CN117720901A - Water-based polymer fracturing fluid and application thereof - Google Patents
Water-based polymer fracturing fluid and application thereof Download PDFInfo
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- CN117720901A CN117720901A CN202311722170.6A CN202311722170A CN117720901A CN 117720901 A CN117720901 A CN 117720901A CN 202311722170 A CN202311722170 A CN 202311722170A CN 117720901 A CN117720901 A CN 117720901A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 120
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- 239000003431 cross linking reagent Substances 0.000 claims abstract description 50
- 239000002562 thickening agent Substances 0.000 claims abstract description 28
- 239000000839 emulsion Substances 0.000 claims abstract description 25
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 25
- 230000000269 nucleophilic effect Effects 0.000 claims abstract description 23
- 230000004048 modification Effects 0.000 claims abstract description 15
- 238000012986 modification Methods 0.000 claims abstract description 15
- 238000010276 construction Methods 0.000 claims abstract description 12
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- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 229920001661 Chitosan Polymers 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 32
- 239000000178 monomer Substances 0.000 abstract description 7
- 230000002209 hydrophobic effect Effects 0.000 abstract description 6
- 238000004090 dissolution Methods 0.000 abstract description 5
- 238000006845 Michael addition reaction Methods 0.000 abstract description 3
- 239000002585 base Substances 0.000 description 30
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 18
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 14
- 239000013535 sea water Substances 0.000 description 12
- 239000003446 ligand Substances 0.000 description 11
- LYPJRFIBDHNQLY-UHFFFAOYSA-J 2-hydroxypropanoate;zirconium(4+) Chemical group [Zr+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O LYPJRFIBDHNQLY-UHFFFAOYSA-J 0.000 description 9
- 230000001105 regulatory effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004576 sand Substances 0.000 description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
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- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
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- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- -1 alkyl quaternary ammonium salt Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 description 2
- SYZRZLUNWVNNNV-UHFFFAOYSA-N 2-bromoacetyl chloride Chemical compound ClC(=O)CBr SYZRZLUNWVNNNV-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
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- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of fracturing fluids, in particular to a water-based polymer fracturing fluid and application thereof. The water-based polymer fracturing fluid comprises a base fluid, a normal-temperature cross-linking agent and an organozirconium cross-linking agent; the base solution contains a thickening agent, wherein the thickening agent is an emulsion of a polymer obtained by polymerizing polyethylene glycol methacrylate, acrylamide and comonomer and then modifying the polymer by nucleophilic groups. According to the invention, through Michael addition reaction of nucleophilic groups in the polymer and mercapto groups of the normal-temperature cross-linking agent at normal temperature, the polymer is cross-linked to form gel, the normal-temperature cross-linking agent does not influence the cross-linking of the organic zirconium cross-linking agent at high temperature, and functional monomers in the polymer do not contain hydrophobic structures before and after modification, so that the dissolution speed and viscosity release of the polymer are not influenced. The water-based polymer fracturing fluid can freely regulate and control the crosslinking time of the system without influencing the high temperature resistance of the system, and is particularly suitable for fracturing construction of offshore high temperature oil reservoirs.
Description
Technical Field
The invention relates to the technical field of fracturing fluids, in particular to a water-based polymer fracturing fluid and application thereof.
Background
Compared with land fracturing, offshore fracturing has the limited conditions of single well cost far higher than that of land, limited working space and loading capacity, small fracturing scale, poor continuity, deep buried low permeability reservoir, high temperature and the like. The artificially synthesized polyacrylamide emulsion or suspension prepared by processing polyacrylamide dry powder has the characteristics of instant dissolution, no mixing and the like, can save the working space of a platform, and meanwhile, the temperature-resistant and salt-resistant polymer has good high-temperature-resistant and salt-resistant rheological properties. Therefore, the water-based polymer fracturing fluid can effectively improve the dilemma of offshore fracturing construction.
In order to improve the temperature resistance and salt tolerance of the water-based polymer fracturing fluid, at present, organic zirconium is mostly adopted as a cross-linking agent, and a ligand contained in the water-based polymer fracturing fluid can chelate calcium and magnesium ions in seawater, so that the phenomena of cross-linking and gel dehydration caused by the increase of the degree of hydrolysis of the polymer at high temperature are avoided, and meanwhileThe zirconium ion can be controlled to be released continuously after being higher than a certain temperature, a reticular cross-linking structure with certain strength is ensured to be maintained in the gel under the condition of high-temperature shearing, and the stable sand carrying is convenient to realize, so that the offshore fracturing construction requirement is met. The existing problem is that the organic zirconium cross-linking agent has low cross-linking degree with the polymer at normal temperature, and the whole fracturing fluid presents a linear gel state. The construction displacement is more than 4m due to limited offshore conditions 3 Below/min, the linear glue cannot carry sand effectively. Although the temperature of the offshore hypotonic reservoir is higher, the fracturing fluid can be rapidly crosslinked after the temperature of the fracturing fluid is increased, a large amount of low-temperature fluid enters a shaft and a stratum, the temperature rising speed of the fluid is slower, the fracturing fluid can have the phenomenon of crosslinking hysteresis, the sand carrying performance of the fluid is affected, and even sand blockage is caused.
In view of the above problems, there are generally two methods to solve. Petrochemical applications, 2021, 40 (7): 45-49., in the ocean, (in the ocean, temperature control cross-linking fracturing fluid research and application, petrochemical technology, 2022, 29 (7): 28-29.)) control cross-linking time by adjusting the addition of cross-linking agent, korean non (Korean non-polymer slow-release cross-linking system research and development and application in fracturing fluid, siam: shanxi science and technology university, 2022.)) control cross-linking time by adjusting the kind of ligand in cross-linking agent, and the several researches directly adjust the composition or the amount of organic zirconium cross-linking agent, which can affect the performance of the fracturing fluid at high temperature while not solving the problems of low cross-linking degree, low viscosity and poor portability of the fracturing fluid at normal temperature; the second method is to realize effective crosslinking at normal temperature by adjusting the structure of the polymer, such as Zhang Yin and the like (Zhang Yin, liu Tongyi, huang Junxiong. A chemically crosslinkable self-association polymer research. Applied chemical industry, 2023, 52 (3): 697-700, 707.) designs and synthesizes a chemically crosslinkable molecular self-association polymer which can form a self-association network structure similar to crosslinking in aqueous solution, and solves the problem of low crosslinking degree of fracturing fluid at normal temperature, but the polymer of the hydrophobic association structure is difficult to prepare into polymer emulsion because of amphipathy of hydrophobic monomer, and if the polymer dry powder is used for preparing suspension, the hydrophobic association structure can lead the dissolution rate of the polymer to be slower than that of the conventional polymer, and is difficult to avoid being mixed and used, so the polymer is not suitable for application in offshore fracturing construction. In summary, no method for controlling the effective crosslinking of water-based polymer fracturing fluids at both normal and elevated temperatures has been found.
Disclosure of Invention
The invention aims to solve the problem that the water-based polymer fracturing fluid in the prior art cannot be effectively crosslinked at normal temperature and high temperature, and provides the water-based polymer fracturing fluid and the application thereof.
To achieve the above object, a first aspect of the present invention provides a water-based polymer fracturing fluid comprising: a base liquid, a normal temperature cross-linking agent and an organic zirconium cross-linking agent; the base solution contains a thickening agent, wherein the thickening agent is an emulsion of a polymer obtained by polymerizing polyethylene glycol methacrylate, acrylamide and comonomer and then modifying the polymer by nucleophilic groups.
The second aspect of the invention provides an application of the water-based polymer fracturing fluid in offshore high-temperature oil reservoir fracturing construction.
Through the technical scheme, the invention has the following advantages:
the invention uses the polyethylene glycol methacrylate, acrylamide and comonomer to polymerize, and then the base solution of the polymer emulsion thickener obtained by nucleophilic group modification and the sulfhydryl group on the normal temperature cross-linking agent are subjected to Michael addition reaction under the normal temperature condition, so that the polymer is cross-linked to form gel; meanwhile, the normal-temperature crosslinking agent does not occupy carboxyl groups required by crosslinking of the organozirconium crosslinking agent, the crosslinking of the organozirconium crosslinking agent at high temperature is not influenced, the functional monomer introduced into the polymer does not contain a hydrophobic structure before and after modification, and the dissolution speed and viscosity release of the polymer are not influenced.
The water-based polymer fracturing fluid disclosed by the invention is applied to offshore high-temperature oil reservoir fracturing construction, and has the advantages of freely regulating and controlling the crosslinking time of a system, simultaneously not affecting the high-temperature resistance of the system, effectively crosslinking at normal temperature and high temperature, and ensuring stable sand carrying in the whole offshore fracturing construction process.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a water-based polymer fracturing fluid, which comprises the following components: a base liquid, a normal temperature cross-linking agent and an organic zirconium cross-linking agent; the base solution contains a thickening agent, wherein the thickening agent is an emulsion of a polymer obtained by polymerizing polyethylene glycol methacrylate, acrylamide and comonomer and then modifying the polymer by nucleophilic groups.
The invention uses the polyethylene glycol methacrylate, acrylamide and comonomer to polymerize, and then the base solution of the polymer emulsion thickener obtained by nucleophilic group modification and the sulfhydryl group on the normal temperature cross-linking agent are subjected to Michael addition reaction under the normal temperature condition, so that the polymer is cross-linked to form gel; meanwhile, the normal-temperature crosslinking agent does not occupy carboxyl groups required by crosslinking of the organozirconium crosslinking agent, the crosslinking of the organozirconium crosslinking agent at high temperature is not influenced, the functional monomer introduced into the polymer does not contain a hydrophobic structure before and after modification, and the dissolution speed and viscosity release of the polymer are not influenced.
According to a preferred embodiment of the present invention, the nucleophilic group is at least one of a bromine-containing, iodine-containing, and maleic anhydride-containing group. By adopting the preferable scheme, the normal-temperature crosslinking time of the water-based polymer fracturing fluid can be further shortened and regulated, and the temperature resistance and shearing resistance of the water-based polymer fracturing fluid can be improved.
To get further onThe step of shortening and adjusting the normal temperature crosslinking time of the water-based polymer fracturing fluid and improving the temperature and shear resistance of the water-based polymer fracturing fluid, according to a preferred embodiment of the invention, the nucleophilic group is at least one of the following groups:
in the present invention, the comonomer may be a conventional choice in the art as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the comonomer is acrylic acid and/or 2-acrylamido-2-methylpropanesulfonic acid.
According to a preferred embodiment of the invention, the comonomer is both acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid.
According to a preferred embodiment of the invention, the polymer has a viscosity average molecular weight of 1500-2500 ten thousand g/mol.
In the present invention, the morphology and the polymer mass content of the thickener are not particularly required as long as the object of the present application can be achieved, and according to a preferred embodiment of the present invention, the thickener is a polymer inverse emulsion and/or a polymer suspension emulsion, and the polymer mass content in the thickener is 40 to 50%. By adopting the preferable scheme, the cross-linking time of the water-based polymer fracturing fluid can be further shortened and regulated, and the temperature resistance of the water-based polymer fracturing fluid can be regulated at the same time.
According to a preferred embodiment of the present invention, the polymer has a structure as shown in formula (1) before modification with nucleophilic groups:
in formula (1), a, b, c, d is the mole percent of the structural units, wherein a=62-78 mole%, b=20-25 mole%, c=2-8 mole%, and d=0.5-5 mole%.
According to a preferred embodiment of the present invention, the polymer has a structure as shown in formula (2):
in formula (2), R is the nucleophilic group.
According to a preferred embodiment of the present invention, the normal temperature cross-linking agent is sulfhydryl chitosan.
According to a preferred embodiment of the invention, the mercaptochitosan has a number average molecular weight ranging from 1000 to 20000g/mol. By adopting the preferable scheme, the normal-temperature crosslinking time of the water-based polymer fracturing fluid can be further shortened and regulated.
According to a preferred embodiment of the present invention, the normal temperature crosslinking agent is an aqueous solution of sulfhydryl chitosan.
In order to further shorten and adjust the normal-temperature crosslinking time of the water-based polymer fracturing fluid, the mass fraction of the sulfhydryl chitosan in the sulfhydryl chitosan aqueous solution is 10-20%.
According to a preferred embodiment of the present invention, the water-based polymer fracturing fluid comprises: base solution: the weight of the thickening agent is 1.2-1.8 percent, the weight of the additive is 0.3-0.6 percent, the weight of the gel breaker is 0.05-0.1 percent and the balance is water; organozirconium crosslinking agent: the content is 0.6-1.0wt% of the total mass of the base solution; normal temperature crosslinking agent: the content is 0.2-0.5wt% of the total mass of the base solution.
In the present invention, the organozirconium crosslinking agent may be a conventional choice in the art as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the organozirconium crosslinking agent is zirconium lactate containing ethanolamine ligands.
In the present invention, the type of the additive is not particularly limited as long as the object of the present application can be achieved, and according to a preferred embodiment of the present invention, the additive is a long-chain alkyl quaternary ammonium salt, preferably at least one of cetyltrimethylammonium chloride, octadecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, and dodecyltrimethylammonium chloride.
In the present invention, the breaker may be a conventional choice in the art as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the breaker is ammonium persulfate.
The invention provides an application of the water-based polymer fracturing fluid in offshore high-temperature oil reservoir fracturing construction.
The water-based polymer fracturing fluid disclosed by the invention is applied to offshore high-temperature oil reservoir fracturing construction, and has the advantages of freely regulating and controlling the crosslinking time of a system, simultaneously not affecting the high-temperature resistance of the system, effectively crosslinking at normal temperature and high temperature, and ensuring stable sand carrying in the whole offshore fracturing construction process.
The present invention will be described in detail by examples.
In the following examples, the normal temperature crosslinking time was determined according to the method in SY/T7627-2021 technical requirement for Water-based fracturing fluids;
the temperature and shear resistance is measured according to the method in SY/T7627-2021 technical requirement for Water-based fracturing fluid.
Unless otherwise specified, the raw materials were all commercially available.
In the following examples:
the preparation method of the polymer inverse emulsion comprises the following steps: preparing 50-70% monomer aqueous solution by mass percent of polyethylene glycol methacrylate and comonomer, regulating the pH value to be neutral by alkali liquor, adding the monomer aqueous solution into an oil phase system formed by an emulsifier, solvent oil and an azo initiator while strongly stirring, controlling the temperature between 10 ℃ and 15 ℃ by a circulating water bath in the emulsion preparation process, introducing high-purity nitrogen to drive oxygen for 1h, keeping stirring, dropwise adding an oxidant during the period of dropwise adding the oxidant, introducing nitrogen to remove oxygen, slowly dropwise adding a reducing agent for 0.5-2h, finishing polymerization, regulating the temperature of the circulating water bath to 20 ℃, dropwise adding a phase inverter after the temperature of the system is reduced to 20-30 ℃, and discharging after uniform stirring.
The preparation method of the polymer dry powder comprises the following steps: preparing 20-30% monomer aqueous solution by mass percent of polyethylene glycol methacrylate, acrylamide, acrylic acid and 2-acrylamide-2-methylpropanesulfonic acid, regulating the pH value to be neutral by alkali liquor, controlling the temperature of the solution to be between 10 and 15 ℃ by circulating water bath, introducing high-purity nitrogen to drive oxygen for 1h, dropwise adding an oxidant during the period, slowly dropwise adding a reducing agent for 0.5-2h after nitrogen is introduced to remove oxygen, completing polymerization, washing the product with methanol for multiple times, drying in vacuum at 35-45 ℃, taking out and granulating to obtain the product.
The preparation method of the polymer suspension emulsion comprises the following steps: sequentially adding solvent oil and an emulsifier into the reaction kettle in proportion under the conditions that the rotating speed of the reaction kettle is 250-350r/min and the temperature is 30-50 ℃, stirring for 1h, adding the polymer dry powder into the reaction kettle, and continuously stirring for 1h to obtain the polymer dry powder.
Polymer modification method: the brominated end group modification is prepared by reacting bromoacetyl chloride with the hydroxyl of the polyethylene glycol methacrylate in the polymer, the iodized end group modification is prepared by performing a Finclestat reaction on the polymer modified by the brominated end group, and the maleated end group modification is prepared by reacting p-toluenesulfonyl chloride with the hydroxyl of the polyethylene glycol methacrylate in the polymer to obtain a p-toluenesulfonylated end group polymer, then reacting with ethylenediamine to obtain an amino end group polymer and then reacting with maleic anhydride.
The preparation method of the fracturing fluid comprises the following steps: during fracturing operation, seawater, a thickening agent, long-chain alkyl quaternary ammonium salt, ammonium persulfate, sulfhydryl chitosan and zirconium lactate containing ethanolamine ligands are simultaneously added into a liquid tank of a sand mixing vehicle or a sand mixing sled in proportion, and the prepared fracturing liquid is pumped into a target stratum by a fracturing pump.
Example 1
A polymer fracturing fluid comprises a base fluid, a normal-temperature cross-linking agent accounting for 0.2 weight percent of the base fluid and a zirconium lactate cross-linking agent containing ethanolamine ligand accounting for 0.9 weight percent of the base fluid; wherein the base solution comprises the following components in percentage by mass: 1.7wt% of thickener, 0.6wt% of cetyl trimethyl ammonium chloride, 0.1wt% of ammonium persulfate and the balance of seawater;
the thickening agent is polyacrylamide suspension emulsion, the polymer content in the emulsion is 45wt%, the viscosity average molecular weight of the polymer is 2500 ten thousand g/mol, and the structural formula of the polymer before modification by nucleophilic groups is as follows:
a. b, c, d are mole percentages of structural units, where a=71 mol%, b=23 mol%, c=3 mol%, d=3 mol%.
The polymer modified by nucleophilic groups has the following structural formula:
wherein R is a new group obtained by modifying and substituting hydroxyl, and the structure of the group is that
The normal temperature cross-linking agent is a sulfhydryl chitosan aqueous solution, the sulfhydryl chitosan accounts for 12 percent of the mass fraction of the solution, and the sulfhydryl chitosan has the number average molecular weight of 18000g/mol.
Example 2
The difference from example 1 is that: r is
Example 3
The difference from example 1 is that: r is
Example 4
A controllable crosslinking high-temperature-resistant seawater-based polymer fracturing fluid comprises a base fluid, a normal-temperature crosslinking agent accounting for 0.3wt% of the mass of the base fluid and a zirconium lactate crosslinking agent containing ethanolamine ligand accounting for 0.8wt% of the mass of the base fluid; wherein the base solution comprises the following components in percentage by mass: 1.6wt% of thickener, 0.5wt% of octadecyl trimethyl ammonium chloride, 0.1wt% of ammonium persulfate and the balance of seawater;
the thickening agent is polyacrylamide suspension emulsion, the polymer content in the emulsion is 44%, the viscosity average molecular weight of the polymer is 2200 ten thousand g/mol, and the structural formula of the polymer before modification by nucleophilic groups is as follows:
a. b, c, d are mole percentages of structural units, where a=69 mol%, b=24 mol%, c=5 mol%, d=2 mol%.
The polymer modified by nucleophilic groups has the following structural formula:
wherein R is a new group obtained by modifying and substituting hydroxyl, and the structure of the group is that
The normal temperature cross-linking agent is a sulfhydryl chitosan aqueous solution, the sulfhydryl chitosan accounts for 14 percent of the mass fraction of the solution, and the sulfhydryl chitosan has the number average molecular weight of 12000g/mol.
Example 5
The controllable crosslinking high-temperature-resistant seawater-based polymer fracturing fluid comprises a base fluid, a normal-temperature crosslinking agent accounting for 0.4wt% of the mass of the base fluid and a zirconium lactate crosslinking agent containing ethanolamine ligand accounting for 0.7wt% of the mass of the base fluid, wherein the base fluid comprises the following components in percentage by mass: 1.5wt% of thickener, 0.4wt% of tetradecyl trimethyl ammonium chloride, 0.08wt% of ammonium persulfate and the balance of seawater;
the thickening agent is polyacrylamide suspension emulsion, the polymer content in the emulsion is 42%, the viscosity average molecular weight of the polymer is 2000 ten thousand g/mol, and the structural formula of the polymer before modification by nucleophilic groups is as follows:
a. b, c, d are mole percentages of structural units, where a=72 mol%, b=21 mol%, c=6 mol%, d=1 mol%.
The polymer modified by nucleophilic groups has the following structural formula:
wherein R is a new group obtained by modifying and substituting hydroxyl, and the structure of the group is that
The normal temperature cross-linking agent is a sulfhydryl chitosan aqueous solution, the sulfhydryl chitosan accounts for 16 percent of the mass fraction of the solution, and the sulfhydryl chitosan has the number average molecular weight of 6000g/mol.
Example 6
The controllable crosslinking high-temperature-resistant seawater-based polymer fracturing fluid comprises a base fluid, a normal-temperature crosslinking agent accounting for 0.5wt% of the mass of the base fluid and a zirconium lactate crosslinking agent containing ethanolamine ligand accounting for 0.6wt% of the mass of the base fluid, wherein the base fluid comprises the following components in percentage by mass: 1.3wt% of thickener, 0.3wt% of dodecyl trimethyl ammonium chloride, 0.06wt% of ammonium persulfate and the balance of seawater;
the thickening agent is polyacrylamide inverse emulsion, the polymer content in the emulsion is 40%, the viscosity average molecular weight of the polymer is 1600 ten thousand g/mol, and the structural formula of the polymer before modification by nucleophilic groups is as follows:
a. b, c, d are mole percentages of structural units, where a=67 mol%, b=22 mol%, c=7 mol%, d=4 mol%.
The polymer modified by nucleophilic groups has the following structural formula:
wherein R is a new group obtained by modifying and substituting hydroxyl, and the structure of the group is that
The normal temperature cross-linking agent is a sulfhydryl chitosan aqueous solution, the sulfhydryl chitosan accounts for 18 percent of the mass fraction of the solution, and the sulfhydryl chitosan has the number average molecular weight of 4000g/mol.
Comparative example 1
The high-temperature-resistant seawater-based polymer fracturing fluid comprises a base fluid and a zirconium lactate cross-linking agent containing ethanolamine ligand accounting for 0.9 weight percent of the base fluid, wherein the base fluid comprises the following components in percentage by mass: 1.7wt% of thickener, 0.6wt% of cetyl trimethyl ammonium chloride, 0.1wt% of ammonium persulfate and the balance of seawater;
the thickening agent is polyacrylamide suspension emulsion, the polymer content in the emulsion is 45%, the viscosity average molecular weight of the polymer is 2500 ten thousand, and the structural formula of the polymer is as follows:
a. b and c are mole percentages of structural units, wherein a=74 mol%, b=23 mol%, and c=3 mol%.
Comparative example 2
Zirconium lactate crosslinking agent containing ethanolamine ligand accounts for 1.1wt% of the base solution, and the other is the same as in comparative example 1.
Comparative example 3
Zirconium lactate crosslinking agent containing ethanolamine ligand accounts for 1.3wt% of the base solution, and the other is the same as in comparative example 1.
Comparative example 4
The same as in example 1, except that no room temperature crosslinking agent was contained.
Comparative example 5
The same as in example 1, except that the polymer did not passAnd (3) modification.
The high temperature resistant seawater-based polymer fracturing fluids prepared in examples 1-6 and comparative examples 1-5 were evaluated according to SY/T7627-2021 technical requirement for Water-based fracturing fluids, and the results are shown in the following table:
the preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A water-based polymer fracturing fluid, comprising: a base liquid, a normal temperature cross-linking agent and an organic zirconium cross-linking agent;
the base solution contains a thickening agent, wherein the thickening agent is an emulsion of a polymer obtained by polymerizing polyethylene glycol methacrylate, acrylamide and comonomer and then modifying the polymer by nucleophilic groups.
2. The aqueous-based polymeric fracturing fluid of claim 1, wherein the nucleophilic group is at least one of a bromine-, iodine-, and maleic anhydride-containing group, preferably,
the nucleophilic group is at least one of the following groups:
3. a water-based polymer fracturing fluid according to claim 1 or 2, wherein the comonomer is acrylic acid and/or 2-acrylamide-2-methylpropanesulfonic acid, preferably both acrylic acid and 2-acrylamide-2-methylpropanesulfonic acid.
4. A water-based polymer fracturing fluid according to any of claims 1-3, wherein the viscosity average molecular weight of the polymer is 1500-2500 ten thousand g/mol.
5. The water-based polymer fracturing fluid according to any of claims 1 to 4, wherein the thickener is a polymer inverse emulsion and/or a polymer suspension emulsion, and the mass content of the polymer in the thickener is 40-50%.
6. The water-based polymer fracturing fluid of any of claims 1-5, wherein the polymer has a structure as shown in formula (1) before modification with nucleophilic groups:
in formula (1), a, b, c, d is the mole percent of the structural units, wherein a=62-78 mole%, b=20-25 mole%, c=2-8 mole%, and d=0.5-5 mole%.
7. The water-based polymer fracturing fluid of any of claims 1-6, wherein the polymer has a structure as shown in formula (2):
in formula (2), R is the nucleophilic group.
8. The water-based polymer fracturing fluid according to any of claims 1-7, wherein the normal temperature cross-linking agent is sulfhydryl chitosan, preferably the sulfhydryl chitosan has a number average molecular weight of 1000-20000g/mol; it is further preferred that the composition comprises,
the normal temperature cross-linking agent is a sulfhydryl chitosan aqueous solution, and more preferably the sulfhydryl chitosan in the sulfhydryl chitosan aqueous solution has a mass fraction of 10-20%.
9. The water-based polymer fracturing fluid of any of claims 1-8, wherein the water-based polymer fracturing fluid comprises:
base solution: the weight of the thickening agent is 1.2-1.8 percent, the weight of the additive is 0.3-0.6 percent, the weight of the gel breaker is 0.05-0.1 percent and the balance is water;
organozirconium crosslinking agent: the content is 0.6-1.0wt% of the total mass of the base solution;
normal temperature crosslinking agent: the content is 0.2-0.5wt% of the total mass of the base solution.
10. Use of the water-based polymer fracturing fluid according to any one of claims 1-9 in offshore high temperature reservoir fracturing construction.
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