 1: 2 in combination.
Comparative example 10
The composition and preparation method of the surfactant for high-efficiency enhanced recovery are basically the same as those of the example 4, and the differences are only that: the mass ratio of the sodium alkyl benzene sulfonate to the sodium octadecyl benzene sulfonate is 1: 4 in combination.
Comparative example 11
The composition and preparation method of the surfactant for high-efficiency enhanced recovery are basically the same as those of the example 4, and the differences are only that: the mass ratio of the sodium alkyl benzene sulfonate to the sodium octadecyl benzene sulfonate is 4: 11 in combination.
Comparative example 12
The composition of the surfactant for high efficiency enhanced oil recovery is substantially the same as that of example 4, except that the following one-step preparation process is adopted:
the raw materials are directly mixed according to the measurement and then stirred for 30 minutes.
Oil-water interfacial tension test and test results
The test conditions were: the testing temperature is 75 ℃, the water sample is Daqing oil field stratum water, the oil sample is Daqing oil field wellhead crude oil, and the measuring instrument is a 500-type rotary drop interfacial tensiometer of the university of Texas USA; the oil-water interfacial tension of the high efficiency enhanced recovery surfactants of examples 1 to 4 and comparative examples 1 to 12 were measured in the range of 0.6 to 1.2 wt.% sodium carbonate concentration, and the results are shown in tables 1 to 16, respectively.
TABLE 1 oil-water interfacial tension data for example 1
TABLE 2 oil-water interfacial tension data for example 2
TABLE 3 oil-water interfacial tension data for example 3
TABLE 4 oil-water interfacial tension data for example 4
TABLE 5 oil-water interfacial tension data for comparative example 1
TABLE 6 oil-water interfacial tension data for comparative example 2
TABLE 7 oil-water interfacial tension data for comparative example 3
TABLE 8 oil-water interfacial tension data for comparative example 4
TABLE 9 oil-Water interfacial tension data for comparative example 5
TABLE 10 oil-water interfacial tension data for comparative example 6
TABLE 11 oil-Water interfacial tension data for comparative example 7
TABLE 12 oil-water interfacial tension data for comparative example 8
TABLE 13 oil-Water interfacial tension data for comparative example 9
TABLE 14 oil-water interfacial tension data for comparative example 10
TABLE 15 oil-Water interfacial tension data for comparative example 12
TABLE 16 oil-water interfacial tension data for comparative example 13
As can be seen from the test results of tables 1-4 (i.e., examples 1-4), the surfactant concentrations of 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, and the sodium carbonate concentrations of 0.6 wt.%, 0.8 wt.%, 1.0 wt.%, and 1.2 wt.% for high efficiency enhanced oil recovery produced by the present invention all decreased to 1.0 × 10 wt.% twelve-point interfacial tension-4The mN/m is lower than the mN/m, and the ultralow oil-water interfacial tension is realized; the surfactant for high-efficiency enhanced oil recovery in example 4 (i.e., the composition of sodium alkylbenzene sulfonate is 13 wt.%, sodium benzenesulfonate is 14 wt.%, industrial sodium chloride is 20 wt.%, and water is the balance, and the sodium alkylbenzene sulfonate is a combination of sodium octadecyl alkylbenzene sulfonate and sodium octadecyl toluene sulfonate in a mass ratio of 1: 2) has relatively optimal comprehensive performance of reducing oil-water interfacial tension; to be more concreteIn example 2, although the oil-water interfacial tension was reduced, the contents of alkylbenzene sulfonic acid and sodium benzenesulfonate were high, and the production cost was significantly increased.
As can be seen from the test results of tables 5 to 6 and 14 to 15 (i.e., comparative examples 1 to 2 and 10 to 11), the composition of the surfactant for high efficiency enhanced oil recovery is not within the range defined by the present invention or the oil-water interfacial tension cannot be lowered to 1.0X 10- 4mN/m or less, or the production cost is extremely increased, and the economical efficiency is extremely poor.
As can be seen from the test results of tables 7 to 9 (i.e., comparative examples 3 to 5), the absence of any one of sodium alkylbenzenesulfonate, sodium benzenesulfonate and industrial sodium chloride in the composition of the surfactant for high-efficiency enhanced oil recovery failed to lower the oil-water interfacial tension to 1.0X 10 even though the sum of the contents of the components other than water was the same as in example 4-4The mN/m is lower than that, so that the synergistic effect exists among sodium alkyl benzene sulfonate, sodium benzene sulfonate and industrial sodium chloride in the surfactant for efficiently improving the recovery efficiency, and the performance of reducing the oil-water interfacial tension is obviously deteriorated if any one of the three components is lacked.
As can be further seen from the test results of tables 11-12 (i.e., comparative examples 6-7), when sodium alkyl benzene sulfonate is selected from the combination of sodium octadecyl benzene sulfonate and sodium octadecyl toluene sulfonate, particularly the mass ratio of the two is 1: 2, compared with the comparative examples 6-7, the oil-water interfacial tension value of the example 4 is even reduced by orders of magnitude, and the two are indeed synergistic, so that the performance of reducing the oil-water interfacial tension is unexpectedly improved.
It can also be seen from the results of the tests in tables 13 to 15 (i.e., comparative examples 8 to 11) that when the composition of sodium alkylbenzenesulfonate is changed, for example, one of sodium octadecylbenzenesulfonate and sodium octadecyltoluenesulfonate is replaced with the other, for example, sodium hexadecylbenzenesulfonate, the oil-water interfacial tension-lowering property thereof is remarkably deteriorated and the oil-water interfacial tension cannot be lowered to 1.0X 10-4mN/m or less.
Comparing the test results of table 16 (i.e., comparative example 12) and table 4 (i.e., example 4), it can be seen that the interfacial tension of oil and water can be significantly reduced by the preparation process of the present invention, compared to the one-step process. Although the mechanism is not currently particularly clear, it may be associated with a pretreatment step of the feedstock that effectively improves the properties of the micelles or microemulsions formed by mixing.
Oil displacement test and test result of composite oil displacement system
The preparation method comprises the steps of preparing a mixed surfactant solution by using injected water (injected clear water, reinjected sewage or formation water), wherein the mixed surfactant solution contains 0.1 wt.% of surfactant for high-efficiency enhanced recovery, 1.0 wt.% of sodium carbonate and 0.15 wt.% of polyacrylamide (molecular weight 2000 ten thousand) with the hydrolysis degree of 25, and uniformly stirring to prepare an oil displacement solution of a ternary composite system (alkali-surfactant-polyacrylamide).
The testing steps are as follows: the method comprises the steps of evacuating saturated water from the beret core, saturating crude oil, transferring the injection of a slug of a composite oil displacement system to 0.3PV when the water content is 94%, stopping the test when the water content is more than 98% continuously, and recording the recovery ratio of the water displacement and the increased value of the injection of the composite oil displacement system respectively, wherein the test results are shown in Table 17.
TABLE 17 recovery data
From the test results in table 17, it can be seen that the surfactant for high efficiency enhanced oil recovery produced by the present invention can improve the oil recovery by at least 45% compared with water flooding, and especially the surfactant for high efficiency enhanced oil recovery of example 4 can improve the oil recovery by more than 54% compared with water flooding, and the obvious improvement of the oil recovery is completely beyond the reasonable expectation range of those skilled in the art, which is a strong reflection of the intelligent contribution made by the inventors of the present invention.
Throughout this disclosure, various publications are referenced. The disclosures of these publications in their entireties are hereby incorporated by reference into this application in order to more fully describe the compounds, compositions, and methods described herein.
Various modifications and variations can be made in the compounds, compositions, and methods described herein. Other aspects of the compounds, compositions, and methods described herein will be apparent from consideration of the specification and practice of the disclosed compounds, compositions, and methods. It is intended that the specification and examples be considered as exemplary.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (9)
1. The surfactant for high efficiency enhanced recovery consists of the following components:
10-16 wt.% of sodium alkyl benzene sulfonate, 10-18 wt.% of sodium benzene sulfonate, 15-25 wt.% of industrial sodium chloride and the balance of water, wherein the content of each component is calculated by the total weight of the surfactant for efficiently improving the recovery ratio; the sodium alkyl benzene sulfonate is a combination of sodium octadecyl benzene sulfonate and sodium octadecyl toluene sulfonate; wherein the mass ratio of the sodium octadecyl benzene sulfonate to the sodium octadecyl toluene sulfonate is 1: 3-3: 1.
2. the surfactant for high efficiency enhanced oil recovery according to claim 1, wherein the mass ratio of sodium octadecyl benzene sulfonate to sodium octadecyl toluene sulfonate is 1: 2.
3. the surfactant for high efficiency enhanced oil recovery according to claim 1, wherein the sodium alkylbenzenesulfonate is contained in an amount of 12 to 15 wt.%, the sodium benzenesulfonate is contained in an amount of 12 to 16 wt.%, and the industrial sodium chloride is contained in an amount of 18 to 22 wt.%.
4. The method for preparing a surfactant for high efficiency enhanced oil recovery according to any one of claims 1 to 3, comprising the steps of:
1) preparing a material A: mixing and stirring sodium octadecyl benzene sulfonate and sodium octadecyl toluene sulfonate according to a metering ratio, then adding sodium benzene sulfonate, and continuously stirring for a certain time to obtain a material A;
2) preparing a material B: according to the metering ratio, firstly adding water, then adding industrial sodium chloride, and stirring for a certain time to obtain a material B;
3) mixing: and mixing the material B with the material A, and stirring for a certain time.
5. The preparation method of claim 4, wherein in step 1), sodium octadecyl benzene sulfonate and sodium octadecyl toluene sulfonate are mixed and stirred for 10-15 min, sodium benzene sulfonate is added, and stirring is continued for 10-15 min to obtain material A.
6. The method according to claim 4, wherein the industrial sodium chloride is added and stirred for 10-15 minutes in the step 2).
7. The method according to claim 4, wherein the stirring is carried out for 15 to 30 minutes in the step 3).
8. Use of the surfactant for high efficiency enhanced oil recovery according to any one of claims 1 to 3 or the surfactant for high efficiency enhanced oil recovery produced by the production method according to any one of claims 4 to 7 for enhanced oil recovery.
9. The use of claim 8, wherein the surfactant for high efficiency enhanced oil recovery forms a binary or ternary complex flooding system with a base and/or polyacrylamide.
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| CN102131890A (en) * | 2008-08-22 | 2011-07-20 | 科聚亚公司 | Enhanced oil recovery using sulfonate mixtures |
| CN103193689A (en) * | 2013-04-17 | 2013-07-10 | 中国石油天然气股份有限公司 | Hexadecyl toluene sulfonate for oil displacement, preparation method thereof, surfactant and application thereof |
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| CN102131890A (en) * | 2008-08-22 | 2011-07-20 | 科聚亚公司 | Enhanced oil recovery using sulfonate mixtures |
| CN103193689A (en) * | 2013-04-17 | 2013-07-10 | 中国石油天然气股份有限公司 | Hexadecyl toluene sulfonate for oil displacement, preparation method thereof, surfactant and application thereof |
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