CN105175627B - Foaming type Surfactant for EOR polymer and preparation method thereof - Google Patents
Foaming type Surfactant for EOR polymer and preparation method thereof Download PDFInfo
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- CN105175627B CN105175627B CN201510444392.5A CN201510444392A CN105175627B CN 105175627 B CN105175627 B CN 105175627B CN 201510444392 A CN201510444392 A CN 201510444392A CN 105175627 B CN105175627 B CN 105175627B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 55
- 238000005187 foaming Methods 0.000 title claims abstract description 37
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000178 monomer Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 14
- 239000003995 emulsifying agent Substances 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 230000033228 biological regulation Effects 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 235000010265 sodium sulphite Nutrition 0.000 claims description 7
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000003444 phase transfer catalyst Substances 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 6
- 238000005292 vacuum distillation Methods 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- AJSHDAOMUKXVDC-UHFFFAOYSA-N butan-1-amine;sulfuric acid Chemical compound CCCC[NH3+].OS([O-])(=O)=O AJSHDAOMUKXVDC-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 16
- 238000006073 displacement reaction Methods 0.000 abstract description 13
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000003921 oil Substances 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- OWXJKYNZGFSVRC-UHFFFAOYSA-N 1-chloroprop-1-ene Chemical class CC=CCl OWXJKYNZGFSVRC-UHFFFAOYSA-N 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 238000003408 phase transfer catalysis Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000011218 binary composite Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011206 ternary composite Substances 0.000 description 2
- 238000007445 Chromatographic isolation Methods 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention provides a kind of foaming type Surfactant for EOR polymer and preparation method thereof, the molecular structure of foaming type Surfactant for EOR polymer is, the foaming type Surfactant for EOR polymer surfaces tension force is relatively low, and foaming effect is good, and tackifying is good, and oil recovery factor is high, additionally, water-soluble good, temperature-resistant anti-salt performance is good, is suitable as three oil displacement agents of exploitation in oil field.
Description
Technical field
The present invention relates to high molecular polymer oil displacement agent, more particularly to a kind of foaming type Surfactant for EOR polymer and
Its preparation method.
Background technology
At present, China's major part oil field has been enter into developing latter stage, and yield has certain decline, because exploration cost increases
It is the most direct approach for solving energy crisis at this stage so farthest improving recovery ratio and difficulty is increasing.
The use of polymer flooding is the conventional approach of agent for improving oilfield recovery, polymer is added in water, can increase water-soluble
The viscosity of liquid, adjusts intake profile, increases displacing phase sweep efficiency, so as to improve recovery ratio.In order to be able to more by crude oil from
Underground produces, and method the more commonly used at present is to use binary or ternary composite driving, by effective collaboration effect between each component
Should, can significantly improve the viscosity of system, reduce the tension force of oil-water interfaces, so as to improve recovery ratio, its oil displacement efficiency is than independent
Polymer flooding effect is good, but when the drive of polymer binary and ternary composite driving, institute poor because there is migration velocity between different component
Can there is chromatographic isolation phenomenon, the synergy between different oil displacement agents is caused to weaken, oil displacement efficiency is deteriorated.
The content of the invention
The purpose of the present invention is：In view of the shortcomings of the prior art, there is provided a kind of surface tension is relatively low, foaming effect is good, increasing
Sticky good, oil recovery factor foaming type Surfactant for EOR polymer high and preparation method thereof.
In order to achieve the above object, one aspect of the present invention provides a kind of foaming type Surfactant for EOR polymer, tool
There is following molecular structure：
In formula, x:y:Z=100:15~40:0.2~2, n=8~15.
Second aspect present invention provides a kind of preparation method of foaming type Surfactant for EOR polymer, including following
Step：
Step one, prepares the mixed solution of OP emulsifying agents, NaOH or KOH, phase transfer catalyst and organic solvent, in inertia
Chloropropene is added dropwise under protective atmosphere, 12-24h is reacted under the conditions of 45 DEG C -70 DEG C, suction filtration is cooled down after the completion of reaction, then depressurize
Distillation obtains pi-allyl NPE monomer, wherein, chloropropene, OP emulsifying agents, NaOH or KOH and phase transfer catalysis (PTC)
The mol ratio of agent is 1.5-2:1:1-1.5:0.05；
Step 2,2- acrylamide-2-methyl propane sulfonic monomers are dissolved in water, and add alkali, and regulation pH is 7-8, plus
Enter pi-allyl NPE monomer and acrylamide monomer, control 2- acrylamide-2-methyl propane sulfonics, pi-allyl
The total monomer quality of NPE and acrylamide accounts for mixed liquor mass ratio for 20~25wt%, and acrylamide list
The mol ratio of body, 2- acrylamide-2-methyl propane sulfonics monomer and pi-allyl NPE monomer is 100:15~
40:0.2~2, the initiator for accounting for total monomer quality 0.2%-1% is added under inert protective atmosphere, in 25-35 DEG C, react 3-
After 6h, colloidal product is obtained, white precipitate is obtained after washing, drying is crushed, and obtains target product.
The beneficial effects of the invention are as follows：The present invention provide foaming type Surfactant for EOR polymer, surface tension compared with
Low, foaming effect is good, and tackifying is good, and oil recovery factor is high, additionally, water-soluble good, temperature-resistant anti-salt performance is good, is suitable as
Three oil displacement agents of exploitation in oil field.
Brief description of the drawings
Fig. 1 is the pi-allyl NPE sample and NPE sample of the gained of embodiment one
Infrared spectrogram.
Fig. 2 is the infrared spectrogram of the foaming type Surfactant for EOR polymer of the gained of embodiment one.
Fig. 3 is the curve of the concentration to surface tension of the foaming type Surfactant for EOR polymer of the gained of embodiment one
Figure.
Fig. 4 is the curve of the concentration to apparent viscosity of the foaming type Surfactant for EOR polymer of the gained of embodiment one
Figure.
Fig. 5 is the curve of the concentration to surface tension of the foaming type Surfactant for EOR polymer of the gained of embodiment two
Figure.
Fig. 6 is the curve of the concentration to foaming volume of the foaming type Surfactant for EOR polymer of the gained of embodiment two
Figure.
Specific embodiment
One aspect of the present invention provides a kind of foaming type Surfactant for EOR polymer, with following molecular structure：
In formula, x:y:Z=100:15~40:0.2~2, n=8~15.
Second aspect present invention provides a kind of preparation method of foaming type Surfactant for EOR polymer, including following
Step：
Step one, prepares the mixed solution of OP emulsifying agents, NaOH or KOH, phase transfer catalyst and organic solvent, in inertia
Chloropropene is added dropwise under protective atmosphere, 12-24h is reacted under the conditions of 45 DEG C -70 DEG C, suction filtration is cooled down after the completion of reaction, then depressurize
Distillation obtains pi-allyl NPE monomer, wherein, chloropropene, OP emulsifying agents, NaOH or KOH and phase transfer catalysis (PTC)
The mol ratio of agent is 1.5-2:1:1-1.5:0.05；
Step 2,2- acrylamide-2-methyl propane sulfonic monomers are dissolved in water, and add alkali, and regulation pH is 7-8, plus
Enter pi-allyl NPE monomer and acrylamide monomer, control 2- acrylamide-2-methyl propane sulfonics, pi-allyl
The total monomer quality of NPE and acrylamide accounts for mixed liquor mass ratio for 20~25wt%, and acrylamide list
The mol ratio of body, 2- acrylamide-2-methyl propane sulfonics monomer and pi-allyl NPE monomer is 100:15~
40:0.2~2, the initiator for accounting for total monomer quality 0.2%-1% is added under inert protective atmosphere, in 25-35 DEG C, react 3-
After 6h, colloidal product is obtained, white precipitate is obtained after washing, drying is crushed, and obtains target product.
Preferably, in the step one, organic solvent is CH2Cl2, chloroform, benzene, toluene, dimethylbenzene, in isopropanol
One or more.
Preferably, in the step one, OP emulsifying agents are OP-8, OP-10, one or more in OP-15.
Preferably, in the step one, phase transfer catalyst is TBAB, benzyltriethylammoinium chloride, 12
One or more in alkyl trimethyl ammonium chloride, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate.
Preferably, in the step 2, initiator is mass ratio=1:1 ammonium persulfate, sodium sulfite, or mass ratio=
1:1 potassium peroxydisulfate and sodium hydrogensulfite.
With reference to embodiment in detail foaming type Surfactant for EOR polymer of the invention and preparation method thereof is described in detail.
Embodiment 1
Step one, pi-allyl NPE monomer, i.e. COP, synthesis
0.1mol OP-10 emulsifying agents, 0.12molNaOH, 0.05mol TBAB, 50ml dichloromethane are taken in three
In mouth flask, nitrogen 30min is stirred and be passed through, 0.15mol chloropropenes are then added dropwise, 12h is reacted under the conditions of 50 DEG C, reacted
Into rear cooling suction filtration, then vacuum distillation obtains pi-allyl NPE monomer, i.e. COP-10.
Step 2, the synthesis of foaming type Surfactant for EOR polymer
3.42g 2- acrylamide-2-methyl propane sulfonic monomers, i.e. AMPS are dissolved in 48g distilled water, alkali is added,
Regulation pH is 7；To 0.77g COP-10, and 7.81g acrylamide monomers, i.e. AM is added in the AMPS aqueous solution, stirring and dissolving is led to
Enter nitrogen 30min, add 0.048g sodium sulfites and 0.048g ammonium persulfates, temperature is controlled at 35 DEG C, using aqueous solution polymerization
Method copolymerization；After reaction 3h, colloidal product is obtained, repeatedly washed on a small quantity with ethanol, obtain white depositions, dries pulverizing is obtained
To surface-active polymer.
The pi-allyl NPE sample that a small amount of step one is obtained is taken, a small amount of NPE is separately taken
1. and 2. sample, is respectively labeled as, carrying out infrared spectrum analysis, obtains the result shown in Fig. 1.As shown in Figure 1：Curve 2. in
There is 3475cm-1- OH absworption peaks, curve 1. in herein without absworption peak, illustrate the modified-OH of NPE
By the substitution of-C=C- double bonds.
Taking the surface-active polymer that a small amount of step 2 obtains carries out infrared spectrum analysis, obtains result shown in Fig. 2.By scheming
2 understand, 3349.8cm-1Locate the N-H stretching vibration peaks for acid amides, 3199.377cm-1Locate on phenyl ring=stretching vibration of C-H
Peak, 2931.66cm-1Locate as-CH2C-H symmetrical stretching vibrations peak, 2858.36cm-1Locate as-CH3C-H stretching vibration peaks,
1663.14cm-1Locate the C=O stretching vibration peaks for acid amides, 1041.389cm-1Locate the C-O stretching vibration peaks for ether,
1186.026cm-1Locate as-SO3 -Vibration absorption peak, the above infrared spectrum analysis result explanation subject polymer be synthesized out
Come.
The surface-active polymer surface tension obtained by JK99B type Full-automatic tension instrument determination step two, as a result such as Fig. 3
It is shown.
Apparent viscosity is determined by the type viscosimeters of BROOKFIELD III of Brookfield companies of the U.S., as a result as shown in Figure 4.
The oil displacement efficiency of polymer：The surface-active polymer that step 2 is obtained is configured to the solution that concentration is 0.2%,
It is 30cm in length, a diameter of 2.5cm, permeability is 50 × 10-3μm2Rock core on carry out imitation oil displacement experiment experiment.First with triumph
To aqueous 93%, saturation crude oil continues water drive to oil field G89 blocks stratum water drive, and it is 38.53% to measure the recovery ratio of water drive, note
Enter the surface-active polymer of 0.3PV, water drive can again improve oil recovery factor 15.6%, as a result as shown in table 1.
Embodiment 2
Step one, pi-allyl NPE monomer, i.e. COP, synthesis
0.1mol OP-10 emulsifying agents, 0.15molNaOH, 0.05mol tetrabutylammonium chloride, 40ml dichloromethane are taken in three
In mouth flask, nitrogen 30min is stirred and be passed through, 0.2mol chloropropenes are then added dropwise, 10h is reacted under the conditions of 50 DEG C, reacted
Into rear cooling suction filtration, then vacuum distillation obtains pi-allyl NPE monomer, i.e. COP-10.
Step 2, the synthesis of foaming type Surfactant for EOR polymer
3.51g AMPS are dissolved in 48g distilled water, alkali is added, regulation pH is 7；Added in the AMPS aqueous solution
0.47g pi-allyl NPE monomers and 8.02g acrylamide monomers, stirring and dissolving, are passed through nitrogen 30min, plus
Enter 0.06g sodium sulfites and 0.06g ammonium persulfates, temperature is controlled at 30 DEG C, using water solution polymerization process copolymerization；After reaction 4h,
Colloidal product is obtained, is repeatedly washed on a small quantity with ethanol, obtain white depositions, dries pulverizing obtains surface-active polymer.
The surface-active polymer surface tension obtained by JK99B type Full-automatic tension instrument determination step two, as a result such as Fig. 5
It is shown.
Self-control foaming instrument on test foaming volume, i.e., under normal temperature condition to solution in be passed through gas, the stream of gas
Speed is 400ml/min, and ventilate 2min, you can obtains experimental result, as shown in Figure 6.
The oil displacement efficiency of polymer：The surface-active polymer that step 2 is obtained is configured to the solution that concentration is 0.2%,
It is 30cm in length, a diameter of 2.5cm, permeability is 45 × 10-3μm2Rock core on carry out imitation oil displacement experiment experiment.First with triumph
To aqueous 93%, saturation crude oil continues water drive to oil field G89 blocks stratum water drive, and it is 40.03% to measure the recovery ratio of water drive, note
Enter the surface-active polymer of 0.3PV, water drive can again improve oil recovery factor 15.2%, as a result as shown in table 1.
Embodiment 3
Step one, pi-allyl NPE monomer, i.e. COP, synthesis
0.1mol OP-15 emulsifying agents, 0.15molNaOH, 0.05mol TBAB, 50ml dichloromethane are taken in three
In mouth flask, nitrogen 30min is stirred and be passed through, 0.15mol chloropropenes are then added dropwise, 10h is reacted under the conditions of 50 DEG C, reacted
Into rear cooling suction filtration, then vacuum distillation obtains pi-allyl NPE monomer, i.e. COP-15.
Step 2, the synthesis of foaming type Surfactant for EOR polymer
3.46gAMPS is dissolved in 48g distilled water, alkali is added, regulation pH is 7；To adding 0.63g in the AMPS aqueous solution
Pi-allyl NPE monomer and 7.91g acrylamide monomers, stirring and dissolving, are passed through nitrogen 30min, add
0.06g sodium sulfites and 0.06g ammonium persulfates, control temperature at 35 DEG C, using water solution polymerization process copolymerization；After reaction 4h, obtain
To colloidal product, repeatedly washed on a small quantity with ethanol, obtain white depositions, dries pulverizing obtains surface-active polymer.
The oil displacement efficiency of polymer：The surface-active polymer that step 2 is obtained is configured to the solution that concentration is 0.2%,
It is 30cm in length, a diameter of 2.5cm, permeability is 58 × 10-3μm2Rock core on carry out imitation oil displacement experiment experiment.First with triumph
To aqueous 93%, saturation crude oil continues water drive to oil field G89 blocks stratum water drive, and it is 39.25% to measure the recovery ratio of water drive, note
Enter the surface-active polymer of 0.3PV, water drive can again improve oil recovery factor 14.92%, as a result as shown in table 1.
Embodiment 4
Step one, pi-allyl NPE monomer, i.e. COP, synthesis
0.1mol OP-8 emulsifying agents, 0.12molNaOH, 0.05mol TBAB, 50ml dichloromethane are taken in three
In mouth flask, nitrogen 30min is stirred and be passed through, 0.15mol chloropropenes are then added dropwise, 12h is reacted under the conditions of 50 DEG C, reacted
Into rear cooling suction filtration, then vacuum distillation obtains pi-allyl NPE monomer, i.e. COP-8.
Step 2, the synthesis of foaming type Surfactant for EOR polymer
3.42g 2- acrylamide-2-methyl propane sulfonic monomers, i.e. AMPS are dissolved in 48g distilled water, alkali is added,
Regulation pH is 7；To 0.154g COP-8, and 7.81g acrylamide monomers, i.e. AM is added in the AMPS aqueous solution, stirring and dissolving is led to
Enter nitrogen 30min, add 0.048g sodium sulfites and 0.048g ammonium persulfates, temperature is controlled at 35 DEG C, using aqueous solution polymerization
Method copolymerization；After reaction 3h, colloidal product is obtained, repeatedly washed on a small quantity with ethanol, obtain white depositions, dries pulverizing is obtained
To surface-active polymer.
Embodiment 5
Step one, pi-allyl NPE monomer, i.e. COP, synthesis
0.1mol OP-8 emulsifying agents, 0.12molKOH, 0.05mol TBAB, 50ml dichloromethane are taken in three mouthfuls
In flask, nitrogen 30min is stirred and be passed through, 0.15mol chloropropenes are then added dropwise, 12h is reacted under the conditions of 50 DEG C, reaction is completed
After cool down suction filtration, then vacuum distillation obtains pi-allyl NPE monomer, i.e. COP-8.
Step 2, the synthesis of foaming type Surfactant for EOR polymer
9.12g 2- acrylamide-2-methyl propane sulfonic monomers, i.e. AMPS are dissolved in 48g distilled water, alkali is added,
Regulation pH is 7；To 1.54g COP-8, and 7.81g acrylamide monomers, i.e. AM is added in the AMPS aqueous solution, stirring and dissolving is led to
Enter nitrogen 30min, add 0.048g sodium sulfites and 0.048g ammonium persulfates, temperature is controlled at 35 DEG C, using aqueous solution polymerization
Method copolymerization；After reaction 3h, colloidal product is obtained, repeatedly washed on a small quantity with ethanol, obtain white depositions, dries pulverizing is obtained
To surface-active polymer.
The different polymer displacement of reservoir oil experimental results of table 1
| Sequence number | AM:AMPS:COP | Waterflood recovery efficiency factor % | Enhancing oil recovery in polymer flooding % |
| Embodiment 1 | 100:15:1 | 38.53 | 15.6 |
| Embodiment 2 | 100:20:1.5 | 40.03 | 15.2 |
| Embodiment 3 | 100:25:1.8 | 39.25 | 14.92 |
As shown in Table 1, using foaming type Surfactant for EOR polymer of the invention, surface tension is relatively low, foaming effect
Really good, tackifying is good, and oil recovery factor can improve more than 15%.
Claims (6)
1. a kind of foaming type Surfactant for EOR polymer, with following molecular structure：
In formula, x:y:Z=100:15~40:0.2~2, n=8~15.
2. a kind of preparation method of foaming type Surfactant for EOR polymer, comprises the following steps：
Step one, prepares the mixed solution of OP emulsifying agents, NaOH or KOH, phase transfer catalyst and organic solvent, in inertia protection
Chloropropene is added dropwise under atmosphere, 12-24h is reacted under the conditions of 45 DEG C -70 DEG C, suction filtration is cooled down after the completion of reaction, then vacuum distillation
Pi-allyl NPE monomer is obtained, wherein, chloropropene, OP emulsifying agents, NaOH or KOH and phase transfer catalyst
Mol ratio is 1.5-2:1:1‐1.5:0.05；
Step 2,2- acrylamide-2-methyl propane sulfonic monomers are dissolved in water, and add alkali, and regulation pH is 7-8, adds alkene
Propyl group NPE monomer and acrylamide monomer, control 2- acrylamide-2-methyl propane sulfonics, pi-allyl nonyl
The total monomer quality of phenol polyethenoxy ether and acrylamide accounts for mixed liquor mass ratio for 20~25wt%, and acrylamide monomer,
The mol ratio of 2- acrylamide-2-methyl propane sulfonics monomer and pi-allyl NPE monomer is 100:15~40:
0.2~2, the initiator for accounting for total monomer quality 0.2%-1% is added under inert protective atmosphere, in 25-35 DEG C, react 3-6h
Afterwards, colloidal product is obtained, white precipitate is obtained after washing, drying is crushed, and obtains target product.
3. the preparation method of foaming type Surfactant for EOR polymer as claimed in claim 2, it is characterised in that：The step
In rapid one, organic solvent is CH2Cl2, chloroform, benzene, toluene, dimethylbenzene, at least one in isopropanol.
4. the preparation method of foaming type Surfactant for EOR polymer as claimed in claim 2, it is characterised in that：The step
In rapid one, OP emulsifying agents are OP-8, OP-10, at least one in OP-15.
5. the preparation method of foaming type Surfactant for EOR polymer as claimed in claim 2, it is characterised in that：The step
In rapid one, phase transfer catalyst is TBAB, benzyltriethylammoinium chloride, DTAC, four fourths
At least one in ammonium chloride, 4-butyl ammonium hydrogen sulfate.
6. the preparation method of foaming type Surfactant for EOR polymer as claimed in claim 2, it is characterised in that：The step
In rapid two, initiator is mass ratio=1:1 ammonium persulfate, sodium sulfite, or mass ratio=1:1 potassium peroxydisulfate and sulfurous acid
Hydrogen sodium.
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| US4485224A (en) * | 1983-09-02 | 1984-11-27 | The Goodyear Tire & Rubber Company | Acrylamide polymerization |
| CN102127407A (en) * | 2010-12-10 | 2011-07-20 | 邓天东 | Thickening-resistant agent for cementing pad fluid |
| CN103058895A (en) * | 2012-12-21 | 2013-04-24 | 江苏美思德化学股份有限公司 | Heat resistance and salt tolerance type polyether sulfonic acid salt and synthetic method thereof |
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| CN101543747B (en) * | 2009-03-31 | 2011-12-28 | 成都理工大学 | Method for preparing allyl surface-active macromonomer |
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| US4485224A (en) * | 1983-09-02 | 1984-11-27 | The Goodyear Tire & Rubber Company | Acrylamide polymerization |
| CN102127407A (en) * | 2010-12-10 | 2011-07-20 | 邓天东 | Thickening-resistant agent for cementing pad fluid |
| CN103058895A (en) * | 2012-12-21 | 2013-04-24 | 江苏美思德化学股份有限公司 | Heat resistance and salt tolerance type polyether sulfonic acid salt and synthetic method thereof |
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Denomination of invention: Surface active polymers for foaming oil recovery and their preparation methods Granted publication date: 20170630 Pledgee: Fushun Dongzhou sub branch of Bank of China Ltd. Pledgor: FUSHUN DRAGON CHEMICAL PLANT Registration number: Y2024210000041 |