CN101914182B - The synthetic method of base underground crosslinked thickening agent - Google Patents
The synthetic method of base underground crosslinked thickening agent Download PDFInfo
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- CN101914182B CN101914182B CN201010260450.6A CN201010260450A CN101914182B CN 101914182 B CN101914182 B CN 101914182B CN 201010260450 A CN201010260450 A CN 201010260450A CN 101914182 B CN101914182 B CN 101914182B
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Abstract
A kind of base underground crosslinked thickening agent, is specifically related to oil field further storey increase design polyacrylamide viscosifying agent after a kind of ternary composite oil-displacing, is particularly useful for High water cut, strong basicity, the oil reservoir profile control and water plugging that has exhibiting high surface promoting agent to exist.This base underground crosslinked thickening agent is synthesized by aqueous solution copolymerization method by acrylamide (AM), vinylformic acid (AA), 2-acrylamide-2-methyl propane sulfonic acid salt (AMPS) and vinyl pyrrolidone (NVP) four kinds of monomers.This base underground crosslinked thickening agent has (be applicable to various water base tune, block up, drive) applied widely, under the existence of alkali and tensio-active agent, dissolution rate is fast, anti-shear ability strong, to features such as environment fanout free region.
Description
Technical field
The present invention relates to the oilfield stimulation technology after a kind of ternary composite oil-displacing, be specifically related to a kind of synthesis of base underground crosslinked thickening agent, be applicable to after polyacrylamide, alkali and tensio-active agent add simultaneously and carry out ternary composite oil-displacing, ground environment becomes High water cut strong basicity, the volume increase such as the profile control taked, water blockoff technology of reservoir sweep.
Background technology
Usually utilizing oil reservoir energy recover petroleum to call primary oil recovery: inject water, gas to oil reservoir, be called secondary oil recovery to oil reservoir supplementing energy recover petroleum; And improve oil, gas, water and rock performance each other with the material of chemistry, exploit out more oil, be called tertiary oil recovery.Also known as raising recovery ratio (EOR) method.
Successfully adopt polyacrylamide to carry out three to adopt as major contribution has been made in crude oil in China volume increase.The degree of depth of adopting along with three is carried out, and efficiency is more and more lower.Domesticly from 2005 bring into use four to adopt technology, namely PAM+ alkali+tensio-active agent carries out the 4th time and recovers the oil, also referred to as ternary composite driving.Due to adding of alkali, volume increase obviously.But also bring new problem to water blockoff simultaneously.Is technology in the past no longer applicable, how effective water blockoff under the existence having highly basic? that we develop the final purpose of this product, the underground crosslinked thickening agent that Development and Production is a kind of to be adapted under base condition.
The principal feature of base underground crosslinked thickening agent is: (be applicable to various water base tune, block up, drive) applied widely, under the existence of alkali and tensio-active agent, dissolution rate is fast, anti-shear ability strong, to environment fanout free region.In building-up process, we find that the alkali resistant of AMPS monomer is very competent to this viscosifying agent, especially the AMPS monomer performance not under neutrality condition more superior, in this polymkeric substance, we use acrylamide, AMPS, acrylic acid, vinyl pyrrolidone tetrapolymer.We also find that the adaptability of the conformability of AMPS monomer Surfactant and vinyl pyrrolidone is suitable.
Summary of the invention
The object of this invention is to provide a kind of synthetic method of the base underground crosslinked thickening agent for oilfield stimulation after ternary composite driving, be applicable to the ternary composite oil-displacing later stage, the Gel Flooding Technology field crosslinked in strong alkali environment that the further storey increase design in oil field is taked.This base underground crosslinked thickening agent has: (be applicable to various water base tune, block up, drive) applied widely, under the existence of alkali and tensio-active agent, dissolution rate is fast, anti-shear ability strong, to environment fanout free region.
In order to synthesize above-mentioned base underground crosslinked thickening agent, the technical scheme taked is as follows: synthesized by the method for aqueous free radical copolymerization by acrylamide (AM), vinylformic acid (AA), 2-acrylamide-2-methyl propane sulfonic acid (AMPS) and vinyl pyrrolidone (NVP) four kinds of monomers.
In aqueous solution copolymerization process, the weight of each monomer and water accounts for the proportioning of reacting feed liquid gross weight and is:
The acrylamide (AM) of (a) 15 to 25 % by weight;
The vinylformic acid (AA) of (b) 5 to 10 % by weight;
2-acrylamide-2-methyl propane sulfonic acid (AMPS) of (c) 5 to 15 % by weight;
The vinyl pyrrolidone (NVP) of (d) 5 to 15 % by weight;
E () surplus is distilled water.
More preferably, the optimum weight per-cent of each monomer and water consists of:
(a) acrylamide (AM): 20%;
Vinylformic acid (AA): 8%;
(c) 2-acrylamide-2-methyl propane sulfonic acid (AMPS): 10%;
(d) vinyl pyrrolidone (NVP): 10%;
(e) distilled water: 52%.
In the building-up process of described base underground crosslinked thickening agent, comprise the steps:
(1) selected acrylamide (AM), vinylformic acid (AA), 2-acrylamide-2-methyl propane sulfonic acid (AMPS) and vinyl pyrrolidone (NVP) four kinds of monomers carry out proportioning according to a certain percentage;
(2) vinylformic acid (AA) and 2-acrylamide-2-methyl propane sulfonic acid (AMPS) are added appropriate distilled water to dissolve, control degree of neutralization be mol ratio 0% ~ 100% to add in alkali and after, add acrylamide (AM) and vinyl pyrrolidone (NVP), filling into distilled water makes monomer concentration reach suitable concn, stirs monomer solution and forms homogeneous system;
(3) adjust solution temperature, cause starting temperature and control within 10-20 DEG C of scope.Preferred starting temperature is 15 ± 1 DEG C.
(4) monomer solution prepared is added in reaction vessel, carry out protection 20 minutes to the monomer solution nitrogen blowing prepared, then in solution, add initiator, bring out 15-20 minute to produce free radical, thus monomer is polymerized.
Need in the process of aqueous solution polymerization solution nitrogen blowing 20 minutes; with except the dissolved oxygen in anhydrating; then under the protection of nitrogen, initiator is added; stopping nitrogen blowing is also airtight by polymeric kettle; bringing out 10-15 minute, observing whether have temperature rise, when there being the temperature rise of 2 DEG C in inductive phase; be considered as causing successfully, otherwise need to rejoin initiator and again cause.Until the end that heats up under insulation air tight condition, be incubated 3 hours.
In the synthesis step of described viscosifying agent, alkali used is one or more in sodium hydroxide, potassium hydroxide, calcium hydroxide, salt of wormwood, sodium carbonate, bicarbonate of ammonia, calcium carbonate, ammoniacal liquor.
Described initiator is not particularly limited.The oxygenant of polymerization starter is persulphate or superoxide, such as ammonium persulphate, Potassium Persulphate, Sodium Persulfate, hydrogen peroxide, benzoyl peroxide or tert-butyl peroxide.Persulphate or superoxide can be used in the present invention together with reductive agent to form redox system, and described reductive agent can be sulphite, hydrosulphite, organic amine etc.
Azo-compound is also one of preferred initiator of the present invention, and the typical azo-compound be suitable for is Diisopropyl azodicarboxylate (AZDN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (V65), azo diisobutyl amidine hydrochloride (V50) etc.
Can use two or more above-mentioned initiator, the amount of initiator is generally the 0.001-3% weight of monomer simultaneously.
Vinyl pyrrolidone (NVP) monomer is a kind of rigid unitary with ring texture, restraining effect is had to the hydrolysis of polyacrylamide in alkaline environment, be conducive to the stable of polyacrylamide polymers, and pyrrolidone five-ring is more stable structure on its molecular structure, be insensitive to salt and alkali, thus there is anti-salt, temperature resistance and alkali-resistivity.2-acrylamide-2-methyl propane sulfonic acid (AMPS) monomer contains sulfonic acid group salt being failed to understand to sense, and can not be hydrolyzed, and its alkali resistant is very competent, the AMPS monomer performance especially not under neutrality condition more superior.And the conformability of research discovery AMPS monomer Surfactant is suitable with the adaptability of vinyl pyrrolidone, containing tertiary amine nitrogen atom on pyrrole ring, can a small amount of hydrogen ion be adsorbed and make PVP be with weak positive charge.Therefore, the method synthesis that base underground crosslinked thickening agent adopts acrylamide, 2-acrylamide-2-methyl propane sulfonic acid, vinylformic acid, vinyl pyrrolidone quarternary copolymerized, there is heat and salinity tolerance and anti-strong basicity, containing groups such as carboxyl, amide group, sulfonic groups on polymer molecular chain, slow crosslinking reaction can be there is under metal ion complex, aldehyde radical or macromolecule crosslink agent exist, form gel.
The most of oil field of current China is in the oilfield exploitation middle and later periods, and the sustainability problems demand of oilfield exploitation solves, and base underground crosslinked thickening agent of the present invention is intended to the approach that the oil field after proposing a kind of ternary composite driving is exploited further.
Embodiment
Be described in detail according to the synthetic method of specific embodiment to base underground crosslinked thickening agent of the present invention below.
Embodiment 1
The weight of each monomer and water is by following proportions: AM: AA: AMPS: NVP: H
2o=20: 8: 10: 10: 52.
The preparation of solution: add distilled water 300g in 2000ml beaker, adds AA monomer 80g and AMPS monomer 100g, and reinforcing body sodium hydroxide 63.7g (degree of neutralization 100%) neutralizes, attentional manipulation temperature, do not exceed 40 DEG C, suitably cool, in order to avoid temperature is too high; Add AM monomer 200g, NVP monomer 100g, adds distilled water 156.3g, and stirring and dissolving forms homogeneous system in 30 minutes.
The adjustment of solution: regulator solution temperature 15 ± 1 DEG C.
The polymerization of solution: nitrogen blowing deoxygenation 20 minutes; add initiator V650.5g/L successively under nitrogen protection; V500.05g/L, ammonium persulphate 0.03g/L, sodium formaldehyde sulphoxylate 0.03g/L; stopping nitrogen blowing is also airtight by reactor; bringing out 15-20 minute, observing whether have temperature rise, when there being the temperature rise of 2 DEG C in inductive phase; be considered as causing successfully, otherwise need to rejoin initiator and again cause.Until the end that heats up under insulation air tight condition, be incubated 3 hours.
The aftertreatment of product: the colloid be polymerized is carried out granulation, dries, is ground into 30 orders.
Claims (5)
1. for a synthetic method for the base underground crosslinked thickening agent of oilfield stimulation after ternary composite driving, it is characterized in that: described viscosifying agent is synthesized by the mode of aqueous solution copolymerization by acrylamide (AM), vinylformic acid (AA), 2-acrylamide-2-methyl propane sulfonic acid (AMPS) and vinyl pyrrolidone (NVP) four kinds of monomers;
In aqueous solution copolymerization process, the weight of each monomer and water accounts for the proportioning of reacting feed liquid gross weight and is:
The acrylamide (AM) of (a) 15 to 25 % by weight;
The vinylformic acid (AA) of (b) 5 to 10 % by weight;
2-acrylamide-2-methyl propane sulfonic acid (AMPS) of (c) 10 to 20 % by weight;
The vinyl pyrrolidone (NVP) of (d) 1 to 10 % by weight;
E () surplus is water,
The building-up process of described viscosifying agent comprises the steps:
(1) selected acrylamide (AM), vinylformic acid (AA), 2-acrylamide-2-methyl propane sulfonic acid (AMPS) and vinyl pyrrolidone (NVP) four kinds of monomers carry out proportioning according to a certain percentage;
(2) vinylformic acid (AA) and 2-acrylamide-2-methyl propane sulfonic acid (AMPS) are added appropriate distilled water to dissolve, controlling degree of neutralization is mol ratio 0% ~ 100%, to add in alkali and after, add acrylamide (AM) and vinyl pyrrolidone (NVP), fill into distilled water and make concentration suitable;
(3) adjust solution temperature, described temperature is 15 ± 1 DEG C;
(4) monomer solution prepared is added in reaction vessel, carry out protection 20 minutes to the monomer solution nitrogen blowing prepared, then in solution, add initiator, bring out 15-20 minute to produce free radical, thus monomer is polymerized.
2. as claimed in claim 1 for the synthetic method of the base underground crosslinked thickening agent of oilfield stimulation after ternary composite driving, it is characterized in that: in the synthesis step of described viscosifying agent, alkali used is sodium hydroxide, potassium hydroxide, calcium hydroxide, salt of wormwood, sodium carbonate, bicarbonate of ammonia, calcium carbonate, one or more in ammoniacal liquor.
3., as claimed in claim 1 for the synthetic method of the base underground crosslinked thickening agent of oilfield stimulation after ternary composite driving, it is characterized in that: described initiator is persulphate or superoxide; Or for persulphate or superoxide form redox system together with reductive agent; Or be azo-compound; Described initiator also can be made up of two or more initiators in above-mentioned initiator type.
4., as claimed in claim 3 for the synthetic method of the base underground crosslinked thickening agent of oilfield stimulation after ternary composite driving, it is characterized in that: described persulphate is one or more in ammonium persulphate, Potassium Persulphate, Sodium Persulfate; Described superoxide is one or more in hydrogen peroxide, benzoyl peroxide and tert-butyl peroxide; Described reductive agent is one or more in sulphite, hydrosulphite, organic amine; Described azo-compound is one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo diisobutyl amidine hydrochloride.
5., as claimed in claim 1 for the synthetic method of the base underground crosslinked thickening agent of oilfield stimulation after ternary composite driving, it is characterized in that: the amount of initiator is the 0.001-3% of monomer weight.
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| CN102086386A (en) * | 2010-12-27 | 2011-06-08 | 大庆石油管理局 | Anti-sedimentation agent for cement capable of resisting 200 DEG C of oil well and preparation method thereof |
| CN102775552B (en) * | 2011-05-13 | 2014-05-28 | 中国石油化工股份有限公司 | Random copolymer, its preparation method and application |
| CN102775711B (en) * | 2011-05-13 | 2014-04-02 | 中国石油化工股份有限公司 | Oil-displacing agent composition and preparation method thereof |
| FR2986034B1 (en) * | 2012-01-20 | 2016-08-12 | Snf Sas | PROCESS FOR ASSISTED OIL RECOVERY BY INJECTION OF A POLYMERIC SOLUTION |
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| CN103305204A (en) * | 2013-05-28 | 2013-09-18 | 西南石油大学 | Temperature-resistant salt-resistant acrylamide terpolymer sulfonate oil-displacing agent and synthesis |
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| CN104140805A (en) * | 2013-10-28 | 2014-11-12 | 中国石油化工股份有限公司 | Modified acrylamide polymer fracturing fluid |
| CN104140806A (en) * | 2013-10-29 | 2014-11-12 | 中国石油化工股份有限公司 | Modified acrylamide polymer thickening agent and preparation method thereof |
| CN105461852B (en) * | 2014-09-03 | 2017-07-28 | 中国石油化工股份有限公司 | A kind of acrylamide based copolymer and its preparation method and application |
| CN104277801A (en) * | 2014-09-29 | 2015-01-14 | 中国石油天然气集团公司 | Anti-high-temperature emulsion tackifier for water-based drilling fluid and preparation method of tackifier |
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| CN115677904A (en) * | 2021-07-29 | 2023-02-03 | 中国石油天然气股份有限公司 | Water shutoff agent and preparation method and application thereof |
| CN113549438A (en) * | 2021-08-11 | 2021-10-26 | 中海石油(中国)有限公司深圳分公司 | Water plugging agent and preparation method and application thereof |
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