CN111088021B - Low-density gel particle profile control and flooding agent and preparation method thereof - Google Patents
Low-density gel particle profile control and flooding agent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a low-density gel particle profile control and flooding agent and a preparation method thereof. The low-density gel particle profile control and flooding agent is prepared by polymerizing the following raw materials in percentage by weight: 15-20% of acrylamide, 3-5% of 2-acrylamide-2-methyl propyl sodium sulfonate, 0.2-0.5% of N, N-methylene bisacrylamide, 8-17% of inorganic light filler, 2-6% of silane coupling agent, 0.2-1.0% of initiator and the balance of water. According to the low-density gel particle profile control and flooding agent provided by the invention, the density of the gel particle profile control and flooding agent is smaller than that of injected water and is adjustable through the inorganic light filler, the inorganic light filler is connected with the main chain of the gel particle profile control and flooding agent through a chemical bond through the silane coupling agent, and the problems that the filler is easy to separate out and the strength is reduced after the gel particles expand after absorbing water are solved.
Description
Technical Field
The invention belongs to the field of gel particles for profile control and flooding of an oil reservoir water injection well, and particularly relates to a low-density gel particle profile control and flooding agent and a preparation method thereof.
Background
In the later stage of oilfield flooding development, reservoir heterogeneity is intensified, water drive efficiency is reduced, and a profile control and drive technology becomes one of key technologies for improving the water drive development effect. The gel particle profile control and flooding agent is a high water absorption resin, and has certain elasticity, strength and water retention after water absorption and expansion. When the gel particle profile control agent is prepared, the requirements of temperature resistance and mineralization resistance (such as 130 ℃ temperature resistance and 24 multiplied by 10 mineralization resistance) are often met by improving the molecular structure and adding a filler or a reinforcing agent4Requirement of mg/L).
The existing gel particle profile control agent has defects in different oil reservoir field applications due to the limitation of molecular structure characteristics, and is mainly shown in the following steps: firstly, the filler or the reinforcing agent is only filled in gaps among the three-dimensional network structures of the gel particle profile control agent body and is not connected with the three-dimensional network structures of the gel particle body, so that the gel particle profile control agent is injected into a stratum to absorb water and expand, the filler or the reinforcing agent is easy to separate out, the strength and the aging resistance of the gel particle are reduced, and the effective period of measures is shortened. Secondly, the gel particle profile control agent has higher density and is easy to deposit and bury layer during site construction; the density of the water injected on site is 1.01-1.05g/cm3The density of the conventional gel particles is 1.07-1.14g/cm3The density of the gel particles added with the calcareous soil and the sodic soil is 1.15-1.26g/cm3The density of the gel particles added with the oily sludge is 1.22-1.47g/cm3And the phenomena of sedimentation and burying easily occur when the gel particles and injected water are applied to field profile control and flooding due to the large density difference.
Chinese patent with publication No. CN102850488B discloses a low-density secondary expansion type gel particle, which is prepared by polymerizing and crosslinking acrylamide monomer, temperature-resistant and salt-resistant monomer, reinforcing agent and gas-generating agent under the action of initiator and crosslinking agent to obtain gel, and then granulating and crushing the gel, wherein the raw materials comprise the following components in percentage by mass: 8-12% of acrylamide monomer, 1-5% of temperature and salt resistant monomer, 15-20% of reinforcing agent, 1-4% of gas generating agent, 0.03-0.1% of initiator, 0.05-1% of cross-linking agent and the balance of water. The gel particles are formed by filling gas generated by pyrolysis of a gas generating agent between three-dimensional network structures of the gel particle profile control and flooding agent, so that the density of the gel particle profile control and flooding agent is effectively reduced, and the problems of high density and easiness in burying of field construction of the gel particle profile control and flooding agent are solved. However, when the gel particles are used on site, the problem that the filler or the reinforcing agent is easy to separate out still exists, so that the strength and the aging resistance of the gel particle profile control agent are reduced, and the construction period of validity is shortened.
Disclosure of Invention
The invention aims to provide a low-density gel particle profile control and flooding agent, so as to solve the problem that a filler is easy to separate out after the existing gel particle profile control and flooding agent absorbs water and expands.
The second purpose of the invention is to provide a preparation method of the low-density gel particle profile control and flooding agent, thereby solving the problem that the gel particles prepared by the existing method are easy to precipitate a filler, so that the strength and the aging performance are reduced.
In order to achieve the purpose, the technical scheme adopted by the low-density gel particle profile control and flooding agent is as follows:
a low-density gel particle profile control and flooding agent is prepared by polymerizing the following raw materials in percentage by weight: 15-20% of acrylamide, 3-5% of 2-acrylamide-2-methyl propyl sodium sulfonate, 0.2-0.5% of N, N-methylene bisacrylamide, 8-17% of inorganic light filler, 2-6% of silane coupling agent, 0.2-1.0% of initiator and the balance of water.
According to the low-density gel particle profile control and flooding agent provided by the invention, the density of the gel particle profile control and flooding agent is smaller than that of injected water and is adjustable through the inorganic light filler, the inorganic light filler is connected with the main chain of the gel particle profile control and flooding agent through a chemical bond through the silane coupling agent, and the problems that the filler is easy to separate out and the strength is reduced after the gel particles expand after absorbing water are solved.
Preferably, the inorganic lightweight filler is floating beads and/or hollow glass microspheres, in terms of strength, density and cost of the inorganic lightweight filler. The bulk density of the floating beads can be selected to be 0.27-0.65g/cm3(ii) a The hollow glass microsphere has particle size of 18-65 μm and density of 0.31-0.67g/cm3。
In order to improve the reactivity of the silane coupling agent with the inorganic light-weight filler and the organic raw material such as acrylamide and to enable the inorganic light-weight filler to be bonded into the gel particles in a chemical bonding manner, the silane coupling agent is preferably gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane and/or methacryloxypropyltrimethoxysilane.
The initiator has certain influence on the polymerization reaction, and preferably consists of sodium bisulfite and ammonium persulfate so as to ensure that the polymerization crosslinking reaction is uniformly and stably carried out and obtain gel particles with uniform and regular crosslinking structures. More preferably, the mass ratio of the sodium bisulfite in the raw material is 0.1-0.5%, and the mass ratio of the ammonium persulfate in the raw material is 0.1-0.5%. Under the mass ratio, a better crosslinking polymerization effect can be obtained, and the comprehensive properties of the gel particle profile control agent, such as aging resistance, elastic modulus, shear resistance and the like, are further improved.
A low-density gel particle profile control agent has the following structural general formula:
in the formula, X1、X2Independently selected from SiO2·Al2O3、SiO2·B2O3·Na2O，Y1、Y2Independently selected from the group consisting of:
wherein m, n, o, p, 1, (4.0-16.8), (6.5-7.4), (86.8-162.7).
The invention provides a low-density gel particle profile control and flooding agent, X1、X2The represented inorganic light filler is connected with the gel particle body structure through chemical bonds, so that the problem that the gel particle filler is easy to separate out after swelling in water can be effectively avoided.
The preparation method of the low-density gel particle profile control and flooding agent adopts the technical scheme that:
a preparation method of a low-density gel particle profile control and flooding agent comprises the following steps: uniformly mixing acrylamide, 2-acrylamide-2-methyl sodium propanesulfonate, N-methylene bisacrylamide, inorganic light filling agent and silane coupling agent in water, and then adding an initiator to carry out polymerization reaction to obtain the acrylic resin composition.
The preparation method of the low-density gel particle profile control and flooding agent provided by the invention selects proper comonomer, cross-linking agent and reactive inorganic light filler to carry out polymerization reaction under the condition of initiator to prepare the low-density gel particle profile control and flooding agent; the low-density gel particle profile control agent has the characteristics of small density, high strength and the like, and is suitable for profile control application of oil reservoirs under the conditions of high temperature and high salinity.
In order to obtain better raw material mixing effect and prepare conditions for preparing gel particles with good uniformity, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid sodium salt and N, N-methylenebisacrylamide are preferably dissolved in water, and then inorganic light fillers and silane coupling agents are added and uniformly mixed.
In order to control the polymerization crosslinking reaction to smoothly and orderly proceed and finally obtain gel particles with uniform structure, preferably, the polymerization reaction comprises polymerizing for 15-20min at 25-30 ℃ to obtain solid gel blocks, and then placing the solid gel blocks for at least 24 h.
Drawings
FIG. 1 is a pictorial representation of a low density gel particle profile control agent of the present invention, wherein a-d are low density gel particle profile control agents of examples 1-4, respectively;
FIG. 2 is a diagram of a low-density gel particle profile control agent according to the present invention in suspension in water.
Detailed Description
The following examples are provided to further illustrate the practice of the invention.
The low-density gel particle profile control agent disclosed by the invention is prepared in the following raw materials in percentage by weight: 15% of acrylamide, 5% of sodium 2-acrylamido-2-methylpropanesulfonate, 0.2% of N, N-methylenebisacrylamide, and floating beads (the bulk density is 0.27 g/cm)3)8 percent of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 2 percent of sodium bisulfite, 0.1 percent of ammonium persulfate and the balance of water.
The structural formula of the low-density gel particle profile control agent of the embodiment is as follows:
the embodiment 2 of the low-density gel particle profile control and flooding agent is prepared from the following raw materials in percentage by weight: 20% of acrylamide, 3% of 2-acrylamide-2-methyl sodium propanesulfonate, 0.5% of N, N-methylene bisacrylamide and hollow glass microspheres (the density is 0.67 g/cm)3)17 percent of methacryloxypropyltrimethoxysilane, 6 percent of methacryloxypropyltrimethoxysilane, 0.5 percent of sodium bisulfite, 0.5 percent of ammonium persulfate and the balance of water.
The structural formula of the low-density gel particle profile control agent of the embodiment is as follows:
example 3 of the low-density gel particle profile control agent of the present invention is prepared from the following raw materials by weight: 15% of acrylamide, 5% of 2-acrylamide-2-methyl sodium propanesulfonate, 0.2% of N, N-methylene bisacrylamide and hollow glass microspheres (the density is 0.67 g/cm)3)8 percent of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane 2.1 percent,0.1 percent of sodium bisulfite, 0.1 percent of ammonium persulfate and the balance of water.
The structural formula of the low-density gel particle profile control agent of the embodiment is as follows:
example 4 of the low-density gel particle profile control agent of the present invention is prepared from the following raw materials by weight: 20% of acrylamide, 3% of 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 0.5% of N, N-methylenebisacrylamide, and floating beads (bulk density of 0.27 g/cm)3)17 percent, 5.7 percent of methacryloxypropyltrimethoxysilane, 0.5 percent of sodium bisulfite, 0.5 percent of ammonium persulfate and the balance of water.
The structural formula of the low-density gel particle profile control agent of the embodiment is as follows:
example 1 of the method for preparing a low density gel particle profile control agent of the present invention, the gel particles involved in the low density gel particle profile control agent example 1 were prepared by the following steps:
dissolving acrylamide, 2-acrylamide-2-methyl sodium propanesulfonate and N, N-methylene bisacrylamide in water, adding floating beads and gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane under stirring, and uniformly stirring to obtain a suspension; adding sodium bisulfite and ammonium persulfate at 25 deg.C, stirring for 20min to form solid gel block as shown in figure 1(a), standing at not lower than 20 deg.C for 24 hr, cutting, and granulating to obtain low density gel granule modifying and flooding agent. A cutting machine can be used for granulation, and gel particles with different sizes are formed by adjusting parameters, wherein the particle size range is 1-10 mm.
In example 2 of the preparation method of the low-density gel particle profile control and flooding agent of the present invention, the gel particles related to the low-density gel particle profile control and flooding agent in example 2 are prepared by the following steps:
dissolving acrylamide, 2-acrylamido-2-methylpropanesulfonic acid sodium salt and N, N-methylene bisacrylamide in water, adding hollow glass microspheres and methacryloxypropyltrimethoxysilane into the mixture under stirring, and stirring the mixture uniformly to obtain a suspension; adding sodium bisulfite and ammonium persulfate at 30 deg.C, stirring for 15min to obtain solid gel block shown in figure 1(b), standing at room temperature for 24h, cutting, and granulating to obtain low density gel particle modifying and flooding agent.
In example 3 of the method for preparing the low-density gel particle profile control and flooding agent of the present invention, the gel particles related to the low-density gel particle profile control and flooding agent in example 3 are prepared by the following steps:
dissolving acrylamide, 2-acrylamide-2-methyl sodium propanesulfonate and N, N-methylene bisacrylamide in water, adding hollow glass microspheres and gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane under stirring, and uniformly stirring to obtain a suspension; adding sodium bisulfite and ammonium persulfate at 25 deg.C, stirring for 20min to obtain solid gel block as shown in figure 1(c), standing at room temperature for 24 hr, cutting, and granulating to obtain low density gel particle modifying and flooding agent.
Example 4 of the method for preparing a low density gel particle profile control agent of the present invention, the gel particles involved in the low density gel particle profile control agent example 4 were prepared by the following steps:
dissolving acrylamide, 2-acrylamido-2-methylpropanesulfonic acid sodium salt and N, N-methylene bisacrylamide in water, adding floating beads and methacryloxypropyl trimethoxysilane into the mixture under stirring, and uniformly stirring the mixture to obtain a suspension; adding sodium bisulfite and ammonium persulfate at 30 deg.C, stirring for 15min to obtain solid gel block shown in figure 1(d), standing at room temperature for 24h, cutting, and granulating to obtain low density gel particle modifying and flooding agent.
Comparative example
Gel particles were prepared as described in chinese patent No. CN102850488B, example 1.
Test example 1
This test example tests the density of the gel particles of the examples and comparative examples. 10.12g, 9.85g, 10.81g, 10.97g and 9.96g of the gel particles of examples 1 to 4 and comparative example were weighed, respectively, and then placed in a 100ml measuring cylinder containing clear water, and the volume of the gel particles was calculated from the change in the volume of the clear water in the measuring cylinder, as shown in Table 1.
Table 1 comparison of densities of gel particles of examples and comparative examples
As is clear from the results in Table 1, the density of the gel particles of examples 1 to 4 was 0.723g/cm, respectively3、0.985g/cm3、0.901g/cm3And 0.844g/cm3The density can be 0.723-0.985g/cm according to the addition of the inorganic light filler3Adjusted in between, the gel particles of the comparative example had a density of 0.913g/cm3The density of the gel particles of the examples and comparative examples was less than 1.01g/cm3And has the characteristic of low density. The gel particles of the examples are put into water and can be suspended in the water (as shown in figure 2), and the basic application requirements of the profile control agent are met.
Test example 2
The present test example evaluates the aging resistance of the gel particles of the examples and comparative examples. Samples (each having a particle size of 8mm to 10mm) of the gel particles of examples 1 to 4 and comparative example 2.57g, 2.89g, 2.64g, 2.95g and 2.79g were weighed and placed in 100ml temperature-resistant glass test tubes with stoppers, and a concentration of 24X 10 was added to each test tube480ml of standard saline water of mg/L is sealed and put into an oven of 130 ℃ for constant-temperature soaking, the change of the particles in the test tube is observed and the breaking time of the particles is recorded, and the results are shown in Table 2.
TABLE 2 comparison of the ageing resistance of the gel particles of the examples and comparative examples
As can be seen from the test results in Table 2, the gel particles of the comparative example were at a temperature of 130 deg.CDegree of mineralization 24X 104mg/L, the reinforcing agent is separated out after 3 days, the particles are completely crushed after 25 days, and the phenomena of filler separation and particle crushing are observed after 60 days for the gel particles of the examples 1 to 4.
Test example 3
The present test example tests the shear resistance and elastic modulus of the gel particles of the examples and comparative examples. The gel particles of the examples and comparative examples were trimmed to a cylindrical shape having a diameter of 3cm and a mass of 10g each (the mass was adjusted to 0.1g by trimming). 3 parts of each of the gel particles of examples 1 to 4 and comparative example were sampled, one part was tested for shear resistance and modulus of elasticity directly on an Antopa high temperature high pressure rheometer MCR302 plate system, and the other two parts were immersed in a standard saline solution (concentration 24X 10)4mg/L), taking out one part of the test tube after 24 hours, and taking out the other part of the test tube after 30 days; the taken out sample is tested for the shear resistance and the elastic modulus by an Antopa high-temperature high-pressure rheometer MCR302 flat plate system. When the shear resistance and the elastic modulus are tested, the flat rotor frequency f is 0.316Hz, and the specific test results are shown in Table 3.
Table 3 shear resistance and elastic modulus test results of gel particles of examples and comparative examples
As can be seen from the test results of table 3, the comparative example has a small elastic modulus and weak shear resistance due to the gas filling when the gel particles are not soaked; the gel particles of the embodiment have the characteristics of light weight and high strength due to the chemical bonding of the inorganic light filler, and the synthesized gel particle profile control agent has high elastic modulus and strong shear resistance.
After the gel particles are soaked, the elastic modulus and the shear resistance of the comparative example are obviously reduced due to the precipitation of the reinforcing agent; the gel particles of the examples can still maintain higher elastic modulus and shear resistance after being soaked for 30 days.
From the above test results, it can be seen that the low-density gel particle profile control agent of the present inventionHas the following characteristics: the density is low and is between 0.723 and 0.985g/cm3The distance between the two parts is adjustable; the strength is high, the elastic modulus reaches 3240-3760Pa, and the yield stress reaches 2150-2790 Pa; has excellent ageing resistance and the concentration is 24 multiplied by 104The granules are intact and not broken after being placed for 60 days under the conditions of standard saline of mg/L and 130 ℃. The gel particle profile control agent with the performances can meet the deep profile control requirements of various domestic high-temperature and high-salinity oil reservoirs.
Claims (7)
1. The low-density gel particle profile control and flooding agent is characterized by being prepared by polymerizing the following raw materials in percentage by weight: 15-20% of acrylamide, 3-5% of 2-acrylamide-2-methyl sodium propanesulfonate, 0.2-0.5% of N, N-methylene bisacrylamide, 8-17% of inorganic light filler, 2-6% of silane coupling agent, 0.2-1.0% of initiator and the balance of water;
the silane coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and/or methacryloxypropyl trimethoxy silane;
the preparation method of the low-density gel particle profile control and flooding agent comprises the following steps: uniformly mixing acrylamide, 2-acrylamide-2-methyl sodium propanesulfonate, N-methylene bisacrylamide, inorganic light filling agent and silane coupling agent in water, and then adding an initiator to carry out polymerization reaction to obtain the acrylic resin composition;
the inorganic light filler is floating beads and/or hollow glass microspheres.
2. The low density gel particle profile control agent of claim 1, wherein said initiator is comprised of sodium bisulfite and ammonium persulfate.
3. The low-density gel particle profile control agent according to claim 2, wherein the mass ratio of sodium bisulfite in the raw materials is 0.1-0.5%, and the mass ratio of ammonium persulfate in the raw materials is 0.1-0.5%.
4. The low-density gel particle profile control and flooding agent is characterized by having the following structural general formula:
in the formula, X1、X2Independently selected from SiO2·Al2O3、SiO2·B2O3·Na2O，Y1、Y2Independently selected from the group consisting of:
wherein m, n, o, p, 1, (4.0-16.8), (6.5-7.4), (86.8-162.7).
5. A method of preparing the low density gel particle profile control agent of claim 1, comprising the steps of: uniformly mixing acrylamide, 2-acrylamide-2-methyl sodium propanesulfonate, N-methylene bisacrylamide, inorganic light filling agent and silane coupling agent in water, and then adding an initiator to carry out polymerization reaction to obtain the acrylic resin composition.
6. The method for preparing the low-density gel particle profile control agent as claimed in claim 5, wherein the acrylamide, the sodium 2-acrylamido-2-methylpropanesulfonate and the N, N-methylenebisacrylamide are dissolved in water, and then the inorganic light filler and the silane coupling agent are added and mixed uniformly.
7. The method of claim 5 or 6, wherein the polymerization comprises polymerizing at 25-30 ℃ for 15-20min to obtain a solid mass, and then leaving the solid mass for at least 24 h.
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| CN115707721B (en) * | 2021-08-20 | 2024-01-26 | 中国石油天然气股份有限公司 | Underground secondary cross-linked gel particles and preparation method and application thereof |
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