CN105175627A - Foam-type surfactant polymer used for displacement of reservoir oil and preparation method therefor - Google Patents
Foam-type surfactant polymer used for displacement of reservoir oil and preparation method therefor Download PDFInfo
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- CN105175627A CN105175627A CN201510444392.5A CN201510444392A CN105175627A CN 105175627 A CN105175627 A CN 105175627A CN 201510444392 A CN201510444392 A CN 201510444392A CN 105175627 A CN105175627 A CN 105175627A
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Abstract
The present invention provides a foam-type surfactant polymer used for displacement of reservoir oil and a preparation method therefor. A molecular structure of the foam-type surfactant polymer used for displacement of reservoir oil is FORMULA as shown in the specification. The surfactant polymer used for displacement of reservoir oil has low surface tension, good foaming effect, good tackability, and a high oil recovery rate; besides, the surfactant polymer used for displacement of reservoir oil is good in water solubility, strong in temperature resistance and salt resistance, and suitable for being used as an oil displacement agent for tertiary-recovery development of oilfields.
Description
Technical field
The present invention relates to high molecular polymer oil-displacing agent, particularly relate to a kind of foaming type Surfactant for EOR polymkeric substance and preparation method thereof.
Background technology
At present, China's major part oil field has entered exploitation latter stage, and output has certain decline, because prospecting prime cost increases and difficulty is increasing, so farthest improve recovery ratio, is present stage solve the most direct approach of energy dilemma.
Use polymer flooding to be the approach that agent for improving oilfield recovery is conventional, add polymkeric substance, can increase the viscosity of the aqueous solution in water, adjustment intake profile, increases sweeping phase sweep efficiency, thus improves recovery ratio.In order to can more by crude oil from underground extraction, method relatively more conventional at present uses binary or ternary composite driving, by synergistic effect effective between each component, the viscosity of system can be improved significantly, reduce the tension force of water-oil interface, thus raising recovery ratio, its oil displacement efficiency is more effective than independent polymer flooding, but polymkeric substance binary is driven and ternary composite driving time, because there is migration velocity difference between different components, so chromatographic separation phenomenon can be there is, cause the synergy between different oil-displacing agent to weaken, oil displacement efficiency is deteriorated.
Summary of the invention
The object of the invention is: for the deficiencies in the prior art, foaming type Surfactant for EOR polymkeric substance that a kind of surface tension is lower, foaming effect good, tackifying is good, oil recovery factor is high and preparation method thereof is provided.
In order to achieve the above object, one aspect of the present invention provides a kind of foaming type Surfactant for EOR polymkeric substance, has 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 polymkeric substance, comprises the following steps:
Step one, the mixing solutions of preparation OP emulsifying agent, NaOH or KOH, phase-transfer catalyst and organic solvent, propenyl chloride is dripped under inert protective atmosphere, 12-24h is reacted under 45 DEG C of-70 DEG C of conditions, react rear cooling suction filtration, then underpressure distillation obtains allyl group polyoxyethylene nonylphenol ether monomer, and wherein, the mol ratio of propenyl chloride, OP emulsifying agent, NaOH or KOH and phase-transfer catalyst is 1.5-2:1:1-1.5:0.05;
Step 2, 2-acrylamide-2-methyl propane sulfonic monomer is dissolved in water, add alkali, adjustment pH is 7-8, add allyl group polyoxyethylene nonylphenol ether monomer and acrylamide monomer, control 2-acrylamide-2-methyl propane sulfonic, it is 20 ~ 25wt% that the total monomer quality of allyl group polyoxyethylene nonylphenol ether and acrylamide accounts for mixed solution mass ratio, and acrylamide monomer, the mol ratio of 2-acrylamide-2-methyl propane sulfonic monomer and allyl group polyoxyethylene nonylphenol ether monomer is 100:15 ~ 40:0.2 ~ 2, the initiator accounting for total monomer quality 0.2%-1% is added under inert protective atmosphere, in 25-35 DEG C, after reaction 3-6h, obtain colloidal product, white precipitate is obtained after washing, drying is pulverized, obtain target product.
The invention has the beneficial effects as follows: foaming type Surfactant for EOR polymkeric substance provided by the invention, surface tension is lower, and foaming effect is good, tackifying is good, and oil recovery factor is high, in addition, well water-soluble, temperature resistant antisalt performance is good, is suitable as the oil-displacing agent of three exploitations in oil field.
Accompanying drawing explanation
Fig. 1 is the allyl group polyoxyethylene nonylphenol ether sample of embodiment one gained and the infrared spectrogram of polyoxyethylene nonylphenol ether sample.
Fig. 2 is the infrared spectrogram of the foaming type Surfactant for EOR polymkeric substance of embodiment one gained.
Fig. 3 is the graphic representation of the concentration effects on surface tension force of the foaming type Surfactant for EOR polymkeric substance of embodiment one gained.
Fig. 4 is that the concentration of the foaming type Surfactant for EOR polymkeric substance of embodiment one gained is to the graphic representation of apparent viscosity.
Fig. 5 is the graphic representation of the concentration effects on surface tension force of the foaming type Surfactant for EOR polymkeric substance of embodiment two gained.
Fig. 6 is that the concentration of the foaming type Surfactant for EOR polymkeric substance of embodiment two gained is to the graphic representation of foaming volume.
Embodiment
One aspect of the present invention provides a kind of foaming type Surfactant for EOR polymkeric substance, has 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 polymkeric substance, comprises the following steps:
Step one, the mixing solutions of preparation OP emulsifying agent, NaOH or KOH, phase-transfer catalyst and organic solvent, propenyl chloride is dripped under inert protective atmosphere, 12-24h is reacted under 45 DEG C of-70 DEG C of conditions, react rear cooling suction filtration, then underpressure distillation obtains allyl group polyoxyethylene nonylphenol ether monomer, and wherein, the mol ratio of propenyl chloride, OP emulsifying agent, NaOH or KOH and phase-transfer catalyst is 1.5-2:1:1-1.5:0.05;
Step 2, 2-acrylamide-2-methyl propane sulfonic monomer is dissolved in water, add alkali, adjustment pH is 7-8, add allyl group polyoxyethylene nonylphenol ether monomer and acrylamide monomer, control 2-acrylamide-2-methyl propane sulfonic, it is 20 ~ 25wt% that the total monomer quality of allyl group polyoxyethylene nonylphenol ether and acrylamide accounts for mixed solution mass ratio, and acrylamide monomer, the mol ratio of 2-acrylamide-2-methyl propane sulfonic monomer and allyl group polyoxyethylene nonylphenol ether monomer is 100:15 ~ 40:0.2 ~ 2, the initiator accounting for total monomer quality 0.2%-1% is added under inert protective atmosphere, in 25-35 DEG C, after reaction 3-6h, obtain colloidal product, white precipitate is obtained after washing, drying is pulverized, obtain target product.
Preferably, in described step one, organic solvent is CH
2cl
2, trichloromethane, benzene, toluene, dimethylbenzene, one or more in Virahol.
Preferably, in described step one, OP emulsifying agent is one or more in OP-8, OP-10, OP-15.
Preferably, in described step one, phase-transfer catalyst is one or more in Tetrabutyl amonium bromide, benzyltriethylammoinium chloride, Dodecyl trimethyl ammonium chloride, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate.
Preferably, in described step 2, initiator is ammonium persulphate, the S-WAT of mass ratio=1:1, or the Potassium Persulphate of mass ratio=1:1 and sodium bisulfite.
Below in conjunction with embodiment in detail foaming type Surfactant for EOR polymkeric substance of the present invention and preparation method thereof is described in detail.
Embodiment 1
Step one, allyl group polyoxyethylene nonylphenol ether monomer, i.e. COP, synthesis
Get 0.1molOP-10 emulsifying agent, 0.12molNaOH, 0.05mol Tetrabutyl amonium bromide, 50ml methylene dichloride in there-necked flask, stir and pass into nitrogen 30min, then 0.15mol propenyl chloride is dripped, 12h is reacted under 50 DEG C of conditions, react rear cooling suction filtration, then underpressure distillation obtains allyl group polyoxyethylene nonylphenol ether monomer, i.e. COP-10.
Step 2, the synthesis of foaming type Surfactant for EOR polymkeric substance
By 3.42g2-acrylamide-2-methyl propane sulfonic monomer, i.e. AMPS, is dissolved in 48g distilled water, adds alkali, regulates pH to be 7; 0.77gCOP-10 is added in the AMPS aqueous solution, and 7.81g acrylamide monomer, i.e. AM, stirring and dissolving, passes into nitrogen 30min, adds 0.048g S-WAT and 0.048g ammonium persulphate, and control temperature, at 35 DEG C, adopts water solution polymerization process copolymerization; After reaction 3h, obtain colloidal product, repeatedly wash on a small quantity with ethanol, obtain white depositions, dry and pulverize, obtain surface-active polymer.
The allyl group polyoxyethylene nonylphenol ether sample that the step one that takes a morsel obtains, separately take a morsel polyoxyethylene nonylphenol ether sample, is labeled as respectively 1. and 2., carries out infrared spectrum analysis, obtaining the result shown in Fig. 1.As shown in Figure 1: curve 2. in have 3475cm
-1-OH absorption peak, curve 1. in there is no absorption peak herein, illustrate that the modified-OH of polyoxyethylene nonylphenol ether is replaced by-C=C-double bond.
The surface-active polymer that the step 2 that takes a morsel obtains carries out infrared spectrum analysis, obtains result shown in Fig. 2.As shown in Figure 2,3349.8cm
-1place is the N-H stretching vibration peak of acid amides, 3199.377cm
-1place on phenyl ring=stretching vibration peak of C-H, 2931.66cm
-1place is-CH
2c-H symmetrical stretching vibration peak, 2858.36cm
-1place is-CH
3c-H stretching vibration peak, 1663.14cm
-1place is the C=O stretching vibration peak of acid amides, 1041.389cm
-1place is the C-O stretching vibration peak of ether, 1186.026cm
-1place is-SO
3 -vibration absorption peak, above infrared spectrum analytical results illustrates that subject polymer is synthesized out.
The surface-active polymer surface tension obtained by JK99B type Full-automatic tension instrument determination step two, result as shown in Figure 3.
Apparent viscosity is by the BROOKFIELD III type viscometer determining of Brookfield company of the U.S., and result as shown in Figure 4.
The oil displacement efficiency of polymkeric substance: surface-active polymer step 2 obtained is mixed with the solution that concentration is 0.2% is 30cm in length, and diameter is 2.5cm, and rate of permeation is 50 × 10
-3μm
2rock core on carry out imitation oil displacement experiment experiment.First be driven to moisture 93%, saturated crude oil with Shengli Oil Field G89 block local water, continue water drive, the recovery ratio recording water drive is 38.53%, and inject the surface-active polymer of 0.3PV, water drive can improve oil recovery factor 15.6% again, and result is as shown in table 1.
Embodiment 2
Step one, allyl group polyoxyethylene nonylphenol ether monomer, i.e. COP, synthesis
Get 0.1molOP-10 emulsifying agent, 0.15molNaOH, 0.05mol tetrabutylammonium chloride, 40ml methylene dichloride in there-necked flask, stir and pass into nitrogen 30min, then 0.2mol propenyl chloride is dripped, 10h is reacted under 50 DEG C of conditions, react rear cooling suction filtration, then underpressure distillation obtains allyl group polyoxyethylene nonylphenol ether monomer, i.e. COP-10.
Step 2, the synthesis of foaming type Surfactant for EOR polymkeric substance
3.51gAMPS is dissolved in 48g distilled water, adds alkali, regulate pH to be 7; 0.47g allyl group polyoxyethylene nonylphenol ether monomer and 8.02g acrylamide monomer is added in the AMPS aqueous solution, stirring and dissolving, passes into nitrogen 30min, adds 0.06g S-WAT and 0.06g ammonium persulphate, control temperature, at 30 DEG C, adopts water solution polymerization process copolymerization; After reaction 4h, obtain colloidal product, repeatedly wash on a small quantity with ethanol, obtain white depositions, dry and pulverize, obtain surface-active polymer.
The surface-active polymer surface tension obtained by JK99B type Full-automatic tension instrument determination step two, result as shown in Figure 5.
Foaming volume tested by self-control foaming instrument, and namely under normal temperature condition, pass into gas in solution, the flow velocity of gas is 400ml/min, and ventilation 2min, can obtain experimental result, as shown in Figure 6.
The oil displacement efficiency of polymkeric substance: surface-active polymer step 2 obtained is mixed with the solution that concentration is 0.2% is 30cm in length, and diameter is 2.5cm, and rate of permeation is 45 × 10
-3μm
2rock core on carry out imitation oil displacement experiment experiment.First be driven to moisture 93%, saturated crude oil with Shengli Oil Field G89 block local water, continue water drive, the recovery ratio recording water drive is 40.03%, and inject the surface-active polymer of 0.3PV, water drive can improve oil recovery factor 15.2% again, and result is as shown in table 1.
Embodiment 3
Step one, allyl group polyoxyethylene nonylphenol ether monomer, i.e. COP, synthesis
Get 0.1molOP-15 emulsifying agent, 0.15molNaOH, 0.05mol Tetrabutyl amonium bromide, 50ml methylene dichloride in there-necked flask, stir and pass into nitrogen 30min, then 0.15mol propenyl chloride is dripped, 10h is reacted under 50 DEG C of conditions, react rear cooling suction filtration, then underpressure distillation obtains allyl group polyoxyethylene nonylphenol ether monomer, i.e. COP-15.
Step 2, the synthesis of foaming type Surfactant for EOR polymkeric substance
3.46gAMPS is dissolved in 48g distilled water, adds alkali, regulate pH to be 7; 0.63g allyl group polyoxyethylene nonylphenol ether monomer and 7.91g acrylamide monomer is added in the AMPS aqueous solution, stirring and dissolving, passes into nitrogen 30min, adds 0.06g S-WAT and 0.06g ammonium persulphate, control temperature, at 35 DEG C, adopts water solution polymerization process copolymerization; After reaction 4h, obtain colloidal product, repeatedly wash on a small quantity with ethanol, obtain white depositions, dry and pulverize, obtain surface-active polymer.
The oil displacement efficiency of polymkeric substance: surface-active polymer step 2 obtained is mixed with the solution that concentration is 0.2% is 30cm in length, and diameter is 2.5cm, and rate of permeation is 58 × 10
-3μm
2rock core on carry out imitation oil displacement experiment experiment.First be driven to moisture 93%, saturated crude oil with Shengli Oil Field G89 block local water, continue water drive, the recovery ratio recording water drive is 39.25%, and inject the surface-active polymer of 0.3PV, water drive can improve oil recovery factor 14.92% again, and result is as shown in table 1.
Embodiment 4
Step one, allyl group polyoxyethylene nonylphenol ether monomer, i.e. COP, synthesis
Get 0.1molOP-8 emulsifying agent, 0.12molNaOH, 0.05mol Tetrabutyl amonium bromide, 50ml methylene dichloride in there-necked flask, stir and pass into nitrogen 30min, then 0.15mol propenyl chloride is dripped, 12h is reacted under 50 DEG C of conditions, react rear cooling suction filtration, then underpressure distillation obtains allyl group polyoxyethylene nonylphenol ether monomer, i.e. COP-8.
Step 2, the synthesis of foaming type Surfactant for EOR polymkeric substance
By 3.42g2-acrylamide-2-methyl propane sulfonic monomer, i.e. AMPS, is dissolved in 48g distilled water, adds alkali, regulates pH to be 7; 0.154gCOP-8 is added in the AMPS aqueous solution, and 7.81g acrylamide monomer, i.e. AM, stirring and dissolving, passes into nitrogen 30min, adds 0.048g S-WAT and 0.048g ammonium persulphate, and control temperature, at 35 DEG C, adopts water solution polymerization process copolymerization; After reaction 3h, obtain colloidal product, repeatedly wash on a small quantity with ethanol, obtain white depositions, dry and pulverize, obtain surface-active polymer.
Embodiment 5
Step one, allyl group polyoxyethylene nonylphenol ether monomer, i.e. COP, synthesis
Get 0.1molOP-8 emulsifying agent, 0.12molKOH, 0.05mol Tetrabutyl amonium bromide, 50ml methylene dichloride in there-necked flask, stir and pass into nitrogen 30min, then 0.15mol propenyl chloride is dripped, 12h is reacted under 50 DEG C of conditions, react rear cooling suction filtration, then underpressure distillation obtains allyl group polyoxyethylene nonylphenol ether monomer, i.e. COP-8.
Step 2, the synthesis of foaming type Surfactant for EOR polymkeric substance
By 9.12g2-acrylamide-2-methyl propane sulfonic monomer, i.e. AMPS, is dissolved in 48g distilled water, adds alkali, regulates pH to be 7; 1.54gCOP-8 is added in the AMPS aqueous solution, and 7.81g acrylamide monomer, i.e. AM, stirring and dissolving, passes into nitrogen 30min, adds 0.048g S-WAT and 0.048g ammonium persulphate, and control temperature, at 35 DEG C, adopts water solution polymerization process copolymerization; After reaction 3h, obtain colloidal product, repeatedly wash on a small quantity with ethanol, obtain white depositions, dry and pulverize, obtain surface-active polymer.
The different polymer flooding experimental result 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, adopt foaming type Surfactant for EOR polymkeric substance of the present invention, surface tension is lower, and foaming effect is good, and tackifying is good, and oil recovery factor can improve more than 15%.
Claims (6)
1. a foaming type Surfactant for EOR polymkeric substance, has following molecular structure:
In formula, x:y:z=100:15 ~ 40:0.2 ~ 2, n=8 ~ 15.
2. a preparation method for foaming type Surfactant for EOR polymkeric substance, comprises the following steps:
Step one, the mixing solutions of preparation OP emulsifying agent, NaOH or KOH, phase-transfer catalyst and organic solvent, propenyl chloride is dripped under inert protective atmosphere, 12-24h is reacted under 45 DEG C of-70 DEG C of conditions, react rear cooling suction filtration, then underpressure distillation obtains allyl group polyoxyethylene nonylphenol ether monomer, and wherein, the mol ratio of propenyl chloride, OP emulsifying agent, NaOH or KOH and phase-transfer catalyst is 1.5-2:1:1-1.5:0.05;
Step 2, 2-acrylamide-2-methyl propane sulfonic monomer is dissolved in water, add alkali, adjustment pH is 7-8, add allyl group polyoxyethylene nonylphenol ether monomer and acrylamide monomer, control 2-acrylamide-2-methyl propane sulfonic, it is 20 ~ 25wt% that the total monomer quality of allyl group polyoxyethylene nonylphenol ether and acrylamide accounts for mixed solution mass ratio, and acrylamide monomer, the mol ratio of 2-acrylamide-2-methyl propane sulfonic monomer and allyl group polyoxyethylene nonylphenol ether monomer is 100:15 ~ 40:0.2 ~ 2, the initiator accounting for total monomer quality 0.2%-1% is added under inert protective atmosphere, in 25-35 DEG C, after reaction 3-6h, obtain colloidal product, white precipitate is obtained after washing, drying is pulverized, obtain target product.
3. the preparation method of foaming type Surfactant for EOR polymkeric substance as claimed in claim 2, it is characterized in that: in described step one, organic solvent is CH
2cl
2, trichloromethane, benzene, toluene, dimethylbenzene, one or more in Virahol.
4. the preparation method of foaming type Surfactant for EOR polymkeric substance as claimed in claim 2, is characterized in that: in described step one, and OP emulsifying agent is one or more in OP-8, OP-10, OP-15.
5. the preparation method of foaming type Surfactant for EOR polymkeric substance as claimed in claim 2, it is characterized in that: in described step one, phase-transfer catalyst is one or more in Tetrabutyl amonium bromide, benzyltriethylammoinium chloride, Dodecyl trimethyl ammonium chloride, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate.
6. the preparation method of foaming type Surfactant for EOR polymkeric substance as claimed in claim 2, it is characterized in that: in described step 2, initiator is ammonium persulphate, the S-WAT of mass ratio=1:1, or the Potassium Persulphate of mass ratio=1:1 and sodium bisulfite.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110734526A (en) * | 2019-10-09 | 2020-01-31 | 中国石油天然气股份有限公司 | Preparation method and application of double-braid polymer surfactants containing long carbon chains |
| CN116064019A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Oil displacement composition and preparation method and application thereof |
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| CN116064019A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Oil displacement composition and preparation method and application thereof |
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