CN115703959B - Method for preparing composite gel - Google Patents

Method for preparing composite gel Download PDF

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CN115703959B
CN115703959B CN202110890101.0A CN202110890101A CN115703959B CN 115703959 B CN115703959 B CN 115703959B CN 202110890101 A CN202110890101 A CN 202110890101A CN 115703959 B CN115703959 B CN 115703959B
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water
mass
composite gel
percent
glue solution
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CN115703959A (en
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武俊文
牛骏
张汝生
杨立红
王孟江
路熙
吴川
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China Petroleum and Chemical Corp
Sinopec Exploration and Production Research Institute
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China Petroleum and Chemical Corp
Sinopec Exploration and Production Research Institute
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Abstract

The invention provides a method for preparing composite gel. The preparation method for preparing the composite gel comprises the following steps: 1) Mixing 1, 5-dihydroxynaphthalene, hydroquinone, formaldehyde, ethylene glycol butyl ether, thiourea and polypropylene fibers with water to obtain a first mixed solution; 2) Mixing acrylamide-2-acrylamido-2-methylpropanesulfonic acid copolymer with water to obtain a second mixed solution; 3) Uniformly mixing the first mixed solution and the second mixed solution to obtain a glue solution; 4) And (3) after the glue solution is glued, obtaining the composite gel.

Description

Method for preparing composite gel
Technical Field
The invention provides a method for preparing composite gel.
Background
More than 80% of land petroleum in China is developed by water flooding, and injected water can project into the land along a high permeability layer due to the difference of permeability of each oil layer, so that the oil well is flooded prematurely. To fundamentally solve the problem, a method of profile control and water shutoff is needed to improve the water absorption profile. Therefore, for the oil field developed by water injection, reasonable and effective measures, namely profile control and water shutoff measures, are very necessary.
In recent years, chemical agents for deep profile control are greatly developed, and polymer gels are the most widely used profile control water shutoff agents in foreign countries at present due to low price, simple preparation and good construction effect. However, the polymer gel has poor stability under high-temperature and high-salt oil reservoirs, which is a difficult problem faced by the profile control technology. For some high-temperature deep well oil reservoirs in China, the oil reservoir temperature is up to 130-150 ℃, and the common polyacrylamide is easy to degrade under the high-temperature condition, so that gel is dehydrated and contracted, the profile control plugging measure is failed, and the common polyacrylamide gel is not suitable for being applied to the high-temperature oil reservoirs. In order to solve the problem of poor gel temperature resistance, plugging agents such as inorganic particles, resins, lignin/tannin extract gels and the like are generated. The inorganic particle type plugging agent comprises main components such as cement, fly ash and the like, is injected into a stratum in a suspension form to achieve the effect of plugging the stratum during site construction, has the advantages of high plugging strength and good temperature resistance, has no selectivity on plugging water, and is easy to cause irrecoverable damage to the whole reservoir; meanwhile, a very sensitive matching relation exists between the inorganic particle plugging agent and the stratum pore, so that the plugging agent particle is very easy to block the stratum pore roar channel in the injection process, the plugging agent is prevented from going deep, and stratum injury and construction failure are caused. Resins such as furfuryl alcohol Gao Wendu also have the problem of poor oil-water selectivity. The gel formed by the lignin/tannin extract gel plugging agent has better temperature resistance, but the crosslinking agent and the lignin/tannin extract in the lignin/tannin extract gel system have higher use concentration, so that the field construction cost of the oil field is very high. In view of the increasingly serious water outlet problem of high-temperature oil reservoirs, the development of a novel high-temperature-resistant plugging agent is becoming more and more urgent.
Disclosure of Invention
One of the present invention provides a method of preparing a composite gel comprising the steps of:
1) Mixing 1, 5-dihydroxynaphthalene, hydroquinone, formaldehyde, ethylene glycol butyl ether, thiourea and polypropylene fibers with water to obtain a first mixed solution;
2) Mixing acrylamide-2-acrylamido-2-methylpropanesulfonic acid copolymer with water to obtain a second mixed solution;
3) Uniformly mixing the first mixed solution and the second mixed solution to obtain a glue solution;
4) And (3) after the glue solution is glued, obtaining the composite gel.
In one embodiment, the water is mineralized water.
In one embodiment, the mineralized water comprises 5 to 15 mass percent of sodium chloride, based on 100% of the total mass of the mineralized water.
In one embodiment, the mineralized water further comprises 0.1 to 0.5 mass percent of calcium chloride, based on 100% of the total mass of the mineralized water.
In one embodiment, the mineralized water further contains 0.1 to 0.5 mass percent of magnesium chloride, based on 100% of the total mass of the mineralized water.
In a specific embodiment, in step 1), the mass percentage of the 1, 5-dihydroxynaphthalene is 0.2% to 0.4%, based on 100% of the total mass of water in the glue solution; the mass percentage of the hydroquinone is 0.1 to 0.2 percent; the formaldehyde accounts for 0.1 to 0.5 percent by mass; the mass percentage of the ethylene glycol butyl ether is 0.3 to 0.7 percent; the mass percentage of the thiourea is 0.3 to 0.7 percent; the mass percentage of the polypropylene fiber is 0.5 to 1 percent; the mass percentage content of the acrylamide-2-acrylamido-2-methylpropanesulfonic acid copolymer is 1 to 3 percent.
In a specific embodiment, the polypropylene fibers have an average diameter of 15 to 40 μm and an average length of 3 to 9nm.
In one embodiment, the acrylamide-2-acrylamido-2-methylpropanesulfonic acid copolymer is a random copolymer having a number average molecular weight of 1000 to 1400 tens of thousands.
In a specific embodiment, in step 4), the glue solution is glued at 110 to 140 ℃ for more than 16 hours, resulting in the composite gel.
In a specific embodiment, in step 4), the glue solution is glued at 110 to 140 ℃ for 16 to 25 hours, resulting in the composite gel.
The second invention provides a composite gel prepared by the method according to any one of the first invention.
The third invention provides the application of the composite gel prepared by the method according to any one of the first invention or the composite gel according to the second invention as a plugging agent at high temperature.
In one embodiment, the elevated temperature is an elevated temperature of 110 to 140 ℃.
The invention has the beneficial effects that:
by contrast, the 1, 5-dihydroxynaphthalene is used in the preparation process of the composite gel, so that the prepared composite gel has excellent temperature resistance, has low viscosity, thus good injection performance, can enhance the strength of the gel, has no dehydration phenomenon and the like on the premise of prolonging the aging time, can effectively block the effluent under the condition of 140 ℃, and can be used for profile control and water shutoff of oil reservoirs and gas channeling blocking in the thermal recovery process.
Detailed Description
The invention is further illustrated below with reference to the examples, which are merely illustrative of the invention and do not constitute a limitation of the invention in any way.
Example 1
The polypropylene fibers had an average diameter of 15 μm and an average length of 4nm.
Adding 0.3g of 1, 5-dihydroxynaphthalene, 0.1g of hydroquinone, 0.3g of formaldehyde, 0.3g of ethylene glycol butyl ether, 0.3g of thiourea and 0.5g of polypropylene fiber into 50g of tap water, fully and uniformly stirring, and fully mixing 50g of acrylamide/2-acrylamido-2-methylpropanesulfonic acid copolymer with the concentration of 1.0% and the number average molecular weight of 1000 ten thousand prepared by tap water with the solution, and uniformly stirring to obtain the glue solution. The gel forming time of the gel forming liquid is 18 hours at 110 ℃.
Gel strength measured by breaking through vacuum degree method is 0.123MPa, and no dehydration phenomenon appears when aging for 150 days under 110 ℃.
Example 2
The polypropylene fibers had an average diameter of 20 μm and an average length of 5nm.
Adding 0.4g of 1, 5-dihydroxynaphthalene, 0.2g of hydroquinone, 0.3g of formaldehyde, 0.5g of ethylene glycol butyl ether, 0.5g of thiourea and 0.5g of polypropylene fiber into 50g of 5% NaCl aqueous solution, fully and uniformly stirring, and fully mixing 50g of acrylamide/2-acrylamido-2-methylpropanesulfonic acid copolymer with the concentration of 1.5% and the number average molecular weight of 1100 ten thousand prepared by tap water with the solution, and uniformly stirring to obtain the glue solution. The gel forming time of the gel forming liquid is 16 hours at 120 ℃.
Gel strength measured by breaking through vacuum degree method is 0.140MPa, and no dehydration phenomenon appears when aging for 150 days under 120 ℃.
Example 3
The polypropylene fibers had an average diameter of 25 μm and an average length of 6nm.
Adding 0.2g of 1, 5-dihydroxynaphthalene, 0.1g of hydroquinone, 0.3g of formaldehyde, 0.7g of ethylene glycol butyl ether, 0.3g of thiourea and 0.8g of polypropylene fiber into 50g of 15% NaCl aqueous solution, fully and uniformly stirring, and fully mixing 50g of acrylamide/2-acrylamido-2-methylpropanesulfonic acid copolymer with the concentration of 2.0% and the number average molecular weight of 1200 ten thousand prepared by tap water with the solution, and uniformly stirring to obtain the glue solution. The gel forming time of the gel forming liquid is 22 hours at 130 ℃.
Gel strength measured by breaking through vacuum degree method is 0.108MPa, and no dehydration phenomenon appears when aging for 150 days under 130 ℃.
Example 4
The polypropylene fibers had an average diameter of 30 μm and an average length of 7nm.
At 50g of 15% NaCl+0.1% CaCl 2 Adding 0.1g of 1, 5-dihydroxynaphthalene, 0.4g of hydroquinone, 0.1g of formaldehyde, 0.3g of ethylene glycol butyl ether, 0.7g of thiourea and 0.5g of polypropylene fiber into the aqueous solution, fully and uniformly stirring, and fully mixing 50g of acrylamide/2-acrylamido-2-methylpropanesulfonic acid copolymer with the concentration of 2.5% and the number average molecular weight of 1300 ten thousand prepared by tap water with the solution, and uniformly stirring to obtain the glue solution. The gel forming time of the gel forming liquid is 25 hours at 135 ℃.
Gel strength measured by breaking through vacuum degree method is 0.0983MPa, and no dehydration phenomenon appears when aging for 150 days under 135 ℃.
Example 5
The polypropylene fibers had an average diameter of 35 μm and an average length of 8nm.
At 50g of 15% NaCl+0.5% CaCl 2 +0.1%MgCl 2 Adding 0.3g of 1, 5-dihydroxynaphthalene, 0.1g of hydroquinone, 0.5g of formaldehyde, 0.7g of ethylene glycol butyl ether, 0.7g of thiourea and 1.0g of polypropylene fiber into the aqueous solution, fully and uniformly stirring, and fully mixing 50g of acrylamide/2-acrylamido-2-methylpropanesulfonic acid copolymer with the number average molecular weight of 1400 ten thousand, which is prepared by tap water and has the concentration of 3.0%, with the solution, and uniformly stirring to obtain the glue solution. The gel forming time of the gel forming liquid is 17 hours at 140 ℃.
Gel strength measured by breaking through vacuum degree method is 0.136MPa, and no dehydration phenomenon appears when aging for 150 days at 140 ℃.
Example 6
The polypropylene fibers had an average diameter of 40 μm and an average length of 9nm.
At 50g of 15% NaCl+0.2% CaCl 2 +0.5%MgCl 2 Adding 0.3g of 1, 5-dihydroxynaphthalene, 0.1g of hydroquinone, 0.5g of formaldehyde, 0.7g of ethylene glycol butyl ether, 0.7g of thiourea and 1.0g of polypropylene fiber into the aqueous solution, fully and uniformly stirring, and fully mixing 50g of acrylamide/2-acrylamido-2-methylpropanesulfonic acid copolymer with the concentration of 2.0% and the number average molecular weight of 1400 ten thousand prepared by tap water with the solution, and uniformly stirring to obtain the glue solution.The gel forming time of the gel forming liquid is 20 hours at 140 ℃.
Gel strength measured by breaking through vacuum degree method is 0.142MPa, and no dehydration phenomenon appears when aging for 150 days at 140 ℃.
Comparative example 1
The polypropylene fibers had an average diameter of 35 μm and an average length of 8nm.
At 50g of 15% NaCl+0.2% CaCl 2 +0.1%MgCl 2 Adding 0.1g of hydroquinone, 0.5g of formaldehyde, 0.7g of ethylene glycol butyl ether, 0.7g of thiourea and 1.0g of polypropylene fiber into the aqueous solution, fully and uniformly stirring, and fully mixing 50g of acrylamide/2-acrylamido-2-methylpropanesulfonic acid copolymer with the concentration of 2.0% and the number average molecular weight of 1400 ten thousand prepared by tap water with the solution, and uniformly stirring to obtain the glue solution. The gel forming time of the gel forming liquid is 28h at 140 ℃.
Gel strength measured by breaking through vacuum degree method is 0.053MPa, and obvious dehydration phenomenon appears when aging for 60 days under 140 ℃.
Comparing the gel forming time, gel strength and aging time of examples 1 to 6 with those of comparative example 1, it is apparent that the gel forming time of comparative example 1 is prolonged to a different extent than examples 1 to 6, the strength of the gel prepared by the method of comparative example 1 is also greatly reduced, and the aging time is shortened to 60 days, so that a remarkable dehydration phenomenon occurs.
Example 7
Taking the glue solution obtained in each example as a research object, examining the blocking capability of the composite gel prepared by the invention. The experimental procedure was as follows: two sand filling pipes with the inner diameter of 2.5cm and the length of 40cm are filled with quartz sand with different meshes to obtain simulated porous media, and the two sand filling pipes are respectively marked as No. 1 and No. 2. Firstly, obtaining the permeability k1 of original water of a medium before plugging after water flooding to pressure difference stabilization, then respectively reversely injecting glue solution prepared in each embodiment into two sand filling pipes, wherein the injection amount of the glue solution is 0.3PV (core pore volume), then injecting 0.3PV to simulate water to replace the glue solution, then sealing two ends of the two sand filling pipes injected with the glue solution, placing the two sand filling pipes in a 140 ℃ oven for aging for 5 days and 150 days respectively, and then respectively water-filling the two sand filling pipesAnd driving until the pressure difference is stable, and obtaining the simulated porous medium plugging water permeability k2. Calculating the blocking rate of the porous medium according to the permeability k1 and k2, wherein the blocking rate R of the porous medium P = (k 1-k 2)/k 1 x 100%. The experimental results are shown in table 1.
TABLE 1
The results in table 1 show that: the glue solution prepared by the invention has excellent thermal stability under high temperature condition after forming composite gel, so that the glue solution has excellent long-term plugging capability, can effectively plug water channeling, reduce water outlet of an oil well and improve water absorption profile, and further can greatly improve crude oil recovery ratio.
Although the invention has been described with reference to specific embodiments, those skilled in the art will appreciate that various modifications might be made without departing from the true spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation, material, composition of materials, and method to the essential scope, spirit, and scope of the present invention. All such modifications are intended to be included within the scope of this invention as defined in the following claims.

Claims (10)

1. A method of preparing a composite gel comprising the steps of:
1) Mixing 1, 5-dihydroxynaphthalene, hydroquinone, formaldehyde, ethylene glycol butyl ether, thiourea and polypropylene fibers with water to obtain a first mixed solution;
2) Mixing acrylamide-2-acrylamido-2-methylpropanesulfonic acid copolymer with water to obtain a second mixed solution;
3) Uniformly mixing the first mixed solution and the second mixed solution to obtain a glue solution;
4) After the glue solution is glued, the composite gel is obtained;
taking the total mass of water in the glue solution as 100%, wherein the mass percentage of the 1, 5-dihydroxynaphthalene is 0.2-0.4%; the mass percentage of the hydroquinone is 0.1 to 0.2 percent; the formaldehyde accounts for 0.1 to 0.5 percent by mass; the mass percentage of the ethylene glycol butyl ether is 0.3 to 0.7 percent; the mass percentage of the thiourea is 0.3 to 0.7 percent; the mass percentage of the polypropylene fiber is 0.5 to 1 percent; the mass percentage content of the acrylamide-2-acrylamido-2-methylpropanesulfonic acid copolymer is 1 to 3 percent.
2. The method of claim 1, wherein the water is mineralized water.
3. The method according to claim 2, wherein the mineralized water contains 5 to 15 mass% of sodium chloride, based on 100% of the total mass of mineralized water.
4. A method according to claim 3, characterized in that the mineralized water also contains 0.1 to 0.5% by mass of calcium chloride, based on 100% by mass of the total mineralized water.
5. A method according to claim 3, characterized in that the mineralized water also contains magnesium chloride in an amount of 0.1 to 0.5% by mass, based on 100% by mass of the total mineralized water.
6. The method according to claim 1, wherein the acrylamide-2-acrylamido-2-methylpropanesulfonic acid copolymer is a random copolymer having a number average molecular weight of 1000 to 1400 tens of thousands.
7. The method according to claim 1, wherein in step 4) the glue solution is glued at 110 to 140 ℃ for more than 16 hours, resulting in the composite gel.
8. The method according to claim 1, wherein in step 4) the glue solution is glued at 110 to 140 ℃ for 16 to 25 hours, resulting in the composite gel.
9. A composite gel prepared by the method of any one of claims 1 to 8.
10. Use of a composite gel prepared according to the method of any one of claims 1 to 8 or of a composite gel according to claim 9 as a plugging agent at elevated temperature; the elevated temperature is an elevated temperature of 110 to 140 ℃.
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CN116694310A (en) * 2022-02-24 2023-09-05 中国石油化工股份有限公司 High-temperature-resistant and high-salt-resistant composite gel and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN88100516A (en) * 1987-02-03 1988-09-07 菲利普石油公司 The method of delaying gelatification of water-solubility polymer
US4934456A (en) * 1989-03-29 1990-06-19 Phillips Petroleum Company Method for altering high temperature subterranean formation permeability
CN104629699A (en) * 2015-01-19 2015-05-20 中国石油大学(华东) Low-crosslinking-agent-consumption temperature-resistant salt-resistant gel
CN110724508A (en) * 2018-07-16 2020-01-24 长江大学 Fiber composite gel particle bridging agent for fractured reservoir and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN88100516A (en) * 1987-02-03 1988-09-07 菲利普石油公司 The method of delaying gelatification of water-solubility polymer
US4934456A (en) * 1989-03-29 1990-06-19 Phillips Petroleum Company Method for altering high temperature subterranean formation permeability
CN104629699A (en) * 2015-01-19 2015-05-20 中国石油大学(华东) Low-crosslinking-agent-consumption temperature-resistant salt-resistant gel
CN110724508A (en) * 2018-07-16 2020-01-24 长江大学 Fiber composite gel particle bridging agent for fractured reservoir and preparation method thereof

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