CN114106800A - Bisphenol S and formaldehyde cross-linked high-temperature-resistant gel blocking agent - Google Patents
Bisphenol S and formaldehyde cross-linked high-temperature-resistant gel blocking agent Download PDFInfo
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- CN114106800A CN114106800A CN202010868382.5A CN202010868382A CN114106800A CN 114106800 A CN114106800 A CN 114106800A CN 202010868382 A CN202010868382 A CN 202010868382A CN 114106800 A CN114106800 A CN 114106800A
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 78
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000002981 blocking agent Substances 0.000 title claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 18
- 230000003111 delayed effect Effects 0.000 claims abstract description 14
- 239000003381 stabilizer Substances 0.000 claims abstract description 14
- 238000011084 recovery Methods 0.000 claims abstract description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 30
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 20
- 239000003921 oil Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 235000019270 ammonium chloride Nutrition 0.000 claims description 10
- 235000006408 oxalic acid Nutrition 0.000 claims description 10
- 239000000295 fuel oil Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 238000010795 Steam Flooding Methods 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 230000000638 stimulation Effects 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 238000009933 burial Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 239000000499 gel Substances 0.000 description 55
- 239000008098 formaldehyde solution Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 6
- 229920006037 cross link polymer Polymers 0.000 description 5
- 238000009472 formulation Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 238000010793 Steam injection (oil industry) Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/516—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls characterised by their form or by the form of their components, e.g. encapsulated material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/592—Compositions used in combination with generated heat, e.g. by steam injection
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Sealing Material Composition (AREA)
Abstract
The invention discloses a high-temperature resistant gel blocking agent crosslinked by bisphenol S and formaldehyde. The high-temperature resistant gel plugging agent comprises the following components in percentage by mass: 0.148 to 0.37 percent of formaldehyde; 0.4 to 1.0 percent of bisphenol S; 0.4 to 1.0 percent of polyacrylamide; 0.04 to 0.10 percent of stabilizer; 0.04 to 0.10 percent of delayed crosslinking agent; the balance of water. The high-temperature resistant gel plugging agent disclosed by the invention has the gelling time of 4-48 h at the ambient temperature of 100-150 ℃, has the characteristics of low initial viscosity, gelling at high temperature and stable viscosity at high temperature, has good plugging property at high temperature, and can be used for thermal recovery of high-temperature oil reservoirs.
Description
Technical Field
The invention relates to a high-temperature-resistant gel blocking agent, in particular to a high-temperature-resistant gel blocking agent crosslinked by bisphenol S and formaldehyde. .
Background
The high-temperature resistant plugging agent is also adopted when profile control is carried out on the oil reservoir thermally produced by adopting modes of steam injection or in-situ combustion and the like. Currently, the most widely studied and used plugging agent is the gel plugging agent. The gel blocking agent is generally an inorganic metal ion crosslinked polymer gel system, a phenolic resin crosslinked polymer gel system and a polyethyleneimine crosslinked polymer gel system. Wherein the gel system formed by the organic cross-linking agent has better high-temperature resistance than the gel system formed by the metal cross-linking agent. The conventional organic crosslinked polymer gel has a low gelling temperature and becomes poor in plugging ability at a temperature higher than 120 ℃. Therefore, when the conventional organic crosslinked polymer gel is used for plugging the thermal recovery high-temperature oil reservoir, the plugging effect is not ideal because the temperature resistance of the plugging agent cannot meet the temperature requirement of the oil and gas reservoir. In order to overcome the defect of poor temperature resistance of the conventional gel plugging agent, the high-temperature-resistant gel plugging agent needs to be researched, and the profile control requirement of a thermal recovery high-temperature oil reservoir is met.
Disclosure of Invention
The invention aims to provide a high-temperature-resistant gel plugging agent, which is crosslinked by adopting bisphenol S and formaldehyde, and can be used for profile control or plugging of an oil reservoir under a high-temperature condition, so that the exploitation effect of the oil reservoir is improved.
The high temperature resistant gel blocking agent of the invention refers to the characteristic of high temperature (such as 100 ℃ to 150 ℃) gelling.
The high-temperature resistant gel plugging agent provided by the invention comprises the following components in percentage by mass:
0.4 to 1.0 percent of polyacrylamide;
0.148 to 0.37 percent of formaldehyde;
0.4 to 1.0 percent of bisphenol S;
0.04 to 0.10 percent of stabilizer;
0.04 to 0.10 percent of delayed crosslinking agent;
the balance of water;
wherein formaldehyde and bisphenol S are used as crosslinking agents.
In the high-temperature resistant gel plugging agent, the molecular weight of the polyacrylamide can be 300-2000 ten thousand, and the hydrolysis degree can be 10-15%.
In the high-temperature resistant gel blocking agent, the chemical name of the bisphenol S is 4,4' -dihydroxy diphenyl sulfone.
In the high-temperature resistant gel blocking agent, the formaldehyde can be added in the form of a formaldehyde aqueous solution; for example, a formaldehyde aqueous solution with a formaldehyde mass concentration of 37% is adopted.
In the high-temperature resistant gel blocking agent, the stabilizing agent can be ammonium chloride and/or ammonium sulfate.
In the high-temperature resistant gel blocking agent, the delayed crosslinking agent can be oxalic acid and/or sodium phosphate.
The high-temperature resistant gel blocking agent can be any one of the following 1) to 9), wherein the formaldehyde solution is a formaldehyde aqueous solution with the formaldehyde mass concentration of 37 percent:
1)0.4 to 1.0 percent of formaldehyde solution, 0.4 to 1.0 percent of bisphenol S, 0.4 to 1.0 percent of polyacrylamide, 0.04 to 0.10 percent of delayed crosslinking agent, 0.04 to 0.10 percent of stabilizer and the balance of water;
2)0.4 to 0.8 percent of formaldehyde solution, 0.4 to 0.8 percent of bisphenol S, 0.4 to 0.8 percent of polyacrylamide, 0.04 to 0.08 percent of delayed crosslinking agent, 0.02 to 0.08 percent of stabilizer and the balance of water;
3)0.4 to 0.6 percent of formaldehyde solution, 0.4 to 0.6 percent of bisphenol S, 0.4 to 0.6 percent of polyacrylamide, 0.04 to 0.06 percent of delayed crosslinking agent, 0.04 to 0.06 percent of stabilizer and the balance of water;
5) 0.4% formaldehyde solution, 0.4% bisphenol S, 0.4% polyacrylamide, 0.04% delayed crosslinking agent, 0.04% stabilizer, and the balance of water;
6) 0.6% of formaldehyde solution, 0.6% of bisphenol S, 0.6% of polyacrylamide, 0.06% of delayed crosslinking agent, 0.06% of stabilizing agent and the balance of water;
7) 0.8% of formaldehyde solution, 0.8% of bisphenol S, 0.8% of polyacrylamide, 0.08% of delayed crosslinking agent, 0.08% of stabilizer and the balance of water;
8) 1.0% formaldehyde solution, 1.0% bisphenol S, 1.0% polyacrylamide, 0.10% delayed crosslinking agent, 0.10% stabilizer, and the balance of water;
the high-temperature resistant gel plugging agent can be prepared by the following method:
preparing the polyacrylamide aqueous solution, then adding the formaldehyde, the bisphenol S, the delayed crosslinking agent and the stabilizing agent into the polyacrylamide aqueous solution, and stirring to obtain the high-temperature-resistant gel blocking agent.
After the high-temperature resistant gel plugging agent is prepared, the gel with high temperature resistance, high profile control and plugging performance can be formed after the constant temperature of 100-150 ℃ for 4-48 h.
The high-temperature-resistant gel plugging agent can be used for profile control of an injection well or plugging of an oil production well of a thermal recovery high-temperature oil reservoir.
Specifically, the high-temperature-resistant gel plugging agent can be used for steam stimulation heavy oil reservoir exploitation;
specifically, the high-temperature-resistant gel plugging agent can be used for steam flooding heavy oil reservoir exploitation;
specifically, the high-temperature-resistant gel plugging agent can be used for high-temperature hot water flooding heavy oil reservoir exploitation;
the high-temperature resistant gel plugging agent has the characteristics of low initial viscosity, gelling at high temperature and stable viscosity at high temperature, has good plugging property at high temperature, and can be used for high-temperature oil and gas reservoirs or thermal recovery high-temperature oil reservoirs.
Drawings
Fig. 1 is a microscopic scanning electron microscope image of the high temperature resistant gel plugging agent prepared in example 4 of the present invention after gelling.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The molecular weight of polyacrylamide used in the following examples is 500 to 800 ten thousand, and the degree of hydrolysis is 10 to 15%.
The aqueous formaldehyde solution used in the following examples was 37% by mass.
Example 1:
0.4g of polyacrylamide is added into 98.72g of water, stirred for 2 hours, then 0.4g of formaldehyde aqueous solution, 0.4g of bisphenol S, 0.04g of oxalic acid and 0.04g of ammonium chloride are added, and the mixture is continuously stirred for 20 minutes to form the temperature-resistant gel plugging agent.
The high temperature resistant gel blocking agent prepared in this example comprises the following components (by mass percent): 0.4% polyacrylamide + 0.148% formaldehyde + 0.4% bisphenol S + 0.04% oxalic acid + 0.04% ammonium chloride.
The high-temperature resistant gel plugging agent prepared by the embodiment has the gelling time of 48 hours at the ambient temperature of 100 ℃; the gelling time is 26h at the ambient temperature of 120 ℃; the gelling time is 10h at the ambient temperature of 150 ℃.
Example 2:
0.6g of polyacrylamide is added into 98.08g of water, stirred for 2 hours, then 0.6g of formaldehyde aqueous solution, 0.6g of bisphenol S, 0.06g of oxalic acid and 0.06g of ammonium chloride are added, and the mixture is continuously stirred for 20 minutes to form the temperature-resistant gel plugging agent.
The high temperature resistant gel blocking agent prepared in this example comprises the following components (by mass percent): 0.4% polyacrylamide + 0.222% formaldehyde + 0.6% bisphenol S + 0.06% oxalic acid + 0.06% ammonium chloride.
The high-temperature resistant gel plugging agent prepared in the embodiment has the gelling time of 40h at the ambient temperature of 100 ℃; gelling time is 21h at the ambient temperature of 120 ℃; the gelling time is 8h at the ambient temperature of 150 ℃.
Example 3:
adding 0.8g of polyacrylamide into 97.44g of water, stirring for 2h, adding 0.8g of formaldehyde aqueous solution, 0.8g of bisphenol S, 0.08g of oxalic acid and 0.08g of ammonium chloride, and continuously stirring for 20min to form the temperature-resistant gel plugging agent.
The high temperature resistant gel blocking agent prepared in this example comprises the following components (by mass percent): 0.8% polyacrylamide + 0.296% formaldehyde + 0.8% bisphenol S + 0.08% oxalic acid + 0.08% ammonium chloride.
The high-temperature resistant gel plugging agent prepared by the embodiment has the gelling time of 34h at the ambient temperature of 100 ℃; the gelling time is 18h at the ambient temperature of 120 ℃; the gelling time is 6.5h at the ambient temperature of 150 ℃.
Example 4:
adding 1.0g of polyacrylamide into 96.8g of water, stirring for 2h, adding 1.0g of formaldehyde aqueous solution, 1.0g of bisphenol S, 0.1g of oxalic acid and 0.1g of ammonium chloride, and continuously stirring for 20min to form the temperature-resistant gel plugging agent.
The high temperature resistant gel blocking agent prepared in this example comprises the following components (by mass percent): 1.0% polyacrylamide + 0.37% formaldehyde + 1.0% bisphenol S + 0.1% oxalic acid + 0.1% ammonium chloride.
The high-temperature resistant gel plugging agent prepared in the embodiment has the gelling time of 26h at the ambient temperature of 100 ℃; gelatinizing at 120 deg.C for 12 h; the gelling time is 4h at the ambient temperature of 150 ℃.
Example 5:
the high temperature resistant gel blocking agent formulations of examples 1 to 4 were subjected to a gelling experiment at 120 ℃, and the gelling time and the viscosity test results before and after gelling are shown in table 1. As can be seen from Table 1, the high temperature resistant gel blocking agent formulation of example 4 has the highest viscosity after gelling.
Scanning electron microscope microscopic experiments were performed on the high temperature resistant gel blocking agent formulation of example 4.
Sampling, freezing and drying the gelled high-temperature-resistant gel plugging agent, and further preparing a sample and observing the microstructure of the sample by a scanning electron microscope, wherein the result is shown in figure 1. As can be seen from figure 1, the three-dimensional network structure of the high-temperature resistant gel plugging agent after gelling is uniform and stable.
TABLE 1 gelling time (Experimental temperature 120 ℃ C.) and viscosity test results
Example 6:
a physical simulation experiment was performed on the high temperature resistant gel blocking agent formulation of example 4.
Permeability measured at initial water as K1Respectively injecting 0.5PV of salt-resistant and high-temperature-resistant gel plugging agent into the sand-filled pipe model, keeping the temperature of the sand-filled pipe model constant at 120 ℃ for 18 hours to ensure that the salt-resistant and high-temperature-resistant gel plugging agent gels, and measuring the water permeability K again2And breakthrough pressure. The plugging rate calculation formula is as follows: f1＝(K1-K2)/K1X 100%, after subsequent water flooding by 10PV, measuring the water permeability K again3And the plugging rate calculation formula is as follows: f2＝(K1-K3)/K1X 100%, the results are shown in table 2.
As can be seen from Table 2, the salt-resistant and high-temperature-resistant gel plugging agent has good plugging capability and scouring resistance, and the system is suitable for profile control and water plugging work, and is particularly suitable for high-salt and high-temperature oil and gas reservoir plugging work.
Table 2 sand-packed pipe model plugging experimental results
Claims (7)
1. The high-temperature-resistant gel plugging agent comprises the following components in percentage by mass:
0.4 to 1.0 percent of polyacrylamide;
0.148 to 0.37 percent of formaldehyde;
0.4 to 1.0 percent of bisphenol S;
0.04 to 0.10 percent of stabilizer;
0.04 to 0.10 percent of delayed crosslinking agent;
the balance of water;
wherein formaldehyde and bisphenol S are used as crosslinking agents.
2. The high temperature resistant gelling plugging agent of claim 1, wherein: the molecular weight of the polyacrylamide is 300-2000 ten thousand, and the degree of hydrolysis is 10-15%.
3. The high temperature resistant gelling plugging agent of claim 1 or 2, wherein: the stabilizer is ammonium chloride and/or ammonium sulfate.
4. The high temperature resistant gel blocking agent according to any one of claims 1 to 3, wherein: the delayed crosslinking agent is oxalic acid and/or sodium phosphate.
5. The preparation method of the high temperature resistant gel blocking agent of any one of claims 1 to 4, comprising the following steps:
preparing the aqueous solution of polyacrylamide, adding the formaldehyde, the bisphenol S, the delayed crosslinking agent and the stabilizing agent into the aqueous solution of polyacrylamide, and stirring to obtain the high-temperature-resistant gel plugging agent.
6. The use of the high temperature resistant gel plugging agent of any one of claims 1 to 4 in injection well profile control and oil or gas well plugging of a high temperature oil and gas reservoir with deep burial.
7. The application of the high-temperature-resistant gel plugging agent of any one of claims 1 to 4 in the exploitation of any one of the following thermal recovery heavy oil reservoirs 1) to 3):
1) steam stimulation heavy oil reservoirs;
2) steam flooding heavy oil reservoir;
3) high-temperature hot water flooding heavy oil reservoir.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010868382.5A CN114106800A (en) | 2020-08-26 | 2020-08-26 | Bisphenol S and formaldehyde cross-linked high-temperature-resistant gel blocking agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010868382.5A CN114106800A (en) | 2020-08-26 | 2020-08-26 | Bisphenol S and formaldehyde cross-linked high-temperature-resistant gel blocking agent |
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| CN114106800A true CN114106800A (en) | 2022-03-01 |
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Application publication date: 20220301 |