CN115385870B - Surfactant for improving crude oil recovery ratio and preparation method thereof - Google Patents
Surfactant for improving crude oil recovery ratio and preparation method thereof Download PDFInfo
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 50
- 239000010779 crude oil Substances 0.000 title claims abstract description 43
- 238000011084 recovery Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 98
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 84
- 238000010438 heat treatment Methods 0.000 claims abstract description 43
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 40
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000010992 reflux Methods 0.000 claims abstract description 32
- 238000001816 cooling Methods 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 239000012153 distilled water Substances 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 17
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 14
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- AKTHLFYZKHPYBY-UHFFFAOYSA-M sodium;1-chloroethanesulfonate Chemical compound [Na+].CC(Cl)S([O-])(=O)=O AKTHLFYZKHPYBY-UHFFFAOYSA-M 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 90
- 239000003921 oil Substances 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 230000001603 reducing effect Effects 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000010926 purge Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 230000001502 supplementing effect Effects 0.000 claims description 8
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 4
- 239000001639 calcium acetate Substances 0.000 claims description 4
- 229960005147 calcium acetate Drugs 0.000 claims description 4
- 235000011092 calcium acetate Nutrition 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- 239000000693 micelle Substances 0.000 abstract description 13
- 230000009467 reduction Effects 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 9
- 239000003208 petroleum Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 40
- 238000006073 displacement reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 5
- 125000001033 ether group Chemical group 0.000 description 5
- -1 polyoxypropylene Polymers 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000011435 rock Substances 0.000 description 4
- 239000003876 biosurfactant Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000193830 Bacillus <bacterium> Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000010795 Steam Flooding Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000002361 compost Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000003113 dilution method Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000770534 Compostibacillus humi Species 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
- C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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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
- C08G65/2636—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 sulfur
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—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
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
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- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of petroleum exploitation, and particularly relates to a surfactant for improving crude oil recovery efficiency and a preparation method thereof. The preparation method comprises the following steps: piperazine, sodium chloroethanesulfonate and isopropanol are added into a four-mouth flask, heating reflux is carried out, and cooling is carried out after the reaction is finished; adding chloroethanol, heating and refluxing, and distilling under reduced pressure after the reaction is finished; adding a catalyst, vacuumizing, adding propylene oxide, and cooling to room temperature after the completion of the addition of propylene oxide to obtain a toluene solution product; and (3) distilling the toluene solution under reduced pressure to obtain viscous liquid, adding distilled water, heating to dissolve, cooling to separate out solid, and filtering to obtain the surfactant for improving the crude oil recovery ratio. The surfactant for improving the crude oil recovery ratio has low Critical Micelle Concentration (CMC), and the critical micelle concentration is below 40 mg/L; the surfactant for improving the crude oil recovery ratio has a good viscosity reduction effect, and the viscosity reduction rate reaches more than 99%.
Description
Technical Field
The invention belongs to the technical field of petroleum exploitation, relates to a chemical agent and a preparation method thereof, and in particular relates to a surfactant for improving crude oil recovery efficiency and a preparation method thereof.
Background
At present, most oil reservoirs enter the later development period, the proportion of the oil reservoirs which are difficult to exploit in the residual reserves is increased year by year, the comprehensive water content is increased, the stratum pressure is reduced, and the oil reservoir temperature is reduced. As the pressure and temperature of the oil layer decrease, the viscosity of the crude oil increases, the fluidity becomes poor, and the capillary of the oil layer is blocked, so that a large amount of crude oil stays in the oil layer and is not easy to be extracted.
The existing methods for taking over water flooding exploitation mainly comprise a steam flooding method, a dilution method and a chemical viscosity-reducing method, wherein the steam flooding and dilution method has high exploitation cost, and is difficult to popularize in a large area in an oil field. The chemical method has the advantages of low investment, simple process and quick response, and is widely applied to oil fields. The chemical flooding comprises surfactant flooding, polymer flooding, alkaline flooding and compound flooding, wherein surfactant flooding oil extraction is one of main research directions for improving crude oil recovery rate in current three-production.
The surfactant oil extraction technology is a method for improving the recovery ratio of crude oil, which is used for improving the oil displacement efficiency by adding the surfactant into injection water, effectively reducing the oil-water interfacial tension, changing the wettability of an oil reservoir, solubilizing crude oil and reducing the viscosity of crude oil and improving the oil washing capacity by reducing the oil-water interfacial tension, and has good recovery ratio improving effect, wide application range and great development potential.
CN1131292C discloses a surfactant composition for enhanced oil recovery in tertiary oil recovery, which consists of an alkylbenzenesulfonate of known carbon number and a heavy alkylbenzenesulfonate, and can be applied under low alkali condition to enhance oil recovery. The invention also discloses an application method of the oil displacement system formed by the surfactant composition in improving the recovery ratio of crude oil in tertiary oil recovery. However, sodium hydroxide is used in the surfactant system, and the sodium hydroxide can cause saponification of components with higher acid values in crude oil, so that the produced crude oil is difficult to demulsify and more difficulties are brought to the later crude oil processing although the oil extraction effect is good.
CN108060094a discloses a bacillus soil compost (Compostibacillus humi) BLG74 CGMCC No.11219. The bacillus soil compost provided by the invention can grow under the oil reservoir condition of 37-60 ℃ by taking crude oil as the only carbon source, degrade crude oil and heavy components and increase fluidity, so that the oil recovery rate is improved, and biosurfactants, biogas, organic acid and the like generated by metabolism of the strain interact with the crude oil to further increase the fluidity of the crude oil in the oil reservoir and improve the recovery rate of the crude oil. The biosurfactant has poor viscosity reduction effect on crude oil, uniform O/W emulsion cannot be formed, and the oil-water interfacial tension is usually 1-10mN/m, so that the biosurfactant has limited influence on the improvement of recovery ratio.
Disclosure of Invention
The invention provides a surfactant for improving crude oil recovery efficiency and a preparation method thereof, aiming at the defects of the prior art. The surfactant disclosed by the invention has low surface tension, low interfacial tension and low critical micelle concentration; meanwhile, the viscosity reducing agent has the advantages of good viscosity reducing effect, temperature resistance, salt resistance and hardness resistance.
According to a first aspect of the invention, the invention discloses a surfactant for improving crude oil recovery, wherein the surfactant has the following molecular structural formula:
wherein: m=2 to 20, more preferably m=5 to 12;
n=2 to 20, more preferably n=5 to 10.
According to a second aspect of the invention, the invention discloses a preparation method of the surfactant for improving the recovery ratio of crude oil, which comprises the following specific steps:
(1) Adding piperazine, sodium chloroethanesulfonate and isopropanol into a four-neck flask, heating and refluxing, maintaining the pH value to 7-8 by using a sodium hydroxide solution with the concentration of 2mol/L during the reaction period, and cooling to below 50 ℃ after the reaction is finished;
(2) Adding chloroethanol into the four-neck flask, heating and refluxing, and supplementing isopropanol for a plurality of times in the refluxing process to maintain the total amount of the solvent unchanged during the reaction, and maintaining the pH value to 7-8 by using a sodium hydroxide solution of 2mol/L during the reaction, and distilling under reduced pressure to obtain viscous liquid after the reaction is finished;
(3) Transferring the viscous liquid into a high-pressure reaction kettle by using toluene, adding a catalyst, purging the reaction kettle and a pipeline by using nitrogen for 2-3min, closing the reaction kettle, stirring and heating to 80-90 ℃, vacuumizing, adding propylene oxide at one time, continuously heating to 150-160 ℃ after the completion of the reaction, enabling the pressure of the reaction kettle to reach 0.3-0.5MPa, gradually reducing the pressure along with the progress of the reaction, and cooling the system to room temperature by using circulating water after the pressure is not reduced any more and the reaction is continued for 1-2h, so as to obtain a toluene solution product;
(4) And (3) distilling the toluene solution under reduced pressure to obtain a viscous liquid, adding distilled water, heating to dissolve, regulating the pH to 2-3 with 2mol/L hydrochloric acid, cooling to below 10 ℃, precipitating solid, filtering, washing with 10 ℃ distilled water for 2 times, regulating the pH to 8-9 with 5mol/L sodium hydroxide solution, and dissolving the solid to obtain the surfactant for improving the crude oil recovery ratio.
In the invention, the dosages of the sodium chloroethanesulfonate, the chloroethanol and the epoxypropane are respectively 1.8 to 2.4 mole parts, 2.0 to 2.6 mole parts and 5 to 50 mole parts based on 1 mole part of piperazine; preferably, the amounts of sodium chloroethanesulfonate, chloroethanol, propylene oxide are 1.9-2.2 molar parts, 2.2-2.4 molar parts, 10-50 molar parts, respectively, based on 1 molar part of piperazine.
In the present invention, preferably, the weight ratio of isopropyl alcohol to piperazine in the step (1) is 30 to 50:1.
preferably, the reflux time in step (1) is 2-4 hours; more preferably, the reflux time is 2-3 hours.
In the present invention, preferably, the reflux time in step (2) is 24 to 48 hours; more preferably, the reflux time is 32-42 hours.
In the present invention, preferably, the weight ratio of toluene to piperazine in the step (3) is 20 to 30:1.
preferably, the catalyst in the step (3) is one of potassium hydroxide, sodium hydroxide and calcium acetate; the weight ratio of the catalyst to piperazine is 0.2-0.5:1.
in the present invention, preferably, the weight ratio of the distilled water and the distilled water at 10 ℃ in the step (4) to piperazine is 20-30:30-50:1.
the synthetic reaction equation of the surfactant is as follows:
the surfactant of the invention belongs to Gemini surfactants, and hydrophilic groups comprise two sulfonic groups and two quaternary ammonium salts; the lipophilic group has two polyoxypropylene ether groups. The surfactant is higher in surface activity, lower in critical micelle concentration and therefore lower in required amount than conventional surfactants having a single hydrophilic lipophilic group. The polyoxypropylene ether group has larger content in the whole molecule and longer molecular chain, so the polyoxypropylene ether group can go deep into the crude oil, has good flexibility, is easy to intertwine with the crude oil, and can form O/W emulsion with the crude oil under the action of low power. Under the action of sulfonic acid group and quaternary ammonium salt group, the external phase forms continuous water film, so that the flow resistance can be reduced, the viscosity of crude oil can be greatly reduced, and the recovery ratio of crude oil can be improved. The polyoxypropylene ether group can be adsorbed on the rock surface, so that the rock surface is converted from oleophylic to hydrophilic, the wetting angle of crude oil on the rock surface is increased, the adhesion work is reduced, the crude oil is more easily stripped from the rock surface, and the recovery ratio is improved. The functional groups in the molecule are sulfonic acid groups, quaternary ammonium salts and polyoxypropylene ether groups, so that the whole molecule has the characteristics of temperature resistance, salt resistance and hardness resistance.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The surfactant for improving the crude oil recovery ratio has higher surface activity, the surface tension reaches below 28mN/m, and the interfacial tension reaches 1.0x10 -3 mN/m or less;
(2) The surfactant for improving the crude oil recovery ratio has low Critical Micelle Concentration (CMC), and the critical micelle concentration is below 40 mg/L;
(3) The surfactant for improving the recovery ratio of crude oil has good viscosity reduction effect, and the viscosity reduction rate reaches more than 99%.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Example 1
(1) Adding 0.1mol of piperazine, 0.18mol of sodium chloroethanesulfonate and 258g of isopropanol into a four-necked flask, heating and refluxing for 2 hours, maintaining the pH value to be 7 by using 2mol/L of sodium hydroxide solution during the reaction, and cooling to below 50 ℃ after the reaction is finished;
(2) Adding 0.2mol of chloroethanol into the four-neck flask, heating and refluxing for 24 hours, and supplementing isopropanol for many times in the refluxing process to maintain the total solvent amount unchanged during the reaction, wherein 2mol/L of sodium hydroxide solution is used for maintaining the pH value of 7 during the reaction, and then the solution is distilled to be a viscous liquid under reduced pressure after the reaction is finished;
(3) Transferring the viscous liquid into a high-pressure reaction kettle by using 172g of toluene, adding 1.72g of potassium hydroxide catalyst, purging the reaction kettle and a pipeline by using nitrogen for 2min, closing the reaction kettle, stirring and heating to 80 ℃, vacuumizing, adding 0.5mol of propylene oxide at one time, continuously heating to 150 ℃ after the completion of the reaction, enabling the pressure of the reaction kettle to reach 0.3MPa, gradually reducing the pressure along with the progress of the reaction, and cooling the system to room temperature by using circulating water after the pressure is not reduced any more and the reaction is continued for 1h, so as to obtain a toluene solution of a product;
(4) Distilling the toluene solution of the product to a viscous liquid under reduced pressure, adding 172g of distilled water, heating to dissolve, adjusting the pH to 2.5 with 2mol/L hydrochloric acid, cooling to below 10 ℃, separating out solid, filtering, washing with 258g of distilled water at 10 ℃ for 2 times, adjusting the pH to 8 with 5mol/L sodium hydroxide solution, and dissolving the solid to obtain the product A.
Example 2
(1) Adding 0.1mol of piperazine, 0.24mol of sodium chloroethanesulfonate and 430g of isopropanol into a four-necked flask, heating and refluxing for 4 hours, maintaining the pH value to be 7 by using 2mol/L of sodium hydroxide solution during the reaction, and cooling to below 50 ℃ after the reaction is finished;
(2) Adding 0.26mol of chloroethanol into the four-neck flask, heating and refluxing for 48 hours, and supplementing isopropanol for many times in the refluxing process to maintain the total amount of the solvent unchanged during the reaction, maintaining the pH value to be 7 by using 2mol/L sodium hydroxide solution during the reaction, and distilling under reduced pressure to obtain viscous liquid after the reaction is finished;
(3) Transferring the viscous liquid into a high-pressure reaction kettle by 258g of toluene, adding 4.3g of potassium hydroxide catalyst, purging the reaction kettle and a pipeline for 2min by nitrogen, closing the reaction kettle, stirring and heating to 85 ℃, vacuumizing, adding 5mol of propylene oxide at one time, continuously heating to 160 ℃ after the completion of the reaction, enabling the pressure of the reaction kettle to reach 0.5MPa, gradually reducing the pressure along with the progress of the reaction, cooling the system to room temperature by adopting circulating water after the pressure is not reduced any more, and obtaining toluene solution of a product;
(4) Distilling the toluene solution of the product to a viscous liquid under reduced pressure, adding 258g of distilled water, heating to dissolve, adjusting the pH to 2.5 with 2mol/L hydrochloric acid, cooling to below 10 ℃, separating out solid, filtering, washing 2 times with 430g of 10 ℃ distilled water, adjusting the pH to 9 with 5mol/L sodium hydroxide solution, and dissolving the solid to obtain the product B.
Example 3
(1) Adding 0.1mol of piperazine, 0.19mol of sodium chloroethanesulfonate and 279g of isopropanol into a four-necked flask, heating and refluxing for 3 hours, maintaining the pH value to be 8 by using 2mol/L sodium hydroxide solution during the reaction, and cooling to below 50 ℃ after the reaction is finished;
(2) Adding 0.22mol of chloroethanol into the four-neck flask, heating and refluxing for 32h, and supplementing isopropanol for many times in the refluxing process to maintain the total amount of the solvent unchanged during the reaction, maintaining the pH value to be 8 by using 2mol/L sodium hydroxide solution during the reaction, and distilling under reduced pressure to obtain viscous liquid after the reaction is finished;
(3) Transferring the viscous liquid into a high-pressure reaction kettle by using 192g of toluene, adding 2.64g of sodium hydroxide catalyst, purging the reaction kettle and a pipeline for 3min by using nitrogen, closing the reaction kettle, stirring and heating to 90 ℃, vacuumizing, adding 1mol of propylene oxide at one time, continuously heating to 153 ℃ after the completion of the reaction, enabling the pressure of the reaction kettle to reach 0.4MPa, gradually reducing the pressure along with the progress of the reaction, cooling the system to room temperature by using circulating water after the pressure is not reduced, and obtaining a toluene solution of a product after the reaction is continued for 2 h;
(4) And (3) distilling the toluene solution of the product to a viscous liquid under reduced pressure, adding 200g of distilled water, heating to dissolve, adjusting the pH to 3 by using 2mol/L hydrochloric acid, cooling to below 10 ℃, separating out solid, filtering, washing 2 times by 314g of 10 ℃ distilled water, adjusting the pH to 8 by using 5mol/L sodium hydroxide solution, and dissolving the solid to obtain the product C.
Example 4
(1) Adding 0.1mol of piperazine, 0.22mol of sodium chloroethanesulfonate and 402g of isopropanol into a four-necked flask, heating and refluxing for 2.5h, maintaining the pH value to be 8 by using 2mol/L sodium hydroxide solution during the reaction, and cooling to below 50 ℃ after the reaction is finished;
(2) Adding 0.25mol of chloroethanol into the four-neck flask, heating and refluxing for 40h, and supplementing isopropanol for many times in the refluxing process to maintain the total amount of the solvent unchanged during the reaction, wherein 2mol/L sodium hydroxide solution is used for maintaining pH7.5 during the reaction, and then decompressing and distilling to obtain viscous liquid after the reaction is finished;
(3) Transferring the viscous liquid into a high-pressure reaction kettle by 243g of toluene, adding 4.02g of sodium hydroxide catalyst, purging the reaction kettle and a pipeline for 3min by using nitrogen, closing the reaction kettle, stirring and heating to 82 ℃, vacuumizing, adding 4mol of propylene oxide at one time, continuously heating to 155 ℃ after the completion of the reaction, enabling the pressure of the reaction kettle to reach 0.3MPa, gradually reducing the pressure along with the progress of the reaction, cooling the system to room temperature by adopting circulating water after the pressure is not reduced, and obtaining a toluene solution of a product after the reaction is continued for 1 h;
(4) And (3) distilling the toluene solution of the product to a viscous liquid under reduced pressure, adding 218g of distilled water, heating to dissolve, adjusting the pH to 3 by using 2mol/L hydrochloric acid, cooling to below 10 ℃, separating out solid, filtering, washing 2 times by using 366g of 10 ℃ distilled water, adjusting the pH to 8 by using 5mol/L sodium hydroxide solution, and dissolving the solid to obtain the product D.
Example 5
(1) Adding 0.1mol of piperazine, 0.2mol of sodium chloroethanesulfonate and 338g of isopropanol into a four-necked flask, heating and refluxing for 3h, maintaining pH7.5 by using 2mol/L sodium hydroxide solution during the reaction, and cooling to below 50 ℃ after the reaction is finished;
(2) Adding 0.23mol of chloroethanol into the four-neck flask, heating and refluxing for 33 hours, and supplementing isopropanol for many times in the refluxing process to maintain the total amount of the solvent unchanged during the reaction, wherein 2mol/L of sodium hydroxide solution is used for maintaining the pH value to 8 during the reaction, and then the solution is distilled to be a viscous liquid under reduced pressure after the reaction is finished;
(3) Transferring the viscous liquid into a high-pressure reaction kettle by using 217g of toluene, adding 3.14g of calcium acetate catalyst, purging the reaction kettle and a pipeline for 2min by using nitrogen, closing the reaction kettle, stirring and heating to 87 ℃, vacuumizing, adding 2mol of propylene oxide at one time, continuously heating to 160 ℃ after the completion of the reaction, enabling the pressure of the reaction kettle to reach 0.5MPa, gradually reducing the pressure along with the progress of the reaction, cooling the system to room temperature by using circulating water after the pressure is not reduced, and obtaining a toluene solution of a product after the reaction is continued for 2 h;
(4) Distilling the toluene solution of the product to a viscous liquid under reduced pressure, adding 223g of distilled water, heating to dissolve, adjusting the pH to 2 with 2mol/L hydrochloric acid, cooling to below 10 ℃, precipitating solid, filtering, washing 2 times with 3838 g of distilled water at 10 ℃, adjusting the pH to 8.5 with 5mol/L sodium hydroxide solution, and dissolving the solid to obtain the product E.
Example 6
(1) Adding 0.1mol of piperazine, 0.21mol of sodium chloroethanesulfonate and 356g of isopropanol into a four-necked flask, heating and refluxing for 3h, maintaining pH7.5 by using 2mol/L sodium hydroxide solution during the reaction, and cooling to below 50 ℃ after the reaction is finished;
(2) Adding 0.24mol of chloroethanol into the four-neck flask, heating and refluxing for 36h, and supplementing isopropanol for many times in the refluxing process to maintain the total amount of the solvent unchanged during the reaction, wherein 2mol/L sodium hydroxide solution is used for maintaining pH7.5 during the reaction, and then decompressing and distilling to obtain viscous liquid after the reaction is finished;
(3) Transferring the viscous liquid into a high-pressure reaction kettle by using 235g of toluene, adding 3.66g of calcium acetate catalyst, purging the reaction kettle and a pipeline for 3min by using nitrogen, closing the reaction kettle, stirring and heating to 83 ℃, vacuumizing, adding 3mol of propylene oxide at one time, continuously heating to 158 ℃ after the completion of the reaction, enabling the pressure of the reaction kettle to reach 0.4MPa, gradually reducing the pressure along with the progress of the reaction, cooling the system to room temperature by using circulating water after the pressure is not reduced, and obtaining a toluene solution of a product after the reaction is continued for 1 h;
(4) And (3) distilling the toluene solution of the product to a viscous liquid under reduced pressure, adding 243g of distilled water, heating to dissolve, adjusting the pH to 2 with 2mol/L hydrochloric acid, cooling to below 10 ℃, precipitating solid, filtering, washing with 400g of distilled water at 10 ℃ for 2 times, adjusting the pH to 9 with 5mol/L sodium hydroxide solution, and dissolving the solid to obtain the product F.
Example 7 testing of surface tension and interfacial tension
The surface tension and interfacial tension were measured according to the methods in SY/T5370-2018 method for surface and interfacial tension determination, and the test samples were formulated into 200mg/L aqueous solutions, and the results are shown in Table 1. Meanwhile, surfactant produced by Shandong Bao Momo Biochemical Co., ltd is used for comparison, and model code is 1030.
Example 8 testing of Critical micelle concentration
The critical micelle concentration was measured according to the method in GB/T11276-2007 determination of critical micelle concentration of surfactant, and the results are shown in Table 1. Meanwhile, surfactant produced by Shandong Bao Momo Biochemical Co., ltd is used for comparison, and model code is 1030.
TABLE 1 surface tension, interfacial tension, critical micelle concentration test results
As can be seen from table 1: the surfactant A, B, C, D, E, F of the invention has low surface tension, interfacial tension and critical micelle concentration. The surface tension is lower than 28mN/m, wherein F is the lowest of 26.3mN/m; interfacial tension is lower than 5.0X10 -4 mN/m, where F is at least 1.3X10 -4 mN/m; the critical micelle concentration is below 40mg/L, with a minimum F of 25mg/L. The surface tension, interfacial tension and critical micelle concentration values of the comparative examples were 31.8mN/m and 800X 10, respectively -4 mN/m, 120mg/L, all highIn the present invention.
EXAMPLE 9 evaluation of viscosity reduction Rate
The viscosity reduction rate was measured according to the method of Q/SH 10201519-2016 general technical Condition for heavy oil viscosity reducer, the crude oil for measurement was an oil sample of a block of a winning oil field, the initial viscosity of the crude oil at 60℃was 12000mPa.s, and the measured samples were prepared into 200mg/L and 500mg/L solutions, and the results are shown in Table 2. Meanwhile, surfactant produced by Shandong Bao Momo Biochemical Co., ltd is used for comparison, and model code is 1030.
TABLE 2 viscosity reduction test results
As can be seen from table 2: the surfactant A, B, C, D, E, F has obvious viscosity reduction effect, the viscosity reduction rate is more than 99.2% when the concentration is 200mg/L, and the comparative example is layered without emulsification; the viscosity reduction rate was greater than 99.4% at a concentration of 500mg/L used, whereas the viscosity reduction rate of the comparative example was 92.75%, which is significantly lower than the present invention.
Example 10 evaluation of oil displacement Effect
And (3) establishing an oil displacement model under the stratum condition of a certain area of the victory oil field, driving with water until the produced liquid does not contain crude oil, preparing a surfactant into a solution with the concentration of 200mg/L, continuing to displace the oil by 0.5PV, and then continuing to drive with water until the water content is 100%. The final displacement was calculated according to formula (1), the average was taken three times, and the experimental results are shown in table 3. Meanwhile, surfactant produced by Shandong Bao Momo Biochemical Co., ltd is used for comparison, and model code is 1030.
η＝V 1 /V 0 ×100％ (1)
Wherein: η -displacement of reservoir oil,%;
V 1 -expelling oil volume, ml;
V 0 -initial saturated crude oil volume, ml.
Specific reservoir parameters: the oil reservoir temperature is 60 ℃, the crude oil viscosity is 12000mPa.s, the mineralization degree of injected water is 38210mg/L, and the calcium and magnesium ion concentration is 2560mg/L.
Table 3 results of oil displacement performance experiments
| Surface active agent | V 0 ，ml | V 1 ，ml | η，/％ |
| A | 40.25 | 16.88 | 41.94 |
| B | 40.36 | 17.23 | 42.69 |
| C | 40.58 | 17.8 | 43.86 |
| D | 40.22 | 18.17 | 45.18 |
| E | 40.36 | 18.29 | 45.32 |
| F | 40.55 | 18.55 | 45.75 |
| Comparative example | 40.33 | 10.33 | 25.61 |
As can be seen from table 3: the surfactant A, B, C, D, E, F has higher oil displacement rate, the oil displacement efficiency is more than 40%, and the oil displacement efficiency of the comparative example is 25.61%, which is obviously lower than that of the present invention.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A surfactant for improving crude oil recovery, characterized in that the molecular structural formula of the surfactant is as follows:
wherein: m=2-20;
n＝2-20。
2. the surfactant for enhanced oil recovery according to claim 1, wherein the surfactant has a molecular structural formula as follows:
wherein: m=5-12;
n＝5-10。
3. the method for preparing a surfactant for enhanced oil recovery according to claim 1 or 2, wherein the preparation method comprises the following specific steps:
(1) Adding piperazine, sodium chloroethanesulfonate and isopropanol into a four-neck flask, heating and refluxing, maintaining the pH value to 7-8 by using a sodium hydroxide solution with the concentration of 2mol/L during the reaction period, and cooling to below 50 ℃ after the reaction is finished;
(2) Adding chloroethanol into the four-neck flask, heating and refluxing, and supplementing isopropanol for a plurality of times in the refluxing process to maintain the total amount of the solvent unchanged during the reaction, and maintaining the pH value to 7-8 by using a sodium hydroxide solution of 2mol/L during the reaction, and distilling under reduced pressure to obtain viscous liquid after the reaction is finished;
(3) Transferring the viscous liquid into a high-pressure reaction kettle by using toluene, adding a catalyst, purging the reaction kettle and a pipeline by using nitrogen for 2-3min, closing the reaction kettle, stirring and heating to 80-90 ℃, vacuumizing, adding propylene oxide at one time, continuously heating to 150-160 ℃ after the completion of the reaction, enabling the pressure of the reaction kettle to reach 0.3-0.5MPa, gradually reducing the pressure along with the progress of the reaction, and cooling the system to room temperature by using circulating water after the pressure is not reduced any more and the reaction is continued for 1-2h, so as to obtain a toluene solution of a product;
(4) Distilling the toluene solution under reduced pressure to obtain viscous liquid, adding distilled water, heating to dissolve, regulating pH to 2-3 with 2mol/L hydrochloric acid, cooling to below 10deg.C, separating out solid, filtering, washing with 10deg.C distilled water for 2 times, regulating pH to 8-9 with 5mol/L sodium hydroxide solution, and dissolving the solid to obtain the final product;
the catalyst is one of potassium hydroxide, sodium hydroxide and calcium acetate.
4. The method for producing a surfactant for enhanced oil recovery according to claim 3, wherein the amounts of sodium chloroethanesulfonate, chloroethanol and propylene oxide are 1.8 to 2.4 parts by mole, 2.0 to 2.6 parts by mole and 5 to 50 parts by mole, respectively, based on 1 part by mole of piperazine.
5. The method for producing a surfactant for enhanced oil recovery according to claim 4, wherein the amounts of sodium chloroethanesulfonate, chloroethanol and propylene oxide are 1.9 to 2.2 parts by mole, 2.2 to 2.4 parts by mole and 10 to 50 parts by mole, respectively, based on 1 part by mole of piperazine.
6. The method for producing a surfactant for enhanced oil recovery according to claim 3, wherein the reflux time in the step (1) is 2 to 4 hours.
7. The method for producing a surfactant for enhanced oil recovery according to claim 3, wherein the weight ratio of isopropyl alcohol to piperazine in the step (1) is 30 to 50:1.
8. the method for producing a surfactant for enhanced oil recovery according to claim 3, wherein the reflux time in the step (2) is 24 to 48 hours.
9. The method for producing a surfactant for enhanced oil recovery according to claim 3, wherein the weight ratio of the catalyst to piperazine is 0.2 to 0.5:1.
10. the method for producing a surfactant for enhanced oil recovery according to claim 3, wherein the weight ratio of toluene to piperazine in the step (3) is 20 to 30:1.
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| US4773484A (en) * | 1987-03-24 | 1988-09-27 | Atlantic Richfield Company | Enhanced oil recovery process with reduced gas drive mobility |
| US4853138A (en) * | 1987-08-05 | 1989-08-01 | The Standard Oil Company | C-branched zwitterionic surfactants and enhanced oil recovery method using same |
| WO2015161812A1 (en) * | 2014-04-23 | 2015-10-29 | Jiangnan University | Compounds, compositions thereof and methods for hydrocarbon extraction using the same |
| CN108314999A (en) * | 2017-01-17 | 2018-07-24 | 中国石油化工股份有限公司 | The method for efficiently improving oil recovery factor |
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| US4773484A (en) * | 1987-03-24 | 1988-09-27 | Atlantic Richfield Company | Enhanced oil recovery process with reduced gas drive mobility |
| US4853138A (en) * | 1987-08-05 | 1989-08-01 | The Standard Oil Company | C-branched zwitterionic surfactants and enhanced oil recovery method using same |
| WO2015161812A1 (en) * | 2014-04-23 | 2015-10-29 | Jiangnan University | Compounds, compositions thereof and methods for hydrocarbon extraction using the same |
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