CN102757777B - Inhibition water locking type high temperature resistant fracturing fluid for tight gas reservoir fracturing - Google Patents

Inhibition water locking type high temperature resistant fracturing fluid for tight gas reservoir fracturing Download PDF

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CN102757777B
CN102757777B CN201210212021.0A CN201210212021A CN102757777B CN 102757777 B CN102757777 B CN 102757777B CN 201210212021 A CN201210212021 A CN 201210212021A CN 102757777 B CN102757777 B CN 102757777B
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linking agent
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gas reservoir
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CN102757777A (en
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刘德基
刘建伟
张坚平
龚万兴
张佩玉
刘海廷
王涛
郭伦文
隋阳
王燕
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China Petroleum and Natural Gas Co Ltd
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Abstract

The invention discloses an inhibition water locking type high temperature resistant fracturing fluid for a tight gas reservoir, applied to the technical field of yield increase of the tight gas reservoirs in the oil industry. The fracturing fluid mainly comprises a base fluid, a crosslinking agent solution and a gel breaker, wherein the base fluid comprises the following components by weight percent: 0.5-0.6 percent of hydroxypropyl guar gum, 0.3-0.5 percent of poly diallyl dimethyl ammonium chloride, 0.3-0.5 percent of PFA (Paraformaldehyde) type polyoxyethylene polyoxypropylene polyethylene segmented copolymer, 0.06-0.10 percent of N, N-di-sec-butyl-p-phenylenediamine, 1-2 percent of potassium chloride, 0.3-0.5 percent of tall polyoxyethylene oleate, 0.10-0.12 percent of an alkaline PH regulator (Na2CO3) and the balance of water; and the crosslinking agent solution comprises the following components by weight percent: 0.3-0.5 percent of organic borate cross-linker BCL-61 and the balance of water. The inhibition water locking type high temperature resistant fracturing fluid for tight gas reservoir fracturing is simple to prepare and has low surface tension, good water locking resistance and small harm on a tight gas reservoir formation.

Description

A kind of high temperature resistant fracturing liquid of inhibition water lock for tight gas reservoir pressure break
Technical field
The present invention relates to petroleum industry chemical technical field, relate in particular in a kind of oil, Natural gas extraction, the fracturing yield increasing technical field of tight gas reservoir.A kind of to the low injury of tight gas reservoir, Waterproof lock, high temperature resistant fracturing liquid.
Background technology
" water lock effect " refers in the processes such as drilling well, completion and pressure break, the water fluids such as drilling well, completion and fracturing liquid are invaded after reservoir, make reservoir water saturation to variation between 100% water saturation, increase again from initial water saturation to irreducible water saturation, vapor phase stream dynamic resistance increases, the phenomenon that causes gas phase permeability to decline.Essence is because capillary pressure has produced additional epidermis pressure drop, equals the poor of the non-wetting phase pressure in capillary menicus both sides and wetting phase pressure, and large I is determined by the Laplace equation at any bent interface.
For hyposmosis or tight gas reservoir, less for the free-pouring pore throat size of fluid in reservoir, gas phase flow passage is narrow, seepage resistance is large, liquid-solid interface and liquid gas interface interaction force are large, make water lock effect particularly outstanding, once there is water lock, permeability damage rate can reach more than 70%, gas well output can be down to original below 1/3, research shows, reservoir CLAY MINERALS AND THEIR SIGNIFICANCE (especially expanded polystyrene veneer clay mineral) and other authigenic mineral are in certain salinity, when low salinity water enters after reservoir, change due to salinity, these mineral will expand, disperse, come off and migrate, cause hole to diminish or crack closure, there is more fine pore, produce strong suction zones and cause extremely strong water blocking damage.
The current domestic on-the-spot fracturing fluid system using mostly is water base, when the fracturing liquid rubber-breaking liquid row of returning in time, easily produces strong suction zones and produces serious fracturing liquid water blocking damage, can not increase production after causing pressure break, especially tight gas reservoir pressure break.
China Patent Publication No.: CN101531892A, provides a kind of " ultra low temperature super guanidine gum fracturing fluid ".Fracturing liquid comprises following each component proportioning by mass percentage: super guanidine gum 0.20%, organic silicon polyether 0.12%, polyoxyethylene polyoxypropylene polyoxypropylene stearyl alcohol ether 0.07%, organic amine positively charged ion 0.32%, positively charged ion long chain polymer 0.09%, organic silicone oil 0.03%, borax 0.0003%, persulphate 0.00027%, high price oxysalt 0.00009%, superoxide 0.00014%, surplus is water.Good, the broken glue of this fracturing liquid anti-shear performance is thorough.
Summary of the invention
The object of the invention is: provide a kind of tight gas reservoir pressure break with suppressing the high temperature resistant fracturing liquid of water lock, preparation is simple, and excellent property, at 90 ℃, 170S -1velocity of shear down cut after one hour gel viscosity still can reach 600mPa.S above (90 ℃), Waterproof lock ability is strong, can make under the same terms reducing by 46% with a layer core damage rate, little to formation damage.
The technical solution used in the present invention is:
One, a kind of high temperature resistant of the fracturing fluid raw material of inhibition water lock for tight gas reservoir:
Raw material comprises:
1, hydroxypropylguar gum (industrial goods) English name: HPG
Character: its aqueous solution is more stable in the scope 2.0~12.0 at normal temperature or pH value, is heated to 70 ℃ of above viscositys and sharply reduces, and meets strong oxidizer degradable.Odorless, tasteless.Be insoluble to the organic solvents such as alcohol, ether, ketone, soluble in water.White or buff powder.Purposes: in fracturing liquid, general consumption is 0.3%~0.5%.Be mainly used in oil field fracturing fluid and drilling mud.Can use, and there is excellent electrolyte-resistant performance and shear thinning performance with negatively charged ion, positively charged ion, nonionogenic tenside compatibility.In drilling mud, add hydroxypropylguar gum, generally play and keep moisture, lubricated effect, reduce the dehydration of mud, alleviate the injury to stratum.Be a kind of senior non-ionic thickening agent, in water, there is good dispersing and dissolving performance.Hydroxypropylguar gum is mixed with to solution and adds linking agent, mixed with proppants together, make fracturing liquid, for oil field compression fracture, improve the oil offtake of oil well.Security: be stored in cool place, ventilation, dry storehouse, keep fire away, avoid Exposure to Sunlight, drench with rain.Factory: CNPC's goods and materials Kunshan company.
2, poly-diallyl alkyl dimethyl ammonium chloride
Song Wanchao edits " application of water-soluble cationic polymer in oil field " book, petroleum industry press, date of publication: the 1st edition the 1st printing May in 2002, the 41st page.
Character: colourless or faint yellow uniform liquid, density >=0.95g/cm3 (20 ℃), dissolves each other with water.Acid (pH=6-8), anti-swollen rate >=80, soak and wash away rate of weight loss %≤10; Purposes: the anti-expansion of oil field stratum clay stabilization; Factory: Dancheng, Henan Shun Xing petroleum assistant company limited.
3, Repone K
4, PFA type polyoxyethylene polyoxypropylene phenolic aldehyde polyethylene polyamine segmented copolymer
" exploitation volume " book in Liu Baohe chief editor " Oil Exploration in China exploitation encyclopedia ", petroleum industry press, date of publication: the 1st edition the 2nd printing July in 2009, the 530th page.Character: colourless to yellow liquid, density 0.950~1.080, pH value: 6.5~7.5; Purposes: oil-water emulsion emulsion splitter; Factory: Wanke Petroleum & Natural-Gas Technical Engineering Co., Ltd., Langfang City;
5, N, N-di-sec-butyl-p-phenyl enediamine (industrial goods)
Molecular formula: C 14h 24n 2
Structural formula:
Figure BDA00001793458500031
Character: reddish-brown liquid, density 0.942, specific refractory power 1.539; Purposes: oxidation inhibitor, antioxidant; Factory: Nanjing Hua Lida Chemical Co., Ltd..
6, tall oil acid polyoxyethylene ester (OKM)
Liu Cheng chief editor tensio-active agent application manual one book, Chemical Industry Press, date of publication: the 1st edition the 1st printing May in 1992, the 606th page.Character: yellow thick liquid, density>=0.90g/cm 3(20 ℃), dissolve each other with water.Acid (pH=6-9), surface tension≤21%mN/m, interfacial tension≤27mN/m; Purposes: suppress compact reservoir pore throat water lock; Factory: Beijing Shi great bounties company limited
7, sodium carbonate (alkaline PH conditioning agent, Na 2cO 3)
8, organic borate cross-linker BCL-61
Wang Desheng edits " the modern oil fracture acidizing mining novel technology application manual " book, Beijing petroleum industry press, date of publication: the 1st edition the 1st printing November in 2006, the 1189th page.Character: weak yellow liquid, density is 1.17g/cm 3(20 ℃), dissolve each other with water.Viscosity 4.23mPa.S(20 ℃ of .1h.170S-1), shelf-stability is good, and cross-linking properties is good, can hang with glass stick anti-shear ability>=100mPa.S(160 ℃ of .1h.170S after being cross-linked -1); Temperature resistant capability is good, can reach 150~160 ℃, has the slowly-releasing crosslinking feature of 3~12min, is applicable to high temperature deep well pressure break.Purposes: plant gel linking agent; Factory: Wanke Petroleum & Natural-Gas Technical Engineering Co., Ltd., Langfang City.
9, " organic titanium cross-linking agent " (trolamine titanic acid ester)
Wang Desheng edits " the modern oil fracture acidizing mining novel technology application manual " book, Beijing petroleum industry press, date of publication: the 1st edition the 1st printing November in 2006, the 1189th page.Character: brown liquid, density>=0.90g/cm 3(20 ℃), dissolve each other with water.Acid (PH>=7), cross-linking properties is good, can hang with glass stick anti-shear ability>=100mPa.S(180 ℃ of .1h.170S after being cross-linked -1); Temperature tolerance is greater than 170 ℃, can meet the deep well fracturing construction of 4000-5000 rice, and consumption is few, and heatproof is high.Purposes: the high temperature resistant linking agent of plant gel; Factory: Guangzhou Zheng Qingran Science and Technology Ltd..
10, water.
A kind of high temperature resistant fracturing liquid of inhibition water lock for tight gas reservoir comprises that base fluid, cross-linking agent solution and gel breaker form.The volume ratio of base fluid, cross-linking agent solution, gel breaker solution is 100:10:1.
Wherein, each weight percentages of components of base fluid is:
Hydroxypropyl guar gum: 0.5~0.6%;
Poly-diallyl alkyl dimethyl ammonium chloride: 0.3~0.5%;
PFA type polyoxyethylene polyoxypropylene phenolic aldehyde polyethylene polyamine segmented copolymer: 0.3~0.5%;
N, N-di-sec-butyl-p-phenyl enediamine: 0.06~0.10%;
Repone K: 1~2%;
Tall oil acid polyoxyethylene ester: 0.3~0.5%;
Sodium carbonate (alkaline PH conditioning agent Na 2cO 3): 0.10~0.12%;
All the other are water; Each weight percentages of components sum is 100%.
Each weight percentages of components of cross-linking agent solution is:
Organic borate cross-linker BCL-61:0.3~0.5% or organic titanium cross-linking agent 0.3~0.4%;
All the other are water; Each weight percentages of components sum is 100%.
Each weight percentages of components of gel breaker solution is:
Ammonium persulphate: 0.5~1%;
All the other are water; Each weight percentages of components sum is 100%.
Two, a kind of high temperature resistant of the fracturing fluid preparation method of inhibition water lock for tight gas reservoir:
Major equipment: with the large tank of container, scale, storage of agitator, circulation pump truck etc.
Preparation method:
A, prepare base fluid:
A, get required a certain amount of water and pour in the container with agitator; Start agitator;
B, under normal temperature and agitation condition, by formulation weight per-cent, add successively a certain amount of hydroxypropyl guar gum, poly-diallyl alkyl dimethyl ammonium chloride, PFA type polyoxyethylene polyoxypropylene phenolic aldehyde polyethylene polyamine segmented copolymer, N, N-di-sec-butyl-p-phenyl enediamine, Repone K and tall oil acid polyoxyethylene ester; Then stir 30 minutes;
C, under agitation condition, add sodium carbonate, regulate pH value to 8 ~ 10;
D, stir, make base fluid.
B, prepare cross-linking agent solution:
A, get required a certain amount of water and pour in the container with agitator; Start agitator;
B, under normal temperature and agitation condition, by formulation weight per-cent, add a certain amount of organic borate cross-linker BCL-61 or organic titanium cross-linking agent, then stir 2 minutes; Make cross-linking agent solution.
C, prepare gel breaker solution:
A, get required a certain amount of water and pour in the container with agitator; Start agitator;
B, under normal temperature and agitation condition, by formulation weight per-cent, add a certain amount of ammonium persulphate pulvis, then stir 2 minutes; Make gel breaker solution.
D, prepare the high temperature resistant fracturing liquid of inhibition water lock of tight gas reservoir:
A, get the base fluid preparing and pour in the container with agitator, start agitator;
B, the ratio that is 100:10:1 in the volume ratio of base fluid, cross-linking agent solution, gel breaker solution, add the cross-linking agent solution preparing while stirring, then adds while stirring gel breaker solution, makes tight gas reservoir and suppress the high temperature resistant fracturing liquid of water lock.
Effect of the present invention: tight gas reservoir pressure break of the present invention is with suppressing the high temperature resistant fracturing liquid of water lock, and preparation is simple, and excellent property, at 90 ℃, 170S -1velocity of shear down cut after one hour gel viscosity still can reach 600mPa.S above (90 ℃), Waterproof lock ability is strong, can make under the same terms reducing by 30~46% with a layer core damage rate, little to formation damage.
Embodiment:
Embodiment 1: tight gas reservoir waterproof lock is high temperature resistant, and fracturing liquid is comprised of base fluid, cross-linking agent solution and gel breaker.The volume ratio of base fluid, cross-linking agent solution, gel breaker solution is 100:10:1.
Wherein, each weight percentages of components of base fluid is: hydroxypropyl guar gum: 0.5%; Poly-diallyl alkyl dimethyl ammonium chloride: 0.35%; PFA type polyoxyethylene polyoxypropylene phenolic aldehyde polyethylene polyamine segmented copolymer: 0.3%; N, N-di-sec-butyl-p-phenyl enediamine: 0.07%; Repone K: 1.5%; Tall oil acid polyoxyethylene ester: 0.4%; Sodium carbonate (alkaline PH conditioning agent Na 2cO 3): 0.1%; All the other are water; Each weight percentages of components sum is 100%.
Each weight percentages of components of cross-linking agent solution is: organic borate cross-linker BCL-61:0.4%; All the other are water; Each weight percentages of components sum is 100%.
Each weight percentages of components of gel breaker solution is: ammonium persulphate: 0.5%; All the other are water; Each weight percentages of components sum is 100%.
Tight gas reservoir waterproof lock is high temperature resistant, and of the fracturing fluid preparation method comprises following operation steps:
A, prepare base fluid:
A, get required a certain amount of water and pour in the container with agitator; Start agitator;
B, under normal temperature and agitation condition, by formulation weight per-cent, add successively a certain amount of hydroxypropyl guar gum, poly-diallyl alkyl dimethyl ammonium chloride, PFA type polyoxyethylene polyoxypropylene phenolic aldehyde polyethylene polyamine segmented copolymer, N, N-di-sec-butyl-p-phenyl enediamine, Repone K and tall oil acid polyoxyethylene ester; Then stir 30 minutes;
C, under agitation condition, add sodium carbonate, regulate pH value to 8 ~ 10;
D, stir, make base fluid.
B, prepare cross-linking agent solution:
A, get required a certain amount of water and pour in the container with agitator; Start agitator;
B, under normal temperature and agitation condition, by formulation weight per-cent, add a certain amount of organic borate cross-linker BCL-61, then stir 2 minutes; Make cross-linking agent solution.
C, prepare gel breaker solution:
A, get required a certain amount of water and pour in the container with agitator; Start agitator;
B, under normal temperature and agitation condition, by formulation weight per-cent, add a certain amount of ammonium persulphate pulvis, then stir 2 minutes; Make gel breaker solution.
D, prepare the high temperature resistant fracturing liquid of inhibition water lock of tight gas reservoir:
A, get the base fluid preparing and pour in the container with agitator, start agitator;
B, the ratio that is 100:10:1 in the volume ratio of base fluid, cross-linking agent solution, gel breaker solution, add the cross-linking agent solution preparing while stirring, then adds while stirring gel breaker solution, makes tight gas reservoir and suppress the high temperature resistant fracturing liquid of water lock.
The fracturing liquid result of use of embodiment 1: at 90 ℃, 170S -1velocity of shear down cut after one hour gel viscosity still can reach 600mPa.S above (90 ℃), Waterproof lock ability is strong, can make under the same terms reducing by 36% with a layer core damage rate, little to formation damage.
Embodiment 2: tight gas reservoir waterproof lock is high temperature resistant, and fracturing liquid is comprised of base fluid, cross-linking agent solution and gel breaker.The volume ratio of base fluid, cross-linking agent solution, gel breaker solution is 100:10:1.
Wherein, each weight percentages of components of base fluid is: hydroxypropyl guar gum: 0.6%; Poly-diallyl alkyl dimethyl ammonium chloride: 0.4%; PFA type polyoxyethylene polyoxypropylene phenolic aldehyde polyethylene polyamine segmented copolymer: 0.4%; N, N-di-sec-butyl-p-phenyl enediamine: 0.08%; Repone K: 1%; Tall oil acid polyoxyethylene ester: 0.5%; Sodium carbonate (alkaline PH conditioning agent Na 2cO 3): 0.12%; All the other are water; Each weight percentages of components sum is 100%.
Each weight percentages of components of cross-linking agent solution is: organic titanium cross-linking agent 0.4%; All the other are water; Each weight percentages of components sum is 100%.
Each weight percentages of components of gel breaker solution is: ammonium persulphate: 0.8%; All the other are water; Each weight percentages of components sum is 100%.
In preparation method, the preparation of linking agent is different from embodiment 1, and other steps are identical with embodiment 1, but adds weight ratio different.Prepare cross-linking agent solution:
A, get required a certain amount of water and pour in the container with agitator; Start agitator;
B, under normal temperature and agitation condition, by formulation weight per-cent, add a certain amount of organic titanium cross-linking agent 0.4%, then stir 2 minutes; Make cross-linking agent solution.
The result of use of embodiment 2: at 90 ℃, 170S -1velocity of shear down cut after one hour gel viscosity still can reach 600mPa.S above (90 ℃), Waterproof lock ability is strong, can make under the same terms reducing by 45% with a layer core damage rate, little to formation damage.
Embodiment 3: tight gas reservoir waterproof lock is high temperature resistant, and fracturing liquid is comprised of base fluid, cross-linking agent solution and gel breaker.The volume ratio of base fluid, cross-linking agent solution, gel breaker solution is 100:10:1.
Wherein, each weight percentages of components of base fluid is: hydroxypropyl guar gum: 0.5%; Poly-diallyl alkyl dimethyl ammonium chloride: 0.5%; PFA type polyoxyethylene polyoxypropylene phenolic aldehyde polyethylene polyamine segmented copolymer: 0.5%; N, N-di-sec-butyl-p-phenyl enediamine: 0.09%; Repone K: 2%; Tall oil acid polyoxyethylene ester: 0.5%; Sodium carbonate (alkaline PH conditioning agent Na 2cO 3): 0.12%; All the other are water; Each weight percentages of components sum is 100%.
Each weight percentages of components of cross-linking agent solution is: organic borate cross-linker BCL-61:0.4%; All the other are water; Each weight percentages of components sum is 100%.
Each weight percentages of components of gel breaker solution is: ammonium persulphate: 0.8%; All the other are water; Each weight percentages of components sum is 100%.
Preparation method is identical with embodiment 1, but adds weight ratio different.
The result of use of embodiment 3: at 90 ℃, 170S -1velocity of shear down cut after one hour gel viscosity still can reach 600mPa.S above (90 ℃), Waterproof lock ability is strong, can make under the same terms reducing by 46% with a layer core damage rate, little to formation damage.

Claims (2)

1. for the high temperature resistant fracturing liquid of inhibition water lock of tight gas reservoir, it is characterized in that: comprise that base fluid, cross-linking agent solution and gel breaker form; The volume ratio of base fluid, cross-linking agent solution, gel breaker solution is 100:10:1;
Wherein, each weight percentages of components of base fluid is:
Hydroxypropyl guar gum: 0.5~0.6%;
Poly-diallyl alkyl dimethyl ammonium chloride: 0.3~0.5%;
PFA type polyoxyethylene polyoxypropylene phenolic aldehyde polyethylene polyamine segmented copolymer: 0.3~0.5%;
N, N-di-sec-butyl-p-phenyl enediamine: 0.06~0.10%;
Repone K: 1~2%;
Tall oil acid polyoxyethylene ester: 0.3~0.5%;
Sodium carbonate: 0.10~0.12%;
All the other are water; Each weight percentages of components sum is 100%;
Each weight percentages of components of cross-linking agent solution is:
Organic borate cross-linker BCL-61:0.3~0.5% or organic titanium cross-linking agent 0.3~0.4%;
All the other are water; Each weight percentages of components sum is 100%;
Each weight percentages of components of gel breaker solution is:
Ammonium persulphate: 0.5~1%;
All the other are water; Each weight percentages of components sum is 100%.
2. a kind of high temperature resistant fracturing liquid of inhibition water lock for tight gas reservoir according to claim 1, is characterized in that: preparation method comprises following operation steps:
A, prepare base fluid:
A, get required a certain amount of water and pour in the container with agitator; Start agitator;
B, under normal temperature and agitation condition, by formulation weight per-cent, add successively a certain amount of hydroxypropyl guar gum, poly-diallyl alkyl dimethyl ammonium chloride, PFA type polyoxyethylene polyoxypropylene phenolic aldehyde polyethylene polyamine segmented copolymer, N, N-di-sec-butyl-p-phenyl enediamine, Repone K and tall oil acid polyoxyethylene ester; Then stir 30 minutes;
C, under agitation condition, add sodium carbonate, regulate pH value to 8~10;
D, stir, make base fluid;
B, prepare cross-linking agent solution:
A, get required a certain amount of water and pour in the container with agitator; Start agitator;
B, under normal temperature and agitation condition, by formulation weight per-cent, add a certain amount of organic borate cross-linker BCL-61 or organic titanium cross-linking agent, then stir 2 minutes; Make cross-linking agent solution;
C, prepare gel breaker solution:
A, get required a certain amount of water and pour in the container with agitator; Start agitator;
B, under normal temperature and agitation condition, by formulation weight per-cent, add a certain amount of ammonium persulphate pulvis, then stir 2 minutes; Make gel breaker solution;
D, prepare the high temperature resistant fracturing liquid of inhibition water lock of tight gas reservoir:
A, get the base fluid preparing and pour in the container with agitator, start agitator;
B, the ratio that is 100:10:1 in the volume ratio of base fluid, cross-linking agent solution, gel breaker solution, add the cross-linking agent solution preparing while stirring, then adds while stirring gel breaker solution, makes tight gas reservoir and suppress the high temperature resistant fracturing liquid of water lock.
CN201210212021.0A 2012-06-21 2012-06-21 Inhibition water locking type high temperature resistant fracturing fluid for tight gas reservoir fracturing Active CN102757777B (en)

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CN108611082A (en) * 2016-12-13 2018-10-02 中国石油天然气股份有限公司 Clean fracturing fluid and preparation method thereof
CN113310867B (en) * 2021-05-14 2022-03-18 西南石油大学 Experimental test method for simulating gas reservoir high-temperature high-pressure stratum reverse osmosis water absorption lock damage
CN113462373B (en) * 2021-07-13 2022-08-02 中国石油大学(华东) Low-permeability oil and gas reservoir waterproof locking agent and preparation method and application thereof

Citations (3)

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Publication number Priority date Publication date Assignee Title
CN101531892A (en) * 2009-04-16 2009-09-16 大庆油田有限责任公司 Ultra low temperature super guanidine gum fracturing fluid
CN101633840A (en) * 2009-07-08 2010-01-27 中国石油天然气股份有限公司 Hydrophobic group grafted and modified guar gum fracturing fluid gel
CN102329602A (en) * 2011-08-03 2012-01-25 西安长庆化工集团有限公司 Ultralow-concentration fracturing fluid and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101531892A (en) * 2009-04-16 2009-09-16 大庆油田有限责任公司 Ultra low temperature super guanidine gum fracturing fluid
CN101633840A (en) * 2009-07-08 2010-01-27 中国石油天然气股份有限公司 Hydrophobic group grafted and modified guar gum fracturing fluid gel
CN102329602A (en) * 2011-08-03 2012-01-25 西安长庆化工集团有限公司 Ultralow-concentration fracturing fluid and preparation method thereof

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