CN117720684B - Amphoteric polymer and preparation method and application thereof - Google Patents
Amphoteric polymer and preparation method and application thereof Download PDFInfo
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- CN117720684B CN117720684B CN202410177914.9A CN202410177914A CN117720684B CN 117720684 B CN117720684 B CN 117720684B CN 202410177914 A CN202410177914 A CN 202410177914A CN 117720684 B CN117720684 B CN 117720684B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- -1 2-acrylamide-2-methylpropanesulfonic acid sodium salt Chemical class 0.000 claims abstract description 42
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229940117986 sulfobetaine Drugs 0.000 claims abstract description 31
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 29
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 29
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 29
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 19
- 239000003999 initiator Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 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 description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 238000011084 recovery Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 4
- FWFUWXVFYKCSQA-UHFFFAOYSA-M sodium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C FWFUWXVFYKCSQA-UHFFFAOYSA-M 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 125000001204 arachidyl 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])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])[H] 0.000 claims description 2
- 125000002511 behenyl 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])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])C([H])([H])[H] 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 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 claims description 2
- 125000001421 myristyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000913 palmityl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004079 stearyl 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])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])[H] 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000004094 surface-active agent Substances 0.000 abstract description 4
- 238000013375 chromatographic separation Methods 0.000 abstract description 3
- 239000003208 petroleum Substances 0.000 abstract description 3
- 238000004391 petroleum recovery Methods 0.000 abstract description 3
- 229910002056 binary alloy Inorganic materials 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 239000003921 oil Substances 0.000 description 13
- 230000001105 regulatory effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical group C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 5
- 229960003237 betaine Drugs 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- OPRIWFSSXKQMPB-UHFFFAOYSA-N 2-methyl-2-(prop-2-enoylamino)propane-1-sulfonic acid;sodium Chemical compound [Na].OS(=O)(=O)CC(C)(C)NC(=O)C=C OPRIWFSSXKQMPB-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000002463 lignoceryl 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])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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The application discloses an amphoteric polymer and a preparation method and application thereof, and belongs to the technical field of petroleum exploitation chemicals. The polymer is prepared from acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid sodium salt and alkyl diallyl hydroxypropyl sulfobetaine according to a molar ratio of 6-8:1.8-3.8:0.5-1: 0.3-1. The polymer prepared by the application can increase the viscosity of water phase, reduce the tension of oil-water interface, overcome the chromatographic separation effect of a polymer/surfactant binary system in the prior art, and improve the petroleum recovery ratio; the water solubility is good, and the temperature resistance and the salt resistance are good; can also be used as flocculant in sewage treatment.
Description
Technical Field
The application belongs to the technical field of petroleum exploitation chemicals, and particularly relates to an amphoteric polymer and a preparation method and application thereof.
Background
The recovery ratio of the water-flooding reservoir is generally only 25-40%, a large amount of ascertained petroleum resources cannot be effectively exploited and utilized, chemical oil extraction is an important means for improving the recovery ratio, and the recovery ratio can be improved by 15-25% on the basis of water flooding. The partially hydrolyzed polyacrylamide and the surfactant are main chemicals used in chemical oil extraction, the polymer has the functions of increasing the viscosity of an aqueous phase, expanding the swept volume, reducing the interfacial tension of oil and water, improving the oil displacement efficiency, and realizing the purpose of improving the recovery ratio through the synergistic effect. However, the difference of adsorption and hydrodynamic retention in oil layers causes different migration speeds, so that chromatographic separation is generated, the synergistic effect is lost, and the oil displacement effect is affected. The above problems can be solved by synthesizing the polymer and the surfactant on the same molecule.
Disclosure of Invention
In order to solve the problems, an amphoteric polymer is provided, which can overcome the chromatographic separation effect of a polymer/surfactant binary system in the prior art and improve the petroleum recovery ratio; greatly reduces the interfacial tension of oil and water, and increases the viscosity of water phase; the water solubility is good, and the temperature resistance and the salt resistance are good; can also be used as flocculant in sewage treatment.
The specific technical scheme of the application is as follows:
in one aspect, the application provides an amphoteric polymer, wherein the molecular structural formula of the polymer is shown as formula I:
formula (I)
In the formula I, R is any one of C6H13、C8H17、C10H21、C12H25、C14H29、C16H33、C18H37、C20H41、C22H45、C24H49.
In another aspect, the present application also provides a method for preparing an amphoteric polymer, comprising the steps of:
firstly, weighing acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid sodium and alkyl diallyl hydroxypropyl sulfobetaine, adding deionized water for dissolution, and adjusting the pH value to 7-10 by alkali solution;
Step two, introducing nitrogen for 8-12min at 40-80 ℃, adding an initiator, and reacting for 2-5h to obtain a product;
and thirdly, washing, crushing and drying the product by using absolute ethyl alcohol to obtain the amphoteric polymer.
Optionally, in the first step, the mass percentage of the acrylamide is 60-80%, the mass percentage of the acrylic acid is 18-38%, the mass percentage of the 2-acrylamido-2-methylpropanesulfonic acid sodium is 2-10%, and the mass percentage of the alkyl diallyl hydroxypropyl sulfobetaine is 0.3-1.0%; preferably, 6.5 to 7.5:1.5-3.5:0.6-0.8:0.4-0.8.
Optionally, in the second step, the initiator is any one of azodiisobutylamidine hydrochloride and dibenzoyl peroxide, and is preferably azodiisobutylamidine hydrochloride.
Optionally, in the second step, the addition amount of the initiator is 0.3-1.0% of the total mass of the acrylamide, the acrylic acid, the 2-acrylamide-2-methylpropanesulfonic acid sodium salt and the alkyl diallyl hydroxypropyl sulfobetaine monomer.
In another aspect, the application also provides the following applications:
The application of the amphoteric polymer in oil reservoir recovery.
The preparation method is applied to the improvement of the oil reservoir recovery ratio.
The beneficial effects of the application include, but are not limited to:
1. The amphoteric polymer prepared by the application is introduced with groups such as amide, carboxylic acid, hydroxypropyl sulfo and the like, has stronger hydration capability, and has better water solubility.
2. The amphoteric polymer prepared by the application is introduced with the zwitterionic group, so that the effect of electrolyte in the prepared water can be shielded, and the molecular chain is more stretched, thereby showing better salt resistance.
3. The amphoteric polymer prepared by the application introduces betaine structure monomer, can greatly reduce oil-water interfacial tension and improve oil displacement efficiency.
4. The polymer provided by the application has good water solubility, temperature resistance, salt resistance and shearing resistance, can greatly reduce the interfacial tension of oil and water, and can better improve the oil recovery rate by 18%. Has wide market prospect.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
The starting materials and catalysts in the examples of the present application were purchased commercially, unless otherwise specified.
Example 1
An amphoteric polymer, the molecular structural formula of which is shown in formula I:
formula (I);
In the formula I, R is C 24H49; x: Y: Z: q=6: 2.8:0.5:0.7;
A method for preparing the amphoteric polymer, which comprises the following steps: the method comprises the following steps:
Step one, a molar ratio of 6:2.8:0.5:0.7, weighing acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid sodium salt and alkyl diallyl hydroxypropyl sulfobetaine, dissolving with deionized water, and regulating the pH to 7 with 5% NaOH solution;
Step two, introducing nitrogen for 8min at 60 ℃, adding azo diisobutylamidine hydrochloride, and reacting for 2h to obtain a product; the addition amount of the initiator is 0.3 percent of the total mass of the acrylamide, the acrylic acid, the 2-acrylamide-2-methylpropanesulfonic acid sodium and the alkyl diallyl hydroxypropyl sulfobetaine monomer in the first step;
and thirdly, washing, crushing and drying the product by using absolute ethyl alcohol to obtain the amphoteric polymer.
The reaction formula of the preparation process is as follows:
Formula (II).
Example 2
An amphoteric polymer, the molecular structural formula of which is shown in formula I, wherein R is C 22H45; x: Y: Z: q=6: 2.8:0.5:0.7.
Step one, a molar ratio of 6:2.8:0.5:0.7, weighing acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid sodium salt and alkyl diallyl hydroxypropyl sulfobetaine, dissolving with deionized water, and regulating the pH to 7 with 5% NaOH solution;
Step two, introducing nitrogen for 8min at 60 ℃, adding azo diisobutylamidine hydrochloride, and reacting for 2h to obtain a product; the addition amount of the initiator is 0.3 percent of the total mass of the acrylamide, the acrylic acid, the 2-acrylamide-2-methylpropanesulfonic acid sodium and the alkyl diallyl hydroxypropyl sulfobetaine monomer in the first step;
and thirdly, washing, crushing and drying the product by using absolute ethyl alcohol to obtain the amphoteric polymer.
Example 3
An amphoteric polymer, the molecular structural formula of which is shown in formula I, wherein R is C 20H41; x: Y: Z: q=6: 2.8:0.5:0.7.
Step one, a molar ratio of 6:2.8:0.5:0.7, weighing acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid sodium salt and alkyl diallyl hydroxypropyl sulfobetaine, dissolving with deionized water, and regulating the pH to 7 with 5% NaOH solution;
Step two, introducing nitrogen for 8min at 60 ℃, adding azo diisobutylamidine hydrochloride, and reacting for 2h to obtain a product; the addition amount of the initiator is 0.3 percent of the total mass of the acrylamide, the acrylic acid, the 2-acrylamide-2-methylpropanesulfonic acid sodium and the alkyl diallyl hydroxypropyl sulfobetaine monomer in the first step;
and thirdly, washing, crushing and drying the product by using absolute ethyl alcohol to obtain the amphoteric polymer.
Example 4
An amphoteric polymer, the molecular structural formula of which is shown in formula I, wherein R is C 18H37; x: Y: Z: q=6: 2.8:0.5:0.7.
Step one, a molar ratio of 6:2.8:0.5:0.7, weighing acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid sodium salt and alkyl diallyl hydroxypropyl sulfobetaine, dissolving with deionized water, and regulating the pH to 7 with 5% NaOH solution;
Step two, introducing nitrogen for 8min at 60 ℃, adding azo diisobutylamidine hydrochloride, and reacting for 2h to obtain a product; the addition amount of the initiator is 0.3 percent of the total mass of the acrylamide, the acrylic acid, the 2-acrylamide-2-methylpropanesulfonic acid sodium and the alkyl diallyl hydroxypropyl sulfobetaine monomer in the first step;
and thirdly, washing, crushing and drying the product by using absolute ethyl alcohol to obtain the amphoteric polymer.
Example 5
An amphoteric polymer, the molecular structural formula of which is shown in formula I, wherein R is C 16H33; x: Y: Z: q=6: 2.8:0.5:0.7.
Step one, a molar ratio of 6:2.8:0.5:0.7, weighing acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid sodium salt and alkyl diallyl hydroxypropyl sulfobetaine, dissolving with deionized water, and regulating the pH to 7 with 5% NaOH solution;
Step two, introducing nitrogen for 8min at 60 ℃, adding azo diisobutylamidine hydrochloride, and reacting for 2h to obtain a product; the addition amount of the initiator is 0.3 percent of the total mass of the acrylamide, the acrylic acid, the 2-acrylamide-2-methylpropanesulfonic acid sodium and the alkyl diallyl hydroxypropyl sulfobetaine monomer in the first step;
and thirdly, washing, crushing and drying the product by using absolute ethyl alcohol to obtain the amphoteric polymer.
Example 6
An amphoteric polymer, the molecular structural formula of which is shown in formula I, wherein R is C 14H29; x: Y: Z: q=6: 2.8:0.5:0.7.
Step one, a molar ratio of 6:2.8:0.5:0.7, weighing acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid sodium salt and alkyl diallyl hydroxypropyl sulfobetaine, dissolving with deionized water, and regulating the pH to 7 with 5% NaOH solution;
Step two, introducing nitrogen for 8min at 60 ℃, adding azo diisobutylamidine hydrochloride, and reacting for 2h to obtain a product; the addition amount of the initiator is 0.3 percent of the total mass of the acrylamide, the acrylic acid, the 2-acrylamide-2-methylpropanesulfonic acid sodium and the alkyl diallyl hydroxypropyl sulfobetaine monomer in the first step;
and thirdly, washing, crushing and drying the product by using absolute ethyl alcohol to obtain the amphoteric polymer.
Example 7
An amphoteric polymer, the molecular structural formula of which is shown in formula I, wherein R is C 12H25; x: Y: Z: q=6: 2.8:0.5:0.7.
Step one, a molar ratio of 6:2.8:0.5:0.7, weighing acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid sodium salt and alkyl diallyl hydroxypropyl sulfobetaine, dissolving with deionized water, and regulating the pH to 7 with 5% NaOH solution;
Step two, introducing nitrogen for 8min at 60 ℃, adding azo diisobutylamidine hydrochloride, and reacting for 2h to obtain a product; the addition amount of the initiator is 0.3 percent of the total mass of the acrylamide, the acrylic acid, the 2-acrylamide-2-methylpropanesulfonic acid sodium and the alkyl diallyl hydroxypropyl sulfobetaine monomer in the first step;
and thirdly, washing, crushing and drying the product by using absolute ethyl alcohol to obtain the amphoteric polymer.
Example 8
An amphoteric polymer, the molecular structural formula of which is shown in formula I, wherein R is C 10H21; x: Y: Z: q=6: 2.8:0.5:0.7.
Step one, a molar ratio of 6:2.8:0.5:0.7, weighing acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid sodium salt and alkyl diallyl hydroxypropyl sulfobetaine, dissolving with deionized water, and regulating the pH to 7 with 5% NaOH solution;
Step two, introducing nitrogen for 8min at 60 ℃, adding azo diisobutylamidine hydrochloride, and reacting for 2h to obtain a product; the addition amount of the initiator is 0.3 percent of the total mass of the acrylamide, the acrylic acid, the 2-acrylamide-2-methylpropanesulfonic acid sodium and the alkyl diallyl hydroxypropyl sulfobetaine monomer in the first step;
and thirdly, washing, crushing and drying the product by using absolute ethyl alcohol to obtain the amphoteric polymer.
Example 9
An amphoteric polymer, the molecular structural formula of which is shown in formula I, wherein R is C 8H17; x: Y: Z: q=6: 2.8:0.5:0.7.
Step one, a molar ratio of 6:2.8:0.5:0.7, weighing acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid sodium salt and alkyl diallyl hydroxypropyl sulfobetaine, dissolving with deionized water, and regulating the pH to 7 with 5% NaOH solution;
Step two, introducing nitrogen for 8min at 60 ℃, adding azo diisobutylamidine hydrochloride, and reacting for 2h to obtain a product; the addition amount of the initiator is 0.3 percent of the total mass of the acrylamide, the acrylic acid, the 2-acrylamide-2-methylpropanesulfonic acid sodium and the alkyl diallyl hydroxypropyl sulfobetaine monomer in the first step;
and thirdly, washing, crushing and drying the product by using absolute ethyl alcohol to obtain the amphoteric polymer.
Example 10
An amphoteric polymer, the molecular structural formula of which is shown in formula I, wherein R is C 6H13; x: Y: Z: q=6: 2.8:0.5:0.7.
Step one, a molar ratio of 6:2.8:0.5:0.7, weighing acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid sodium salt and alkyl diallyl hydroxypropyl sulfobetaine, dissolving with deionized water, and regulating the pH to 7 with 5% NaOH solution;
Step two, introducing nitrogen for 8min at 60 ℃, adding azo diisobutylamidine hydrochloride, and reacting for 2h to obtain a product; the addition amount of the initiator is 0.3 percent of the total mass of the acrylamide, the acrylic acid, the 2-acrylamide-2-methylpropanesulfonic acid sodium and the alkyl diallyl hydroxypropyl sulfobetaine monomer in the first step;
and thirdly, washing, crushing and drying the product by using absolute ethyl alcohol to obtain the amphoteric polymer.
Example 11
An ampholytic polymer differs from example 2 in that in the molecular structural formula of the polymer, R is C 4H9; x: Y: Z: q=6: 2.8:0.5:0.7.
Example 12
The difference from example 2 is that the starting materials in this example are, in molar ratio, acrylamide: acrylic acid: sodium 2-acrylamido-2-methylpropanesulfonate: alkyl diallyl hydroxypropyl sulfobetaine = 6.2:2.5:0.5:0.8.
Comparative example 1, using one polymer of the prior art in reservoir recovery; the polymer was free of betaine monomer compared to the polymer prepared in example 2.
Formula (III).
Comparative example 2, using one polymer of the prior art in reservoir recovery; the polymer used was structurally different from the polymer prepared in example 2, and did not contain long hydrophobic chains R. The structural formula of betaine monomer used in the comparative example is specifically shown in a formula (I) in a [0007] section of CN 107739422A.
Comparative example 3
The sulfobetaine type amphoteric ion polymer in the prior art is applied to oil reservoir collection; as shown in formula (IV), the polymer used has a different betaine monomer structure than the polymer prepared in example 2, and does not contain a long hydrophobic chain R. (see, sulfobetaine type zwitterionic polymer synthesis and performance study-Mao Cheng).
Formula (IV).
The polymers of examples 1 to 11 and comparative examples 1 to 3 were examined for interfacial tension, dissolution property and salt resistance, respectively, in petroleum recovery; the specific detection method comprises the following steps:
water solubility: the target block was injected with water to prepare a 0.15% polymer solution, which was stirred at 40 ℃ at 700rpm, and the time of complete dissolution was observed and recorded, and if the solution was uniform and free of fish eyes within 2 hours, it was judged that the solubility was good, otherwise the solubility was poor.
Interfacial tension: a0.15% polymer solution 100 g was prepared with a 1% NaCl solution and the interfacial tension was measured at 70℃using a rotary drop interfacial tensiometer according to the SY/T5370-1999 assay.
Salt resistance: a solution containing 1% NaCl and 2+ mg/L Ca was prepared, a 0.15% polymer solution 100 g was prepared from this water, and the interfacial tension was measured, and if the interfacial tension was kept at the same order of magnitude as that of the solution prepared with no Ca 2+ added, it was judged that the salt resistance was good, otherwise it was judged that the salt resistance was poor.
Apparent viscosity: a0.15% polymer solution was prepared with a 1% NaCl solution and the apparent viscosity was measured at 70℃using a DV-III type rotational viscometer with a 0# spindle.
The crude oil in the experiment was taken from the western region of the island field.
The results of the measurements are shown in Table 1 below.
TABLE 1 comparison of the Properties of the different polymers
As can be seen from the data in the table, in example 1 and example 11, when the hydrophobic chain length R of betaine monomer in the polymer exceeds 22, the solubility is poor, and other data cannot be measured; when R is less than 6, there is no significant advantage in interfacial tension, salt resistance and apparent viscosity as compared with the comparative example; in examples 2-10, the R value is reduced from 22 to 6, the solubility is good, the salt resistance is good, and the interfacial tension can be reduced to the order of magnitude of 10-2mN/m when the R value is between 12 and 20; as the R value decreases, the apparent viscosity decreases because long carbon chains can form an associated structure, increasing the unstructured viscosity; in example 12, apparent viscosity increased due to increased betaine monomer content; in 3 comparative examples, the solubility and the salt resistance are both good, and the effect of reducing the interfacial tension is poor because the long carbon chain is not contained, and the interfacial tension is high; meanwhile, the apparent viscosity is low because an association structure cannot be formed.
The above description is only an example of the present application, and the scope of the present application is not limited to the specific examples, but is defined by the claims of the present application. Various modifications and variations of the present application will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.
Claims (7)
1. An ampholytic polymer, which is characterized in that the molecular structural formula of the polymer is shown as formula I:
In the formula I, R is any one of C6H13、C8H17、C10H21、C12H25、C14H29、C16H33、C18H37、C20H41、C22H45; x, Y, Z and Q are 6-8:1.8-3.8:0.5-1:0.3-1, and the molecular weight of the polymer is 600-1500 ten thousand.
2. A method of preparing the amphoteric polymer of claim 1, comprising the steps of:
Firstly, weighing acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid sodium and alkyl diallyl hydroxypropyl sulfobetaine, adding into deionized water for dissolution, and adjusting the pH to 7-10 with alkali solution;
Step two, introducing nitrogen for 8-12min at 40-80 ℃, adding an initiator, and reacting for 2-5h to obtain a product;
and thirdly, washing, crushing and drying the product by using absolute ethyl alcohol to obtain the amphoteric polymer.
3. The method according to claim 2, wherein in the first step, the addition amount of acrylamide, acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid sodium salt, alkyl diallyl hydroxypropyl sulfobetaine is 6-8:1.8-3.8:0.5-1:0.3-1.
4. The method according to claim 2, wherein in the second step, the initiator is any one of azobisisobutyrimidine hydrochloride and dibenzoyl peroxide.
5. The preparation method according to claim 2, wherein in the second step, the addition amount of the initiator is 0.3-1.0% of the total mass of acrylamide, acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid sodium salt and alkyl diallyl hydroxypropyl sulfobetaine monomer.
6. The preparation method according to claim 2, wherein in the second step, the addition amount of the initiator is 0.3-0.85% of the total mass of acrylamide, acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid sodium salt and alkyl diallyl hydroxypropyl sulfobetaine monomer.
7. Use of the amphiphilic polymer of claim 1 in oil reservoir recovery.
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| CN107739422A (en) * | 2017-06-05 | 2018-02-27 | 西南石油大学 | A kind of betaine type amphoteric ionomer oil displacement agent and synthetic method |
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