CN116751575A - Alkali-free compound oil displacement agent composition, alkali-free compound oil displacement agent and preparation method thereof - Google Patents
Alkali-free compound oil displacement agent composition, alkali-free compound oil displacement agent and preparation method thereof Download PDFInfo
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- 238000006073 displacement reaction Methods 0.000 title claims abstract description 67
- 150000001875 compounds Chemical class 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 74
- 239000004094 surface-active agent Substances 0.000 claims abstract description 45
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 37
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 29
- 230000029936 alkylation Effects 0.000 claims abstract description 19
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 19
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 19
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 16
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 229920000058 polyacrylate Polymers 0.000 claims description 24
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical group O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000002131 composite material Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 11
- 229940100198 alkylating agent Drugs 0.000 claims description 10
- 239000002168 alkylating agent Substances 0.000 claims description 10
- 239000010413 mother solution Substances 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- UMEMJLBVOVXVBT-UHFFFAOYSA-N 2-(2-amino-2-oxoethoxy)acetamide dodecanoic acid Chemical compound NC(=O)COCC(N)=O.CCCCCCCCCCCC(O)=O UMEMJLBVOVXVBT-UHFFFAOYSA-N 0.000 claims description 7
- 229920001897 terpolymer Polymers 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012452 mother liquor Substances 0.000 claims description 6
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- JSYPRLVDJYQMAI-ODZAUARKSA-N (z)-but-2-enedioic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)\C=C/C(O)=O JSYPRLVDJYQMAI-ODZAUARKSA-N 0.000 claims description 4
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical group CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims description 4
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 4
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 claims description 4
- ATMLPEJAVWINOF-UHFFFAOYSA-N acrylic acid acrylic acid Chemical compound OC(=O)C=C.OC(=O)C=C ATMLPEJAVWINOF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 229920006029 tetra-polymer Polymers 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 5
- 239000003921 oil Substances 0.000 description 101
- 239000007788 liquid Substances 0.000 description 8
- 238000011084 recovery Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000605 extraction Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 230000006378 damage Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- 239000002332 oil field water Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- CNDWHJQEGZZDTQ-UHFFFAOYSA-N 2-(2-amino-2-oxoethoxy)acetamide Chemical compound NC(=O)COCC(N)=O CNDWHJQEGZZDTQ-UHFFFAOYSA-N 0.000 description 1
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- 235000015842 Hesperis Nutrition 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000005406 washing 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
- C09K8/58—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 the technical field of oil field compound oil displacement, and discloses an alkali-free compound oil displacement agent composition, an alkali-free compound oil displacement agent and a preparation method thereof, wherein the alkali-free compound oil displacement agent composition contains an acrylic acid polymer, a sulfonate surfactant and a nonionic surfactant, the sulfonate surfactant is a product obtained by sequentially carrying out sulfonation reaction and neutralization reaction on two-line distillate oil, bottom oil and wash oil alkylation derivatives, and the interfacial tension of the sulfonate surfactant is not more than 10 ‑2 mN/m. The composition can prepare the alkali-free compound oil displacement agent with ultralow interfacial tension and high oil displacement efficiency under the condition of no alkali addition.
Description
Technical Field
The invention relates to the technical field of oil field compound oil displacement, in particular to an alkali-free compound oil displacement agent composition, an alkali-free compound oil displacement agent and a preparation method thereof.
Background
Petroleum is an important energy source, and has the advantages of high energy density, convenient transportation and storage, small pollution degree to the atmosphere after combustion, and the like compared with coal. Liquefied gas and pipeline gas using petroleum as raw materials are high-quality fuels for urban resident living applications, and airplanes, tanks, ships, rockets and other spacecrafts are also used as fuels.
Petroleum extraction refers to the act of excavating and extracting petroleum in a place where it is stored, and is divided into three phases: primary oil recovery, which relies on the natural energy of the stratum to carry out the recovery; secondary oil extraction, wherein the secondary oil extraction is carried out by manual water injection or gas injection; tertiary oil recovery relies on physical and chemical methods for recovery. The tertiary oil recovery method mainly comprises thermal flooding, mixed phase flooding, chemical flooding and microbial flooding.
Chemical flooding is an oil extraction method in which various chemical agents are added into injected water to improve the oil displacement and sweep performance of the water, thereby improving the recovery ratio of crude oil. In order to make the oil-water interfacial tension ultra-low (10) -3 mN/m) to increase recovery, typically by adding high concentrations of alkali, which reduces the viscosity and viscoelasticity of the displacement system, affects the mobility control ability of the complex displacement agent, and which acts on the reservoir rock to produce severe scaling and reservoir damage that can deposit downhole and in the reservoirAnd on the screw pump, a clamping pump is caused. Therefore, it is needed to provide an alkali-free compound oil displacement agent with low interfacial tension, which can realize high oil displacement efficiency while avoiding the influence of alkali on oil exploitation.
Disclosure of Invention
The invention aims to solve the problems that an alkali-free compound oil displacement agent cannot have low interfacial tension and high oil displacement efficiency in the prior art, and provides an alkali-free compound oil displacement agent composition, an alkali-free compound oil displacement agent and a preparation method thereof.
In order to achieve the above object, according to one aspect of the present invention, there is provided an alkali-free composite oil-displacing agent composition comprising:
5-15 parts by mass of an acrylic polymer;
3-9 parts by mass of sulfonate surfactant;
1 part by mass of a nonionic surfactant;
optionally, 975-991 parts by mass of water are also contained in the composition;
wherein the number average molecular weight of the acrylic polymer is 2000-3000 ten thousand;
the sulfonate surfactant is a product obtained by sequentially carrying out sulfonation reaction and neutralization reaction on the two-wire distillate oil, the bottom oil and the wash oil alkylation derivative, and the interfacial tension of the sulfonate surfactant is not more than 10 - 2 mN/m；
The nonionic surfactant is octyl phenol polyoxyethylene ether and/or lauric acid diglycolamide.
Preferably, the content of the acrylic polymer is 8 to 10 parts by mass and the content of the sulfonate type surfactant is 6 to 9 parts by mass per 1 part by mass of the nonionic surfactant.
Preferably, the nonionic surfactant is in a mass ratio of 1-3:1 and lauric acid diglycolamide.
Preferably, the alkyl content in the wash oil alkylated derivative is 25wt% to 65wt%, and the relative average molecular weight of the wash oil alkylated derivative is 400-600.
Preferably, the wash oil alkylation derivative is obtained by alkylation treatment of wash oil, wherein the aromatic hydrocarbon content of the wash oil is 80-95 wt%, the relative average molecular weight is 450-550, and the kinematic viscosity at 50 ℃ is 15m 2 /s-20m 2 /s。
More preferably, the alkylation treatment conditions at least satisfy: the alkylating agent is olefin with 12-28 carbon atoms, and the mass ratio of the wash oil to the alkylating agent is 1:0.4-0.8, the treatment temperature is 30-80 ℃ and the treatment time is 1-8 h.
Preferably, the aromatic hydrocarbon content of the two-wire distillate is 25-40 wt%, the relative average molecular weight is 290-360, and the kinematic viscosity at 50 ℃ is 12m 2 /s-16m 2 /s。
Preferably, the aromatic hydrocarbon content of the bottom oil is 70wt% to 85wt%, the relative average molecular weight is 400-600, and the kinematic viscosity at 50 ℃ is 14m 2 /s-18m 2 /s。
Preferably, the weight ratio of the two-wire cut, the bottom oil and the wash oil alkylated derivative for carrying out the sulfonation reaction is 2.3-9:0.6-2.4:1, a step of;
more preferably, the sulfonating agent of the sulfonation treatment is sulfur trioxide and/or chlorosulfonic acid, and the ratio of the sulfonating agent to the amount of the two-wire cut fraction is 1 to 1.5:1, the temperature of the sulfonation reaction is 50-80 ℃ and the time is 1-4 h.
Preferably, the neutralizing agent of the neutralization reaction is sodium hydroxide solution, the mass concentration of the sodium hydroxide solution is 20-40 wt%, and the end point pH value of the neutralization reaction is 8-13.
Preferably, the acrylic polymer is one or more of polyacrylic acid, polymethacrylic acid, acrylic acid-hydroxypropyl acrylate copolymer, acrylic acid-sulfonate-amido copolymer, acrylic acid-acrylic ester-phosphonic acid-sulfonate copolymer, acrylic acid-acrylic ester-sulfonate terpolymer, maleic acid-acrylic acid copolymer and carboxylate-sulfonate-acrylic ester terpolymer.
The second aspect of the invention provides a preparation method of an alkali-free compound oil displacement agent, which is carried out by applying the components in the alkali-free compound oil displacement agent composition, and comprises the following steps:
s1: mixing a sulfonate surfactant, a nonionic surfactant and a part of water to obtain a surfactant mother liquor;
mixing the acrylic acid polymer with the rest of water to obtain an acrylic acid polymer mother solution;
s2: and mixing the surfactant mother solution and the acrylic polymer mother solution to obtain the alkali-free compound oil displacement agent.
Preferably, in step S1, the total water amount of the part of water and the remaining part of water is 975 to 991 parts by mass with respect to 1 part by mass of the nonionic surfactant, and the part of water is used in an amount of 50 to 70% by weight of the total water amount.
The third aspect of the invention provides an alkali-free compound oil-displacing agent prepared by the alkali-free compound oil-displacing agent composition or the alkali-free compound oil-displacing agent prepared by the preparation method.
In the alkali-free compound oil-displacing agent composition provided by the first aspect of the invention, the specific sulfonate surfactant, the anionic surfactant and the acrylic polymer with the number average molecular weight of 2000-3000 ten thousand are compounded according to a specific proportion, and the components are synergistic mutually, so that the alkali-free compound oil-displacing agent with ultralow interfacial tension and high oil-displacing efficiency can be prepared.
According to the preparation method provided by the second aspect of the invention, the alkali-free composite oil displacement agent composition provided by the first aspect of the invention is applied, and the prepared alkali-free composite oil displacement agent has ultralow interfacial tension and high oil displacement efficiency according to a specific mixing sequence.
The alkali-free compound oil displacement agent provided by the third aspect of the invention can avoid the problems of formation injury, reservoir permeability reduction, serious emulsion of produced liquid, difficult separation and the like caused by alkali, and can also have ultralow interfacial tension and high oil displacement efficiency.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides an alkali-free composite oil-displacing agent composition, which comprises:
5-15 parts by mass of an acrylic polymer;
3-9 parts by mass of sulfonate surfactant;
1 part by mass of a nonionic surfactant;
optionally, 975-991 parts by mass of water are also contained in the composition;
wherein the number average molecular weight of the acrylic polymer is 2000-3000 ten thousand;
the sulfonate surfactant is a product obtained by sequentially carrying out sulfonation reaction and neutralization reaction on the two-wire distillate oil, the bottom oil and the wash oil alkylation derivative, and the interfacial tension of the sulfonate surfactant is not more than 10 - 2 mN/m；
The nonionic surfactant is octyl phenol polyoxyethylene ether and/or lauric acid diglycolamide.
In the alkali-free compound oil displacement agent composition provided by the invention, the specific sulfonate surfactant is compounded with the anionic surfactant and the acrylic acid polymer with the number average molecular weight of 2000-3000 ten thousand according to the specific proportion, so that a synergistic effect can be generated, and the prepared alkali-free compound oil displacement agent can avoid the problems of formation injury, reduced reservoir permeability, serious emulsion of produced liquid, difficult separation and the like caused by adding alkali, can generate ultralow interfacial tension, has good emulsifying property and further achieves good oil displacement efficiency.
According to some preferred embodiments of the present invention, the content of the acrylic polymer is 8 to 10 parts by mass and the content of the sulfonate type surfactant is 6 to 9 parts by mass per 1 part by mass of the nonionic surfactant. More preferably, the content of the sulfonate surfactant is 7 to 8 parts by mass per 1 part by mass of the nonionic surfactant. Under the preferable condition, the swept volume of the alkali-free compound oil displacement agent can be further improved, and the oil displacement efficiency of the alkali-free compound oil displacement agent is improved.
According to some particularly preferred embodiments of the invention, the nonionic surfactant is present in a mass ratio of 1 to 3:1 and lauric acid diglycolamide. Under the preferable condition, the prepared object accords with the lower interfacial tension of the oil displacement agent and has higher oil displacement efficiency.
According to some preferred embodiments of the invention, the alkyl content of the wash oil alkylated derivative is from 25wt% to 65wt%, and the relative average molecular weight of the wash oil alkylated derivative is from 400 to 600. Under the preferable condition, the prepared sulfonate surfactant has stronger synergistic effect with other components after being compounded, and can prepare the alkali-free compound oil displacement agent with higher oil displacement efficiency.
According to some preferred embodiments of the present invention, the wash oil alkylated derivatives are obtained by alkylation of a wash oil having an aromatic content of 80wt% to 95wt%, a relative average molecular weight of 450 to 550, and a kinematic viscosity at 50 ℃ of 15m 2 /s-20m 2 And/s. The washing oil alkylation derivative prepared under the preferable condition can prepare the sulfonate type surfactant which is more suitable for the alkali-free compound oil displacement agent composition system.
More preferably, the alkylation treatment conditions at least satisfy: the alkylating agent is olefin with 12-28 carbon atoms, and the mass ratio of the wash oil to the alkylating agent is 1:0.4-0.8, the treatment temperature is 30-80 ℃ and the treatment time is 1-8 h. The sulfonate surfactant prepared under the preferable condition has stronger synergistic effect with other components after being compounded, and can prepare the alkali-free compound oil displacement agent with higher oil displacement efficiency.
According to some preferred embodiments of the present invention, the reduced second fraction has an aromatics content of 25wt% to 40wt%, a relative average molecular weight of 290-360, and a kinematic viscosity of 12m at 50 DEG C 2 /s-16m 2 And/s. The sulfonate surfactant prepared from the two-wire distillate oil under the preferred condition can be compounded with other components to prepare the alkali-free compound oil displacement agent with higher oil displacement efficiency.
According to some preferred embodiments of the invention, the aromatic hydrocarbon content of the bottom oil is 70wt% to 85wt%, the relative average molecular weight is 400 to 600, and the kinematic viscosity at 50 ℃ is 14m 2 /s-18m 2 And/s. The oil displacement efficiency of the alkali-free compound oil displacement agent obtained by compounding the sulfonate surfactant prepared from the bottom oil under the preferred condition with other components is higher.
According to some preferred embodiments of the invention, the weight ratio of the two-wire cut, the bottom oil and the wash oil alkylated derivative for carrying out the sulfonation reaction is from 2.3 to 9:0.6-2.4:1. the sulfonate surfactant prepared under the preferable condition has more excellent performance and the oil displacement efficiency of the alkali-free compound oil displacement agent obtained after being compounded with other components is higher.
Further preferably, the sulfonating agent of the sulfonation treatment is sulfur trioxide and/or chlorosulfonic acid, and the ratio of the sulfonating agent to the amount of the two-wire cut fraction is 1 to 1.5:1, the temperature of the sulfonation reaction is 50-80 ℃ and the time is 1-4 h. Under the preferable condition, the prepared sulfonate surfactant has more excellent performance.
Further preferably, the neutralizing agent of the neutralization reaction is sodium hydroxide solution, the mass concentration of the sodium hydroxide solution is 20-40 wt%, and the end point pH value of the neutralization reaction is 8-13. Under the preferable condition, the sulfonate surfactant with excellent effect can be prepared, and the sodium hydroxide solution is not wasted, so that the method is economical and environment-friendly.
According to some preferred embodiments of the present invention, the acrylic polymer is one or more of polyacrylic acid, polymethacrylic acid, acrylic acid-hydroxypropyl acrylate copolymer, acrylic acid-sulfonate-amido copolymer, acrylic acid-acrylic acid ester-phosphonic acid-sulfonate tetrapolymer, acrylic acid-acrylic acid ester-sulfonate terpolymer, maleic acid-acrylic acid copolymer, and carboxylate-sulfonate-acrylic acid ester terpolymer.
Preferably, the acrylic polymer is one or more of polyacrylic acid, polymethacrylic acid, acrylic acid-hydroxypropyl acrylate copolymer, acrylic acid-acrylic ester-sulfonate terpolymer and maleic acid-acrylic acid copolymer.
The source of the acrylic polymer is not particularly limited, and the acrylic polymer may be any commercially available product in the art.
The water in the alkali-free composite oil-displacing agent composition is not particularly limited, and is exemplified by deionized water, mineral-containing water, or the like, wherein the mineral-containing water is tap water, river water, or oilfield water injection. But is preferably oilfield water injection from environmental and economic considerations.
The second aspect of the invention provides a preparation method of an alkali-free compound oil displacement agent, which is carried out by applying the components in the alkali-free compound oil displacement agent composition, and comprises the following steps:
s1: mixing a sulfonate surfactant, a nonionic surfactant and a part of water to obtain a surfactant mother liquor;
mixing the acrylic acid polymer with the rest of water to obtain an acrylic acid polymer mother solution;
s2: and mixing the surfactant mother solution and the acrylic polymer mother solution to obtain the alkali-free compound oil displacement agent.
Preferably, in step S1, the total water amount of the part of water and the remaining part of water is 975 to 991 parts by mass with respect to 1 part by mass of the nonionic surfactant, and the part of water is used in an amount of 50 to 70% by weight of the total water amount.
According to the preparation method provided by the second aspect of the invention, the alkali-free composite oil displacement agent composition provided by the first aspect of the invention can be used for preparing the alkali-free composite oil displacement agent with ultralow interfacial tension and high oil displacement efficiency.
The third aspect of the invention provides an alkali-free compound oil-displacing agent prepared by the alkali-free compound oil-displacing agent composition or the alkali-free compound oil-displacing agent prepared by the preparation method.
The present invention will be described in detail by examples. In the following examples, 1 part by mass represents 1g; in the following examples, the amount of material M of the two-wire distillate was calculated as follows: m = mass/relative average molecular weight. In the following examples, room temperature and normal pressure are 25℃and 0.1013MPa; in the following examples, interfacial tension was measured using an interfacial tensiometer available from Beijing Cheng Wei basic technology Co.
Acrylic polymer A (hereinafter referred to as B-A): polymethacrylic acid, number average molecular weight 2000 ten thousand, purchased from Heilongjiang Jidi oilfield services Co., ltd;
acrylic polymer B (hereinafter referred to as B-B): acrylic acid-hydroxypropyl acrylate copolymer with a number average molecular weight of 2500 ten thousand purchased from Heilongjiang Jidi oilfield services Co., ltd;
nonionic surfactant Sub>A (hereinafter referred to as F-Sub>A): octyl phenol polyoxyethylene ether is purchased from Jiangsu province sea-An petrochemical plant;
nonionic surfactant B (hereinafter F-B): lauric acid diglycolamide, self-made, 95 weight percent, is obtained by adopting lauric acid and diglycolamine to undergo condensation reaction;
nonionic surfactant C (hereinafter F-C): from the octylphenol polyoxyethylene ether and the diglycolamide laurate according to 2:1 are mixed at normal temperature and normal pressure;
sulfonate surfactant a (hereinafter H-a): interfacial tension of 3.7X10 -3 mN/m, from the two-wire cut a, bottom a and wash alkylated derivative a according to 4:1:1.2, and then sequentially carrying out sulfonation reaction and neutralization reaction, wherein the sulfonation reaction conditions are as follows: the sulfonating agent is liquid sulfur trioxide (analytically pure), the mass ratio of the liquid sulfur trioxide to the material of the two-wire cut a is 1.2:1, a step of; the neutralization reaction conditions are as follows: the neutralizer is sodium hydroxide solution with the mass concentration of 30wt%, and the end point pH value is 10;
sulfonate surfactant B (hereinafter referred to as H-B): interfacial tension of 9.5X10 -3 mN/m, alkylation from reduced second line distillate A, bottom A and wash oilThe derivative A is obtained after sulfonation reaction and neutralization reaction are sequentially carried out, wherein the conditions of the sulfonation reaction are as follows: the sulfonating agent is liquid sulfur trioxide (analytically pure), the mass ratio of the liquid sulfur trioxide to the material of the two-wire cut a is 0.9:1, a step of; the neutralization reaction conditions are as follows: the neutralizer is sodium hydroxide solution with the mass concentration of 10wt%, and the end point pH value is 7;
sulfonate surfactant C (hereinafter H-C): interfacial tension of 2.6X10 -2 And mN/m is obtained by sequentially carrying out sulfonation reaction and neutralization reaction on the two-wire distillate oil B, the bottom oil B and the wash oil alkylation derivative B, wherein the sulfonation reaction conditions are as follows: the sulfonating agent is liquid sulfur trioxide (analytically pure), the mass ratio of the liquid sulfur trioxide to the material of the two-wire cut B is 0.9:1, a step of; the neutralization reaction conditions are as follows: the neutralizer is sodium hydroxide solution with the mass concentration of 10wt%, and the end point pH value is 7;
two-wire distillate a: the aromatic hydrocarbon content is 35wt percent to 40wt percent, the relative average molecular weight is 320 to 360, and the kinematic viscosity at 50 ℃ is 14m 2 /s-16m 2 S, purchased from Daqing refining company;
two-wire distillate B: the aromatic hydrocarbon content is 18-24 wt%, the relative average molecular weight is 280-310, and the kinematic viscosity at 50 ℃ is 10m 2 /s-12m 2 S, purchased from Daqing petrochemical company;
bottom oil a: the aromatic hydrocarbon content is 75-85 wt%, the relative average molecular weight is 500-600, and the kinematic viscosity at 50 ℃ is 16m 2 /s-18m 2 S, purchased from Daqing refining company;
bottom oil B: the aromatic hydrocarbon content is 60-68wt%, the relative average molecular weight is 380-480, and the kinematic viscosity at 50 ℃ is 12m 2 /s-14m 2 S, purchased from Daqing petrochemical company;
wash oil alkylated derivative a: the alkyl content is 53wt%, the relative average molecular weight is 560, and the oil is obtained by alkylation treatment of wash oil; the aromatic hydrocarbon content of the wash oil is 80-90 wt%, the relative average molecular weight is 450-500, and the kinematic viscosity at 50 ℃ is 15m 2 /s-18m 2 S, purchased from Heilongjiang Baotai coal chemical group; the alkylation treatment conditions: the alkylating agent isN-hexadecene, the mass ratio of the wash oil to the alkylating agent is 1:0.6, the treatment temperature is 50 ℃, and the treatment time is 4 hours;
wash oil alkylated derivative B: the alkyl content is 20wt% and the relative average molecular weight is 380, and the oil is obtained by alkylation treatment of wash oil; the aromatic hydrocarbon content of the wash oil is 65-75wt%, the relative average molecular weight is 350-400, and the kinematic viscosity at 50 ℃ is 10m 2 /s-13m 2 S, said alkylation treatment conditions: the alkylating agent is n-decene, and the mass ratio of the wash oil to the alkylating agent is 1:0.2, the treatment temperature is 50 ℃ and the treatment time is 4 hours.
Example 1
Preparing an alkali-free compound oil displacement agent:
s1: mixing a sulfonate surfactant, a nonionic surfactant and a part of water to obtain a surfactant mother liquor;
mixing the acrylic acid polymer with the rest of water to obtain an acrylic acid polymer mother solution;
s2: and mixing the surfactant mother solution and the acrylic polymer mother solution to obtain the alkali-free compound oil displacement agent.
Wherein, the mixing in step S1 and step S2 is carried out under the condition of normal temperature and normal pressure, and concretely, each parameter is shown in the following table 1.
Example 2
The procedure of example 1 was followed, except that the component proportions were changed, and specifically, the parameters were as shown in Table 1 below.
Example 3
The procedure of example 1 was followed, except that the component ratios and the kinds of nonionic surfactant and acrylic polymer were changed, and specifically, the parameters were as shown in Table 1 below.
Example 4
The procedure of example 1 was followed, except that the component ratios and the kinds of nonionic surfactant and acrylic polymer were changed, and specifically, the parameters were as shown in Table 1 below.
Example 5
The procedure of example 2 was followed, except that the kind of the sulfonate type surfactant was changed, and specifically, the parameters were as shown in the following Table 1.
Example 6
The procedure of example 4 was followed, except that the kind of the sulfonate type surfactant was changed, and specifically, the parameters were as shown in the following Table 1.
Example 7
The procedure of example 1 was followed, except that the kind of nonionic surfactant was changed, and specifically, the parameters were as shown in the following table 1.
Comparative example 1
The procedure of example 2 was followed, except that the kind of the sulfonate type surfactant was changed, and specifically, the parameters were as shown in the following Table 1.
Comparative example 2
The procedure of example 3 was followed except that no nonionic surfactant was added and the component proportions were changed, specifically, the parameters were as shown in the following Table 1.
Comparative example 3
The procedure of example 3 was followed except that the sulfonate type surfactant was not added and the component proportions were changed, specifically, the parameters were as shown in the following table 1.
Comparative example 4
The procedure of example 3 was followed, except that the component proportions were changed, and specifically, the parameters were as shown in Table 1 below.
Comparative example 5
The procedure of example 3 was followed, except that the component ratios and the kinds of nonionic surfactants were changed, and specifically, the parameters were as shown in the following Table 1.
TABLE 1
Table 1 (subsequent table)
Table 1 (subsequent table)
The alkali-free compound oil displacement agent prepared in the above examples and comparative examples is subjected to performance test according to SY/T6424-2014 "compound oil displacement System Performance test method", and the test results are shown in Table 2 below:
TABLE 2
| Interfacial tension (mN/m) | Oil displacement efficiency (%) | |
| L1 | 0.0026 | 70 |
| L2 | 0.0028 | 68 |
| L3 | 0.0035 | 65 |
| L4 | 0.0030 | 69 |
| L5 | 0.0047 | 60 |
| L6 | 0.0043 | 62 |
| L7 | 0.0012 | 78 |
| DL1 | 0.0086 | 45 |
| DL2 | 0.0068 | 51 |
| DL3 | 0.0083 | 48 |
| DL4 | 0.0059 | 55 |
| DL5 | 0.0062 | 53 |
As can be seen from the results in tables 1 and 2, the alkali-free compound oil displacement agent prepared by the method provided by the embodiment of the invention can realize ultralow interfacial tension and higher oil displacement efficiency.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. An alkali-free compound oil displacement agent composition is characterized in that the composition comprises:
5-15 parts by mass of an acrylic polymer;
3-9 parts by mass of sulfonate surfactant;
1 part by mass of a nonionic surfactant;
optionally, 975-991 parts by mass of water are also contained in the composition;
wherein the number average molecular weight of the acrylic polymer is 2000-3000 ten thousand;
the sulfonate surfactant is a product obtained by sequentially carrying out sulfonation reaction and neutralization reaction on the two-wire distillate oil, the bottom oil and the wash oil alkylation derivative, and the interfacial tension of the sulfonate surfactant is not more than 10 -2 mN/m；
The nonionic surfactant is octyl phenol polyoxyethylene ether and/or lauric acid diglycolamide.
2. The alkali-free composite oil-displacing agent composition as claimed in claim 1, wherein the content of the acrylic polymer is 8-10 parts by mass and the content of the sulfonate surfactant is 6-9 parts by mass per 1 part by mass of the nonionic surfactant;
preferably, the nonionic surfactant is in a mass ratio of 1-3:1 and lauric acid diglycolamide.
3. The alkali-free composite oil displacement agent composition according to claim 1 or 2, wherein the alkyl content in the wash oil alkylated derivative is 25wt% to 65wt%, and the relative average molecular weight of the wash oil alkylated derivative is 400 to 600;
preferably, the wash oil alkylation derivative is obtained by alkylation treatment of wash oil, wherein the aromatic hydrocarbon content of the wash oil is 80-95 wt%, the relative average molecular weight is 450-550, and the kinematic viscosity at 50 ℃ is 15m 2 /s-20m 2 /s；
More preferably, the alkylation treatment conditions at least satisfy: the alkylating agent is olefin with 12-28 carbon atoms, and the mass ratio of the wash oil to the alkylating agent is 1:0.4-0.8, the treatment temperature is 30-80 ℃ and the treatment time is 1-8 h.
4. The alkali-free composite oil-displacing agent composition as claimed in claim 1 or 2, wherein the reduced two-wire distillate has an aromatic hydrocarbon content of 25-40 wt%, a relative average molecular weight of 290-360, and a kinematic viscosity of 12m at 50 °c 2 /s-16m 2 /s。
5. The alkali-free composite oil-displacing agent composition as claimed in claim 1 or 2, wherein the aromatic hydrocarbon content of the bottom oil is 70-85 wt%, the relative average molecular weight is 400-600, and the kinematic viscosity at 50 ℃ is 14m 2 /s-18m 2 /s。
6. The alkali-free complex oil-displacing agent composition as claimed in claim 1 or 2, wherein the weight ratio of the two-wire cut oil, the bottom oil and the wash oil alkylated derivative for carrying out the sulfonation reaction is 2.3-9:0.6-2.4:1, a step of;
preferably, the sulfonating agent of the sulfonation treatment is sulfur trioxide and/or chlorosulfonic acid, and the ratio of the sulfonating agent to the amount of the two-wire fraction oil is 1 to 1.5:1, the temperature of the sulfonation reaction is 50-80 ℃ and the time is 1-4 h.
7. The alkali-free composite oil displacement agent composition according to claim 1 or 2, wherein the neutralizing agent for the neutralization reaction is sodium hydroxide solution, the mass concentration of the sodium hydroxide solution is 20-40 wt%, and the end point pH value of the neutralization reaction is 8-13.
8. The alkali-free composite oil-displacing agent composition as claimed in claim 1 or 2, wherein the acrylic polymer is one or more of polyacrylic acid, polymethacrylic acid, acrylic acid-hydroxypropyl acrylate copolymer, acrylic acid-sulfonate-amide copolymer, acrylic acid-acrylic acid ester-phosphonic acid-sulfonate tetrapolymer, acrylic acid-acrylic acid ester-sulfonate terpolymer, maleic acid-acrylic acid copolymer and carboxylate-sulfonate-acrylic acid ester terpolymer.
9. A method for preparing an alkali-free compound oil displacement agent, which is characterized by comprising the steps of:
s1: mixing a sulfonate surfactant, a nonionic surfactant and a part of water to obtain a surfactant mother liquor;
mixing the acrylic acid polymer with the rest of water to obtain an acrylic acid polymer mother solution;
s2: mixing the surfactant mother liquor and the acrylic polymer mother liquor to obtain an alkali-free compound oil displacement agent;
preferably, in step S1, the total water amount of the part of water and the remaining part of water is 975 to 991 parts by mass with respect to 1 part by mass of the nonionic surfactant, and the part of water is used in an amount of 50 to 70% by weight of the total water amount.
10. An alkali-free composite oil-displacing agent prepared by the alkali-free composite oil-displacing agent composition of any one of claims 1 to 8 or prepared by the preparation method of claim 9.
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