CN111154471A - Composite oil displacement agent containing sodium chloride and preparation method thereof - Google Patents
Composite oil displacement agent containing sodium chloride and preparation method thereof Download PDFInfo
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- CN111154471A CN111154471A CN201811319742.5A CN201811319742A CN111154471A CN 111154471 A CN111154471 A CN 111154471A CN 201811319742 A CN201811319742 A CN 201811319742A CN 111154471 A CN111154471 A CN 111154471A
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 title claims abstract description 250
- 239000011780 sodium chloride Substances 0.000 title claims abstract description 125
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 109
- 238000006073 displacement reaction Methods 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 73
- 239000003208 petroleum Substances 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 47
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 42
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003513 alkali Substances 0.000 claims abstract description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000004094 surface-active agent Substances 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 9
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 81
- 229920002401 polyacrylamide Polymers 0.000 claims description 17
- 239000012452 mother liquor Substances 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000010413 mother solution Substances 0.000 claims description 9
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 3
- 239000003921 oil Substances 0.000 description 75
- 230000000694 effects Effects 0.000 description 22
- 229910001220 stainless steel Inorganic materials 0.000 description 17
- 239000010935 stainless steel Substances 0.000 description 17
- 238000005260 corrosion Methods 0.000 description 11
- 239000010779 crude oil Substances 0.000 description 11
- 238000011084 recovery Methods 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 10
- 238000004945 emulsification Methods 0.000 description 9
- 239000011206 ternary composite Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000013461 design Methods 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000001804 emulsifying effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 125000001033 ether group Chemical group 0.000 description 4
- 238000012854 evaluation process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 125000000963 oxybis(methylene) group Chemical group [H]C([H])(*)OC([H])([H])* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- 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
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
- C09K8/604—Polymeric surfactants
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—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
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- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a compound oil-displacing agent containing sodium chloride and a preparation method thereof, belonging to the field of oilfield chemistry. The oil displacement agent comprises: polymer, surfactant, sodium chloride, alkali and water; wherein the mass percent of the surfactant is 0.05-0.3%, and the surfactant comprises petroleum sulfonate and an emulsifier in a mass ratio of 3-7: 0.5-1.5; the mass ratio of the sodium chloride to the alkali is 10-12: 0.8-1.2, and the total mass percentage of the sodium chloride to the alkali is 0.2-1.4%; the viscosity of the composite oil displacement agent containing sodium chloride is 38-45 mPa & s; the emulsifier is prepared by the following method: adding aliphatic alcohol with 14-16 carbon atoms and a catalyst into a first reactor, introducing nitrogen into the first reactor, heating the first reactor to a first preset temperature, and stopping introducing the nitrogen; dropwise adding ethylene oxide into the first reactor to perform polymerization reaction, heating the first reactor to a second preset temperature, preserving heat, and cooling to a third preset temperature to obtain an emulsifier; wherein the mass ratio of the fatty alcohol to the ethylene oxide is 0.5-1.5: 2-3.
Description
Technical Field
The invention relates to the field of oilfield chemistry, and particularly relates to a compound oil displacement agent containing sodium chloride and a preparation method thereof.
Background
Petroleum is a non-renewable resource, and the demand for petroleum is increasing along with the rapid development of economy in China. However, most oil fields in China enter an ultra-high water content stage, and tertiary oil recovery technology is required to be applied to exploitation. The tertiary oil recovery technology adopts a chemical oil displacement agent to recover an oil field, and a ternary composite oil displacement agent is mostly used in the tertiary oil recovery. Therefore, it is necessary to provide a ternary composite oil displacement agent.
The related art provides a ternary composite oil-displacing agent, which comprises: the oil displacement agent comprises an emulsifier, a polymer and sodium carbonate, and the emulsification effect of the oil displacement agent can be effectively improved through the cooperation of the three components.
The inventors found that the related art has at least the following problems:
the ternary composite oil displacement agent provided by the related technology comprises sodium carbonate, so that the ternary composite oil displacement agent is easy to scale in an oil layer, and the difficulty in subsequent mining treatment is increased.
Disclosure of Invention
The embodiment of the invention provides a compound oil-displacing agent containing sodium chloride and a preparation method thereof, which can solve the technical problems. The specific technical scheme is as follows:
in one aspect, an embodiment of the present invention provides a compound oil displacement agent containing sodium chloride, where the compound oil displacement agent containing sodium chloride includes the following components:
polymer, surfactant, sodium chloride, alkali and water;
the mass percentage of the surfactant is 0.05-0.3%, and the surfactant comprises petroleum sulfonate and an emulsifier in a mass ratio of 3-7: 0.5-1.5;
the mass ratio of the sodium chloride to the alkali is 10-12: 0.8-1.2, and the total mass percentage of the sodium chloride to the alkali is 0.2-1.4%;
the viscosity of the composite oil displacement agent containing sodium chloride is 38-45 mPa & s;
wherein the emulsifier is prepared by the following method:
adding aliphatic alcohol with 14-16 carbon atoms and a catalyst into a first reactor, introducing nitrogen into the first reactor, heating the first reactor to a first preset temperature, and stopping introducing the nitrogen;
dropwise adding ethylene oxide into the first reactor to perform polymerization reaction, heating the first reactor to a second preset temperature, preserving heat, and then cooling to a third preset temperature to obtain the emulsifier;
wherein the mass ratio of the fatty alcohol to the ethylene oxide is 0.5-1.5: 2-3.
In one possible design, the mass ratio of the sodium chloride to the alkali is 10.8-11.5: 1.
in one possible design, the base is sodium hydroxide.
In one possible design, the mass ratio of the petroleum sulfonate to the emulsifier is 4-6: 0.9-1.1.
In one possible design, the catalyst is 0.32 to 0.58 mass percent potassium hydroxide solution or sodium hydroxide solution;
the mass ratio of the catalyst to the fatty alcohol is 8.1-10.1: 490.1-510.1.
In one possible design, the first preset temperature is 100 to 120 ℃;
the second preset temperature is 170-190 ℃;
the third preset temperature is 80-95 ℃.
In one possible design, the heat preservation time is 1.8-2.5 h.
In one possible design, the petroleum sulfonate is prepared by the following method:
sulfonating the second-order-reduced distillate oil and the bottom oil in a mass ratio of 3.5-4.5: 0.8-1.2 by using a sulfonating agent to obtain a sulfonated intermediate;
neutralizing the sulfonated intermediate with sodium hydroxide solution to obtain the petroleum sulfonate.
In one possible design, the polymer is polyacrylamide.
In another aspect, an embodiment of the present invention provides a preparation method of any one of the above-mentioned composite oil-displacing agents containing sodium chloride, where the preparation method includes:
according to the mass percent of each component and the viscosity of the compound oil displacement agent containing sodium chloride,
placing petroleum sulfonate and water in a second reactor, and uniformly stirring to obtain a first mother solution;
putting the emulsifier and water in a third reactor, and uniformly stirring to obtain a second mother solution;
placing sodium chloride, alkali and water in a fourth reactor, and uniformly stirring to obtain a third mother solution;
putting the polymer and water in a fifth reactor, and uniformly stirring to obtain a fourth mother solution;
and (3) placing the first mother liquor, the second mother liquor, the third mother liquor, the fourth mother liquor and water in the sixth reactor, and uniformly stirring to obtain the composite oil-displacing agent containing sodium chloride.
The technical scheme provided by the embodiment of the invention has the beneficial effects that at least:
according to the compound oil-displacing agent containing sodium chloride provided by the embodiment of the invention, sodium chloride and alkali are added in a mass ratio of 10-12: 0.8-1.2, the total mass percentage of the sodium chloride and the alkali is 0.2-1.4%, and the sodium chloride and the alkali are cooperated with other components, so that the corrosion of the compound oil-displacing agent containing sodium chloride to metal materials can be delayed, and the emulsification effect of the compound oil-displacing agent containing sodium chloride can be improved. Mixing by polymerizing a C14-16 aliphatic alcohol with ethylene oxideThe alkyl large carbon chain group in the emulsifier is oleophilic, and the polyoxyethylene ether group is hydrophilic, so that the compatibility among other components of the emulsifier is good, the emulsifying capacity to crude oil is strong, the oil displacement efficiency is high, and the adaptability is wide. The total mass percentage of the petroleum sulfonate and the emulsifier is limited to 0.05-0.3%, so that the viscosity of the composite oil displacement agent is 38-45 mPa & s, and the composite oil displacement agent can reduce the oil-water interfacial tension to 10 in the application of tertiary oil recovery-2The mN/m is lower than that of the water flooding, the specific recovery ratio is improved to more than 20 percent, and the scaling phenomenon is not generated, thereby being beneficial to the subsequent treatment of exploitation.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a flow chart of a preparation method of a composite oil displacement agent containing sodium chloride provided by an embodiment of the invention;
FIG. 2 is a schematic diagram of corrosion rates of a composite oil displacement agent containing sodium chloride provided in application example 1;
FIG. 3 is a graph showing the relationship between the total mass percentages of sodium chloride and alkali, the mass percentage of a surfactant, and the interfacial tension, which are provided in application example 2;
fig. 4 is a schematic diagram of the relationship between the water separation rate and time provided in application example 3.
Detailed Description
Unless defined otherwise, all technical terms used in the examples of the present invention have the same meaning as commonly understood by one of ordinary skill in the art. In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
The chloride ions in the sodium chloride electrochemically react with the metal.
In one aspect, an embodiment of the present invention provides a compound oil displacement agent containing sodium chloride, where the compound oil displacement agent containing sodium chloride includes the following components:
polymer, surfactant, sodium chloride, alkali and water; wherein the mass percent of the surfactant is 0.05-0.3%, and the surfactant comprises petroleum sulfonate and an emulsifier in a mass ratio of 3-7: 0.5-1.5; the mass ratio of the sodium chloride to the alkali is 10-12: 0.8-1.2, and the total mass percentage of the sodium chloride to the alkali is 0.2-1.4%; and the viscosity of the compound oil displacement agent containing sodium chloride is 38-45 mPa. The emulsifier is prepared by the following method:
adding aliphatic alcohol with 14-16 carbon atoms and a catalyst into a first reactor, introducing nitrogen into the first reactor, heating the first reactor to a first preset temperature, and stopping introducing the nitrogen; dropwise adding ethylene oxide into the first reactor to perform polymerization reaction, heating the first reactor to a second preset temperature, preserving heat, and then cooling to a third preset temperature to obtain an emulsifier; wherein the mass ratio of the fatty alcohol to the ethylene oxide is 0.5-1.5: 2-3.
Wherein the total mass percentage of the petroleum sulfonate and the emulsifier can be 0.05%, 0.07%, 0.09%, 0.1%, 0.11%, 0.13%, 0.15%, 0.17%, 0.19%, 0.2%, 0.21%, 0.23%, 0.25%, 0.27%, 0.29%, 0.3% and the like. The mass ratio of the petroleum sulfonate to the emulsifier can be 3:0.5, 4:0.8, 5:1, 6:1.1, 7:1.5 and the like. The mass ratio of sodium chloride to alkali can be 10:0.8, 11:1, 12:1.2, etc. The total mass percentage of sodium chloride and alkali may be 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, etc. The viscosity of the composite oil-displacing agent may be 38 mPas, 39 mPas, 40 mPas, 41 mPas, 42 mPas, 43 mPas, 44 mPas, 45 mPas, or the like.
The fatty alcohol having 14 to 16 carbon atoms includes: a fatty alcohol having 14 carbon atoms, a fatty alcohol having 15 carbon atoms, and a fatty alcohol having 16 carbon atoms. Each fatty alcohol can be polymerized with ethylene oxide to give the corresponding emulsifier. Fatty alcohol and ethylene oxide are subjected to polymerization reaction to generate the emulsifier of fatty alcohol polyoxyethylene ether group containing alkyl large carbon chain group and polyoxyethylene ether group. Thus, the emulsifier is a mixture. The ratio of the components in the emulsifier mixture is not particularly limited.
By heating the first reactor to the first preset temperature and then heating the first preset temperature to the second preset temperature, polymerization reaction of each fatty alcohol and ethylene oxide can be guaranteed, and then sufficient reaction is guaranteed.
The reaction equation for fatty alcohols with ethylene oxide is as follows:
ROH+nC2H4O→RO(C2H4O)nH
wherein R is a carbon chain with 14-16 carbon atoms, ROH is fatty alcohol, C2H4O is ethylene oxide, RO (C)2H4O)nH is an emulsifier, and n can be adjusted according to the demand.
Based on the above, the sodium chloride-containing composite oil-displacing agent provided by the embodiment of the invention is added with the sodium chloride and the alkali in the mass ratio of 10-12: 0.8-1.2, and the total mass percentage of the sodium chloride and the alkali is 0.2% -1.4%, and the sodium chloride-containing composite oil-displacing agent and other components are cooperatively used, so that the corrosion of the sodium chloride-containing composite oil-displacing agent on metal materials can be delayed, and the emulsification effect of the sodium chloride-containing composite oil-displacing agent can be improved. The mixed emulsifier is obtained by polymerization reaction of fatty alcohol with 14-16 carbon atoms and ethylene oxide, the alkyl large carbon chain group in the emulsifier is oleophilic, and the polyoxyethylene ether group is hydrophilic, so that the compatibility among other components of the emulsifier is good, the emulsifying capacity of crude oil is strong, the oil displacement efficiency is high, and the adaptability is wide. The total mass percentage of the petroleum sulfonate and the emulsifier is limited to 0.05-0.3%, so that the viscosity of the composite oil displacement agent is 38-45 mPa & s, and the composite oil displacement agent can reduce the oil-water interfacial tension to 10 in the application of tertiary oil recovery-2The mN/m is lower than that of the water flooding, the specific recovery ratio is improved to more than 20 percent, and the scaling phenomenon is not generated, thereby being beneficial to the subsequent treatment of exploitation.
As an example, the mass ratio of sodium chloride to alkali is 10.8-11.5: 1.
by the arrangement, sodium chloride and alkali can be fully cooperated with other components in the compound oil-displacing agent containing sodium chloride, so that the compound oil-displacing agent containing sodium chloride has excellent corrosion resistance and emulsifying property, and scaling phenomenon is avoided.
Wherein, the alkali can be sodium hydroxide or potassium hydroxide. Preferably, the base may be sodium hydroxide. The sodium hydroxide not only has good effect of synergistic cooperation with other components, but also has low price and is easy to obtain.
The mass ratio of the petroleum sulfonate to the emulsifier has important influence on the emulsification effect of the compound oil-displacing agent containing the sodium chloride. In this regard, the following examples are given in embodiments of the present invention:
the mass ratio of the petroleum sulfonate to the emulsifier is 4-6: 0.9-1.1.
By the arrangement, petroleum sulfonate, an emulsifier, a polymer, sodium chloride and alkali can be cooperatively acted, so that the compound oil displacement agent containing sodium chloride has a good emulsification effect, high oil displacement efficiency and wide adaptability.
In the embodiment of the invention, the number of carbon atoms of the fatty alcohol influences the molecular weight of the prepared emulsifier, and further influences the emulsifying effect of the emulsifier. By selecting the fatty alcohol with 14-16 carbon atoms, the prepared emulsifier is compounded with the polymer, so that the crude oil can be fully emulsified, and the crude oil can be efficiently displaced.
The mass ratio of the fatty alcohol to the ethylene oxide has an important influence on the content of the pure emulsifier in the prepared emulsifier, and in the embodiment of the invention, the mass ratio of the fatty alcohol to the ethylene oxide may be 0.5:2, 0.6:2.1, 0.7:2.2, 0.8:2.3, 0.9:2.4, 1:2.5, 1.1:2.6, 1.2:2.7, 1.3:2.8, 1.4:2.9, 1.5:3, and the like.
As an example, the mass ratio of the fatty alcohol to the ethylene oxide is 0.7-1: 2.3-2.5.
By the arrangement, the full reaction of the fatty alcohol and the ethylene oxide can be ensured, so that the emulsifier with higher pure product content can be obtained.
Further, the mass ratio of the fatty alcohol to the ethylene oxide may be 1: 2.5.
By the arrangement, the full reaction of the fatty alcohol and the ethylene oxide can be ensured to the maximum extent, so that the emulsifier with higher solid content can be obtained.
The polymerization reaction of the fatty alcohol and the ethylene oxide in the reactor can be catalyzed by adding the catalyst. Based on fatty alcohol and ethylene oxide, and considering the factors of good catalytic effect, sufficient reaction and the like, the following examples are given in terms of the kind of catalyst in the embodiments of the present invention:
the catalyst is potassium hydroxide solution or sodium hydroxide solution with the mass percentage of 0.32-0.58%; the mass ratio of the catalyst to the fatty alcohol is 8.1-10.1: 490.1-510.1.
The mass percentage of potassium hydroxide or sodium hydroxide may be 0.32%, 0.4%, 0.5%, 0.58%, or the like. The mass ratio of the catalyst to the fatty alcohol can be 8.1:490.1, 8.5:495, 9:500, 9.5:505, 10.1:510.1, etc.
So set up, can guarantee fatty alcohol and ethylene oxide fully react under the prerequisite that the catalyst use amount is few, avoid producing impurity.
Further, the catalyst can be 0.5 percent by mass of potassium hydroxide solution; the mass ratio of catalyst to fatty alcohol may be 9: 500.
By adopting the device, the fatty alcohol and the ethylene oxide can be fully reacted to the maximum extent on the premise of using a small amount of the catalyst.
Considering that the fatty alcohols are a mixture, in order to enable each fatty alcohol to react with ethylene oxide, the first reactor needs to be heated to a first preset temperature, which may be 100 to 120 ℃, for example, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃ and the like.
At this time, ethylene oxide is dropped into the first reactor, and the ethylene oxide and the fatty alcohol mixture are sufficiently reacted.
Further, in order to enable the reaction of ethylene oxide with the other part of the fatty alcohol in the fatty alcohol mixture, the first reactor is heated to a second predetermined temperature, which may be 170 to 190 ℃, for example, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, etc.
After the first reactor is insulated, the ethylene oxide and the fatty alcohol are fully reacted, and the reactor can be cooled to a third preset temperature so as to pour the emulsifier out of the first reactor, and the color of the emulsifier is also greatly influenced by cooling.
As an example, the third predetermined temperature is 80-95 ℃, for example, 80 ℃, 82 ℃, 84 ℃, 85 ℃, 87 ℃, 89 ℃, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃ and the like.
So set up, not only do benefit to the emulsifier and pour out by first reactor, still make this emulsifier have good colour.
Further, in consideration of sufficient reaction between the aliphatic alcohol and ethylene oxide, the time for the heat preservation may be 1.8 to 2.5 hours, for example, 1.8 hours, 1.9 hours, 2 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, or the like.
In an embodiment of the present invention, the first reactor may be a stainless steel tank reactor.
In the embodiment of the present invention, the type of petroleum sulfonate has an important influence on the oil displacement effect of the compound oil displacement agent containing sodium chloride, and for this reason, the following example is given for the preparation of petroleum sulfonate:
the petroleum sulfonate is prepared by the following method:
sulfonating the second-order-reduced distillate oil and the bottom oil in a mass ratio of 3.5-4.5: 0.8-1.2 by using a sulfonating agent to obtain a sulfonated intermediate; and neutralizing the sulfonated intermediate by using a sodium hydroxide solution to obtain the petroleum sulfonate.
Optionally, the mass ratio of the second-line distillate oil to the tower bottom oil is 4: 1.
By the arrangement, full synergistic cooperation effect among petroleum sulfonate, an emulsifier, a polymer, sodium chloride and alkali is facilitated, so that the compound oil displacement agent containing sodium chloride has a good oil displacement effect.
It should be noted that petroleum sulfonate can be obtained from Daqing refining company, so as to have good compatibility with the oil layer, thereby improving the oil displacement effect.
In view of the availability, low cost, good effect of complexing with petroleum sulfonate and emulsifiers, the polymer may be polyacrylamide in embodiments of the invention.
The amount of the polyacrylamide to be added is not particularly limited, and the viscosity of the sodium chloride-containing composite oil displacement agent may be 38 to 45mPa · s. For example, the mass concentration of polyacrylamide may be 1800-2300 mg/L, such as 1800mg/L, 1900mg/L, 2000mg/L, 2100mg/L, 2200mg/L, 2300mg/L, etc.
On the other hand, the embodiment of the invention also provides a preparation method of any one of the above-mentioned compound oil displacement agents containing sodium chloride, as shown in the attached drawing 1, and the preparation method comprises the following steps:
And 102, placing the emulsifier and the water in a third reactor, and uniformly stirring to obtain a second mother solution.
And 103, placing sodium chloride, alkali and water in a fourth reactor, and uniformly stirring to obtain a third mother liquor.
And step 104, placing the polymer and water in a fifth reactor, and uniformly stirring to obtain a fourth mother liquor.
And 105, placing the first mother liquor, the second mother liquor, the third mother liquor, the fourth mother liquor and water in a sixth reactor, and uniformly stirring to obtain the composite oil displacement agent containing sodium chloride.
The preparation method of the compound oil-displacing agent containing sodium chloride provided by the embodiment of the invention is simple, and the prepared compound oil-displacing agent containing sodium chloride can reduce the oil-water interfacial tension to 10 in the application of tertiary oil recovery-2The recovery ratio of the compound is improved to more than 20 percent below mN/m compared with water drive, the compound can not corrode metal materials, can not generate scaling phenomenon, and is beneficial to mining subsequent treatment.
The present invention will be further described below by way of specific examples.
In the following examples, those whose operations are not subject to the conditions indicated, are carried out according to the conventional conditions or conditions recommended by the manufacturer. The raw materials are conventional products which can be obtained commercially by manufacturers and specifications.
Wherein, the petroleum sulfonate is produced by Daqing oil field Sanan industry company, and the polymer is polyacrylamide with the molecular weight of 1600 ten thousand produced by Daqing refining company. Petroleum sulfonate is obtained by sulfonating second-order distillate oil and bottom oil with a mass ratio of 4:1 by a sulfonating agent by Daqing refining company to obtain a sulfonated intermediate, and neutralizing the sulfonated intermediate by using a sodium hydroxide solution.
Example 1
The embodiment provides a compound oil-displacing agent containing sodium chloride, which comprises the following components: petroleum sulfonate, an emulsifier, sodium chloride, sodium hydroxide, polyacrylamide and water. Wherein the total mass percent of the sodium chloride and the sodium hydroxide is 1.2%, the mass ratio of the sodium chloride to the sodium hydroxide is 11:1, the total mass percent of the petroleum sulfonate and the emulsifier is 0.3%, the mass ratio of the petroleum sulfonate to the emulsifier is 5:1, and the viscosity of the compound oil displacement agent containing the sodium chloride is 40 mPas under the coordination effect of the petroleum sulfonate, the emulsifier and the polyacrylamide.
The emulsifier is prepared by the following method: 1000kg of fatty alcohol with 14-16 carbon atoms is added into a stainless steel kettle type reactor, and then 18kg of potassium hydroxide solution with the mass percent of 0.5% is added. And introducing nitrogen into the stainless steel kettle type reactor, heating to 110 ℃, and stopping introducing the nitrogen. 2500kg of ethylene oxide was added dropwise to a stainless steel kettle-type reactor to carry out a closed polymerization reaction. And then heating the stainless steel kettle type reactor to 180 ℃, preserving the heat for 2 hours, and then cooling to 90 ℃ to obtain the emulsifier in the embodiment.
Example 2
The embodiment provides a compound oil-displacing agent containing sodium chloride, which comprises the following components: petroleum sulfonate, an emulsifier, sodium chloride, sodium hydroxide, polyacrylamide and water. Wherein the total mass percent of the sodium chloride and the sodium hydroxide is 0.4%, the mass ratio of the sodium chloride to the sodium hydroxide is 10:0.8, the total mass percent of the petroleum sulfonate and the emulsifier is 0.08%, the mass ratio of the petroleum sulfonate to the emulsifier is 3:05, and the viscosity of the compound oil displacement agent containing the sodium chloride is 38mPa & s under the coordination of the petroleum sulfonate, the emulsifier and the polyacrylamide.
The emulsifier is prepared by the following method: 1000kg of fatty alcohol with 14-16 carbon atoms is added into a stainless steel kettle type reactor, and then 17kg of potassium hydroxide solution with the mass percent of 0.32% is added. And introducing nitrogen into the stainless steel kettle type reactor, heating to 100 ℃, and stopping introducing the nitrogen. 2200kg of ethylene oxide was added dropwise to the stainless steel tank reactor to carry out a closed polymerization reaction. And then heating the stainless steel kettle type reactor to 170 ℃, preserving the heat for 1.8h, and then cooling to 80 ℃ to obtain the emulsifier provided by the embodiment.
Example 3
The embodiment provides a compound oil-displacing agent containing sodium chloride, which comprises the following components: petroleum sulfonate, an emulsifier, sodium chloride, sodium hydroxide, polyacrylamide and water. Wherein the total mass percent of the sodium chloride and the sodium hydroxide is 0.8%, the mass ratio of the sodium chloride to the sodium hydroxide is 11:0.9, the total mass percent of the petroleum sulfonate and the emulsifier is 0.12%, the mass ratio of the petroleum sulfonate to the emulsifier is 5:1.2, and the viscosity of the compound oil displacement agent containing the sodium chloride is 42mPa · s under the cooperation effect of the petroleum sulfonate, the emulsifier and the polyacrylamide.
The emulsifier is prepared by the following method: 1000kg of fatty alcohol with 14-16 carbon atoms is added into a stainless steel kettle type reactor, and then 20kg of potassium hydroxide solution with the mass percent of 0.58% is added. And introducing nitrogen into the stainless steel kettle type reactor, heating to 120 ℃, and stopping introducing the nitrogen. 2900kg of ethylene oxide was dropped into the stainless steel kettle type reactor to carry out a closed reaction. And then heating the stainless steel kettle type reactor to 190 ℃, preserving the heat for 2.5 hours, and then cooling to 95 ℃ to obtain the emulsifier provided by the embodiment.
Example 4
The embodiment provides a compound oil-displacing agent containing sodium chloride, which comprises the following components: petroleum sulfonate, an emulsifier, sodium chloride, sodium hydroxide, polyacrylamide and water. Wherein the total mass percent of the sodium chloride and the sodium hydroxide is 1.4%, the mass ratio of the sodium chloride to the sodium hydroxide is 12:1.2, the total mass percent of the petroleum sulfonate and the emulsifier is 0.25%, the mass ratio of the petroleum sulfonate to the emulsifier is 7:1.5, and the viscosity of the compound oil displacement agent containing the sodium chloride is 45mPa · s under the cooperation effect of the petroleum sulfonate, the emulsifier and the polyacrylamide.
The emulsifier is prepared by the following method: 1000kg of fatty alcohol with 14-16 carbon atoms is added into a stainless steel kettle type reactor, and then 18kg of potassium hydroxide solution with the mass percent of 0.5% is added. And introducing nitrogen into the stainless steel kettle type reactor, heating to 110 ℃, and stopping introducing the nitrogen. 2500kg of ethylene oxide was added dropwise to a stainless steel kettle-type reactor to carry out a closed polymerization reaction. And then heating the stainless steel kettle type reactor to 180 ℃, preserving the heat for 2 hours, and then cooling to 90 ℃ to obtain the emulsifier provided by the embodiment.
Comparative example
This comparative example provides a ternary composite oil-displacing agent, which includes: 1.2 percent of sodium carbonate, 0.3 percent of petroleum sulfonate, polyacrylamide and water. The viscosity of the ternary composite oil displacement agent is 40 mPas.
Application example 1
The application example evaluates the corrosion prevention effect of the composite oil-displacing agent containing sodium chloride provided in example 1. The specific evaluation process comprises the following steps: the same amount of sewage, the ternary composite oil-displacing agent provided by the comparative example, the composite oil-displacing agent containing sodium chloride provided by example 1, and the sodium chloride solution with the mass percentage of 1.2% are obtained. And respectively placing the iron sheets with the same weight and volume in the four samples to be soaked for 84h, and calculating the corrosion rates of the four iron sheets by a weighing method. The four tests described above can be numbered in sequence as number 1, 2, 3, 4, and figure 2 is made based on the corrosion rates of the four tests.
As can be seen from fig. 2, the corrosion rate of the composite oil-displacing agent containing sodium chloride provided in example 1 and the corrosion rate of the ternary composite oil-displacing agent provided in the comparative example are low, and the corrosion resistance is good. Therefore, the composite oil displacement agent containing sodium chloride provided by the invention has excellent corrosion resistance and can meet the use requirement in the tertiary oil displacement technology.
Application example 2
The application example evaluates the interfacial activity of the provided compound oil-displacing agent containing sodium chloride. The specific evaluation process comprises the following steps: respectively preparing a plurality of composite oil-displacing agent samples with the mixed concentration of sodium chloride and alkali (sodium hydroxide) of 0.2-1.4 wt%, the mass ratio of sodium chloride to sodium hydroxide of 11:1, the concentration of a surfactant of 0.05-0.3 wt%, the mass ratio of petroleum sulfonate to an emulsifier of 5:1 and the system viscosity of 40 mPa.s, respectively mixing the plurality of composite oil-displacing agent samples with crude oil degassed at a well head, respectively testing the interfacial tension between various composite system solutions and the crude oil, and finally drawing an interfacial activity graph 3.
And (3) respectively taking the sodium chloride-containing composite oil displacement agent samples provided in the embodiments 1 to 4, and respectively mixing the four composite oil displacement agent samples with the crude oil degassed at the well head to obtain four composite systems. The oil-water interfacial tension in the complex system was measured and marked with a circle in FIG. 3.
As is clear from FIG. 3, the sodium chloride-containing composite oil-displacing agents provided in examples 1 to 4 had an oil-water interfacial tension of 10-2mN/m or less. Therefore, the compound oil displacement agent containing sodium chloride provided by the implementation of the invention has better interfacial activity and can meet the use requirement in the tertiary oil displacement technology.
Application example 3
The application example evaluates the emulsifying property of the sodium chloride-containing composite oil-displacing agent provided in example 1. The specific evaluation process comprises the following steps: respectively obtaining the same amount of the compound oil-displacing agent containing sodium chloride provided in example 1 and the same amount of the compound oil-displacing agent containing sodium chloride provided in the comparative example as oil-displacing agent samples, respectively mixing the two oil-displacing agent samples with crude oil degassed at a wellhead to obtain two mixed systems, wherein the two mixed systems are respectively numbered as a and b. Wherein the volume ratio of the oil displacement agent sample to the well head degassed crude oil is 1: 1. And (3) placing the two mixed systems in an emulsification oscillator for oscillation, obtaining the water separation rate of the two mixed systems at different time, and drawing 4. The water-separating rate is a percentage of the volume of water separated out to the total volume of the slurry at the initial setting of the slurry. The lower the water separation rate, the better the emulsification effect.
As can be seen from fig. 4, under the same conditions of time, the water evolution rate of the mixed system of the compound oil-displacing agent containing sodium chloride and the crude oil at the well head degassing provided in example 1 increases slowly with time, and the water evolution rate of the mixed system of the compound oil-displacing agent containing sodium chloride and the crude oil at the well head degassing provided in the comparative example increases rapidly. After about 1.5h, the water evolution rates of the two mixed systems were essentially the same. Therefore, the emulsification effect of the sodium chloride-containing composite oil-displacing agent provided by the embodiment of the invention is better than that of the weak-alkali sodium chloride-containing composite oil-displacing agent.
Application example 4
The application example evaluates the oil displacement performance of the compound oil-displacing agent containing sodium chloride provided in example 1. The specific evaluation process comprises the following steps: the oil displacement performance of the sodium chloride-containing composite oil displacement agent provided in example 1 was evaluated according to the method provided in the standard of "SY-T6424-2000 composite oil displacement system performance test method". And obtaining a first beret core and a second beret core, obtaining two equal parts of the composite oil displacement agent containing sodium chloride provided in the embodiment 1, and respectively displacing the first beret core and the second beret core. Specifically, the first beret core and the second beret core are subjected to water flooding, when the water flooding is 100% of water, the composite oil displacement agent containing sodium chloride provided in example 1 and having 0.3 times of Pore Volume (PV) is injected, then the 0.2PV polyacrylamide protective slug solution (the mass percentage of polyacrylamide is 0.18%) is injected, and finally the water flooding is finished when the water flooding is 100% of water. The specific test parameters are detailed in table 1.
TABLE 1
Note: OOIP refers to the original petroleum geological reserve, and is an abbreviation for original oil in place.
As can be seen from table 1, the recovery ratio of the composite displacement agent containing sodium chloride provided in example 1 is higher than that of water flooding, and the recovery ratio of the composite displacement agent containing sodium chloride provided in example 1 to the first beret core and the second beret core is 23.71% (OOIP) and 24.01% (OOIP), respectively. Therefore, the compound oil-displacing agent containing sodium chloride provided by the embodiment of the invention can improve the recovery ratio by more than 20% (OOIP) compared with water drive, and can be used as a high-efficiency oil-displacing agent product with stable performance.
In conclusion, the sodium chloride-containing composite oil displacement agent provided by the embodiment of the invention has excellent anti-corrosion effect and emulsification effect, and can reduce the oil-water interfacial tension to 10-2The mN/m is less than or equal to, the recovery ratio can be improved by more than 20 percent (OOIP) compared with water drive, and the use requirement of tertiary oil recovery can be met.
All the above optional technical solutions may be combined arbitrarily to form the optional embodiments of the present disclosure, and are not described herein again.
The above description is only an illustrative embodiment of the present invention, and should not be taken as limiting the scope of the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The compound oil-displacing agent containing sodium chloride is characterized by comprising the following components:
polymer, surfactant, sodium chloride, alkali and water;
the mass percentage of the surfactant is 0.05-0.3%, and the surfactant comprises petroleum sulfonate and an emulsifier in a mass ratio of 3-7: 0.5-1.5;
the mass ratio of the sodium chloride to the alkali is 10-12: 0.8-1.2, and the total mass percentage of the sodium chloride to the alkali is 0.2-1.4%;
the viscosity of the composite oil displacement agent containing sodium chloride is 38-45 mPa & s;
wherein the emulsifier is prepared by the following method:
adding aliphatic alcohol with 14-16 carbon atoms and a catalyst into a first reactor, introducing nitrogen into the first reactor, heating the first reactor to a first preset temperature, and stopping introducing the nitrogen;
dropwise adding ethylene oxide into the first reactor to perform polymerization reaction, heating the first reactor to a second preset temperature, preserving heat, and then cooling to a third preset temperature to obtain the emulsifier;
wherein the mass ratio of the fatty alcohol to the ethylene oxide is 0.5-1.5: 2-3.
2. The composite oil-displacing agent containing sodium chloride according to claim 1, wherein the mass ratio of the sodium chloride to the alkali is 10.8-11.5: 1.
3. The compound oil-displacing agent containing sodium chloride according to claim 1, characterized in that the alkali is sodium hydroxide.
4. The compound oil-displacing agent containing sodium chloride according to claim 1, wherein the mass ratio of the petroleum sulfonate to the emulsifier is 4-6: 0.9-1.1.
5. The compound oil-displacing agent containing sodium chloride according to claim 1, characterized in that the catalyst is 0.32-0.58% by mass of potassium hydroxide solution or sodium hydroxide solution;
the mass ratio of the catalyst to the fatty alcohol is 8.1-10.1: 490.1-510.1.
6. The compound oil displacement agent containing sodium chloride according to any one of claims 1 to 5, wherein the first preset temperature is 100 to 120 ℃;
the second preset temperature is 170-190 ℃;
the third preset temperature is 80-95 ℃.
7. The compound oil displacement agent containing sodium chloride according to any one of claims 1 to 5, wherein the heat preservation time is 1.8 to 2.5 hours.
8. The compound oil displacement agent containing sodium chloride according to claim 1, characterized in that the petroleum sulfonate is prepared by the following method:
sulfonating the second-order-reduced distillate oil and the bottom oil in a mass ratio of 3.5-4.5: 0.8-1.2 by using a sulfonating agent to obtain a sulfonated intermediate;
neutralizing the sulfonated intermediate with sodium hydroxide solution to obtain the petroleum sulfonate.
9. The composite oil-displacing agent containing sodium chloride according to claim 1, characterized in that the polymer is polyacrylamide.
10. The preparation method of the compound oil displacement agent containing sodium chloride according to any one of claims 1 to 9, characterized by comprising the following steps:
according to the mass percentage of each component and the viscosity of the compound oil displacement agent containing sodium chloride, petroleum sulfonate and water are placed in a second reactor and are uniformly stirred to obtain a first mother solution;
putting the emulsifier and water in a third reactor, and uniformly stirring to obtain a second mother solution;
placing sodium chloride, alkali and water in a fourth reactor, and uniformly stirring to obtain a third mother solution;
putting the polymer and water in a fifth reactor, and uniformly stirring to obtain a fourth mother solution;
and (3) placing the first mother liquor, the second mother liquor, the third mother liquor, the fourth mother liquor and water in a sixth reactor, and uniformly stirring to obtain the composite oil-displacing agent containing sodium chloride.
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