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A kind of acrylamide series copolymer and its preparation method and application

An acrylamide-based, copolymer technology, applied in chemical instruments and methods, drilling compositions, etc., can solve the problems of poor fluid loss resistance, insignificant water-sensitivity effect, limited resistance-reducing performance, etc. Capacitive, simple monomer conversion, high drag reduction effect

Active Publication Date: 2016-06-29
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] At present, the use of guar gum and its derivatives, cellulose and its derivatives as the drag reducing agent in drag reducing water fracturing has improved the pump injection displacement to a certain extent and reduced the frictional resistance in the pipeline (US5697444, US5271466), However, it is still unable to meet the requirements of drag-reducing water fracturing, mainly due to the following disadvantages of the above-mentioned biopolymers: (1) limited drag-reducing performance; The substances are very easy to cause damage to the formation; (3) the dissolution time is long
[0006] In the construction of drag reducing water fracturing, acrylamide polymers (partially hydrolyzed polyacrylamide) are often used as the drag reducing agent in drag reducing water fracturing, which greatly improves the pump injection displacement and reduces the flow rate in the pipeline. However, when used as a drag reducing agent for water fracturing in shale gas reservoirs, there are the following important defects: (1) In order to reduce the "water-sensitive effect" in the fracturing process, the clay component in shale is suppressed Hydration expansion helps the flowback of fracturing fluid to reduce "water plugging". Some alcohol must be added to the fracturing fluid, but the compatibility of partially hydrolyzed polyacrylamide and its emulsion products with alcohol is poor, and precipitation is easy to occur; (2) Partially hydrolyzed polyacrylamide used as a drag reducing agent for shale gas reservoirs has poor fluid loss resistance, and this kind of drag reducing water fracturing fluid is very easy to filter out into the formation; (3) The temperature and salt resistance is poor, especially under the conditions of high salinity and high divalent ion content, the molecular structure is unstable, and the drag reduction effect drops rapidly; (4) the traditional high molecular weight acrylamide polymer is not easy to degrade, Easy to cause permanent damage to extremely tight shale formations
[0007] Patent US20090298721A1 discloses a formula of drag reducing water fracturing fluid: add 0.5 gallons of acrylamide-co-acrylic acid copolymer (FR-56 TM ) and other anionic acrylamide copolymer emulsions as drag reducing agents, and then adding complexing agents such as 0.15wt% sodium carbonate or EDTA-2Na, the drag reducing water fracturing fluid has excellent drag reducing performance, and the indoor average drag reducing rate reaches 65.0%, the salt resistance (especially the tolerance to divalent calcium ions) has been improved to a certain extent, but this kind of drag-reducing water fracturing system is used as a shale gas drag-reducing water fracturing fluid, and there are the following problems (1) The compatibility with alcohol is poor, and it is easy to produce precipitation when it interacts with methanol and other alcohols; (2) The anti-filtration performance is poor, and this kind of drag-reducing water fracturing fluid is very easy to filter into the formation; (3) ) has a significant "water-sensitive effect" in actual construction; (4) "water blockage" is very easy to occur; (5) the high-speed shear resistance is poor, unstable under high-speed shear, and the resistance reduction rate drops rapidly; ( 6) The temperature resistance and salt resistance are poor, especially under the conditions of high salinity and high divalent ion content, the molecular structure is unstable, and the drag reduction effect drops rapidly; Permanent damage, contaminating the formation, and then affecting oil and gas production
The copolymer with this kind of structure has better compatibility with alcohol and better compatibility with clay inhibitors (such as KCl). Not easy to degrade, easy to cause permanent damage to extremely tight shale formations

Method used

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  • A kind of acrylamide series copolymer and its preparation method and application
  • A kind of acrylamide series copolymer and its preparation method and application
  • A kind of acrylamide series copolymer and its preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0084] This example is used to illustrate the preparation of acrylamide copolymer by the solution polymerization method provided by the present invention.

[0085] At room temperature, 38.38g of acrylamide (AM), 39.65g of M1 monomer represented by formula (37), 4.03g of N,N-dimethylacrylamide (purchased from Sigma-Aldrich Company) and 0.41g The M2 monomer represented by the formula (38) (obtained according to the method of document Macromolecular Bioscience, 2006, 6(7), 540-554, the same below) was added into the reaction flask, 329.88g of deionized water was added, and stirred to make the single The body is completely dissolved and stirred evenly. 5.4 g of 1% by weight aqueous EDTA solution, 2.0 g of 1% by weight azobisisobutylamidine hydrochloride aqueous solution, and 0.12 g of urea were respectively added to the flask, and stirred well to make them uniform. Use 1% by weight of sodium hydroxide solution to pH 7.4, add 1.1 g of 0.5% by weight of sodium bisulfite solution, c...

Embodiment 2

[0094] This example is used to illustrate the preparation of acrylamide copolymer by the solution polymerization method provided by the present invention.

[0095] At room temperature, 35.23g of methacrylamide, 72.1g of M3 monomer shown in formula (40), 10.25g of tert-butyl acrylate and 0.01g of M2 monomer shown in formula (38) were added to the polymerization In the bottle, add 218.38g of deionized water, stir to dissolve the monomer completely, add 7.56g of 1% by weight of EDTA aqueous solution to the flask, add 2.13g of 1% by weight of azobisisobutylamidine hydrochloride aqueous solution, add Add 0.20 g of urea to 3.2 g of 0.1% by weight sodium bisulfite solution, and stir well to make it evenly mixed. The initial temperature of the system was controlled to 8°C, and after 30 minutes of deoxygenation with nitrogen, 1.0 g of 1% ammonium persulfate aqueous solution was added and nitrogen deoxygenation was continued for 10 minutes. Seal the reactor and keep it at 8°C. After re...

Embodiment 3

[0099] This example is used to illustrate the preparation of acrylamide copolymer by the solution polymerization method provided by the present invention.

[0100] At room temperature, 14.38g of methacrylamide, 11.61g of M4 monomer shown in formula (42), 7.12g of N-tert-butylacrylamide and 0.06g of M2 monomer shown in formula (38) Add it into the reaction bottle, add 77.26g of deionized water, stir to dissolve the monomer completely, and stir evenly. 4.65 g of 1% by weight aqueous EDTA solution, 1.03 g of 1% by weight azobisisobutylamidine hydrochloride aqueous solution, and 0.21 g of urea were respectively added to the flask, and stirred well to make them evenly mixed. The pH was adjusted to 7.1 with solid sodium hydroxide. Add 1.1 g of 0.5% by weight sodium bisulfite solution, control the initial temperature of the system to 10° C., and add 1.1 g of 1% by weight ammonium persulfate aqueous solution after nitrogen deoxygenation for 30 minutes, and continue nitrogen deoxygena...

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Abstract

The invention discloses an acrylamide copolymer, and a preparation method and an application thereof. The acrylamide copolymer contains a constitutional unit A, a constitutional unit B, a constitutional unit C and a constitutional unit D, wherein the constitutional unit A is a constitutional unit represented by formula (1) and / or a constitutional unit represented by formula (2), the constitutional unit B is one or more of constitutional units represented by formula (3), formula (4), formula (5) and formula (6) respectively, the constitutional unit C is a constitutional unit represented by formula (7) and / or a constitutional unit represented by formula (8), and the constitutional unit D is a constitutional unit represented by formula (9) and / or a constitutional unit represented by formula (10); and the viscosity average molecular weight of the acrylamide copolymer is 2,000,000-25,000,000. The acrylamide copolymer has the advantages of high drag reduction rate, high heat and salt resistance, good high-shear resistance, good water solubility, good compatibleness with clay inhibitors (alcohol), and small damages to the stratum.

Description

technical field [0001] The invention relates to an acrylamide copolymer and its preparation method and application. Background technique [0002] As a typical representative of the utilization of unconventional oil and gas resources - the exploitation of shale gas (oil) resources has become a revolution in the field of unconventional oil and gas resources in the world. Key technologies. Due to the extremely tight oil and gas reservoirs such as shale gas reservoirs have the characteristics of extremely low permeability (generally less than 0.5mD), high fracturing pressure, and easy formation damage. The "drag reducing water (slick water) fracturing" process must be used for mining. [0003] "Slick water (slick water) fracturing" is a kind of hydraulic fracturing. Compared with the current conventional fracturing system (modified guar gum cross-linking system), drag-reducing water (slick water) fracturing does not rely on high-viscosity colloid to carry sand, but carries sa...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F220/56C08F220/58C08F220/60C08F220/54C08F220/18C08F220/36C08F4/40C08F4/04C08F2/32C08F2/10C09K8/68
Inventor 杜凯黄凤兴林蔚然
Owner CHINA PETROLEUM & CHEM CORP
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