CN117659275A - Active polymer and preparation method and application thereof - Google Patents
Active polymer and preparation method and application thereof Download PDFInfo
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- CN117659275A CN117659275A CN202211054867.6A CN202211054867A CN117659275A CN 117659275 A CN117659275 A CN 117659275A CN 202211054867 A CN202211054867 A CN 202211054867A CN 117659275 A CN117659275 A CN 117659275A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims abstract description 21
- -1 acrylic ester Chemical class 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 24
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 230000001376 precipitating effect Effects 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- 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
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000010 aprotic solvent Substances 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 65
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 27
- 230000001603 reducing effect Effects 0.000 description 21
- 239000000047 product Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 230000009467 reduction Effects 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000000295 fuel oil Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000004945 emulsification Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000033558 biomineral tissue development Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 229940087101 dibenzylidene sorbitol Drugs 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- ARZADRIAOMWMOJ-UHFFFAOYSA-M dodecyl-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CCOC(=O)C(C)=C ARZADRIAOMWMOJ-UHFFFAOYSA-M 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000005089 fruit drop Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XZHNPVKXBNDGJD-UHFFFAOYSA-N tetradecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C=C XZHNPVKXBNDGJD-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses an active polymer and a preparation method and application thereof. The active polymer is prepared by dissolving N-acryloylmorpholine, alkyl acrylate/acrylic ester in a solvent and then carrying out free radical copolymerization reaction. The preparation method of the active polymer is simple and only needs one-step synthesis. The active polymer can be used in the field of thick oil exploitation and gathering and transportation, and can obviously reduce the viscosity of thick oil, especially high acid value thick oil, improve the fluidity of thick oil and reduce the exploitation or gathering and transportation cost of thick oil.
Description
Technical Field
The invention belongs to the technical field of heavy oil exploitation and gathering and transportation, and particularly relates to an active polymer and a preparation method and application thereof.
Background
The thick oil has high viscosity and poor fluidity, and the root cause is that polar components such as colloid asphaltene in the thick oil form a super-resolution large conjugated system through hydrogen bonds and large pi bonds, especially the thick oil with higher acid value, polar functional groups such as hydroxyl groups, carboxyl groups, amino groups and the like in the components are easy to form hydrogen bonds, so that the viscosity of the thick oil is increased sharply. For the thick oil containing wax, the wax crystal bone coating effect precipitated at low temperature makes the thick oil flow become extremely difficult. Increasing the difficulty of exploitation and gathering. At present, the viscosity reduction mode of the thick oil mainly comprises heating, thin oil doping and chemical viscosity reduction, and other thick oil adopts a microbial viscosity reduction or ultrasonic microwave and other unconventional viscosity reduction methods. The emulsification viscosity reduction method has the advantages of small dosage, simple process and controllable cost, and is widely applied to the fields of thickened oil exploitation and gathering and transportation. The difference of the components of the thickened oil in different oil fields and even different blocks of the same oil field leads to stronger selectivity of the viscosity reducing agent, and specific emulsification viscosity reducing agent needs to be developed aiming at specific thickened oil.
The conventional emulsification viscosity reducing agent in oil fields at present mainly comprises anionic, nonionic and anionic-nonionic surfactants and their compounds, and although the surfactants have better emulsification viscosity reducing performance in specific thickened oil, different problems still exist in practical application, such as: the pertinence is strong, and the viscosity reducing effect is poor for specific thickened oil and other block thickened oil, especially acid thickened oil. Patent CN107365574A discloses a viscosity reducing system compounded by alkyl alcohol polyoxyethylene ether sulfate, nonionic surfactant, organic solvent and polyacrylamide, which is used for viscosity reducing and oil displacement of common heavy oil reservoirs, and the viscosity reducing rate is more than 90% when the using concentration is 0.3% -0.5%; patent CN107033866A proposes that sodium hydroxide, alkylphenol ethoxylate, n-alcohol and dibenzylidene sorbitol may be used in stratum water with high mineralization degree and viscosity reducing rate of thick oil up to 98%. Patent CN110396401 discloses a surfactant composed of alkylphenol ethoxylate sulfate or fatty alcohol ethoxylate sulfate type anion-nonionic surfactant, alkali and other auxiliary agents, which is mainly suitable for the emulsification and viscosity reduction of extra thick oil and super thick oil with higher colloid content. The emulsified viscosity reducing agent is mainly used for reducing viscosity of conventional thickened oil, has less application to high-acid and high-viscosity thickened oil, and is easy to cause scale blockage due to the fact that inorganic alkali with higher concentration is often added in the use process.
Aiming at the physical properties, the application range and the shortages of small molecular surface active viscosity reducing agents of thick oil, the development of active polymer viscosity reducing agents and the application of the active polymer viscosity reducing agents to the viscosity reduction of thick oil are important in research in recent years. CN110041462a invented an amphiphilic high molecular thickened oil viscosity reducing agent, which can reduce the thickened oil viscosity by more than 98% at 200ppm of use concentration. CN108546315 adopts acrylamide, alkali metal acrylate, dimethyl diallyl ammonium chloride, methacryloxyethyl dimethyl dodecyl ammonium bromide and two amphiphilic dendritic unsaturated monomers with specific structures to prepare a living polymer, so that the viscosity of a test oil sample can be reduced. Patent CN109679639 discloses a viscous oil viscosity reducing agent composed of quaternary oligomer AM-SA-PB-AMPSNa, which is used for reducing viscosity of extra viscous oil. The active polymer viscosity reducer disclosed in the patent has better viscosity reducing performance in test oil, but is not used for reducing viscosity of acidic thickened oil. CN108570315 discloses an imidazoline/imidazoline derivative acidified viscous oil viscosity-reducing agent which is used for reducing viscosity of the thickened oil of a tower river, wherein the viscosity-reducing rate is 5-90%, the viscosity of an oil sample after viscosity reduction is 2500 mPa.S-51000 mPa.S, and the residual viscosity is still very high.
In general, development and application of active polymer type viscosity reducing agents for thick oils with high acid value, high colloid and asphaltene content are less necessary to further develop viscosity reducing agents for reducing the viscosity of thick oils, especially acidic thick oils and improving the fluidity of acidic thick oils.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention provides, in a first aspect, an active polymer for reducing the viscosity of a thick oil, in particular an acidic thick oil, and improving the flowability of the acidic thick oil.
In a second aspect, the invention also provides a method for synthesizing the living polymer.
In a third aspect, the present invention provides a viscosity reducing agent composition.
In a fourth aspect, the present invention provides an application of a living polymer for reducing the viscosity of heavy oil, especially acidic heavy oil, improving the flowability of heavy oil, and reducing the recovery and gathering costs of heavy oil. .
In a first aspect, the present invention provides a living polymer having a structure represented by formula (1) or formula (2):
wherein a, b is an integer of 1 or more, and a/(a+b) is 70% to 96%, preferably 80% to 90%; r1 is C1-C4 linear alkyl or H, R2 is C1-C16 linear alkyl, preferably C3-C14 linear alkyl;
the weight average molecular weight of the living polymer was 0.8X10 4 ～3×10 4 Preferably 1.5X10 4 ～2.5×10 4 。
In a second aspect, the invention also provides a preparation method of a living polymer, wherein the living polymer is formed by copolymerizing N-acryloylmorpholine and acrylic ester compounds, and the preparation method specifically comprises the following steps: adding a reaction monomer acrylic ester compound and N-acryloylmorpholine into a solvent, heating to 30-70 ℃, adding an initiator, stirring for reaction to obtain a mixture, precipitating, separating and drying to obtain an active polymer.
Preferably, the solvent is selected from dipolar aprotic solvents, such as one of dimethyl sulfoxide and dimethylformamide, preferably dimethyl sulfoxide, and the solvent is aprotic polar solvent, and has the characteristics of high polarity, high boiling point, good thermal stability and water miscibility.
Preferably, the acrylic ester compound may be alkyl substituted or unsubstituted acrylic ester, and the structure is as follows:
wherein R1 is C1-C4 alkyl or H, such as methyl, ethyl, propyl, isopropyl, etc., R2 is C1-C16 alkyl, preferably C2-C14 alkyl, more preferably C10-C14 straight-chain alkyl.
Preferably, the total mass of the two reaction monomers accounts for 5-30% of the total mass of the solvent, preferably 10-25%.
Preferably, the mass ratio of the reactive monomer N-acryloylmorpholine to the acrylic ester compound is 70% -96%, 4% -30%, preferably 80% -90%, 10% -20%.
Preferably, the initiator is one or a combination of at least two of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutylaminate, azobisisobutylamidine hydrochloride, benzoyl peroxide and lauroyl peroxide, and further preferably azobisisobutylamidine hydrochloride.
Preferably, the mass concentration of the initiator is 0.05 to 1.0wt%, preferably 0.1 to 0.5. 0.5wt% of the total concentration of the monomers.
Preferably, the reaction temperature is 30 to 70 ℃, preferably 50 to 60 ℃; the reaction time is 2 to 10 hours, more preferably 4 to 8 hours.
Preferably, the preparation method further comprises: washing, drying and crushing the reaction product by adopting a precipitator to obtain a solid product; optionally, the precipitating agent is selected from one of methanol, ethanol and diethyl ether; optionally, the drying temperature is 60-100 ℃; alternatively, the drying time is 4 to 12 hours.
In a third aspect, the present invention also provides a thickened oil viscosity reducing agent composition, based on the total mass of the composition, comprising: the content of the active polymer is 0.01 to 0.5 weight percent, preferably 0.05 to 0.3 weight percent, and the balance is mainly water.
The thickened oil viscosity reducing agent composition of the present invention may optionally also contain other oilfield chemicals such as surfactants, reactive macromolecules, small molecule solvents and/or co-solvents, and other types of viscosity reducing agents.
In a fourth aspect, the present invention also provides a method of using a living polymer comprising: the active polymer of the invention is diluted with water to a viscosity reducing agent with the concentration of 0.01 to 0.5 weight percent, preferably 0.05 to 0.3 weight percent, and the viscosity reducing agent and the thick oil are mixed at the temperature of 20 to 60 ℃ according to the mass ratio of 2:8 to 5:5, preferably 3: 7-5: 5.
the viscosity range of the thickened oil is 100-10000 mPa.S.
The water is the on-site water of the target oil reservoir, and the mineralization degree is less than or equal to 50000mg/L.
Compared with the prior art, the invention has the following advantages:
the main chain carbon chain of the active polymer has oleophylic property, stretches into a thick oil aggregate to damage a thick oil aggregation structure, polar atoms such as N, O on a branched chain and polar components in the thick oil form a new hydrogen bond, a supermolecule system formed by the hydrogen bond among original polar functional groups in the thick oil is damaged, depolymerization and viscosity reduction are realized, meanwhile, hydrophilic functional groups on the branched chain stretch into an oil-water interface to reduce the tension of the oil-water interface, so that the thick oil is promoted to be dispersed into an aqueous phase to form O/W emulsified thick oil, and the viscosity of the thick oil is reduced. Meanwhile, the-NH in the molecule has alkalinity, and can neutralize H in the acidic thickened oil + And the corrosion of the acid environment to the pipeline is reduced. The traditional small molecular viscosity reducing system is used for reducing viscosity of acid heavy oil, and a large amount of alkali is required to be doped, so that the fouling and the blockage of a wellhead and a pipeline are easily caused.
Drawings
FIG. 1 is an infrared spectrum of the living polymer prepared in example 2.
FIG. 2 is a micrograph (100 times) of the living polymer prepared in example 1 after emulsification of the thick oil.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The instruments, reagents, materials, etc. used in the following examples are conventional instruments, reagents, materials, etc. which are already known in the prior art unless otherwise specified; can be purchased through regular commercial paths;
the experimental methods, detection methods, and the like in the examples are conventional experimental methods, detection methods, and the like, unless otherwise specified.
Examples 1 to 6 illustrate the preparation of living polymers.
Example 1
4.0g (0.028 mol) of NAM (N-acryloylmorpholine) and 1.0g (0.01 mol) of ethyl acrylate are weighed and dissolved in 50g of dimethyl sulfoxide (DMSO), and after stirring at room temperature and introducing nitrogen to remove oxygen for 45min, 0.005g of azodiisobutylamidine hydrochloride (AIBA) is added to initiate the polymerization reaction of the system for 6h at 60 ℃. Precipitating the reactant by using absolute ethyl alcohol, filtering and collecting, redissolving in a small amount of water, precipitating by using ethyl alcohol, performing three precipitation-dissolution-precipitation treatments, and drying the obtained product in a vacuum drying oven at 50 ℃ for 12 hours to obtain an active polymer product A1.
Example 2
4.0g of NAM (N-acryloylmorpholine) and 1.0g of dodecyl acrylate are weighed and dissolved in 50g of DMSO, and after stirring at room temperature and introducing nitrogen to remove oxygen for 45min, 0.010g of azobisisobutylamidine hydrochloride (AIBA) is added to initiate the polymerization reaction of the system for 8h at 60 ℃. Precipitating the reactant by using a large amount of absolute ethyl alcohol, filtering and collecting, redissolving in a small amount of water, precipitating by using a large amount of ethyl alcohol, performing three precipitation-dissolution-precipitation treatments, and drying the obtained product in a vacuum drying oven at 50 ℃ for 12 hours to obtain an active polymer product A2.
Example 3
4.0g of NAM (N-acryloylmorpholine) and 1.0g of tetradecyl acrylate are weighed and dissolved in 50g of DMSO, and after stirring at room temperature and introducing nitrogen to remove oxygen for 45min, 0.010g of azobisisobutylamidine hydrochloride (AIBA) is added to initiate the polymerization reaction of the system for 10h at 60 ℃. Precipitating the reactant by using a large amount of absolute ethyl alcohol, filtering and collecting, redissolving in a small amount of water, precipitating by using a large amount of ethyl alcohol, performing three precipitation-dissolution-precipitation treatments, and drying the obtained product in a vacuum drying oven at 50 ℃ for 12 hours to obtain an active polymer product A3.
Example 4
4.5g NAM (N-acryloylmorpholine) and 0.5g dodecyl acrylate were weighed and dissolved in 50g DMSO, and after stirring at room temperature and introducing nitrogen to remove oxygen for 45min, 0.010g azobisisobutylamidine hydrochloride (AIBA) was added to initiate polymerization of the system at 60℃for 8h. Precipitating the reactant by using a large amount of absolute ethyl alcohol, filtering and collecting, redissolving in a small amount of water, precipitating by using a large amount of ethyl alcohol, performing three precipitation-dissolution-precipitation treatments, and drying the obtained product in a vacuum drying oven at 50 ℃ for 12 hours to obtain an active polymer product A4.
Example 5
4.8g NAM (N-acryloylmorpholine) and 0.2g dodecyl acrylate were weighed and dissolved in 50g DMSO, and after stirring at room temperature and introducing nitrogen to remove oxygen for 45min, 0.010g azobisisobutylamidine hydrochloride (AIBA) was added to initiate polymerization of the system at 50℃for 10h. Precipitating the reactant by using a large amount of absolute ethyl alcohol, filtering and collecting, redissolving in a small amount of water, precipitating by using a large amount of ethyl alcohol, performing three precipitation-dissolution-precipitation treatments, and drying the obtained product in a vacuum drying oven at 50 ℃ for 12 hours to obtain an active polymer product A5.
Example 6
4.0g of NAM (N-acryloylmorpholine) and 1.0g of methyl methacrylate are weighed and dissolved in 50g of dimethylformamide, and after stirring at room temperature and introducing nitrogen to remove oxygen for 45min, 0.010g of Azobisisobutyronitrile (AIBN) is added, and the polymerization reaction of the system is initiated at 60 ℃ for 8h. Precipitating the reactant by using a large amount of absolute ethyl alcohol, filtering and collecting, redissolving in a small amount of water, precipitating by using a large amount of ethyl alcohol, performing three precipitation-dissolution-precipitation treatments, and drying the obtained product in a vacuum drying oven at 50 ℃ for 12 hours to obtain an active polymer product A6.
Comparative example 1
5.0g of dodecyl acrylate was weighed and dissolved in 50g of DMSO, and after stirring at room temperature and introducing nitrogen to remove oxygen for 45min, 0.005g of azobisisobutylamidine hydrochloride (AIBA) was added, and the polymerization reaction of the system was initiated at 60℃for 6 hours. Precipitating the reactant by using a large amount of absolute ethyl alcohol, filtering and collecting, redissolving in a small amount of water, precipitating by using a large amount of ethyl alcohol, performing three precipitation-dissolution-precipitation treatments, and drying the obtained product in a vacuum drying oven at 50 ℃ for 12 hours to obtain an active polymer product D1.
Comparative example 2
5.0g NAM (N-acryloylmorpholine) was weighed out and dissolved in 50g DMSO, and after stirring at room temperature and introducing nitrogen to remove oxygen for 45min, 0.005g azobisisobutylamidine hydrochloride (AIBA) was added to initiate polymerization in the system at 60℃for 6h. Precipitating the reactant by using a large amount of absolute ethyl alcohol, filtering and collecting, redissolving in a small amount of water, precipitating by using a large amount of ethyl alcohol, performing three precipitation-dissolution-precipitation treatments, and drying the obtained product in a vacuum drying oven at 50 ℃ for 12 hours to obtain an active polymer product D2.
Comparative example 3
As a comparison reagent D3 (purchased from enokava limited), a commercially available sodium dodecyl benzene sulfonate surfactant was selected.
Comparative example 4
The commercially available amphiphilic polymer polyacrylamide-2-acrylamide-2-methylpropanesulfonic acid (purchased from Aisen (China) Co., ltd., weight average molecular weight 300X 10 was selected 4 g/mol) is comparative reagent D4.
Test example 7
The products obtained in the above examples and comparative examples were subjected to molecular weight testing by Gel Permeation Chromatography (GPC), and the test results are shown in table 1.
Test example 8
The results of the IR spectrum (MPA type of Bruce Germany) detection using the living polymer A2 obtained in example 2 are shown in FIG. 1, wherein 2930cm -1 Near the place is-CH 2 Absorption peaks and, due to the different groups in the vicinity of CH2, different induction effects are produced, splitting into different-CH 2-absorption peaks. 1733cm -1 、1641cm -1 C=O absorption peak, 1450 cm, connected to (-OR and (N) RR' -respectively -1 Is provided with a CH vibration absorption peak of 1121cm -1 、1035cm -1 The C-O absorption peak is 982cm -1 ～808 cm -1 The absorption peak at this point is the out-of-plane fingerprint absorption peak for hydrogen.
Test example 9
The viscosity reduction experiment steps are as follows:
(1) The oil sample was thermostated for 30min in a 50 ℃ water bath, simulating the temperature of the oil sample in the formation.
(2) In the viscosity reducing experiment, the products of the example and the comparative example are diluted into a viscosity reducing agent with the mass fraction of 0.1wt%, the viscosity reducing agent and a thick oil sample are mixed according to the mass ratio of 3:7, and then are slowly stirred for 1min at the constant temperature of 50 ℃, and the viscosity of the emulsion is tested by using HAKKE MARS III. The results are shown in Table 1.
The water used was oilfield field water with a mineralization of 23583 mg/L.
The total acid value of the used thickened oil sample is 3.5mg KOH/g, the colloid is 67.0wt percent, the asphaltene is 0.9wt percent, and the density is 989.5g/cm at 20 DEG C 3 The surface degassing viscosity at 50 ℃ is 27800 mPa.s.
TABLE 1 bonding fruit drop
In Table 1 above, D1 was insoluble in water, and it was difficult to form an oil-in-water emulsion, and the viscosity-reducing effect was poor.
As shown in Table 1, the active polymer in the invention has remarkable viscosity reducing effect on acidic super-thick oil with viscosity as high as 27800 mPas, the viscosity reducing rate is more than 90%, and the active polymer under the preferable condition can reduce the viscosity of the thick oil to below 500 mPas, so that the fluidity of the thick oil is remarkably improved. The viscosity reducing performance of the active polymer in the experiment is better than that of the comparative example.
The applicant states that the detailed process equipment and process flows of the present invention are described by the above examples, but the present invention is not limited to, i.e., does not mean that the present invention must be practiced in dependence upon, the above detailed process equipment and process flows. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, selection of specific modes, etc., fall within the scope of the present invention and the scope of the disclosure.
Claims (14)
1. A living polymer has a structure shown in a formula (1) or a formula (2):
in the formula (1) and the formula (2), a and b are integers which are larger than or equal to 1, a/(a+b) is 70% -96%, R1 is C1-C4 straight-chain alkyl or H, and R2 is C1-C16 straight-chain alkyl.
2. The living polymer according to claim 1, wherein a/(a+b) is 80% to 90%; r2 is C3-C14 straight-chain alkyl.
3. The living polymer according to claim 1, wherein the weight average molecular weight of the living polymer is 0.8X10 4 ～3×10 4 Preferably 1.5X10 4 ～2.5×10 4 。
4. A process for preparing active polymer from N-acryloylmorpholine and acrylate compound through copolymerizing.
5. The preparation method according to claim 4, comprising: adding a reaction monomer acrylic ester compound and N-acryloylmorpholine into a solvent, heating to 30-70 ℃, adding an initiator, stirring for reaction to obtain a mixture, precipitating, separating and drying to obtain an active polymer.
6. The process according to claim 4, wherein the solvent is selected from the group consisting of dipolar aprotic solvents such as one of dimethyl sulfoxide and dimethylformamide.
7. The process according to claim 4, wherein the acrylic acid ester compound is an alkyl substituted or unsubstituted acrylic acid ester having the structure shown below:
wherein R1 is C1-C4 alkyl or H, such as methyl, ethyl, propyl, isopropyl, etc., R2 is C1-C16 alkyl, preferably C2-C14 alkyl, more preferably C10-C14 straight-chain alkyl.
8. The preparation method according to claim 4, wherein the total mass of the two reaction monomers is 5% to 30%, preferably 10% to 25% of the total mass of the solvent.
9. The preparation method according to claim 4, wherein the mass ratio of the reactive monomer N-acryloylmorpholine to the acrylic ester compound is 70-96%, 4-30%, preferably 80-90%, 10-20%.
10. The process according to claim 4, wherein the initiator is selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, azobisisobutylamidine hydrochloride, benzoyl peroxide and lauroyl peroxide.
11. The process according to claim 4, wherein the initiator is present in a mass concentration of 0.05 to 1.0% by weight, preferably 0.1 to 0.5% by weight, based on the total concentration of the monomers.
12. The preparation method according to claim 4, wherein the reaction temperature is 50 to 60 ℃; the reaction time is 2-10 hours.
13. A thickened oil viscosity reducing agent composition which comprises the active polymer of claim 1, wherein the content of the active polymer is 0.01-0.5 wt% based on the total mass of the composition, and the balance is mainly water.
14. A method of using a living polymer, comprising: the active polymer of claim 1 is diluted with water to a viscosity reducing agent with the concentration of 0.01 to 0.5 weight percent, and the viscosity reducing agent and the thick oil are mixed according to the mass ratio of 2:8 to 5:5 at 20 to 60 ℃.
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