CN112111034A - Carbon dioxide viscosity-increasing copolymer and preparation method and application thereof - Google Patents
Carbon dioxide viscosity-increasing copolymer and preparation method and application thereof Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 218
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 118
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 109
- 229920001577 copolymer Polymers 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims description 27
- 238000010526 radical polymerization reaction Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 15
- 150000003254 radicals Chemical class 0.000 claims description 15
- 230000001965 increasing effect Effects 0.000 claims description 14
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 claims description 13
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 9
- 230000001737 promoting effect Effects 0.000 claims description 9
- 239000002318 adhesion promoter Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 6
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 4
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000012530 fluid Substances 0.000 abstract description 17
- 238000006073 displacement reaction Methods 0.000 abstract description 12
- 239000003795 chemical substances by application Substances 0.000 abstract description 11
- 239000011435 rock Substances 0.000 abstract description 3
- 239000000725 suspension Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000011161 development Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005553 drilling Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- -1 n-octyl Chemical group 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000006701 (C1-C7) alkyl group Chemical group 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000003623 enhancer Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229940065472 octyl acrylate Drugs 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229930015698 phenylpropene Natural products 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229920005684 linear copolymer Polymers 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
- 230000000737 periodic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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Abstract
The invention discloses a carbon dioxide viscosity-increasing copolymer and a preparation method and application thereof. The carbon dioxide stripping and bonding copolymer comprises a structural unit A with a structure shown in a formula I, a structural unit B with a structure shown in a formula II and a structural unit C with a structure shown in a formula III;
the invention also provides a preparation method of the carbon dioxide viscosity-increasing copolymer and application of the carbon dioxide viscosity-increasing copolymer as a viscosity-increasing agent in carbon dioxide. The carbon dioxide viscosity-increasing copolymer provided by the invention can effectively increase the viscosity of carbon dioxide, adjust the rheological property, increase the suspension and conveying capacity of the carbon dioxide to rock debris and a propping agent, and increase the displacement efficiency of the carbon dioxide as a displacement fluid.
Description
Technical Field
The invention relates to the technical field of unconventional oil and gas development in the petroleum industry. More particularly, relates to a carbon dioxide viscosity-increasing copolymer, a preparation method and application thereof.
Background
China has abundant shale gas resources, and according to the investigation result of the national resources department, the recoverable reserves of the shale gas in China currently reach 6000 billions of cubic meters. With the development of economy and the adjustment of energy consumption structures, the gap of natural gas in China is larger and larger. Conventional natural gas production has not been able to meet demand, and the development of unconventional natural gas resources represented by shale gas has become a hot spot. China already brings shale gas development into the strategic emerging industry of China, and the supporting force for shale gas exploration and development is increased.
The shale gas reservoir has the characteristics of low pore pressure, low porosity, low permeability, high clay content and the like, the development difficulty is high, and large-scale commercial exploitation is difficult to realize if measures such as fracturing production increase of a horizontal well and the like are not adopted. The shale gas revolution brought by the hydraulic fracturing technology has profoundly influenced the energy industry of the united states and even the world. However, the clay mineral content of the shale gas reservoir in China is often higher, the water sensitivity is stronger, and the shale gas reservoir is mostly distributed in mountainous areas, hills and desert gobi areas with deficient water resources, so that the large-scale hydraulic fracturing is difficult to adapt to the requirements of sustainable commercial exploitation. Therefore, new technologies such as anhydrous fracturing and the like which are developed efficiently become one of the hot development directions of shale gas development. Supercritical carbon dioxide (SC-CO)2) Is considered to be a fracturing fluid with great application potential. Using SC-CO2Advantages of developing shale gas include: the rock breaking efficiency is high; the clay swelling can be avoided; enhanced recovery by promoting methane desorption; the crack expansion is enhanced, and the flowback is easy. In addition, in CO2CO can be realized in the fracturing and displacement processes2And (4) geological sequestration.
As a fracturing fluid, CO2One of the main functions of (a) is to transport proppant deep into the fracture, preventing the fracture from closing. But SC-CO2The viscosity is low, and the sand carrying effect is poor. The most direct approach to this problem is to SC-CO2The chemical viscosity increasing agent is added, so that the sand carrying capacity of the fracturing fluid is improved, and the sand fracturing is realized, thereby greatly improving the yield increasing effect. CO 22The adhesion promoter should also be provided in the presence of CO2The dissolving property and the viscosity-improving property of the composition. However, at present, research on carbon dioxide tackifiers at home and abroad is still in an exploration stage, and the tackifying performance of the small molecular tackifiers is weak, and the shear resistance of the system is poor. The vast majority of polymers are in CO2Has poor dissolving property in CO2The polymer (A) does not necessarily have good thickening properties.
Therefore, the invention provides a carbon dioxide viscosity-increasing copolymer, a preparation method and application thereof, which aim to solve the problems.
Disclosure of Invention
The first purpose of the invention is to provide a carbon dioxide viscosity-increasing copolymer; the carbon dioxide viscosity-increasing copolymer has good solubility and viscosity-increasing effect in carbon dioxide, and solves the problems of low viscosity of carbon dioxide, and poor rock-carrying, sand-carrying and displacement effects.
The second purpose of the invention is to provide a preparation method of the carbon dioxide viscosity-increasing copolymer.
The third purpose of the invention is to provide an application of the carbon dioxide viscosity-increasing copolymer.
In order to achieve the purpose, the invention adopts the following technical scheme:
a carbon dioxide stripping and bonding copolymer comprises a structural unit A with a structure shown in a formula I, a structural unit B with a structure shown in a formula II and a structural unit C with a structure shown in a formula III;
in the formula I, the formula II and the formula III,
R1、R3、R5、R6and R7Each independently represents H or an alkyl group having from C1 to C8,
R2a fluorocarbon group represented by C1 to C8,
R4represents a single bond or an alkylene group having C1 to C8.
Preferably, R1、R3、R5、R6And R7Each independently represents H or C1-C7 alkyl, R2C3-C8 fluorocarbon group, R4Represents a single bond or an alkylene group having C1 to C6.
Preferably, R1、R3、R5And R6Each independently represents H or C1-C4 alkyl, R2C4-C8 fluorocarbon group, R4Represents a single bond or an alkylene group having C1 to C4, R7Represents a C1-C7 alkyl group.
Preferably, R1、R3、R5And R6Each independently represents H, methyl, ethyl, n-propyl, isopropyl or n-butyl; r4Represents a single bond or a methylene group; r7Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl or n-octyl.
Preferably, the weight average molecular weight of the carbon dioxide viscosity-increasing copolymer is 100000-600000 g/mol; further, the weight average molecular weight of the carbon dioxide viscosity-increasing copolymer is 200000-500000 g/mol; more preferably, the weight average molecular weight of the carbon dioxide viscosity-increasing copolymer is 200000-300000 g/mol.
Preferably, the molar ratio of the structural unit A to the structural unit B to the structural unit C is 20-70: 10-40: 20-70 parts of; further, the molar ratio of the structural unit A to the structural unit B to the structural unit C is 20-30: 30-40: 30-70 parts of; more preferably 25 to 30: 35-40: 30-40.
The invention also provides a preparation method of the carbon dioxide viscosity-increasing copolymer, which comprises the following steps:
in the presence of a free radical initiator, carrying out free radical polymerization on a compound D with a structure shown in a formula I ', a compound E with a structure shown in a formula II ' and a compound F with a structure shown in a formula III ' to obtain a carbon dioxide stripping and bonding copolymer; wherein,
in the formulae I ', II ' and III ', R1、R2、R3、R5、R6And R7As previously defined, are not described in detail herein.
Preferably, the molar ratio of the compound D to the compound E to the compound F is 20-70: 10-40: 20-70 parts of; further, the molar ratio of the compound D to the compound E to the compound F is 20-30: 30-40: 30-70 parts of; more preferably 25 to 30: 35-40: 30-40.
Preferably, the free radical initiator is one or more of azobisisobutyronitrile, 4' azo (4-cyanovaleric acid), azobisisobutylamidine hydrochloride, azobisisopropylimidazoline hydrochloride, and azobisisobutylimidazoline hydrochloride.
Preferably, the amount of the radical initiator is 0.08 to 0.21mmol, more preferably 0.10 to 0.15mmol, based on 1mol of the total amount of the compound D, the compound E and the compound F.
Preferably, the conditions of the radical polymerization reaction include: under the protection of inert gas, the temperature of free radical polymerization is 40-80 ℃, and the time of free radical polymerization is 6-36 h.
Preferably, the conditions of the radical polymerization reaction include: under the protection of inert gas, the temperature of free radical polymerization is 55-65 ℃, and the time of free radical polymerization is 20-30 h.
Preferably, the inert gas comprises at least one of nitrogen or a gas of an element of group zero of the periodic table of the elements, which is conventional in the art, and more preferably nitrogen.
Preferably, the preparation method of the carbon dioxide viscosity-increasing copolymer specifically comprises the following steps: firstly, mixing a compound D with a structure shown in a formula I ', a compound E with a structure shown in a formula II ' and a compound F with a structure shown in a formula III ', adding a free radical initiator, and carrying out free radical polymerization reaction under an inert gas atmosphere to obtain the carbon dioxide viscosity-increasing copolymer. The method can better control the progress of the free radical polymerization reaction.
Preferably, the free radical polymerization reaction is followed by a step of vacuum drying the obtained product, thereby extracting the carbon dioxide viscosity-enhanced copolymer from the product of the free radical polymerization reaction.
The invention also provides the carbon dioxide viscosity-increasing copolymer prepared by the preparation method.
The invention also provides the application of the carbon dioxide viscosity-increasing copolymer or the carbon dioxide viscosity-increasing copolymer prepared by the preparation method in carbon dioxide as a viscosity-increasing agent.
The invention also provides the viscosity increasing effect of the carbon dioxide viscosity increasing copolymer in carbon dioxide.
The invention also provides a carbon dioxide drilling fluid, a fracturing fluid and a displacement fluid which use the carbon dioxide viscosity-increasing copolymer or the carbon dioxide viscosity-increasing copolymer prepared by the method as a viscosity-increasing agent.
The invention also provides application of the carbon dioxide drilling fluid, the fracturing fluid and the displacement fluid in oil and gas drilling, oil and gas reservoir transformation and oil and gas displacement respectively.
In addition, unless otherwise specified, any range recited herein includes any value between the endpoints and any sub-range defined by any value between the endpoints or any value between the endpoints.
The invention has the following beneficial effects:
the carbon dioxide viscosity-increasing copolymer provided by the invention can effectively increase the viscosity of carbon dioxide, adjust the rheological property, increase the suspension and conveying capacity of the carbon dioxide to rock debris and a propping agent, and increase the displacement efficiency of the carbon dioxide as a displacement fluid.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows CO at 35 ℃ under 30MPa in example 1 of the present invention2The phase of the adhesion promoter system as a function of the viscosity with the mass concentration of carbon dioxide adhesion promoter copolymer A1.
FIG. 2 shows CO at 35 ℃ under 30MPa in example 2 of the present invention2The phase of the adhesion promoter system as a function of the viscosity with the mass concentration of carbon dioxide adhesion promoter copolymer A2.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
In the invention, the preparation method is a conventional method if no special description is provided; the starting materials used are commercially available from published sources unless otherwise specified.
The invention provides a carbon dioxide stripping and bonding copolymer, which comprises a structural unit A with a structure shown in a formula I, a structural unit B with a structure shown in a formula II and a structural unit C with a structure shown in a formula III;
in the formula I, the formula II and the formula III,
R1、R3、R5、R6and R7Each independently represents H or a C1-C8 alkyl group, and the C1-C8 alkyl group may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, an n-heptyl group, an n-nonyl group, or the like.
R2A fluorocarbon group represented by C1 to C8,
R4represents a single bond or an alkylene group having from C1 to C8, wherein the single bond may be considered to be R4The groups at both ends are directly connected.
The carbon dioxide viscosity-increasing copolymer can fully expand molecular chains in carbon dioxide, is mixed with the carbon dioxide to form a single phase, and forms a spatial network structure through intermolecular association and intermolecular mutual winding, so that the viscosity of the carbon dioxide is greatly increased.
In order to be able to better exert the effect of the copolymer as a viscosity enhancer, R is a preferred embodiment of the present invention1、R3、R5、R6And R7Each independently represents H or C1-C7 alkyl, R2C3-C8 fluorocarbon group, R4Represents a single bond or an alkylene group having C1 to C6.
More preferably, R1、R3、R5And R6Each independently represents H or C1-C4 alkyl, R2C4-C8 fluorocarbon group, R4Represents a single bond or an alkylene group having C1 to C4, R7Represents a C1-C7 alkyl group.
More preferably, R1、R3、R5And R6Each independently represents H, methyl, ethyl, n-propyl, isopropyl or n-butyl; r4Represents a single bond or a methylene group; r7Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl or n-octyl.
According to the invention, the weight average molecular weight of the carbon dioxide viscosity-increasing copolymer is preferably 100000-600000 g/mol, preferably 150000-500000 g/mol, more preferably 200000-300000 g/mol. When the weight average molecular weight of the carbon dioxide adhesion promoting copolymer is within the above range, particularly within the range of 200000 to 300000g/mol, the obtained carbon dioxide adhesion promoting copolymer can be preferably used as an adhesion promoter, and can maintain a good adhesion promoting performance in carbon dioxide.
According to the present invention, although the amount of the structural unit a having a structure represented by formula I, the structural unit B having a structure represented by formula II and the structural unit C having a structure represented by formula III contained in the carbon dioxide stripping and bonding copolymer can be varied within a wide range, it is preferable that the molar ratio of the structural unit a, the structural unit B and the structural unit C is 20 to 70 in view of optimizing the stripping and bonding performance of the resulting carbon dioxide stripping and bonding copolymer: 10-40: 20-70, preferably 20-30: 30-40: 30 to 70, preferably 25 to 30: 35-40: 30-40.
According to the invention, the carbon dioxide viscosity-increasing copolymer is understood to be a linear copolymer, which may be random, block, alternating, but is generally understood to be a linear random copolymer. Although the copolymer may further include some other structural units which do not affect its performance as a viscosity enhancer, it is to be understood that the carbon dioxide viscosity enhancer copolymer is composed of a structural unit a having a structure represented by formula I, a structural unit B having a structure represented by formula II, and a structural unit C having a structure represented by formula III for convenience, but the terminal group is not particularly limited but is generally hydrogen.
The invention also provides a preparation method of the carbon dioxide viscosity-increasing copolymer, which comprises the following steps:
in the presence of a free radical initiator, carrying out free radical polymerization on a compound D with a structure shown in a formula I ', a compound E with a structure shown in a formula II ' and a compound F with a structure shown in a formula III ' to obtain a carbon dioxide stripping and bonding copolymer; wherein,
in the formulae I ', II ' and III ', R1、R3、R5、R6And R7Each independently represents H and/or C1-C8 alkyl, R2C1-C8 fluorocarbon group, R4Represents a single bond or an alkylene group having C1 to C8.
R in the above1、R2、R3、R5、R6And R7As described above, no further description is provided herein. The compound D having the structure represented by formula I ', the compound E having the structure represented by formula II ', and the compound F having the structure represented by formula III ' may also be appropriately selected according to the kinds of the specific structural unit a, structural unit B, and structural unit C of the carbon dioxide stripping copolymer described hereinabove.
The amount of the monomer compound may be selected according to the ratio of the structural units of the desired copolymer and the molecular weight, and as a preferred embodiment of the present invention, the molar ratio of the compound D, the compound E and the compound F is 20 to 70: 10-40: 20-70, preferably 20-30: 30-40: 30 to 70, preferably 25 to 30: 35-40: 30-40, most preferably 25: 40: 35.
the radical polymerization reaction may be initiated using various radical initiators conventionally used in the art, but in view of reactivity among the above-mentioned monomers, the radical initiator is one or more of azobisisobutyronitrile, 4' -azo (4-cyanovaleric acid), azobisisobutylamidine hydrochloride, azobisdiisopropylimidazoline hydrochloride, and azobisisobutylimidazoline hydrochloride, as a preferred embodiment of the present invention. The amount of the radical initiator can vary within wide limits, and is preferably from 0.08 to 0.21mmol, preferably from 0.10 to 0.15mmol, based on 1mol of the total of the compound D, the compound E and the compound F.
In order to be able to maintain the activity of the radical initiator and the like, the method may further include, as a preferred embodiment of the present invention: the radical polymerization is carried out in an inert atmosphere, for example, one or more of nitrogen, helium, neon, argon and the like may be introduced into the system and the air therein may be replaced.
In a preferred embodiment of the present invention, the temperature of the radical polymerization reaction is 40 to 80 ℃, and the time of the radical polymerization reaction is 6 to 36 hours; further preferably, the temperature of the free radical polymerization reaction is 55-65 ℃, and the time of the free radical polymerization reaction is 20-30 h.
In order to better control the proceeding of the above free radical polymerization reaction, as a preferred embodiment of the present invention, the preparation method of the carbon dioxide stripping and bonding copolymer specifically comprises the following steps: mixing a compound D with a structure shown in a formula I ', a compound E with a structure shown in a formula II ' and a compound F with a structure shown in a formula III ', adding a free radical initiator, and carrying out free radical polymerization reaction under an inert gas atmosphere (for example, one or more of nitrogen, helium, neon and argon can be introduced into the system, and air in the system can be replaced), thereby obtaining the carbon dioxide stripping and bonding copolymer.
According to the present invention, in order to be able to extract the carbon dioxide adhesion promoting copolymer from the product of the radical polymerization reaction, the method may further comprise: and (3) drying the product of the free radical polymerization reaction in vacuum to obtain the carbon dioxide viscosity-increasing copolymer.
The invention also provides the carbon dioxide viscosity-increasing copolymer prepared by the preparation method. Although the present invention is not particularly limited, the carbon dioxide adhesion promoting copolymer may be considered as one of the carbon dioxide adhesion promoting copolymers described hereinabove, or a mixture of a plurality of carbon dioxide adhesion promoting copolymers. It will of course be understood that the carbon dioxide visbroken copolymer produced by the above process is generally the direct product of the above process without purification (or after just vacuum drying as described above), and that the present invention includes such cases within the scope of the invention, although such products may be mixtures of polymers.
The invention also provides the application of the carbon dioxide viscosity-increasing copolymer or the carbon dioxide viscosity-increasing copolymer prepared by the preparation method in carbon dioxide as a viscosity-increasing agent.
The invention also provides the viscosity increasing effect of the carbon dioxide viscosity increasing copolymer in carbon dioxide.
The invention also provides a carbon dioxide drilling fluid, a fracturing fluid and a displacement fluid which use the carbon dioxide viscosity-increasing copolymer or the carbon dioxide viscosity-increasing copolymer prepared by the method as a viscosity-increasing agent.
The invention also provides application of the carbon dioxide drilling fluid, the fracturing fluid and the displacement fluid in oil and gas drilling, oil and gas reservoir transformation and oil and gas displacement respectively.
The present invention will be further described with reference to the following examples.
Example 1
The embodiment provides a preparation method of a carbon dioxide viscosity-increasing copolymer A1, which comprises the following steps:
mixing 3,3,4,4,5,5,6,6,7,8,8, 8-dodecafluoro-7- (trifluoromethyl) octyl acrylate, methyl acrylate and allyl benzene (molar ratio 3: 4: 3) in a polymerization tube, and adding azobisisobutyronitrile as a radical initiator thereto; after three times of freeze-thaw cycle to completely remove oxygen, decompressing and sealing the polymerization tube, and reacting for 24 hours at 60 ℃; the reaction product is dissolved in 1,1, 2-trichlorotrifluoroethane, then is precipitated twice in methanol for purification, and the reaction product collected after filtration is dried in vacuum to obtain the carbon dioxide viscosity-increasing copolymer A1.
The weight average molecular weight of the carbon dioxide viscosity-increasing copolymer A1 is 210000g/mol, the molecular weight distribution coefficient is 1.3, and the molar ratio of a structural unit A with a structure shown in a formula I, a structural unit B with a structure shown in a formula II and a structural unit C with a structure shown in a formula III is 3 through infrared and nuclear magnetic resonance hydrogen spectrum and carbon spectrum analysis and detection: 3.5: 3.4.
the embodiment also provides a method for measuring the viscosity increasing effect of the carbon dioxide viscosity increasing copolymer A1, which comprises the following steps:
carbon dioxide and the carbon dioxide viscosity-increasing copolymer A1 prepared in this example were added to a high-pressure viscosity measurement experimental apparatus, and the viscosity-increasing effect of the viscosity-increasing agent was measured by a falling ball method. Introducing CO2Viscosity number of the adhesion promoter System with pure CO measured under the same conditions of temperature and pressure2The viscosity values of (A) and (B) are compared, and the ratio, namely the viscosity-increasing factor, is used for evaluating the viscosity-increasing performance of the viscosity-increasing agent, wherein the larger the viscosity-increasing factor is, the better the viscosity-increasing performance is. As can be seen from FIG. 1, the carbon dioxide viscosity-enhancing copolymer A1 of the present invention shows a significant viscosity-enhancing effect in carbon dioxide, effectively increasing the viscosity of carbon dioxide.
Example 2
The embodiment provides a preparation method of a carbon dioxide viscosity-increasing copolymer A2, which comprises the following steps:
mixing 3,3,4,4,5,5,6,6,7,8,8, 8-dodecafluoro-7- (trifluoromethyl) octyl acrylate, ethyl acrylate and allyl benzene (molar ratio 4: 4: 2) in a polymerization tube, and adding azobisisobutyronitrile as a radical initiator thereto; after three times of freeze-thaw cycle to completely remove oxygen, decompressing and sealing the polymerization tube, and reacting for 24 hours at 60 ℃; the reaction product is dissolved in 1,1, 2-trichlorotrifluoroethane, then is precipitated twice in methanol for purification, and the reaction product collected after filtration is dried in vacuum to obtain the carbon dioxide viscosity-increasing copolymer A2.
The weight average molecular weight of the carbon dioxide viscosity-increasing copolymer A2 is 150000g/mol, the molecular weight distribution coefficient is 1.35, and the molar ratio of a structural unit A with a structure shown in a formula I, a structural unit B with a structure shown in a formula II and a structural unit C with a structure shown in a formula III is 4 through infrared and nuclear magnetic resonance hydrogen spectrum and carbon spectrum analysis and detection: 4.5: 3.8.
the embodiment also provides a method for measuring the viscosity increasing effect of the carbon dioxide viscosity increasing copolymer A2, which comprises the following steps:
carbon dioxide and the carbon dioxide viscosity-increasing copolymer A2 prepared in this example were added to a high-pressure viscosity measurement experimental apparatus, and the viscosity-increasing effect of the viscosity-increasing agent was measured by a falling ball method. As can be seen from FIG. 2, the carbon dioxide-enhanced viscosity-enhancing copolymer A2 of the present invention shows a significant viscosity enhancing effect in carbon dioxide, which effectively enhances the viscosity of carbon dioxide.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. A carbon dioxide viscosity-increasing copolymer is characterized by comprising a structural unit A with a structure shown in a formula I, a structural unit B with a structure shown in a formula II and a structural unit C with a structure shown in a formula III;
in the formula I, the formula II and the formula III,
R1、R3、R5、R6and R7Each independently represents H or an alkyl group having from C1 to C8,
R2a fluorocarbon group represented by C1 to C8,
R4represents a single bond or an alkylene group having C1 to C8.
2. The carbon dioxide viscosity-enhancing copolymer of claim 1, wherein the weight average molecular weight of the carbon dioxide viscosity-enhancing copolymer is 100000-600000 g/mol.
3. The carbon dioxide viscosity increasing copolymer according to claim 1, wherein the molar ratio of the structural unit A to the structural unit B to the structural unit C is 20-70: 10-40: 20 to 70 parts by weight.
4. The preparation method of the carbon dioxide viscosity-increasing copolymer is characterized by comprising the following steps: in the presence of a free radical initiator, carrying out free radical polymerization on a compound D with a structure shown in a formula I ', a compound E with a structure shown in a formula II ' and a compound F with a structure shown in a formula III ' to obtain a carbon dioxide stripping and bonding copolymer; wherein,
in the formulae I ', II ' and III ', R1、R3、R5、R6And R7Each independently represents H or C1-C8 alkyl, R2C1-C8 fluorocarbon group, R4Represents a single bond or an alkylene group having C1 to C8.
5. The method for preparing the carbon dioxide viscosity-increasing copolymer according to claim 4, wherein the molar ratio of the compound D to the compound E to the compound F is 20-70: 10-40: 20 to 70 parts by weight.
6. The method of claim 4, wherein the free radical initiator is one or more of azobisisobutyronitrile, 4' azo (4-cyanovaleric acid), azobisisobutylamidine hydrochloride, azobisdiisopropylimidazoline hydrochloride, and azobisisobutylimidazoline hydrochloride.
7. The method for preparing a carbon dioxide stripping and bonding copolymer according to claim 4, wherein the amount of the free radical initiator is 0.08 to 0.21mmol based on 1mol of the total amount of the compound D, the compound E and the compound F.
8. The method of claim 4, wherein the free-radical polymerization conditions comprise: under the protection of inert gas, the temperature of free radical polymerization is 40-80 ℃, and the time of free radical polymerization is 6-36 h.
9. A carbon dioxide viscosity-increasing copolymer prepared by the preparation method of any one of claims 4 to 8.
10. Use of a carbon dioxide adhesion promoting copolymer as defined in any one of claims 1 to 3 and claim 9 as an adhesion promoter in carbon dioxide.
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