CN113214809A - Environment-friendly profile control and water shutoff system, preparation method thereof and application thereof in medium-low temperature high water-cut oil reservoir - Google Patents
Environment-friendly profile control and water shutoff system, preparation method thereof and application thereof in medium-low temperature high water-cut oil reservoir Download PDFInfo
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Abstract
The invention provides an environment-friendly profile control and water shutoff system, a preparation method thereof and application thereof in medium-low temperature high water-cut oil reservoirs, relating to the technical field of oilfield exploitation. The environment-friendly profile control and water shutoff system provided by the invention comprises the following preparation raw materials in percentage by mass: 0.1-0.6% of polymer monomer, 0.01-2% of cross-linking agent, 0.1-0.5% of nano material and the balance of water. The invention takes one or more of chitosan, chitosan derivatives and carboxymethyl cellulose, which are environment-friendly natural polysaccharide monomers, as a cross-linking agent, and introduces a nano material as a reinforcing agent. The profile control water shutoff system provided by the invention is environment-friendly, has good biocompatibility, high gelling strength and good stability, has good monovalent salt and divalent salt resistance, and can be effectively subjected to profile control water shutoff when being applied to medium-low-temperature high-water-content oil reservoirs.
Description
Technical Field
The invention relates to the technical field of oilfield exploitation, in particular to an environment-friendly profile control and water shutoff system, a preparation method thereof and application thereof in medium-low temperature high water-cut oil reservoirs.
Background
At present, 70% of oil yield in China comes from old oil fields, and after decades of development, the old oil fields generally enter an extra-high water-containing stage (the water content is as high as more than 90%), and the recovery ratio is only about 35%. Aiming at the problem of high water content of old oil fields, profile control and water shutoff are effective treatment measures, and by plugging the superior channel, flow diversion is realized, and a water absorption profile and a liquid production profile are improved, so that swept volume and recovery ratio are improved. The dosage of a profile control and water shutoff system adopted in the profile control operation of an oil well is very large, at present, the profile control and water shutoff system is generally composed of a polymer, a cross-linking agent and water, unnecessary water is blocked by forming a three-dimensional structure, and the polyacrylamide gel is the most popular profile control and water shutoff system applied at home and abroad. However, the crosslinking agent commonly used in polyacrylamide gels is a metal crosslinking agent (e.g., Cr)3+Or Al3+Crosslinking agent) and organic crosslinking agents (such as formaldehyde, phenol or polyethyleneimine), and the crosslinking systems have great influence on the formation due to the problems of environmental pollution and great pollution, and the application of the crosslinking systems is limited.
Disclosure of Invention
In view of the above, the present invention aims to provide an environment-friendly profile control and water shutoff system, a preparation method thereof, and an application thereof in medium-low temperature high water-cut oil reservoirs. The profile control water shutoff system provided by the invention is green and environment-friendly, and has high gelling strength and good stability.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an environment-friendly profile control and water shutoff system which comprises the following preparation raw materials in percentage by mass:
the polymer monomer comprises one or more of nonionic polyacrylamide, cationic polyacrylamide, acrylamide/acrylic acid copolymer, acrylamide/tert-butyl acrylate copolymer and 2-acrylamide-2-methylpropanesulfonic acid/acrylic acid copolymer;
the cross-linking agent comprises one or more of chitosan, chitosan derivatives and carboxymethyl cellulose;
the nano material comprises nano SiO2TiO 2 nanoparticles2One or more of nano ZnO and carbon nano tube.
Preferably, the environment-friendly profile control and water shutoff system comprises the following preparation raw materials in percentage by mass:
preferably, the weight average molecular weight of the nonionic polyacrylamide is 200-1400 ten thousand; the weight average molecular weight of the cationic polyacrylamide is 400-1200 million, and the ionic degree is 5-25%; the weight average molecular weight of the acrylamide/acrylic acid copolymer is 500-700 ten thousand; the weight average molecular weight of the acrylamide/tert-butyl acrylate copolymer is 600-900 ten thousand; the weight average molecular weight of the 2-acrylamide-2-methylpropanesulfonic acid/acrylic acid copolymer is 500-800 ten thousand.
Preferably, the chitosan derivative is one or more of carboxymethyl chitosan, carboxyethyl chitosan, hydroxypropyl chitosan and n-butyl chitosan.
The invention provides a preparation method of an environment-friendly profile control and water shutoff system in the technical scheme, which comprises the following steps:
and mixing the polymer monomer, the cross-linking agent, the nano material and water to obtain the environment-friendly profile control and water shutoff system.
Preferably, the mixing method is as follows:
carrying out first mixing on the polymer monomer and water to obtain a polymer monomer aqueous solution;
and secondly, mixing the polymer monomer aqueous solution, the cross-linking agent and the nano material to obtain the environment-friendly profile control and water shutoff system.
Preferably, the first mixing and the second mixing are carried out under the condition of stirring, and the stirring speed is 300-1000 r/min independently.
Preferably, after the first mixing, the method further comprises standing the obtained liquid; the standing time is 12-72 h.
The invention provides an application of the environment-friendly profile control and water shutoff system in the technical scheme or the environment-friendly profile control and water shutoff system prepared by the preparation method in a medium-low temperature high water-cut oil reservoir; the method of application comprises the steps of:
injecting the environment-friendly profile control and water shutoff system into a medium-low temperature high water-containing oil reservoir stratum needing profile control and water shutoff, wherein the environment-friendly profile control and water shutoff system is crosslinked into gel at the stratum temperature, and profile control and water shutoff are carried out on the stratum;
the temperature of the medium-low temperature high water-cut oil reservoir stratum is 60-80 ℃.
Preferably, the water content of the medium-low temperature high water-containing oil reservoir is more than or equal to 90 percent.
The invention provides an environment-friendly profile control and water shutoff system which comprises the following preparation raw materials in percentage by mass: 0.1-0.6% of polymer monomer, 0.01-2% of cross-linking agent, 0.1-0.5% of nano material and the balance of water; the polymer monomer comprises one or more of nonionic polyacrylamide, cationic polyacrylamide, acrylamide/acrylic acid copolymer, acrylamide/tert-butyl acrylate copolymer and 2-acrylamide-2-methylpropanesulfonic acid/acrylic acid copolymer; the cross-linking agent comprises one or more of chitosan, chitosan derivatives, carboxymethyl cellulose and the like; the nano material comprises nano SiO2TiO 2 nanoparticles2One or more of nano ZnO and carbon nano tube. The invention takes one or more of chitosan, chitosan derivatives and carboxymethyl cellulose which are environment-friendly natural polysaccharide monomers as cross-linking agents, and the natural polysaccharide monomers and polymer monomers can carry out physical reaction through intermolecular force or electrostatic attractionPhysical crosslinking, or chemical crosslinking through amide group reaction and transamidation reaction, thereby forming a stable compact three-dimensional grid structure; according to the invention, the nano material is introduced as a reinforcing agent, and the nano particles can generate cross-linking points with polymer monomers through intermolecular force to generate more entanglement points, so that the stability of a three-dimensional grid structure is further enhanced, and the gel strength and the stability of a profile control water shutoff system are improved. Therefore, the profile control water shutoff system provided by the invention is environment-friendly, has good biocompatibility, and is high in gelling strength and good in stability. In addition, the addition of small molecular salt under low mineralization degree increases the polarity of a profile control water shutoff system, and electrostatic repulsion enables the molecular chain of a natural polysaccharide monomer to be more stretched, the overall structural strength is higher, the viscosity of the system is increased, and good salt resistance is presented, especially the resistance to monovalent salt and divalent salt. The profile control water shutoff system provided by the invention is applied to medium-low temperature high water-cut oil reservoirs, and can effectively perform profile control water shutoff.
The invention also provides a preparation method of the environment-friendly profile control and water shutoff system, and the preparation method provided by the invention is simple in process, easy to operate and convenient for large-scale production.
Detailed Description
The invention provides an environment-friendly profile control and water shutoff system which comprises the following preparation raw materials in percentage by mass:
the polymer monomer comprises one or more of nonionic polyacrylamide, cationic polyacrylamide, acrylamide/acrylic acid copolymer, acrylamide/tert-butyl acrylate copolymer and 2-acrylamide-2-methylpropanesulfonic acid/acrylic acid copolymer;
the cross-linking agent comprises one or more of chitosan, chitosan derivatives and carboxymethyl cellulose;
the nano material comprises nano SiO2TiO 2 nanoparticles2One or more of nano ZnO and carbon nano tube.
The environment-friendly profile control and water shutoff system comprises 0.1-0.6% of polymer monomer by mass percentage, and preferably 0.3-0.6%. In the invention, the polymer monomer comprises one or more of nonionic polyacrylamide, cationic polyacrylamide, acrylamide/acrylic acid copolymer, acrylamide/tert-butyl acrylate copolymer and 2-acrylamide-2-methylpropanesulfonic acid/acrylic acid copolymer; the weight average molecular weight of the nonionic polyacrylamide is preferably 200 to 1400 ten thousand, more preferably 300 to 1200 ten thousand; the weight average molecular weight of the cationic polyacrylamide is preferably 400-1200 ten thousand, more preferably 600-1100 ten thousand, and the ionicity is preferably 5-25%; the weight average molecular weight of the acrylamide/acrylic acid copolymer is preferably 500-700 ten thousand, and more preferably 550-650 ten thousand; the weight average molecular weight of the acrylamide/tert-butyl acrylate copolymer is preferably 600-900 ten thousand, and more preferably 650-850 ten thousand; the weight average molecular weight of the 2-acrylamide-2-methylpropanesulfonic acid/acrylic acid copolymer is preferably 500 to 800 ten thousand, and more preferably 550 to 750 ten thousand. The invention does not require any particular source of the polymer monomers, and can be prepared using commercially available products well known to those skilled in the art or using preparative methods well known to those skilled in the art; in the examples of the present invention, the nonionic polyacrylamide, the cationic polyacrylamide, the acrylamide/acrylic acid copolymer, the acrylamide/t-butyl acrylate copolymer, and the 2-acrylamide-2-methylpropanesulfonic acid/acrylic acid copolymer were obtained from Zipoppy chemical technology, Inc.
The environment-friendly profile control and water shutoff system comprises 0.01-2% of cross-linking agent by mass percentage, and preferably 0.4-2%. In the invention, the cross-linking agent comprises one or more of chitosan, chitosan derivatives and carboxymethyl cellulose, and the chitosan derivatives are preferably one or more of carboxymethyl chitosan, carboxyethyl chitosan, hydroxypropyl chitosan and n-butyl chitosan; the source of the crosslinking agent is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. According to the invention, the chitosan derivative and the carboxymethyl cellulose are natural polysaccharide monomers, and the natural polysaccharide monomers are used as a cross-linking agent, so that the obtained profile control water plugging system is green and environment-friendly and has good biocompatibility.
The environment-friendly profile control and water shutoff system comprises 0.1-0.5% of nano material by mass percentage, and preferably 0.3-0.5%. In the present invention, the nanomaterial includes nano SiO2TiO 2 nanoparticles2One or more of nano ZnO and carbon nano tube; the source of the nano material is not particularly required in the invention, and the corresponding material with the source well known to those skilled in the art can be adopted. In the invention, the nano SiO2Preferably hydrophilic nano SiO2Or hydrophobic nano SiO2(ii) a The hydrophilic nano SiO2Such as A150 nm SiO2V15 nanometer SiO2The hydrophobic nano SiO2Such as R972 nano SiO2XZ-G02 nano SiO2. In the present invention, the nano TiO2Preferably hydrophilic nano TiO2Or hydrophobic nano TiO2(ii) a The hydrophilic nano TiO2Such as P25 nano TiO2VK-T06H nano TiO2The hydrophobic nano TiO2Such as VK-T06S nano TiO2VK-T25 nano TiO2. In the present invention, the nano ZnO is preferably hydrophilic nano ZnO; the hydrophilic nano ZnO can be PZT-15 nano ZnO or PZT-30 nano ZnO. In the present invention, the carbon nanotube is, for example, a CNT-10 carbon nanotube. The nano material has excellent stability, and the nano material is used as a reinforcing agent in the invention.
The environment-friendly profile control and water shutoff system comprises the balance of water in percentage by mass. The water is not particularly required in the present invention, and water well known to those skilled in the art may be used.
The invention takes one or more of chitosan, chitosan derivatives and carboxymethyl cellulose which are environment-friendly natural polysaccharide monomers as cross-linking agents, and the natural polysaccharide monomers and polymer monomers can be physically cross-linked through intermolecular force or electrostatic attraction or chemically cross-linked through an acylamino reaction and a transamidation reaction, thereby forming a stable compact three-dimensional grid structure; according to the invention, the nano material is introduced as a reinforcing agent, and the nano particles can generate cross-linking points with polymer monomers through intermolecular force to generate more entanglement points, so that the stability of a three-dimensional grid structure is further enhanced, and the gel strength and the stability of a profile control water shutoff system are improved. Therefore, the profile control and water shutoff system provided by the invention is green and environment-friendly, has good biocompatibility, and is high in gelling strength and good in stability; and has good resistance to monovalent salt and divalent salt.
The invention provides a preparation method of an environment-friendly profile control and water shutoff system in the technical scheme, which comprises the following steps:
and mixing the polymer monomer, the cross-linking agent, the nano material and water to obtain the environment-friendly profile control and water shutoff system.
In the present invention, the method of mixing is preferably:
carrying out first mixing on the polymer monomer and water to obtain a polymer monomer aqueous solution;
and secondly, mixing the polymer monomer aqueous solution, the cross-linking agent and the nano material to obtain the polymer nano dispersion liquid.
In the invention, the first mixing is preferably carried out under the condition of stirring, and the stirring speed is preferably 300-1000 r/min; the time for the first mixing is not particularly required, and the polymer monomer can be sufficiently dissolved in water. After the first mixing, the present invention also preferably allows the resulting liquid to stand; the standing time is preferably 12-72 hours, and more preferably 24-48 hours; the liquid obtained is stood for a certain time for aging, so that the polymer monomer in the liquid is fully hydrolyzed, and the polymer monomer aqueous solution is obtained after standing. According to the invention, preferably, a cross-linking agent and a nano material are sequentially added into the polymer monomer aqueous solution for second mixing; the second mixing is preferably carried out under the condition of stirring, and the stirring speed is preferably 300-1000 r/min; the time for the second mixing is not particularly required, so that a uniform profile control and water shutoff system can be formed.
The preparation method of the environment-friendly profile control and water shutoff system provided by the invention is simple in process, easy to operate and convenient for large-scale production.
The invention provides the application of the environment-friendly profile control and water shutoff system in the technical scheme or the environment-friendly profile control and water shutoff system prepared by the preparation method in medium-low temperature high water-cut oil reservoirs; the method of application comprises the steps of:
and injecting the environment-friendly profile control water plugging system into a medium-low temperature high water-cut oil reservoir stratum needing profile control water plugging, wherein the environment-friendly profile control water plugging system is crosslinked into gel at the stratum temperature, and profile control water plugging is carried out on the stratum.
In the invention, the temperature of the medium-low temperature high water-cut oil reservoir stratum is 60-80 ℃, and the water content of the medium-low temperature high water-cut oil reservoir is preferably more than or equal to 90%; the environment-friendly profile control water shutoff system starts to gel after being crosslinked for 2 h-5 d at the stratum temperature, and the gel strength reaches the maximum after being crosslinked for 2 d-20 d.
The profile control and water shutoff system provided by the invention is green and environment-friendly, has good biocompatibility, and is high in gelling strength and good in stability; in addition, the water plugging agent has good monovalent salt and divalent salt resistance, and can be effectively used for profile control and water plugging when being applied to medium-low temperature high water-cut oil reservoirs.
The environment-friendly profile control and water shutoff system provided by the invention, the preparation method thereof and the application thereof in medium-low temperature high water-cut oil reservoirs are described in detail below by referring to the examples, but the environment-friendly profile control and water shutoff system cannot be understood as limiting the protection scope of the invention.
In each embodiment, the cross-linking condition of the profile control water shutoff system at the formation temperature is simulated by reacting the profile control water shutoff system in a water bath kettle at the temperature of 60-80 ℃.
According to the embodiments of the invention, a gel code method is adopted to measure the gel forming time and gel forming strength of the polymer gel, the gel forming time is recorded when the gel strength reaches D, and the final gel forming time is recorded when the strength reaches I. The gel strength code is characterized in table 1:
table 1 gel strength code characterization
Example 1
The preparation method of the environment-friendly profile control and water shutoff system comprises the following steps:
weighing 0.1g of nonionic polyacrylamide (PAM, the weight average molecular weight is 200-1400 ten thousand), dissolving the PAM in 99.79g of fresh water by using an electric stirrer under the condition of 500r/min, and standing for 24h after the dissolution is finished to obtain a polyacrylamide aqueous solution;
under the stirring condition of 500r/min, 0.01g of carboxymethyl chitosan (CMCS) and 0.1g A150 nm of SiO are added into the polyacrylamide aqueous solution in sequence2Forming a uniform profile control and water shutoff system;
the obtained profile control and water shutoff system is sealed and respectively placed in constant-temperature water baths at 60, 70 and 80 ℃ for crosslinking reaction, and the gelling condition is shown in table 2:
TABLE 20.1% PAM + 0.01% CMCS + 0.1% A150-SiO2Gel formation at different temperatures
(Note in Table 2: "+" indicates no glue)
As can be seen from Table 2, the formulation 0.1% PAM + 0.01% CMCS + 0.1% A150-SiO2The crosslinking reaction speed of the profile control water plugging system is continuously accelerated along with the rise of the temperature, the gelling time is 3d under the condition of 80 ℃, the gel strength reaches the maximum within 10d, but the dehydration phenomenon occurs at 20d along with the prolonging of the aging time. The result shows that the gel strength of the profile control water shutoff system of the formula can reach H level at 80 ℃.
Example 2
The preparation method of the environment-friendly profile control and water shutoff system comprises the following steps:
weighing 0.3g of nonionic polyacrylamide (PAM, the weight average molecular weight is 200-1400 ten thousand), dissolving the PAM in 98.4g of fresh water by using an electric stirrer under the condition of 500r/min, and standing for 24h after the dissolution is finished to obtain a polyacrylamide aqueous solution;
under the stirring condition of 500r/min, 1g of carboxymethyl chitosan (CMCS) and 0.3g R972 nano SiO 972 nano in sequence are added into the polyacrylamide aqueous solution2Forming a uniform profile control and water shutoff system;
the obtained profile control and water shutoff system is sealed and respectively placed in constant-temperature water baths at 60, 70 and 80 ℃ for crosslinking reaction, and the gelling condition is shown in table 3:
TABLE 30.3% PAM + 1% CMCS + 0.3% R972-SiO2Gel formation at different temperatures
(Note in Table 3: "+" indicates no glue)
As can be seen from Table 3, the formulation 0.3% PAM + 1% CMCS + 0.3% R972-SiO2The cross-linking reaction speed of the profile control water plugging system is increased continuously along with the increase of the temperature, the cross-linking reaction starts to occur within 12 hours at the temperature of 80 ℃, the gel strength reaches the maximum within 5 days, but the dehydration phenomenon occurs at 20 days along with the increase of the aging time. This indicates that the gel strength of the profile control water shutoff system of the formula reaches the maximum level H at 5 d.
Example 3
The preparation method of the environment-friendly profile control and water shutoff system comprises the following steps:
weighing 0.6g of nonionic polyacrylamide (PAM, the weight average molecular weight is 200-1400 ten thousand), dissolving the PAM in 96.9g of fresh water by using an electric stirrer under the condition of 500r/min, and standing for 24 hours after the dissolution is finished to obtain a polyacrylamide aqueous solution;
under the stirring condition of 500r/min, 2g of carboxymethyl chitosan (CMCS) and 0.5g R972 nano SiO 972 are added into the polyacrylamide aqueous solution in sequence2Forming a uniform profile control and water shutoff system;
the obtained profile control and water shutoff system is sealed and respectively placed in constant-temperature water baths at 60, 70 and 80 ℃ for crosslinking reaction, and the gelling condition is shown in table 4:
TABLE 40.6% PAM + 2% CMCS + 0.5% R972-SiO2Gel formation at different temperatures
(Note in Table 4: "+" indicates no glue)
As can be seen from Table 4, the formulation 0.6% PAM + 2% CMCS + 0.5% R972-SiO2The cross-linking reaction speed of the profile control water plugging system is increased continuously along with the increase of the temperature, the cross-linking reaction starts within 10 hours at the temperature of 80 ℃, the gel strength reaches the maximum I level within 2d, and the dehydration phenomenon does not occur within 30d along with the prolonging of the aging time. This shows that the profile control water shutoff system of the formula has good long-term stability and strength under high temperature.
Example 4
The preparation method of the environment-friendly profile control and water shutoff system comprises the following steps:
weighing 0.6g of nonionic polyacrylamide (PAM, the weight average molecular weight is 200-1400 ten thousand), dissolving the PAM in 98.7g of fresh water by using an electric stirrer under the condition of 500r/min, and standing for 24h after the dissolution is finished to obtain a polyacrylamide aqueous solution;
under the stirring condition of 500r/min, 0.4g of carboxymethyl chitosan (CMCS) and 0.3g of V15 nano SiO are sequentially added into the polyacrylamide aqueous solution2Forming a uniform profile control and water shutoff system;
the obtained profile control and water shutoff system is sealed and respectively placed in constant-temperature water baths at 60, 70 and 80 ℃ for crosslinking reaction, and the gelling condition is shown in table 5:
TABLE 50.6% PAM + 0.4% CMCS + 0.3% V15-SiO2Gel formation at different temperatures
(Note in Table 5: "+" indicates no glue)
As can be seen from Table 5, the formulation 0.6% PAM + 0.4% CMCS + 0.3% V15-SiO2The cross-linking reaction speed of the profile control water plugging system is increased continuously along with the increase of the temperature, the cross-linking reaction starts within 2 hours at the temperature of 80 ℃, the gel strength reaches the maximum I level within 3 days, and the dehydration phenomenon does not occur within 30 days along with the prolonging of the aging time. The result shows that the water plugging agent prepared by the formula has good long-term stability and strength under the high-temperature condition.
Example 5
The monovalent salt resistance of the environment-friendly profile control water shutoff system is tested:
weighing 0.6g of nonionic polyacrylamide (PAM, the weight average molecular weight is 200-1400 ten thousand), dissolving the PAM in 98.7g of NaCl aqueous solution (the NaCl concentration is 5000-70000 mg/L) by using an electric stirrer under the condition of 500r/min, and standing for 24h after the dissolution is finished to obtain a polyacrylamide aqueous solution;
under the stirring condition of 500r/min, 0.4g of carboxymethyl chitosan (CMCS) and 0.3g A150 nm of SiO are added into the polyacrylamide aqueous solution in sequence2Forming a uniform profile control and water shutoff system;
the profile control and water shutoff system is sealed and respectively placed in a constant-temperature water bath kettle at 80 ℃ for crosslinking reaction, and the gelling condition is shown in table 6:
TABLE 60.6% PAM + 0.4% CMCS + 0.3% A150-SiO2+ NaCl gel formation at 80 deg.C
(Note in Table 6: "+" indicates no glue)
As can be seen from Table 6, the formulation 0.6% PAM + 0.4% CMCS + 0.3% SiO2The profile control water shutoff system is characterized in that the crosslinking reaction speed is reduced in 5000-70000 mg/L NaCl solution at 80 ℃, and when the NaCl is less than or equal to 30000mg/L, the maximum strength of the gel is not changed and can still reach the I level; when NaCl is more than 30000mg/L, the gel strength in 30d can reach H grade at most. Therefore, the profile control water shutoff system prepared by the invention has better monovalent salt resistance.
Example 6
And (3) testing divalent salt resistance of an environment-friendly profile control water plugging system:
0.6g of non-ionic polyacrylamide (PAM, weight average molecular weight is 200-1400 ten thousand) is weighed and dissolved in 98.7g of CaCl by an electric stirrer under the condition of 500r/min2Aqueous solution (CaCl)2Concentration: 1000-7000 mg/L), standing for 24 hours after the dissolution is finished, and obtaining a polyacrylamide aqueous solution;
under the stirring condition of 500r/min, 0.4g of carboxymethyl chitosan (CMCS) and 0.3g A150 nm of SiO are added into the polyacrylamide aqueous solution in sequence2Forming a uniform profile control and water shutoff system;
the profile control and water shutoff system is sealed and respectively placed in a constant-temperature water bath kettle at 80 ℃ for crosslinking reaction, and the gelling condition is shown in table 7:
TABLE 70.6% PAM + 0.4% CMCS + 0.3% A150-SiO2+CaCl2Gel formation at 80 deg.C
As can be seen from Table 7, the formulation 0.6% PAM + 0.4% CMCS + 0.3% SiO2The CaCl of the profile control and water shutoff system is 1000-7000 mg/L2In the solution, under the condition of 80 ℃, the crosslinking reaction speed is reduced, but the maximum strength of the gel is not changed, and the strength in 30d can still be maintained at the I level; when NaCl and CaCl are present2When the concentration is 5000mg/L, the profile control and water shutoff system starts to react in NaCl for about 12 hours and CaCl2The reaction starts in about 6h, which shows that the water plugging agent resists CaCl in low-concentration saline water2Has stronger NaCl resistance. Therefore, the profile control water shutoff system prepared by the invention has good divalent salt resistance.
Example 7
The monovalent salt resistance of the environment-friendly profile control water shutoff system is tested:
weighing 0.6g of cationic polyacrylamide (CPAM, weight average molecular weight of 400-1200 ten thousand and ionic degree of 5-25%), dissolving the cationic polyacrylamide in 98.9g of NaCl aqueous solution (NaCl concentration: 5000-70000 mg/L) by using an electric stirrer under the condition of 500r/min, and standing for 24h after the dissolution is finished to obtain the cationic polyacrylamide aqueous solution;
under the stirring condition of 500r/min, 0.4g of carboxymethyl cellulose (CMC) and 0.1gVK-T25 nanometer TiO are added into the cationic polyacrylamide aqueous solution in sequence2Forming a uniform profile control and water shutoff system;
the profile control and water shutoff system is sealed and respectively placed in a constant-temperature water bath kettle at 80 ℃ for crosslinking reaction, and the gelling condition is shown in table 8:
TABLE 80.6% CPAM + 0.4% CMC + 0.1% VK-T25 TiO2+ NaCl gel formation at 80 deg.C
(Note in Table 8: "+" indicates no glue)
As can be seen from Table 8, the formulation 0.6% CPAM + 0.4% CMC + 0.1% TiO2The profile control water shutoff system is characterized in that the crosslinking reaction speed is reduced in 5000-70000 mg/L NaCl solution at 80 ℃, and when the NaCl is less than or equal to 30000mg/L, the maximum strength of the gel is not changed and can still reach the I level; when NaCl is more than 30000mg/L, the gel strength in 30d can reach H level to the maximum, and the product shows better monovalent salt resistance stability.
Example 8
And (3) testing divalent salt resistance of an environment-friendly profile control water plugging system:
weighing 0.1g of 2-acrylamide-2-methylpropanesulfonic acid/acrylic acid copolymer (AA/AMPS, weight average molecular weight of 500-800 ten thousand), and dissolving the copolymer in 99.6g of CaCl by using an electric stirrer under the condition of 500r/min2Aqueous solution (CaCl)2Concentration: 1000-7000 mg/L), standing for 24 hours after the dissolution is finished, and obtaining a cationic polyacrylamide aqueous solution;
under the stirring condition of 500r/min, sequentially adding 0.2g of Chitosan (CS) and 0.1g of PZT-15 nano ZnO into a 2-acrylamide-2-methylpropanesulfonic acid/acrylic acid copolymer aqueous solution to form a uniform profile control and water shutoff system;
the profile control and water shutoff system is sealed and respectively placed in a constant-temperature water bath kettle at 80 ℃ for crosslinking reaction, and the gelling condition is shown in table 9:
TABLE 90.1% AA/AMPS + 0.2% CS + 0.1% PZT-15 nm ZnO + CaCl2Gel formation at 80 deg.C
(Note in Table 9: "+" indicates no glue)
As can be seen from Table 9, the profile control and water shutoff system with the formulation of 0.1% of AA/AMPS, 0.4% of CS and 0.1% of PZT-15 nano ZnO is 1000-7000 mg/L of CaCl2In the solution, the maximum strength of the gel in 30 days is not changed at 80 ℃, the strength can be still maintained at H level, and the solution shows better salt resistance stability.
The embodiment shows that the profile control and water shutoff system provided by the invention is green and environment-friendly, and has high strength and good stability; and has good resistance to monovalent salt and divalent salt.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. An environment-friendly profile control and water shutoff system is characterized by comprising the following preparation raw materials in percentage by mass:
the polymer monomer comprises one or more of nonionic polyacrylamide, cationic polyacrylamide, acrylamide/acrylic acid copolymer, acrylamide/tert-butyl acrylate copolymer and 2-acrylamide-2-methylpropanesulfonic acid/acrylic acid copolymer;
the cross-linking agent comprises one or more of chitosan, chitosan derivatives and carboxymethyl cellulose;
the nano material comprises nano SiO2TiO 2 nanoparticles2One or more of nano ZnO and carbon nano tube.
2. The environment-friendly profile control and water shutoff system according to claim 1, which is characterized by comprising the following preparation raw materials in percentage by mass:
3. an environment-friendly profile control and water shutoff system according to claim 1 or 2, wherein the weight average molecular weight of the nonionic polyacrylamide is 200 to 1400 ten thousand; the weight average molecular weight of the cationic polyacrylamide is 400-1200 million, and the ionic degree is 5-25%; the weight average molecular weight of the acrylamide/acrylic acid copolymer is 500-700 ten thousand; the weight average molecular weight of the acrylamide/tert-butyl acrylate copolymer is 600-900 ten thousand; the weight average molecular weight of the 2-acrylamide-2-methylpropanesulfonic acid/acrylic acid copolymer is 500-800 ten thousand.
4. An environment-friendly profile control and water shutoff system according to claim 1 or 2, wherein the chitosan derivative is one or more of carboxymethyl chitosan, carboxyethyl chitosan, hydroxypropyl chitosan and n-butyl chitosan.
5. A preparation method of the environment-friendly profile control and water shutoff system as claimed in any one of claims 1 to 4, which is characterized by comprising the following steps:
and mixing the polymer monomer, the cross-linking agent, the nano material and water to obtain the environment-friendly profile control and water shutoff system.
6. The method of claim 5, wherein the mixing is performed by:
carrying out first mixing on the polymer monomer and water to obtain a polymer monomer aqueous solution;
and secondly, mixing the polymer monomer aqueous solution, the cross-linking agent and the nano material to obtain the environment-friendly profile control and water shutoff system.
7. The method of claim 6, wherein the first mixing and the second mixing are performed under stirring at a speed of 300 to 1000r/min independently.
8. The production method according to claim 6 or 7, characterized by further comprising, after the first mixing, subjecting the resultant liquid to standing; the standing time is 12-72 h.
9. The application of the environment-friendly profile control and water shutoff system of any one of claims 1 to 4 or the environment-friendly profile control and water shutoff system prepared by the preparation method of any one of claims 5 to 8 in medium-low temperature high water-cut oil reservoirs; the method of application comprises the steps of:
injecting the environment-friendly profile control and water shutoff system into a medium-low temperature high water-containing oil reservoir stratum needing profile control and water shutoff, wherein the environment-friendly profile control and water shutoff system is crosslinked into gel at the stratum temperature, and profile control and water shutoff are carried out on the stratum;
the temperature of the medium-low temperature high water-cut oil reservoir stratum is 60-80 ℃.
10. The use according to claim 9, wherein the water content of the medium-low temperature high water-cut reservoir is not less than 90%.
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| CN114854381A (en) * | 2022-05-19 | 2022-08-05 | 长江大学 | Weak-gel profile-control water shutoff agent with salt resistance and adjustable strength as well as preparation and application thereof |
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| CN113755144B (en) * | 2021-08-31 | 2023-03-10 | 中国石油大学(北京) | Gel water shutoff agent and preparation method thereof |
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