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CN100432180C - Densifier for aqueous breakdown fluid and its production method - Google Patents

Densifier for aqueous breakdown fluid and its production method Download PDF

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CN100432180C
CN100432180C CNB200610138449XA CN200610138449A CN100432180C CN 100432180 C CN100432180 C CN 100432180C CN B200610138449X A CNB200610138449X A CN B200610138449XA CN 200610138449 A CN200610138449 A CN 200610138449A CN 100432180 C CN100432180 C CN 100432180C
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monomer
vinyl
acrylamide
weight
acid salt
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CN1995270A (en
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郝春玲
周万富
李红
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BEIJING XITAO DEVELOPMENT TECH Co Ltd
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BEIJING XITAO DEVELOPMENT TECH Co Ltd
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Abstract

The invention discloses a thickener of water-based breakdown fluid, which is polymerized by acrylamide monomer and other olefin monomer through interval method, wherein the interval method puts allocated monomer into reacting container, which is heat to polymerize through catalyzing, heating by microwave and irradiating by ultraviolet.

Description

A kind of viscosifying agent and production method thereof that is used for aqueous fracturing fluid
Technical field
The present invention relates to a kind of viscosifying agent that is used for aqueous fracturing fluid, especially a kind of polyacrylamide polymers viscosifying agent, and a kind of production method of described viscosifying agent.
Background technology
Fracturing technique is conventional yield-increasing technology.Its objective is reservoir is extruded the crack, thus volume increase.Used fracturing liquid must have high viscosity, high shear resistant, high-strength take the characteristics such as the feature of environmental protection that sand and broken glue do not have residue during pressure break.High viscosity has only high viscosity just can make the crack reach the required width and the degree of depth so that it makes seam.Viscosifying agent is as the host of aqueous fracturing fluid, in order to improve of the fracturing fluid viscosity, reduces fracturing fluid leak, suspends and carries propping agent.
At present the viscosifying agent raw material that uses has vegetable jelly and derivative thereof, derivatived cellulose, biological poly-polysaccharide, synthetic polymer, and commonly used is melon glue, hydroxypropyl guar gum, fenugreek gum etc.These materials as the shortcoming of viscosifying agent are: the water-insoluble height, easily cause reservoir damage.General synthetic polymer (polyacrylamide, type methylene polyacrylamide) is to change polymer property by the control synthesis condition, satisfies the construction needs, and resistance-reducing performance is good, more than the problem that exists of two kinds of polymkeric substance be that anti-shearing is poor; Salt tolerance is poor; Cull absorption is stopped up serious.Therefore synthetic polymer does not obtain widely applying.So in recent years, adopting the polymkeric substance fracturing liquid system of not having injury is scientific research task both domestic and external always.But never anti-shear performance is good, and height is taken the polymer thickening agent of sand.
Summary of the invention
The purpose of this invention is to provide a kind of polymer thickening agent that is applied in the water-based fracturing, this viscosifying agent has advantages such as anti-shearing, salt tolerant, noresidue.
Another object of the present invention is produced the method for above-mentioned polymer thickening agent.
Viscosifying agent of the present invention is to be polymerized according to interrupter method by acrylamide monomer and other olefin monomer.Described other olefin monomer is one or more in anionic monomer, cationic monomer, wetting ability nonionic monomers, the hydrophobicity nonionic monomers.
In the anionic monomer, typical ionic comonomer is a unsaturated carboxylic acid, for example vinylformic acid, methacrylic acid, methylene-succinic acid, vinyl sulfonic acid, in vinyl benzenesulfonic acid and acrylamido methyl propane sulfonic acid (AMPS) and their salt thereof one or more.
The example of cationic monomer has, dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac (DAC), methylacryoyloxyethyl trimethyl ammonium chloride (DMC) etc.
The wetting ability nonionic monomers is the acetone acrylamide, hydroxyethyl methylacrylate, one or more in Hydroxyethyl acrylate, Rocryl 410, Propylene glycol monoacrylate and the N-vinyl-2-Pyrrolidone.
Typical hydrophobic type nonionic monomers is one or more in vinyl cyanide, methacrylonitrile, vinyl-acetic ester, vinylchlorid, vinylbenzene, the divinyl.
The weight percent of each monomer of the present invention and water consists of:
(a) acrylamide of 10 to 35 weight %;
(b) the 2-acrylamide of 7 to 45 weight %-2-methyl propane sulfonic acid salt;
(c) 0.5 to 10 weight %'s to vinyl benzenesulfonic acid salt;
(d) vinyl cyanide of 0.3 to 2 weight %;
(e) 0 to 2 weight % Methacrylamide;
(f) one or more described cationic monomers of 0 to 5 weight %;
(g) N-vinyl-2-Pyrrolidone (PVN) of 0 to 2 weight %;
(h) surplus is a water.
More preferably be that the optimum weight per-cent of each monomer and water consists of:
Acrylamide (AM): 15%
2-acrylamide-2-methyl propane sulfonic acid salt (AMPS): 25%
To vinyl benzenesulfonic acid salt (BNS): 5%
Methacrylamide (AAM): 1.5%
Vinyl cyanide (AN): 0.5%
Methylacryoyloxyethyl trimethyl ammonium chloride (DMC): 2%
N-vinyl-2-Pyrrolidone (PVN): 0.5%
Water: 50.5%
In case of necessity, the molecular fraction of acrylamide can be replaced by Methacrylamide or 2-acrylamide-2-methyl propane sulfonic acid salt.
Vinyl benzenesulfonic acid had shear resistant, in pressing crack construction process, product has certain shearing when dissolving, topmost shearing I'm afraid to use by oneself high-pressure pump in the shearing when the stratum is injected, reduce the crosslinked husky performance of taking in order to overcome the molecule chain rupture that causes because of shearing, select the olefin monomer that contains phenyl ring for use, similar monomer comprises: vinylbenzene, to vinyl benzenesulfonic acid etc. adds 0.5-10 weight % its anti-shear ability of vinyl benzenesulfonic acid salt (BNS) is had clear improvement with increasing of add-on through checking repeatedly.
A kind of method of producing above-mentioned viscosifying agent, it comprises the steps:
(1) selected acrylamide monomer and other olefin monomer also carry out proportioning to each monomer as requested;
(2) said ratio is good monomer is put into the preparation that distilled water carries out solution;
(3) the pH value and the temperature of adjustment solution;
(4) make above-mentioned monomer generation polymerization with interrupter method.
Described interrupter method just refers in the building-up process of viscosifying agent the monomer for preparing be added in the reaction vessel simultaneously together, carries out catalysis, microwave heating, UV-irradiation then successively so that monomer generation polymerization.Adopting interrupter method polymeric cardinal principle is hertzian wave and the light wave of wanting by the different wave length of microwave and ultraviolet ray emission, in order to excite the double bond monomer with different unexpectedly poly-rates, has reached the even polymeric purpose of function monomer.We introduce extraordinary polymerization single polymerization monomer to intramolecularly, as heat and salinity tolerance monomer and hydrophobic monomer (wherein anti-salt monomer is 2-acrylamide-2-methyl propane sulfonic acid salt, and hydrophobic monomer is a vinyl cyanide).In entire reaction course, be to form with three kinds of polymerization methods batch polymerizations, the finished product molecule is comparatively complicated, and its building-up process can be envisioned for:
Figure C20061013844900081
To need to carry out with interrupter method in the polymeric process to solution nitrogen blowing 15-20 minute; to remove the dissolved oxygen in anhydrating; under protection of nitrogen gas, add catalyzer then; stop nitrogen blowing and caused 15-20 minute; when being raised to 30 ℃, temperature heated mixing 2 minutes with the little fire of microwave; take out then with UV illumination and penetrate, be incubated 3 hours until the end that heats up.
Initiation starting temperature of the present invention is controlled within the 5-20 ℃ of scope.Preferred starting temperature is 10 ± 1 ℃.The pH value is controlled between the 8-11.PH alkalescence mediator agent mainly contains sodium hydroxide, salt of wormwood, ammoniacal liquor.Acid regulator mainly contains phosphoric acid, sulfuric acid, hydrochloric acid, acetate.Preferred pH value is controlled at 10 ± 0.5.
Be not particularly limited for described catalyzer.Polymerizing catalyst comprises persulphate and superoxide, for example ammonium persulphate, Potassium Persulphate, Sodium Persulfate, hydrogen peroxide, benzoyl peroxide and tert-butyl peroxide.Can use oxygenant to form redox system with reductive agent among the present invention, and can carry out sufficient polymerization under the replenishing of microwave and UV-light, described reductive agent can comprise sulphite, hydrosulphite, protosalt, organic amine etc.
Azo-compound also is one of preferred catalyzer of the present invention, and the typical azo-compound that is suitable for comprises Diisopropyl azodicarboxylate (AZDN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (V65), azo diisobutyl amidine hydrochloride (V50) etc.Can use two or more above-mentioned catalyzer simultaneously, the amount of catalyzer is generally monomeric 0.001-3% weight.
Viscosifying agent of the present invention is applicable in the aqueous fracturing fluid in the oilfield stimulation, be a kind of easy dissolving, pollution-free, do not have injury, take husky performance good, especially shear and take the good novel high molecular polymer of husky performance, its principal feature is to have high anti-shearing, to satisfy the pressing crack construction of high flow capacity, have high sand and the no residue taken, to characteristics such as the no nocuities of storage, can be used as the excellent substitute of guanidine glue.
Embodiment
To be described in detail viscosifying agent of the present invention and production process thereof according to specific embodiment below.
Embodiment 1
The weight percent of each monomer and water: AM: AMPS: BNS: AAM: AN: DMC: PVN: H 2O=15: 25: 5: 1.5: 0.5: 2: 0.5: 50.5.
The preparation of solution: in the 2000ml beaker, add distilled water 370g, add AMPS monomer 250g, BNS monomer 50g, stirring and dissolving 20 minutes slowly adds neutralizing agent (sodium hydroxide) to pH neutrality under agitation condition.Add 98% acrylamide 150g again, AAM monomer 15g, AN monomer 5g, 80% concentration DMC monomer 20g, PVN monomer 5g, stirring and dissolving 30 minutes.
The adjustment of solution: regulate pH value to 10 ± 0.5,10 ± 1 ℃ of attemperation.
The polymerization of solution: nitrogen blowing deoxygenation 15-20 minute; under nitrogen protection, add catalyst A ZDN0.5g/L successively, V500.05g/L, ammonium persulphate 0.03g/L; sodium formaldehyde sulphoxylate 0.03g/L; stop nitrogen blowing, caused 15-20 minute, when temperature is raised to 30 ℃; put the interior little fire heating mixing of microwave box 2 minutes into; taking-up is penetrated with UV illumination, finishes until heating up, and is incubated 3 hours.
The aftertreatment of product: the colloid that polymerization is good is carried out granulation, and oven dry is ground into 30 orders, is numbered A-1 and waits detection.
Embodiment 2
Each monomer is in the weight percent of water: AM: AMPS: BNS: AAM: AN: DMC: PVN: H 2O=30: 25: 0.5: 0: 0.3: 0: 0: 44.2.
The preparation of solution: in the 2000ml beaker, add distilled water 442g, add AMPS monomer 250g, BNS monomer 5g, stirring and dissolving 20 minutes slowly adds neutralizing agent (sodium hydroxide) to pH neutrality under agitation condition.Add 98% acrylamide 300g again, AAM monomer 0g, AN monomer 0.3g, 80% concentration DMC monomer 0g, PVN monomer 0g, stirring and dissolving 30 minutes.
The adjustment of solution: regulate pH value to 10 ± 0.5,10 ± 1 ℃ of attemperation.
The polymerization of solution: nitrogen blowing deoxygenation 15-20 minute; under nitrogen protection, add catalyst A ZDN0.5g/L successively, V500.04g/L, ammonium persulphate 0.03g/L; sodium formaldehyde sulphoxylate 0.03g/L; stop nitrogen blowing, caused 15-20 minute, when temperature is raised to 30 ℃; put the interior little fire heating mixing of microwave box 2 minutes into; taking-up is penetrated with UV illumination, finishes until heating up, and is incubated 3 hours.
The aftertreatment of product: the colloid that polymerization is good is carried out granulation, and oven dry is ground into 30 orders, is numbered A-2 and waits detection.
Embodiment 3
The weight percent of each monomer and water: AM: AMPS: BNS: AAM: AN: DMC: PVN: H 2O=30: 7: 6.5: 0: 2: 0: 0: 54.5.
The preparation of solution: in the 2000ml beaker, add distilled water 545g, add AMPS monomer 70g, BNS monomer 65g, stirring and dissolving 20 minutes slowly adds neutralizing agent (sodium hydroxide) to pH neutrality under agitation condition.Add 98% acrylamide 300g again, AAM monomer 0g, AN monomer 20g, 80% concentration DMC monomer 0g, PVN monomer 0g, stirring and dissolving 30 minutes.
The adjustment of solution: regulate pH value to 10 ± 0.5,10 ± 1 ℃ of attemperation.
The polymerization of solution: nitrogen blowing deoxygenation 15-20 minute; under nitrogen protection, add catalyst A ZDN0.8g/L successively, V500.08g/L, ammonium persulphate 0.04g/L; sodium formaldehyde sulphoxylate 0.04g/L; stop nitrogen blowing, caused 15-20 minute, when temperature is raised to 30 ℃; put the interior little fire heating mixing of microwave box 2 minutes into; taking-up is penetrated with UV illumination, finishes until heating up, and is incubated 3 hours.
The aftertreatment of product: the colloid that polymerization is good is carried out granulation, and oven dry is ground into 30 orders, is numbered A-3 and waits detection.
Embodiment 4
Each monomer is in the weight percent of water: AM: AMPS: BNS: AAM: AN: DMC: PVN: H 2O=10: 25: 6.5: 1.5: 2: 5: 0.8: 49.2.
The preparation of solution: in the 2000ml beaker, add distilled water 492g, add AMPS monomer 250g, BNS monomer 65g, stirring and dissolving 20 minutes slowly adds neutralizing agent (sodium hydroxide) to pH neutrality under agitation condition.Add 98% acrylamide 100g again, AAM monomer 15g, AN monomer 20g, 80% concentration DMC monomer 50g, PVN monomer 8g, stirring and dissolving 30 minutes.
The adjustment of solution: regulate pH value to 10 ± 0.5,10 ± 1 ℃ of attemperation.
The polymerization of solution: nitrogen blowing deoxygenation 15-20 minute; under nitrogen protection, add catalyst A ZDN0.8g/L successively, V500.08g/L, ammonium persulphate 0.05g/L; sodium formaldehyde sulphoxylate 0.05g/L; stop nitrogen blowing, caused 15-20 minute, when temperature is raised to 30 ℃; put the interior little fire heating mixing of microwave box 3 minutes into; taking-up is penetrated with UV illumination, finishes until heating up, and is incubated 3 hours.
The aftertreatment of product: the colloid that polymerization is good is carried out granulation, and oven dry is ground into 30 orders, is numbered A-4 and waits detection.
Embodiment 5
Each monomer is in the weight percent of water: AM: AMPS: BNS: AAM: AN: DMC: PVN: H 2O=10: 45: 0.5: 0: 0.3: 0: 0: 44.2.
The preparation of solution: in the 2000ml beaker, add distilled water 442g, add AMPS monomer 450g, BNS monomer 5g, stirring and dissolving 20 minutes slowly adds neutralizing agent (sodium hydroxide) to pH neutrality under agitation condition.Add 98% acrylamide 100g again, AAM monomer 0g, AN monomer 3g, 80% concentration DMC monomer 0g, PVN monomer 0g, stirring and dissolving 30 minutes.
The adjustment of solution: regulate pH value to 10 ± 0.5,10 ± 1 ℃ of attemperation.
The polymerization of solution: nitrogen blowing deoxygenation 15-20 minute; under nitrogen protection, add catalyst A ZDN0.5g/L successively, V500.04g/L, ammonium persulphate 0.02g/L; sodium formaldehyde sulphoxylate 0.02g/L; stop nitrogen blowing, caused 15-20 minute, when temperature is raised to 30 ℃; put the interior little fire heating mixing of microwave box 2 minutes into; taking-up is penetrated with UV illumination, finishes until heating up, and is incubated 3 hours.
The aftertreatment of product: the colloid that polymerization is good is carried out granulation, and oven dry is ground into 30 orders, is numbered A-5 and waits detection.
The main polymerization catalyzed agent prescription of above-mentioned real embodiment gathers (as table 1).
Table 1
Figure C20061013844900131
Wherein, AO1 is an ammonium persulphate, and NFS is a sodium formaldehyde sulphoxylate
The foregoing description product is carried out fundamental property detect (result such as table 2).
Table 2
Figure C20061013844900132
The said products is carried out the detection (result such as table 3) of use properties aspect
Table 3
Figure C20061013844900141
From top detected result, viscosifying agent of the present invention has that to take husky performance good, and have high anti-shearing, to characteristics such as the no nocuities of storage.

Claims (8)

1, a kind of water-based fracturing fluid gelatinizer, it is characterized in that: this viscosifying agent is polymerized according to interrupter method by acrylamide monomer and other olefin monomer, described other olefin monomer is multiple in anionic monomer, cationic monomer, wetting ability nonionic monomers, the hydrophobicity nonionic monomers, and described interrupter method comprises catalysis, microwave heating and the UV-irradiation of carrying out successively;
Described anionic monomer is vinylformic acid, methacrylic acid, methylene-succinic acid, vinyl sulfonic acid, in the vinyl benzenesulfonic acid one or more; Perhaps, described anionic monomer be acrylate, methacrylate, itaconate, vinylsulfonate, in vinyl benzenesulfonic acid salt and the acrylamido methyl propane sulfonic acid salt one or more;
Described cationic monomer is one or more in dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, the methylacryoyloxyethyl trimethyl ammonium chloride;
Described wetting ability nonionic monomers is the acetone acrylamide, hydroxyethyl methylacrylate, one or more in Hydroxyethyl acrylate, Rocryl 410, Propylene glycol monoacrylate and the N-vinyl-2-Pyrrolidone;
Described hydrophobic type nonionic monomers is one or more in vinyl cyanide, methacrylonitrile, vinyl-acetic ester, vinylchlorid, vinylbenzene, the divinyl.
2, viscosifying agent as claimed in claim 1 is characterized in that: describedly can be replaced by vinylbenzene vinyl benzenesulfonic acid salt.
3, viscosifying agent as claimed in claim 1 or 2 is characterized in that: the weight percent of used each monomer and water is specially:
A) acrylamide of 10 to 35 weight %;
B) the 2-acrylamide of 7 to 45 weight %-2-methyl propane sulfonic acid salt;
C) 0.5 to 10 weight %'s to vinyl benzenesulfonic acid salt;
D) vinyl cyanide of 0.3 to 2 weight %;
E) 0 to 2 weight % Methacrylamide;
F) one or more described cationic monomers of 0 to 5 weight %;
G) N-vinyl-2-Pyrrolidone of 0 to 2 weight %;
H) surplus is a water.
4, viscosifying agent as claimed in claim 3 is characterized in that: the weight percent of used each monomer and water is:
Acrylamide: 15%;
2-acrylamide-2-methyl propane sulfonic acid salt: 25%;
To vinyl benzenesulfonic acid salt: 5%;
Vinyl cyanide: 0.5%;
Methacrylamide: 1.5%;
Methylacryoyloxyethyl trimethyl ammonium chloride: 2%;
N-vinyl-2-Pyrrolidone: 0.5%;
Water: 50.5%.
5, the method for the described viscosifying agent of a kind of production claim 1, described method comprises the steps:
(1) selected acrylamide monomer and other olefin monomer, and as requested each monomer is carried out proportioning;
(2) preparation of solution: the monomer that said ratio is good is put into the preparation that distilled water carries out solution;
(3) the pH value and the temperature of adjustment solution;
(4) make above-mentioned monomer generation polymerization with interrupter method, the monomer that is about to prepare adds in the reaction vessel simultaneously together, carries out catalysis, microwave heating, UV-irradiation then successively so that each monomer generation polymerization.
6, method as claimed in claim 5 is characterized in that: carry out polymerization procedure (4) before the pH value of described solution need be adjusted between the 8-11, temperature need be adjusted within the 5-20 ℃ of scope.
7, method as claimed in claim 5 is characterized in that: described pH value is adjusted to 10 ± 0.5, and described temperature is adjusted to 10 ± 1 ℃.
8, as claim 6 or 7 described methods, it is characterized in that: described polymerization procedure (4) comprises solution nitrogen blowing 15-20 minute, add catalyzer then, stop nitrogen blowing and caused 15-20 minute, when being raised to 30 ℃, temperature heated mixing 2 minutes with the little fire of microwave, taking-up is penetrated until heating up with UV illumination and is finished, and is incubated 3 hours.
CNB200610138449XA 2006-11-15 2006-11-15 Densifier for aqueous breakdown fluid and its production method Expired - Fee Related CN100432180C (en)

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