CN114933560A - Surfactant for improving crude oil recovery ratio and preparation method and application thereof - Google Patents
Surfactant for improving crude oil recovery ratio and preparation method and application thereof Download PDFInfo
- Publication number
- CN114933560A CN114933560A CN202210682258.9A CN202210682258A CN114933560A CN 114933560 A CN114933560 A CN 114933560A CN 202210682258 A CN202210682258 A CN 202210682258A CN 114933560 A CN114933560 A CN 114933560A
- Authority
- CN
- China
- Prior art keywords
- surfactant
- oil
- recovery
- preparation
- carrying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000011084 recovery Methods 0.000 title claims abstract description 44
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 44
- 239000010779 crude oil Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000003921 oil Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 27
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 24
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000605 extraction Methods 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 238000004321 preservation Methods 0.000 claims abstract description 16
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 claims abstract description 13
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical compound NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229960004979 fampridine Drugs 0.000 claims abstract description 13
- 238000010992 reflux Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- AKTHLFYZKHPYBY-UHFFFAOYSA-M sodium;1-chloroethanesulfonate Chemical compound [Na+].CC(Cl)S([O-])(=O)=O AKTHLFYZKHPYBY-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000000376 reactant Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 238000011534 incubation Methods 0.000 claims description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims 4
- 230000009467 reduction Effects 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 8
- 239000000693 micelle Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 7
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 238000000643 oven drying Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 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
- 239000003513 alkali Substances 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 229940077388 benzenesulfonate Drugs 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000009671 shengli Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000008398 formation water Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Mining & Mineral Resources (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- Geochemistry & Mineralogy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention belongs to the technical field of tertiary oil recovery, and particularly relates to a surfactant for improving the recovery ratio of crude oil, and a preparation method and application thereof. The preparation method comprises the following steps: adding paranonyl phenol, 4-aminopyridine, 40 wt% of formaldehyde and water into a sealed high-pressure reactor, stirring, heating, and carrying out heat preservation reaction; slowly cooling the high-pressure reactor to below 30 ℃, adding dichloromethane into the reactants for extraction, combining dichloromethane, and distilling at normal pressure to obtain viscous semisolid; transferring the viscous semisolid into a four-neck flask by using isopropanol, adding sodium chloroethanesulfonate, carrying out heat preservation reaction, adjusting the pH value to 7-8, and cooling to room temperature; adding dodecyl bromine into a four-mouth flask, and heating and carrying out reflux reaction to obtain a mixed solution; and distilling the mixed solution under reduced pressure to obtain a viscous solid, recrystallizing and drying to obtain the product. The surfactant has the characteristics of good viscosity reduction effect and high recovery efficiency, the viscosity reduction rate reaches over 99 percent, and the recovery rate is improved by more than 25 percent.
Description
Technical Field
The invention belongs to the technical field of tertiary oil recovery, relates to a chemical agent and a preparation method thereof, and particularly relates to a surfactant for improving the recovery ratio of crude oil, and a preparation method and application thereof.
Background
The oil extraction of the oil reservoir is divided into three stages, primary oil extraction, which depends on natural energy to extract crude oil and mainly comprises natural water drive and elastic energy drive, but the primary oil extraction rate is very low and the oil extraction speed is also low. Secondary oil recovery, which is a method for recovering oil by injecting liquid or gas into a stratum to supplement energy, is the most extensive oil recovery method adopted in the world at present, but the conventional oil recovery methods can generally recover only one third of the geological reserves of crude oil.
At present, most oil reservoirs enter the later stage of high-water-content development, the proportion of the oil reservoirs which are difficult to develop, such as high-temperature high-salinity, high-water-content high-extraction, low-permeability and the like in residual reserves is increased year by year, and the development by using a secondary oil recovery method is very difficult, so that a new exploitation technology is urgently needed to be developed, the recovery ratio of old oil fields is greatly improved, and the utilization ratio of proven resources is greatly improved, so that the requirements of economic development and national safety are met.
The oil extraction enters a tertiary oil extraction stage, which mainly comprises chemical flooding, gas flooding, thermal flooding and microbial oil extraction. The chemical flooding comprises surfactant flooding, polymer flooding, alkali water flooding and compound flooding, wherein surfactant flooding oil recovery is one of the main research directions for improving the recovery ratio of crude oil by three-recovery currently.
The surfactant oil extraction technology is a method for improving the crude oil recovery efficiency by adding a surfactant into injected water, which can effectively reduce the oil-water interfacial tension, change the oil reservoir wettability, solubilize the crude oil and reduce the crude oil viscosity, and improves the oil washing capacity by reducing the oil-water interfacial tension to improve the oil displacement efficiency.
CN 1131292C discloses a surfactant composition for improving crude oil recovery rate in tertiary oil recovery, which is composed of alkyl benzene sulfonate and heavy alkyl benzene sulfonate with known carbon number, and can be applied to improve crude oil recovery rate under low-alkali conditions. The invention also introduces an application method of an oil displacement system formed by applying the surfactant composition in improving the recovery ratio of crude oil in tertiary oil recovery. However, sodium hydroxide is used in the surfactant system, so that the produced crude oil is difficult to demulsify, and the difficulty is brought to the processing of the crude oil at the later stage.
CN108060094A discloses a Bacillus soil composter (Comptobacillus humi) BLG74 CGMCC No. 11219. The soil composting bacillus provided by the invention can grow under the condition of an oil reservoir at 37-60 ℃ by taking crude oil as a unique carbon source, degrade the crude oil and heavy components, and increase the fluidity, so that the oil recovery rate is improved. However, the surface tension of the surfactant generated by the strain is 32mN/m, the interfacial activity of the surfactant cannot carry out emulsification and viscosity reduction on crude oil, and the effect of improving the recovery efficiency is limited.
Disclosure of Invention
The invention provides a surfactant for improving the recovery efficiency of crude oil, a preparation method and application thereof aiming at the defects of the prior art. The surfactant disclosed by the invention has the advantages of low surface tension, low interfacial tension, low critical micelle concentration, good viscosity reduction effect, temperature resistance, salt tolerance and the like.
One of the purposes of the invention discloses a surfactant for improving the recovery ratio of crude oil, and the molecular structural formula of the surfactant is as follows:
the invention also aims to provide a preparation method of the surfactant for improving the oil recovery, which comprises the following steps:
(1) adding paranonyl phenol, 4-aminopyridine, 40 wt% of formaldehyde and water into a sealed high-pressure reactor, stirring and heating to 150-;
(2) slowly cooling the high-pressure reactor to below 30 ℃, adding dichloromethane into the reactants for extraction, repeatedly extracting for 2-3 times, combining dichloromethane, and distilling at normal pressure to obtain viscous semisolid;
(3) transferring the viscous semisolid into a four-neck flask by using isopropanol, adding sodium chloroacetate, carrying out heat preservation reaction at 60-65 ℃, maintaining the pH value to 7-8 by using 1M sodium hydroxide during the reaction, and cooling to room temperature;
(4) adding dodecyl bromine into a four-mouth flask, and heating and carrying out reflux reaction to obtain a mixed solution;
(5) distilling the mixed solution under reduced pressure to obtain a viscous solid, recrystallizing with ethyl acetate for 2-3 times to obtain crystals, and drying at 105-110 ℃ for 6-12h to obtain the product.
In the present invention, it is preferable that the 4-aminopyridine, 40 wt% of formaldehyde, sodium chloroethanesulfonate, and dodecylbromide are used in amounts of 1.8 to 2.2 parts by mole, 2.0 to 2.4 parts by mole, 1.8 to 2.2 parts by mole, and 3.6 to 4.4 parts by mole, respectively, based on 1 part by mole of nonylphenol; preferably, the 4-aminopyridine, 40 wt% of formaldehyde, sodium chloroethanesulfonate and dodecyl bromide are respectively used in 1.9-2.1 mol parts, 2.1-2.3 mol parts, 1.9-2.1 mol parts and 3.8-4.2 mol parts based on 1mol part of nonyl phenol.
Preferably, in the step (1), the weight ratio of the water to the nonyl phenol is 2-3: 1.
Preferably, in the step (1), the stirring and heat-preserving reaction time is 6-12h, and more preferably 8-10 h.
In the present invention, preferably, in the step (2), the weight ratio of the dichloromethane to the nonylphenol is 2 to 3: 1.
in the present invention, preferably, in the step (3), the weight ratio of the isopropyl alcohol to the nonyl phenol is 20 to 30: 1, more preferably 22 to 25: 1.
preferably, in the step (3), the incubation reaction time is 6-12h, more preferably 6-8 h.
In the present invention, preferably, in the step (4), the reflux reaction time is 24 to 48 hours, and more preferably 30 to 36 hours.
The reaction equation of the surfactant of the present invention is as follows:
the third purpose of the invention discloses the application of the surfactant in the oil reservoir enhanced oil recovery.
The surfactant for improving the crude oil recovery rate contains four cationic and two anionic surfactant groups. The hydrophilic group comprises four quaternary ammonium salts and two sulfonic groups, and compared with the conventional surfactant with single hydrophilic lipophilic group, the surfactant has higher surface activity, lower surface tension and interfacial tension and lower critical micelle concentration, so that the dosage is lower during use, and the viscosity reduction effect is better. The four dodecyl groups and the nonyl groups belong to hydrophobic groups, have better oleophylic property, enable molecules to quickly permeate into an oil phase from a water phase through an oil-water interface, easily generate intermolecular interaction with aromatic ring compounds, long-chain aliphatic hydrocarbons and the like in crude oil, form stable O/W emulsion under low power, greatly reduce the viscosity of the crude oil and improve the recovery ratio. The hydrophobic group of the surfactant can be adsorbed on the rock surface, so that the rock surface is changed from oleophylic to hydrophilic, the wetting angle of the crude oil on the rock surface is increased, the adhesion work is reduced, and the oil washing efficiency is improved. Active groups in the molecule are quaternary ammonium salt and sulfonate, so that the paint has higher tolerance to hardness when in use. Two pyridine rings and one benzene ring are arranged in the molecule, and the structure belongs to a rigid structure and has strong temperature resistance and shearing resistance.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the surfactant for improving the crude oil recovery efficiency has the characteristic of low surface tension, the concentration of 300mg/L and the interfacial tension reach below 25 mN/m;
(2) the surfactant for improving the crude oil recovery rate has the characteristic of low Critical Micelle Concentration (CMC) and reaches below 20 mg/L;
(3) the surfactant for improving the crude oil recovery efficiency has the characteristics of good viscosity reduction effect and high recovery efficiency, when the mass concentration is 300mg/L, the viscosity reduction rate reaches over 99 percent, and the physical model recovery rate improvement value is more than 25 percent.
Drawings
FIG. 1 shows a surfactant G according to the present invention 6 An infrared spectrum.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Example 1
(1) Adding 0.05mol of p-nonyl phenol, 0.09mol of 4-aminopyridine, 0.1mol of 40 wt% formaldehyde and 20.2g of water into a sealed high-pressure reactor, stirring, heating to 150 ℃, and carrying out heat preservation reaction for 6 hours;
(2) slowly cooling the high-pressure reactor to below 30 ℃, adding 20.2g of dichloromethane into the reactant for extraction, repeatedly extracting for 3 times, combining dichloromethane, and distilling at normal pressure to obtain viscous semisolid;
(3) transferring the viscous semisolid into a four-neck flask by 202g of isopropanol, adding 0.09mol of sodium chloroethanesulfonate, carrying out heat preservation reaction at 60 ℃ for 6h, maintaining the pH value of 7-8 by using 1M of sodium hydroxide during the reaction, and cooling to room temperature;
(4) adding 0.18mol of dodecyl bromide into a four-neck flask, and heating and refluxing for reaction for 24 hours to obtain a mixed solution;
(5) distilling the mixed solution under reduced pressure to obtain viscous semisolid, recrystallizing with ethyl acetate for 2 times to obtain crystal, and oven drying at 105 deg.C for 10 hr to obtain product G 1 。
Example 2
(1) Adding 0.05mol of p-nonyl phenol, 0.11mol of 4-aminopyridine, 0.12mol of 40 wt% formaldehyde and 30.3g of water into a sealed high-pressure reactor, stirring, heating to 155 ℃, and carrying out heat preservation reaction for 12 hours;
(2) slowly cooling the high-pressure reactor to below 30 ℃, adding 30.3g of dichloromethane into the reactant for extraction, repeatedly extracting for 2 times, combining dichloromethane, and distilling at normal pressure to obtain viscous semisolid;
(3) transferring the viscous semisolid into a four-neck flask by using 303g of isopropanol, adding 0.11mol of sodium chloroacetate, carrying out heat preservation reaction at 62 ℃ for 12 hours, maintaining the pH value of 7-8 by using 1M sodium hydroxide during the reaction, and cooling to room temperature;
(4) adding 0.22mol of dodecyl bromide into a four-neck flask, and heating and refluxing for reaction for 48 hours to obtain a mixed solution;
(5) distilling the mixed solution under reduced pressure to obtain viscous semisolid, recrystallizing with ethyl acetate for 3 times to obtain crystal, and oven drying at 105 deg.C for 8 hr to obtain product G 2 。
Example 3
(1) Adding 0.05mol of p-nonyl phenol, 0.095mol of 4-aminopyridine, 0.105mol of 40 wt% formaldehyde and 23.4g of water into a sealed high-pressure reactor, stirring, heating to 152 ℃, and carrying out heat preservation reaction for 7 hours;
(2) slowly cooling the high-pressure reactor to below 30 ℃, adding 23.4g of dichloromethane into the reactant for extraction, repeatedly extracting for 2 times, combining dichloromethane, and distilling at normal pressure to obtain viscous semisolid;
(3) transferring the viscous semisolid into a four-neck flask by using 246g of isopropanol, adding 0.092mol of sodium chloroacetate, carrying out heat preservation reaction at 65 ℃ for 11h, maintaining the pH value of 7-8 by using 1M sodium hydroxide during the reaction, and cooling to room temperature;
(4) adding 0.19mol of dodecyl bromide into a four-neck flask, and heating and refluxing for reaction for 30 hours to obtain a mixed solution;
(5) distilling the mixed solution under reduced pressure to obtain viscous semisolid, recrystallizing with ethyl acetate for 3 times to obtain crystal, and oven drying at 110 deg.C for 10 hr to obtain product G 3 。
Example 4
(1) Adding 0.05mol of p-nonyl phenol, 0.105mol of 4-aminopyridine, 0.115mol of 40 wt% formaldehyde and 27.8g of water into a sealed high-pressure reactor, stirring, heating to 154 ℃, and carrying out heat preservation reaction for 11 h;
(2) slowly cooling the high-pressure reactor to below 30 ℃, adding 27.8g of dichloromethane into the reactant for extraction, repeatedly extracting for 3 times, combining dichloromethane, and distilling at normal pressure to obtain viscous semisolid;
(3) transferring the viscous semisolid into a four-neck flask by using 288g of isopropanol, adding 0.1mol of sodium chloroethanesulfonate, carrying out heat preservation reaction at 62 ℃ for 12h, maintaining the pH value of 7-8 by using 1M of sodium hydroxide during the reaction, and cooling to the room temperature;
(4) adding 0.21mol of dodecyl bromide into a four-neck flask, and heating and refluxing for reaction for 32 hours to obtain a mixed solution;
(5) distilling the mixed solution under reduced pressure to obtain viscous semisolid, recrystallizing with ethyl acetate for 2 times to obtain crystal, and oven drying at 108 deg.C for 12 hr to obtain product G 4 。
Example 5
(1) Adding 0.05mol of p-nonyl phenol, 0.098mol of 4-aminopyridine, 0.108mol of 40 wt% formaldehyde and 24.9g of water into a sealed high-pressure reactor, stirring, heating to 153 ℃, and carrying out heat preservation reaction for 8 hours;
(2) slowly cooling the high-pressure reactor to below 30 ℃, adding 24.9g of dichloromethane into the reactant for extraction, repeatedly extracting for 3 times, combining dichloromethane, and distilling at normal pressure to obtain viscous semisolid;
(3) transferring the viscous semisolid into a four-neck flask by using 274g of isopropanol, adding 0.094mol of sodium chloroethanesulfonate, carrying out heat preservation reaction at 60 ℃ for 10h, maintaining the pH value of 7-8 by using 1M of sodium hydroxide during the reaction, and cooling to room temperature;
(4) adding 0.192mol of dodecyl bromide into a four-neck flask, and heating and refluxing for reaction for 36 hours to obtain a mixed solution;
(5) distilling the mixed solution under reduced pressure to obtain viscous semisolid, recrystallizing with ethyl acetate for 3 times to obtain crystal, and oven drying at 107 deg.C for 6 hr to obtain product G 5 。
Example 6
(1) Adding 0.05mol of p-nonyl phenol, 0.1mol of 4-aminopyridine, 0.11mol of 40 wt% formaldehyde and 26.3g of water into a sealed high-pressure reactor, stirring, heating to 152 ℃, and carrying out heat preservation reaction for 8 hours;
(2) slowly cooling the high-pressure reactor to below 30 ℃, adding 26.3g of dichloromethane into the reactant for extraction, repeatedly extracting for 3 times, combining dichloromethane, and distilling at normal pressure to obtain viscous semisolid;
(3) transferring the viscous semisolid into a four-neck flask by using 268g of isopropanol, adding 0.095mol of sodium chloroethanesulfonate, carrying out heat preservation reaction at 65 ℃ for 8h, maintaining the pH value of 7-8 by using 1M of sodium hydroxide during the reaction, and cooling to room temperature;
(4) adding 0.195mol of dodecyl bromide into a four-mouth flask, and heating and refluxing for 40 hours to obtain a mixed solution;
(5) distilling the mixed solution under reduced pressure to obtain viscous semisolid, recrystallizing with ethyl acetate for 2 times to obtain crystal, and oven drying at 105 deg.C for 12 hr to obtain product G 6 。
Example 7 surface tension and interfacial tension testing
The surface tension and interfacial tension were measured according to the method of SY/T5370-2018, surface and interfacial tension measuring method, and the test sample was prepared as an aqueous solution of 300mg/L, and the results are shown in Table 1.
As can be seen from table 1: surfactant G 1 -G 6 The surface tensions are respectively 24.8mN/m, 24.7mN/m, 24.6mN/m, 24.5mN/m and 24.3mN/m, which are all lower than 25 mN/m; and SL-3 surface tension is 28.3mN/m, which is obviously higher than that of the invention. Surfactant G 1 -G 6 Interfacial tension of 0.2X 10 respectively -3 mN/m、0.2×10 -3 mN/m、0.2×10 -3 mN/m、0.2×10 -3 mN/m、0.2×10 -3 mN/m、0.2×10 -3 mN/m, each of which is less than 1.0X 10 -3 mN/m; and the SL-3 interfacial tension is 1400mN/m, which is obviously higher than that of the invention.
Example 8 measurement of critical micelle concentration
The critical micelle concentration was determined according to the method described in GB/T11276-2007 determination of critical micelle concentration of surfactants, and the results are shown in Table 1.
TABLE 1 results of surface tension, interfacial tension, critical micelle concentration test
As can be seen from table 1: surfactant G 1 -G 6 The critical micelle concentration is respectively 19.8mg/L, 19.7mg/L, 19.5mg/L, 19.2mg/L, 19.3mg/L and 19.0mg/L, and the critical micelle concentration is lower than 20 mg/L; and the SL-3 critical micelle concentration is 180mg/L, which is obviously higher than the critical micelle concentration of the 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 viscosity reducer for heavy oil, crude oil to be tested was an oil sample from a block of the Shengli oil field, the initial viscosity of the crude oil was 5200 mPas at 50 ℃, the samples were prepared as solutions of 300mg/L and 3000mg/L, and the results are shown in Table 2.
TABLE 2 viscosity reduction Rate test results
As can be seen from table 2: when the mass concentration is 300mg/L, the surfactant G of the invention 1 -G 6 Has good viscosity reduction effect, the viscosity reduction rate is more than 98 percent, wherein G 6 The highest content is 98.71%; while SL-3 layers did not emulsify. When the mass concentration is 3000mg/L, the surfactant G of the invention 1 -G 6 Has a viscosity reduction rate of more than 99%, wherein G 6 Up to 99.32%; while the viscosity reduction rate of SL-3 is 92.46%, which is obviously lower than that of the invention.
Example 10 enhanced oil recovery evaluation
Filling permeability of 1000X 10 -3 μm 2 The sand-filled core; vacuumizing the core, saturating formation water of a certain oil reservoir E of an oil extraction plant in spring of the Shengli oil field, and calculating the pore volume PV of the core; the dehydrated and degassed crude oil of the saturated oil reservoir E is saturated until the oil content in the output liquid of the core outlet is 100 percent, and the original oil saturation of the core is calculated; aging the core for 7d at the temperature of 65 ℃ of the oil reservoir E; performing primary water drive until the water content of an outlet is 98%, and calculating the primary water drive recovery ratio; separately injecting a surfactant G 1 -G 6 And SL-3, the mass concentration is 300mg/L, the injection amount is 0.3PV, the injection speed is 1.0ml/min, secondary water flooding is carried out until the water content of an outlet is 100% after the injection of the surfactant is finished, and the value of the enhanced recovery ratio is calculated, and the result is shown in Table 3.
TABLE 3 evaluation results of enhanced recovery of surfactants
| Surface active agent | Amount of injection, PV | Concentration, mg/L | Increase the harvest rate by% |
| G 1 | 0.3 | 300 | 25.5 |
| G 2 | 0.3 | 300 | 26.0 |
| G 3 | 0.3 | 300 | 26.5 |
| G 4 | 0.3 | 300 | 26.7 |
| G 5 | 0.3 | 300 | 27.2 |
| G 6 | 0.3 | 300 | 28.6 |
| SL-3 | 0.3 | 300 | 12.3 |
As can be seen from table 3: the mass concentration is 300mg/L, the injection amount is 0.3PV, the injection speed is 1.0ml/min and the core permeability is 1000 multiplied by 10 -3 μm 2 Under the condition of the surfactant G 1 -G 6 The improved recovery rate values are all more than 25 percent, wherein G 6 The highest recovery rate value is 28.6 percent at most; while the SL-3 enhanced recovery is only 12.3%, which is significantly lower than the present invention.
Example 11 Infrared Spectrum characterization
Sample G by infrared spectroscopy 6 The characterization was performed and the results are shown in fig. 1.
The infrared spectral peaks from FIG. 1 were analyzed as follows: 3454cm -1 Is a CH bond stretching vibration absorption peak; 2926cm -1 Is a methylene antisymmetric telescopic vibration absorption peak which exists in a large amount in a molecule; 2838cm -1 Is a methylene symmetric stretching vibration absorption peak which exists in a large amount in molecules; 1618cm -1 Is a characteristic absorption peak of the benzene ring; 1473cm -1 Is a C-N bond stretching vibration peak in the quaternary ammonium salt; 1126cm -1 、1018cm -1 、695cm -1 Characteristic peak of sulfonate of 1126cm -1 、1018cm -1 Belonging to the S ═ O bond deformation vibration band of 695cm -1 Is a small peak of S ═ O bond deformation vibration.
Claims (10)
1. The preparation method of the surfactant for improving the recovery efficiency of crude oil is characterized by comprising the following steps of:
(1) adding paranonyl phenol, 4-aminopyridine, 40 wt% of formaldehyde and water into a sealed high-pressure reactor, stirring and heating to 150-;
(2) slowly cooling the high-pressure reactor to below 30 ℃, adding dichloromethane into the reactants for extraction, repeatedly extracting for 2-3 times, combining dichloromethane, and distilling at normal pressure to obtain viscous semisolid;
(3) transferring the viscous semisolid into a four-neck flask by using isopropanol, adding sodium chloroethanesulfonate, carrying out heat preservation reaction at 60-65 ℃, maintaining the pH value of 7-8 by using 1M sodium hydroxide during the reaction, and cooling to room temperature;
(4) adding dodecyl bromine into a four-mouth flask, and heating and carrying out reflux reaction to obtain a mixed solution;
(5) distilling the mixed solution under reduced pressure to obtain a viscous solid, recrystallizing with ethyl acetate for 2-3 times to obtain crystals, and drying at 105-110 ℃ for 6-12h to obtain the product.
2. The method according to claim 1, wherein the 4-aminopyridine, 40 wt% of formaldehyde, sodium chloroethanesulfonate and dodecylbromide are used in an amount of 1.8-2.2, 2.0-2.4, 1.8-2.2 and 3.6-4.4 parts by mole, respectively, based on 1 part by mole of nonylphenol.
3. The method according to claim 2, wherein the 4-aminopyridine, 40 wt% formaldehyde, sodium chloroethanesulfonate and dodecylbromide are used in amounts of 1.9-2.1 mol parts, 2.1-2.3 mol parts, 1.9-2.1 mol parts and 3.8-4.2 mol parts, respectively, based on 1mol part of nonylphenol.
4. The preparation method according to claim 1, wherein in the step (1), the stirring and heat-preserving reaction time is 6-12 h.
5. The method according to claim 1, wherein in the step (2), the weight ratio of the dichloromethane to the nonyl phenol is 2-3: 1.
6. the method according to claim 1, wherein in the step (3), the weight ratio of the isopropyl alcohol to the nonyl phenol is 20 to 30: 1.
7. the method according to claim 1, wherein in the step (3), the incubation reaction time is 6 to 12 hours.
8. The method according to claim 1, wherein the reflux reaction time in step (4) is 24 to 48 hours.
9. The surfactant prepared by the preparation method according to any one of claims 1 to 8, wherein the molecular structural formula of the surfactant is as follows:
10. use of the surfactant according to claim 9, in enhanced oil recovery of oil reservoirs.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210682258.9A CN114933560B (en) | 2022-06-16 | 2022-06-16 | Surfactant for improving crude oil recovery ratio and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210682258.9A CN114933560B (en) | 2022-06-16 | 2022-06-16 | Surfactant for improving crude oil recovery ratio and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114933560A true CN114933560A (en) | 2022-08-23 |
| CN114933560B CN114933560B (en) | 2023-11-10 |
Family
ID=82867947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210682258.9A Active CN114933560B (en) | 2022-06-16 | 2022-06-16 | Surfactant for improving crude oil recovery ratio and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114933560B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115651185A (en) * | 2022-12-27 | 2023-01-31 | 山东科兴化工有限责任公司 | Viscosity regulator for oil field and preparation method and application thereof |
| CN116283670A (en) * | 2023-03-17 | 2023-06-23 | 胜利油田凯渡石油技术开发有限公司 | Thickened oil viscosity reducer and preparation method thereof |
| CN116283751A (en) * | 2023-03-17 | 2023-06-23 | 胜利油田物华化工厂 | Bactericide for sewage treatment and synthetic method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1373172A (en) * | 2001-02-28 | 2002-10-09 | 大庆开发区鑫诺精细化工有限公司 | Surfactant composition for increasing recovery ratio of crude and its application |
| CN108060094A (en) * | 2016-11-08 | 2018-05-22 | 中国石油天然气股份有限公司 | Soil composting bacillus and microbial agent and application thereof |
| CN111925780A (en) * | 2020-10-15 | 2020-11-13 | 山东科兴化工有限责任公司 | Preparation method of high-temperature-resistant high-strength plugging agent for plugging of oil and gas well |
-
2022
- 2022-06-16 CN CN202210682258.9A patent/CN114933560B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1373172A (en) * | 2001-02-28 | 2002-10-09 | 大庆开发区鑫诺精细化工有限公司 | Surfactant composition for increasing recovery ratio of crude and its application |
| CN108060094A (en) * | 2016-11-08 | 2018-05-22 | 中国石油天然气股份有限公司 | Soil composting bacillus and microbial agent and application thereof |
| CN111925780A (en) * | 2020-10-15 | 2020-11-13 | 山东科兴化工有限责任公司 | Preparation method of high-temperature-resistant high-strength plugging agent for plugging of oil and gas well |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115651185A (en) * | 2022-12-27 | 2023-01-31 | 山东科兴化工有限责任公司 | Viscosity regulator for oil field and preparation method and application thereof |
| CN115651185B (en) * | 2022-12-27 | 2023-05-09 | 山东科兴化工有限责任公司 | Viscosity regulator for oil field and preparation method and application thereof |
| CN116283670A (en) * | 2023-03-17 | 2023-06-23 | 胜利油田凯渡石油技术开发有限公司 | Thickened oil viscosity reducer and preparation method thereof |
| CN116283751A (en) * | 2023-03-17 | 2023-06-23 | 胜利油田物华化工厂 | Bactericide for sewage treatment and synthetic method |
| CN116283670B (en) * | 2023-03-17 | 2024-06-11 | 东营市大舜化工有限责任公司 | Thickened oil viscosity reducer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114933560B (en) | 2023-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114933560A (en) | Surfactant for improving crude oil recovery ratio and preparation method and application thereof | |
| CN102464974B (en) | Composition capable of greatly improving crude oil recovery ratio and preparation method thereof | |
| CN110699058A (en) | Osmotic modified viscosity-reducing oil displacement agent for water-flooding thickened oil and preparation method thereof | |
| CN102181279A (en) | Quaternary ammonium salt type surfactant fracturing fluid | |
| CN111961457B (en) | Oil displacement complexing agent for heavy oil reservoir and preparation method and application thereof | |
| CN109135709A (en) | A kind of viscosity reduction oil displacement agent and oil displacement system suitable for heavy crude reservoir | |
| CN103374341B (en) | Preparation and application of gemini amphiphilic surfactant | |
| CN112226223A (en) | Surfactant composition for pressure reduction and injection increase of ultra-low permeability oil reservoir and preparation method thereof | |
| CN111440604B (en) | Self-demulsification type salt-resistant heavy oil cold recovery oil-displacing agent and preparation method and application thereof | |
| CN105131927B (en) | Surfactant for binary combination flooding and preparation method thereof | |
| CN115385870A (en) | Surfactant for improving crude oil recovery ratio and preparation method thereof | |
| CN108822252B (en) | Amphiphilic high-molecular thickened oil activator and application thereof | |
| CN102277147A (en) | Oil displacement method for high-temperature high-salt oil reservoir | |
| CN112280547A (en) | Viscosity-reducing oil displacement agent for super-thick crude oil and preparation method and application thereof | |
| CN117756682A (en) | Surfactant for oil and gas field and preparation method thereof | |
| CN105566174A (en) | Method for synthesizing betaine by long-chain tertiary amine through normal-pressure anhydrous quaternization | |
| CN104559990B (en) | Chemical flooding surface activator composition and its application | |
| CN110643340B9 (en) | High-efficiency water-soluble viscosity-reduction oil washing agent for heavy oil thermal recovery and preparation method thereof | |
| CN117903080A (en) | Thickened oil viscosity reducer and preparation method thereof | |
| CN104277816B (en) | One class sulfonate amphoteric high molecular surfactant and its synthetic method | |
| CN105175627B (en) | Foaming type Surfactant for EOR polymer and preparation method thereof | |
| CN112694443B (en) | Alkyl imidazoline polyether sulfonate surfactant and preparation method thereof | |
| CN104371063B (en) | One class can the sulfonate type polymkeric substance of emulsification hydrocarbons and synthetic method thereof | |
| CN107216864B (en) | The preparation and its application of sulfobetaines of the one kind containing double long-chain alkoxy bases | |
| CN103508914B (en) | Hydrophobic polymerizable monomer and oil-displacing agent composition as well as preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20231017 Address after: 262700 North 800m west of Gucheng Subdistricts of China, Shouguang City, Weifang, Shandong Province Applicant after: SHOUGUANG XINHAI ENERGY TECHNOLOGY Co.,Ltd. Address before: 257335 grand economic development zone, Guangrao County, Shandong, Dongying Applicant before: SHANDONG KEXING CHEMICAL Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |