CN111154090A - Emulsifier for oil displacement, preparation method thereof and binary composite oil displacement agent - Google Patents
Emulsifier for oil displacement, preparation method thereof and binary composite oil displacement agent Download PDFInfo
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- 238000006073 displacement reaction Methods 0.000 title claims abstract description 101
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 92
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 62
- 239000011218 binary composite Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 48
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 8
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 229920002401 polyacrylamide Polymers 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 3
- 239000003921 oil Substances 0.000 abstract description 101
- 239000010779 crude oil Substances 0.000 abstract description 15
- 230000001804 emulsifying effect Effects 0.000 abstract description 12
- 239000010935 stainless steel Substances 0.000 description 13
- 229910001220 stainless steel Inorganic materials 0.000 description 13
- 239000011206 ternary composite Substances 0.000 description 13
- 238000011084 recovery Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000013461 design Methods 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000005065 mining Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 238000013329 compounding Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 238000012854 evaluation process Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 1
- -1 alkylbenzene sulfonate Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 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
- 239000011148 porous material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- 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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- 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
- C08G65/2642—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 characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2648—Alkali metals or compounds thereof
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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
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
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Abstract
The invention discloses an emulsifier for oil displacement, a preparation method thereof and a binary composite oil displacement agent, and belongs to the field of oilfield chemistry. The preparation method comprises the following steps: adding aliphatic alcohol with 14-16 carbon atoms and a catalyst into a reactor, introducing nitrogen into the reactor, heating the reactor to a first preset temperature, and stopping introducing the nitrogen; dropwise adding ethylene oxide into the reactor to perform polymerization reaction, heating the reactor to a second preset temperature, preserving heat, and then cooling to a third preset temperature to obtain an emulsifier for oil displacement; wherein the mass ratio of the fatty alcohol to the ethylene oxide is 0.5-1.5: 2-3. The emulsifier has good compatibility with polymer, strong emulsifying capacity to crude oil, high oil displacement efficiency and wide adaptability, and can reduce the oil-water interfacial tension to 10 in the application of tertiary oil recovery‑2mN/m or less.
Description
Technical Field
The invention relates to the field of oilfield chemistry, and particularly relates to an emulsifier for oil displacement, a preparation method thereof and a binary composite oil displacement agent.
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 is to adopt chemical oil displacement agent to recover oil field. In tertiary oil recovery, a binary composite oil-displacing agent and a ternary composite oil-displacing agent are mostly used. The binary composite oil displacement agent comprises an emulsifier and a polymer, but has poor emulsifying capacity and low efficiency of improving the crude oil exploitation. The ternary composite oil displacement agent comprises an emulsifier, a polymer and an alkaline agent, and can improve the emulsification effect of the oil displacement agent, so that the crude oil recovery rate is improved, but the alkaline agent is easy to cause scaling, and the subsequent treatment difficulty of exploitation is increased. By avoiding the addition of an alkaline agent, the scaling phenomenon can be avoided, and therefore, it is necessary to provide an emulsifier with good emulsifying effect.
The related art provides an emulsifier, which is petroleum sulfonate. The petroleum sulfonate needs to be matched with sodium carbonate for use, so that a good emulsifying effect can be achieved.
The inventors found that the related art has at least the following problems:
the emulsifier provided by the related technology must be used in combination with sodium carbonate to achieve a good emulsifying effect, but the addition of sodium carbonate can cause a scaling phenomenon, which affects the difficulty of subsequent treatment in mining.
Disclosure of Invention
The embodiment of the invention provides an emulsifier for oil displacement, a preparation method thereof and a binary composite oil displacement agent, and can solve the technical problems. The specific technical scheme is as follows:
on one hand, the embodiment of the invention provides a preparation method of an emulsifier for oil displacement, which comprises the following steps:
adding aliphatic alcohol with 14-16 carbon atoms and a catalyst into a reactor, introducing nitrogen into the reactor, heating the reactor to a first preset temperature, and stopping introducing the nitrogen;
dropwise adding ethylene oxide into the reactor to perform polymerization reaction, heating the reactor to a second preset temperature, preserving heat, and then cooling to a third preset temperature to obtain the emulsifier for oil displacement;
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 fatty alcohol to the ethylene oxide is 0.8-1.1: 2.2-2.6.
In one possible design, the mass ratio of the fatty alcohol to the ethylene oxide is 1: 2.5.
In one possible design, the catalyst is 0.3 to 0.6 mass percent potassium hydroxide solution or sodium hydroxide solution;
the mass ratio of the catalyst to the fatty alcohol is 8-10: 490-510.
In one possible design, the catalyst is 0.5% by mass potassium hydroxide solution;
the mass ratio of the catalyst to the fatty alcohol is 9: 500.
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.
On the other hand, the embodiment of the invention provides an emulsifier for oil displacement, which is prepared by any one of the preparation methods mentioned above;
the emulsifier for oil displacement comprises: 94-98% of emulsifier pure product and the balance of impurities.
On the other hand, the embodiment of the invention provides a binary composite oil-displacing agent, which comprises the following components in parts by weight: the above-mentioned oil-displacing emulsifier, polymer, water;
wherein the mass percent of the emulsifier for oil displacement is 0.05-0.3%;
the viscosity of the binary composite oil displacement agent is 38-45 mPa · s.
In one possible design, the polymer is polyacrylamide.
The technical scheme provided by the embodiment of the invention has the beneficial effects that at least:
the preparation method of the emulsifier for oil displacement provided by the embodiment of the invention is simple, and the mixed emulsifier for oil displacement is obtained by polymerization reaction of fatty alcohol with 14-16 carbon atoms and ethylene oxide. The hydrocarbon group large carbon chain group in the emulsifier for oil displacement is oleophilic, and the polyoxyethylene ether group is hydrophilic, so that the compatibility of the emulsifier for oil displacement and a polymer is good, the emulsifying capacity of crude oil is strong, the oil displacement efficiency is high, the adaptability is wide, and in the application of tertiary oil recovery, the oil-water interfacial tension can be reduced to 10 by compounding the emulsifier for oil displacement and the polymer-2The mN/m is less than or equal to the mN/m, and the scaling phenomenon can not be generated, thereby being beneficial to the subsequent treatment of mining.
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 an emulsifier for oil displacement provided by an embodiment of the invention;
fig. 2 is a schematic diagram of the water separation rate versus time provided in application example 1.
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.
On one hand, the embodiment of the invention provides a preparation method of an emulsifier for oil displacement, as shown in the attached figure 1, the preparation method comprises the following steps:
By introducing nitrogen into the reactor, the reaction between the fatty alcohol and the active gas can be avoided.
102, dropwise adding ethylene oxide into a reactor, carrying out polymerization reaction, heating the reactor to a second preset temperature, preserving heat, and then cooling to a third preset temperature to obtain an emulsifier for oil displacement; wherein the mass ratio of the fatty alcohol to the ethylene oxide is 0.5-1.5: 2-3.
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 fatty alcohol-polyoxyethylene ether emulsifier containing alkyl large carbon chain groups and polyoxyethylene ether groups. Therefore, the emulsifier for oil displacement prepared by the preparation method provided by the embodiment of the invention is a mixture.
The reactor is heated to a first preset temperature and then heated to a second preset temperature from the first preset temperature, so that each fatty alcohol and ethylene oxide can be guaranteed to have polymerization reaction, and further 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 for oil displacement, and n can be adjusted according to the demand.
The preparation method of the emulsifier for oil displacement provided by the embodiment of the invention is simple, and the mixed emulsifier for oil displacement is obtained by polymerization reaction of fatty alcohol with 14-16 carbon atoms and ethylene oxide. In the emulsifier for oil displacementThe oil displacement emulsifier has good compatibility with polymer, strong emulsifying capacity to crude oil, high oil displacement efficiency and wide adaptability, and can reduce the oil-water interfacial tension to 10 by compounding the oil displacement emulsifier and the polymer in the application of tertiary oil recovery-2The mN/m is less than or equal to the mN/m, and the scaling phenomenon can not be generated, thereby being beneficial to the subsequent treatment of mining.
In the embodiment of the invention, the carbon number of the fatty alcohol influences the molecular weight of the prepared emulsifier for oil displacement, and further influences the emulsification effect of the emulsifier for oil displacement. By selecting the fatty alcohol with 14-16 carbon atoms, the prepared emulsifier for oil displacement can be fully emulsified after being compounded with the polymer, so that 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 for oil displacement, and in the embodiment of the invention, the mass ratio of the fatty alcohol to the ethylene oxide can 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 0.8-1.1: 2.2-2.6.
By the arrangement, the full reaction of the fatty alcohol and the ethylene oxide can be ensured, so that the oil displacement emulsifier with higher pure emulsifier 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 for oil displacement can be obtained.
In step 101, a catalyst is added to catalyze the polymerization of the fatty alcohol and ethylene oxide in the reactor. 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 0.3 to 0.6 percent; the mass ratio of the catalyst to the fatty alcohol is 8-10: 490-510.
The mass percentage of potassium hydroxide or sodium hydroxide may be 0.3%, 0.4%, 0.5%, 0.6%, or the like. The mass ratio of the catalyst to the fatty alcohol can be 8:490, 8.5:495, 9:500, 9.5:505, 10:510, 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 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 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 reactor is heated to a second predetermined temperature, which may be 170 to 190 ℃, for example, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, etc.
After the reactor is insulated, the ethylene oxide and the fatty alcohol are fully reacted, the reactor can be cooled to a third preset temperature so as to pour the emulsifier for oil displacement out of the reactor, and the cooling has important influence on the color of the emulsifier.
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.
By the arrangement, the emulsifier for oil displacement is poured out from the reactor, and the emulsifier for oil displacement has good color.
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 reactor may be a stainless steel tank reactor.
On the other hand, the embodiment of the invention provides an emulsifier for oil displacement, which is prepared by any one of the preparation methods mentioned above; the emulsifier for oil displacement comprises: 94-98% of emulsifier pure product and the balance of impurities.
Wherein, the mass percentage of the pure product of the emulsifier can be 94%, 95%, 96%, 97%, 98% and the like.
The emulsifier for oil displacement prepared by any one of the preparation methods has good compatibility with a polymer, strong emulsifying capacity on crude oil, high oil displacement efficiency and wide adaptability, and can reduce the oil-water interfacial tension to 10 by compounding the emulsifier for oil displacement and the polymer in the application of tertiary oil recovery-2The mN/m is less than or equal to the mN/m, and the scaling phenomenon can not be generated, thereby being beneficial to the subsequent treatment of mining.
On the other hand, the embodiment of the invention provides a binary composite oil-displacing agent, which comprises the following components in parts by weight: the above-mentioned oil-displacing emulsifier, polymer, water; wherein, the mass percentage of the emulsifier for oil displacement is 0.05-0.3%; the viscosity of the binary composite oil displacement agent is 38-45 mPa.
Wherein, the mass percentage of the emulsifier for oil displacement can be 0.2%, 0.25%, 0.3%, 0.35%, 0.4% and the like. The viscosity of the binary 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.
According to the binary composite oil-displacing agent provided by the embodiment of the invention, the oil-water interfacial tension can be reduced to 10 within the range that the mass percent of the emulsifier for oil displacement is 0.05-0.3%, and the viscosity of the binary composite oil-displacing agent is 38-45 mPa & s- 2mN/m or less. The binary composite oil displacement agent is used for emulsifying oil displacementOn the premise of lower dosage of the agent, the emulsification effect generated by the agent and the crude oil is superior to that generated by the ternary compound oil displacement agent and the crude oil, the crude oil recovery rate can be effectively improved, and the scaling phenomenon cannot occur.
The polymer can be selected from various polymers, and can be compounded with the emulsifier. On the premise of easy acquisition, good tackifying effect and low price, the polymer can be polyacrylamide.
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 alkylbenzene sulfonate is produced by Daqing oilfield chemical Co. Petroleum sulfonate is produced by Daqing refining company. The polymer is polyacrylamide with the molecular weight of 1600 ten thousand produced by Daqing refining company.
Example 1
The embodiment provides an emulsifier for oil displacement, which 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 dropped into the stainless steel type reactor to carry out a closed polymerization reaction. And then heating the stainless steel type reactor to 180 ℃, preserving the heat for 2 hours, and then cooling to 90 ℃ to obtain the emulsifier for oil displacement provided by the embodiment.
The emulsifier for oil displacement comprises: 97 percent of pure emulsifier and 3 percent of impurities.
Example 2
The embodiment provides an emulsifier for oil displacement, which 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 16kg of potassium hydroxide solution with the mass percent of 0.3% 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 dropped into the stainless steel type reactor to carry out a closed polymerization reaction. And then heating the stainless steel type reactor to 170 ℃, preserving the heat for 1.8h, and then cooling to 80 ℃ to obtain the emulsifier for oil displacement provided by the embodiment.
The emulsifier for oil displacement comprises: the weight percentage of the emulsifier is 95 percent of pure product and 5 percent of impurity.
Example 3
The embodiment provides an emulsifier for oil displacement, which 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 0.6% 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 type reactor to carry out a closed reaction. And then heating the stainless steel type reactor to 190 ℃, preserving the heat for 2.5 hours, and then cooling to 95 ℃ to obtain the emulsifier for oil displacement provided by the embodiment.
The emulsifier for oil displacement comprises: the mass percent of the emulsifier is 98 percent of pure product and 2 percent of impurities.
Example 4
The embodiment provides a binary composite oil-displacing agent, which comprises: the emulsifier for oil displacement, polyacrylamide and water are provided in example 1. Wherein the mass percentage of the emulsifier for oil displacement is 0.3 percent, and the viscosity of the binary composite oil displacement agent is 40 mPa.s.
Example 5
The embodiment provides a binary composite oil-displacing agent, which comprises: the emulsifier for oil displacement, polyacrylamide and water are provided in example 2. Wherein the mass percent of the emulsifier for oil displacement is 0.1 percent, and the viscosity of the binary composite oil displacement agent is 42 mPa.s.
Example 6
The embodiment provides a binary composite oil-displacing agent, which comprises: the emulsifier for oil displacement, polyacrylamide and water are provided in example 3. Wherein the mass percentage of the emulsifier for oil displacement is 0.08 percent, and the viscosity of the binary composite oil displacement agent is 38 mPa.s.
Comparative example 1
This comparative example provides a ternary composite oil-displacing agent, which includes: 1.2 percent of sodium hydroxide, 0.3 percent of alkyltoluene sulfonate, polyacrylamide and water. The viscosity of the ternary composite oil displacement agent is 40 mPas.
Comparative example 2
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 emulsifying property of the binary composite oil-displacing agent provided in example 4. The specific evaluation process comprises the following steps: the method comprises the steps of respectively obtaining the binary composite oil-displacing agent provided by the embodiment 4, the ternary composite oil-displacing agent provided by the comparative example 1 and the ternary composite oil-displacing agent provided by the comparative example 2 in equal amount as oil-displacing agent samples, mixing the three oil-displacing agent samples with crude oil degassed at a well head respectively to obtain three mixed systems, and numbering the three mixed systems as No. 1, No. 2 and No. 3 in sequence. Wherein the volume ratio of the oil displacement agent sample to the well head degassed crude oil is 0.5: 1. And (3) placing the three mixed systems in an emulsification oscillator for oscillation, obtaining water separation rates of the three mixed systems at different times, and plotting 2. 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. 2, under the same time conditions, the water-separating rate of the binary composite oil-displacing agent, the wellhead degassed crude oil and the injected water mixed system provided in example 4 increases slowly with the time, while the water-separating rate of the ternary composite oil-displacing agent, the wellhead degassed crude oil and the injected water mixed system provided in comparative example 1 increases more rapidly with the ternary composite oil-displacing agent, the wellhead degassed crude oil and the injected water mixed system provided in comparative example 2. After 18h, the water evolution rate of the three mixed systems was essentially the same. Therefore, the emulsification effect of the binary composite oil-displacing agent provided by the embodiment of the invention is better than that of the ternary composite oil-displacing agent containing strong base and the ternary composite oil-displacing agent containing weak base.
Application example 2
The application example evaluates the oil displacement performance of the binary composite oil-displacing agent provided in example 4. The specific evaluation process comprises the following steps: the oil displacement performance of the binary composite oil displacement agent provided in example 4 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 equivalent binary composite oil displacement agents provided in the embodiment 4, 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 reaches 100% of water content, the binary composite oil displacement agent provided in example 4 with 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 reaches 100% of water content. 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 binary composite oil displacement agent provided in example 4 is higher than that of water flooding, and the recovery ratio of the binary composite oil displacement agent provided in example 4 to the first beret core and the second beret core is 24.83% (OOIP) and 23.69% (OOIP), respectively. Therefore, the binary composite oil-displacing agent comprising the emulsifier for oil displacement provided by the embodiment of the invention can improve the recovery ratio by more than 20% (OOIP) and can be used as a high-efficiency oil-displacing agent product with stable performance.
In summary, the binary composite oil displacement agent including the above-mentioned oil displacement emulsifier provided by the embodiments of the present invention does not include alkali, but does not include alkaliThe binary composite oil-displacing agent has excellent emulsifying effect, the emulsifying effect is better than that of alkali-containing ternary composite oil-displacing agent, and the oil-water interfacial tension can be reduced to 10-2The mN/m is less than or equal to the mN/m, the recovery ratio can be improved by more than 20 percent (OOIP), 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. A preparation method of an emulsifier for oil displacement is characterized by comprising the following steps:
adding aliphatic alcohol with 14-16 carbon atoms and a catalyst into a reactor, introducing nitrogen into the reactor, heating the reactor to a first preset temperature, and stopping introducing the nitrogen;
dropwise adding ethylene oxide into the reactor to perform polymerization reaction, heating the reactor to a second preset temperature, preserving heat, and then cooling to a third preset temperature to obtain the emulsifier for oil displacement;
wherein the mass ratio of the fatty alcohol to the ethylene oxide is 0.5-1.5: 2-3.
2. The preparation method of the emulsifier for oil displacement according to claim 1, wherein the mass ratio of the fatty alcohol to the ethylene oxide is 0.8-1.1: 2.2-2.6.
3. The preparation method of the emulsifier for flooding according to claim 2, wherein the mass ratio of the fatty alcohol to the ethylene oxide is 1: 2.5.
4. The preparation method of the emulsifier for oil displacement according to claim 1, wherein the catalyst is 0.3-0.6% by mass of potassium hydroxide solution or sodium hydroxide solution;
the mass ratio of the catalyst to the fatty alcohol is 8-10: 490-510.
5. The preparation method of the emulsifier for oil displacement according to claim 4, wherein the catalyst is 0.5% by mass of potassium hydroxide solution;
the mass ratio of the catalyst to the fatty alcohol is 9: 500.
6. The preparation method of the emulsifier for oil displacement 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 preparation method of the emulsifier for oil displacement according to any one of claims 1 to 5, wherein the heat preservation time is 1.8 to 2.5 hours.
8. An emulsifier for oil displacement, which is characterized by being prepared by the preparation method of any one of claims 1 to 7;
the emulsifier for oil displacement comprises: 94-98% of emulsifier pure product and the balance of impurities.
9. A binary composite oil-displacing agent, characterized in that it comprises: the oil-displacing emulsifier of claim 8, a polymer, water;
wherein the mass percent of the emulsifier for oil displacement is 0.05-0.3%;
the viscosity of the binary composite oil displacement agent is 38-45 mPa · s.
10. The binary composite oil-displacing agent according to claim 9, wherein the polymer is polyacrylamide.
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| CN105567208A (en) * | 2014-10-13 | 2016-05-11 | 中国石油化工股份有限公司 | Oil-displacement composition with improved injectivity, and preparation method and application thereof |
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| CN105567208A (en) * | 2014-10-13 | 2016-05-11 | 中国石油化工股份有限公司 | Oil-displacement composition with improved injectivity, and preparation method and application thereof |
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