CN114106799A - Bisphenol S and hexamethylenetetramine cross-linked high-temperature-resistant gel plugging agent - Google Patents

Bisphenol S and hexamethylenetetramine cross-linked high-temperature-resistant gel plugging agent Download PDF

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CN114106799A
CN114106799A CN202010869813.XA CN202010869813A CN114106799A CN 114106799 A CN114106799 A CN 114106799A CN 202010869813 A CN202010869813 A CN 202010869813A CN 114106799 A CN114106799 A CN 114106799A
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temperature
percent
agent
resistant gel
bisphenol
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刘义刚
钟立国
刘建斌
张华�
唐晓旭
韩晓冬
王秋霞
张洪
周法元
张伟
刘昊
王弘宇
刘�东
李军
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China University of Petroleum Beijing
China National Offshore Oil Corp CNOOC
CNOOC China Ltd Tianjin Branch
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China University of Petroleum Beijing
China National Offshore Oil Corp CNOOC
CNOOC China Ltd Tianjin Branch
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/504Compositions based on water or polar solvents
    • C09K8/506Compositions based on water or polar solvents containing organic compounds
    • C09K8/508Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/5083Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/504Compositions based on water or polar solvents
    • C09K8/506Compositions based on water or polar solvents containing organic compounds
    • C09K8/508Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/512Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/516Compositions 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
    • EFIXED CONSTRUCTIONS
    • E21EARTH OR ROCK DRILLING; MINING
    • E21BEARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B33/00Sealing or packing boreholes or wells
    • E21B33/10Sealing or packing boreholes or wells in the borehole
    • E21B33/13Methods or devices for cementing, for plugging holes, crevices or the like
    • EFIXED CONSTRUCTIONS
    • E21EARTH OR ROCK DRILLING; MINING
    • E21BEARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16Enhanced recovery methods for obtaining hydrocarbons
    • E21B43/24Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection

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Abstract

The invention discloses a high-temperature resistant gel blocking agent crosslinked by bisphenol S and hexamethylenetetramine. The high-temperature resistant gel plugging agent comprises the following components in percentage by mass: 0.4 to 1.0 percent of hexamethylene tetramine; 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 6-50 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 hot-production of high-temperature oil.

Description

Bisphenol S and hexamethylenetetramine cross-linked high-temperature-resistant gel plugging agent
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 hexamethylenetetramine.
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 hexamethylenetetramine 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;
0.4 to 1.0 percent of hexamethylene tetramine;
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, hexamethylenetetramine and bisphenol S are taken as cross-linking 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 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):
1)0.4 to 1.0 percent of hexamethylenetetramine, 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 hexamethylenetetramine, 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 hexamethylenetetramine, 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% of hexamethylenetetramine, 0.4% of bisphenol S, 0.4% of polyacrylamide, 0.04% of delayed crosslinking agent, 0.04% of stabilizer and the balance of water;
6) 0.6% of hexamethylenetetramine, 0.6% of bisphenol S, 0.6% of polyacrylamide, 0.06% of delayed crosslinking agent, 0.06% of stabilizer and the balance of water;
7) 0.8% of hexamethylenetetramine, 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% of hexamethylenetetramine, 1.0% of bisphenol S, 1.0% of polyacrylamide, 0.10% of delayed crosslinking agent, 0.10% of 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 hexamethylenetetramine, 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 6-50 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 structural state diagram of the high temperature resistant gel plugging agent prepared in example 3 of the present invention after gelling at 100 ℃.
Fig. 2 is a structural state diagram of the high temperature resistant gel plugging agent prepared in example 3 of the present invention after gelling at 120 ℃.
Fig. 3 is a structural state diagram of the high temperature resistant gel plugging agent prepared in example 3 of the present invention after gelling at 150 ℃.
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%.
Example 1:
0.4g of polyacrylamide is added into 98.72g of water, stirred for 2 hours, then 0.4g of hexamethylenetetramine, 0.4g of bisphenol S, 0.04g of oxalic acid and 0.04g of ammonium chloride are added, and the stirring is continued for 20 minutes, so as 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, 0.4% hexamethylenetetramine, 0.4% bisphenol S, 0.04% oxalic acid, and 0.04% ammonium chloride.
The high-temperature resistant gel plugging agent prepared by the embodiment has the gelling time of 50h at the ambient temperature of 100 ℃; the gelling time is 28h at the ambient temperature of 120 ℃; the gelling time is 12h at the ambient temperature of 150 ℃.
Example 2:
0.6g of polyacrylamide is added into 98.08g of water, stirred for 2 hours, then added with 0.6g of hexamethylenetetramine, 0.6g of bisphenol S, 0.06g of oxalic acid and 0.06g of ammonium chloride, and 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, 0.6% hexamethylenetetramine, 0.6% bisphenol S, 0.06% oxalic acid, and 0.06% ammonium chloride.
The high-temperature resistant gel plugging agent prepared in the embodiment has the gelling time of 41h at the ambient temperature of 100 ℃; gelling time is 22h at the ambient temperature of 120 ℃; the gelling time is 9h at the ambient temperature of 150 ℃.
Example 3:
adding 0.8g of polyacrylamide into 97.44g of water, stirring for 2 hours, adding 0.8g of hexamethylenetetramine, 0.8g of bisphenol S, 0.08g of oxalic acid and 0.08g of ammonium chloride, and continuously stirring 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): 0.8% polyacrylamide, 0.8% hexamethylenetetramine, 0.8% bisphenol S, 0.08% oxalic acid, and 0.08% ammonium chloride.
The high-temperature resistant gel plugging agent prepared in the embodiment has the gelling time of 35 hours at the ambient temperature of 100 ℃, and the structural state after gelling is shown in figure 1; the gelling time is 19h at the ambient temperature of 120 ℃, and the structural state after gelling is shown in figure 2; the gelling time is 7h at the ambient temperature of 150 ℃, and the structural state after gelling is shown in figure 3.
As can be seen from the figures 1-3, the gel system can still form a stable gel system under the condition of 150 ℃, and the gel system has higher strength and can meet the plugging regulation requirement of a high-temperature oil-gas reservoir.
Example 4:
adding 1.0g of polyacrylamide into 96.8g of water, stirring for 2 hours, adding 1.0g of hexamethylenetetramine, 1.0g of bisphenol S, 0.1g of oxalic acid and 0.1g of ammonium chloride, and continuously stirring 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): 1.0% polyacrylamide, 1.0% hexamethylenetetramine, 1.0% bisphenol S, 0.1% oxalic acid and 0.1% ammonium chloride.
The high-temperature resistant gel plugging agent prepared in the embodiment has the gelling time of 28 hours at the ambient temperature of 100 ℃; gelling time is 14h at the ambient temperature of 120 ℃; the gelling time is 6h 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.
TABLE 1 gelling time (Experimental temperature 120 ℃ C.) and viscosity test results
Figure BDA0002650668110000041
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
Figure BDA0002650668110000042

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;
0.4 to 1.0 percent of hexamethylene tetramine;
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, hexamethylenetetramine and bisphenol S are taken as cross-linking 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 the polyacrylamide, adding the hexamethylenetetramine, the bisphenol S, the delayed crosslinking agent and the stabilizing agent into the aqueous solution of the polyacrylamide, and stirring to obtain the high-temperature-resistant gel blocking 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.
CN202010869813.XA 2020-08-26 2020-08-26 Bisphenol S and hexamethylenetetramine cross-linked high-temperature-resistant gel plugging agent Pending CN114106799A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101892037A (en) * 2010-07-19 2010-11-24 中国海洋石油总公司 Novel salt-resistant gel selective water shutoff agent
CN102766449A (en) * 2012-07-12 2012-11-07 中国石油天然气股份有限公司 Low-temperature crosslinking promoter for polyacrylamide and water-soluble phenolic resin
CN102807849A (en) * 2012-04-06 2012-12-05 中国石油大学(华东) Gel plugging agent for deep profile control of higher temperature oil reservoir and preparation method of gel plugging agent
CN102816558A (en) * 2012-09-14 2012-12-12 中国石油大学(华东) Plugging agent for deep profile control and water plugging and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101892037A (en) * 2010-07-19 2010-11-24 中国海洋石油总公司 Novel salt-resistant gel selective water shutoff agent
CN102807849A (en) * 2012-04-06 2012-12-05 中国石油大学(华东) Gel plugging agent for deep profile control of higher temperature oil reservoir and preparation method of gel plugging agent
CN102766449A (en) * 2012-07-12 2012-11-07 中国石油天然气股份有限公司 Low-temperature crosslinking promoter for polyacrylamide and water-soluble phenolic resin
CN102816558A (en) * 2012-09-14 2012-12-12 中国石油大学(华东) Plugging agent for deep profile control and water plugging and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张明锋: "耐温HPAM凝胶动力学及热稳定性研究", 《中国优秀硕士学位论文全文数据库》, no. 5, pages 4 - 11 *

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Application publication date: 20220301