CN111234795A - Wetting reversal agent for ultra-low permeability oil reservoir depressurization and augmented injection and preparation method thereof - Google Patents
Wetting reversal agent for ultra-low permeability oil reservoir depressurization and augmented injection and preparation method thereof Download PDFInfo
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Abstract
The invention provides a wetting reversal agent for reducing pressure and increasing injection of an ultra-low permeability oil reservoir, which is prepared from the following raw materials: cationic gemini surfactant, nonionic surfactant, high-efficiency anti-swelling and anti-swelling agent, ethanol, ethylene glycol ethyl ether and deionized water; the cationic gemini surfactant has a structure shown as the following formula I:
Description
Technical Field
The invention relates to a wetting reversal agent for reducing water injection pressure and improving water injection rate of a water injection well in an oil field aiming at an ultra-low permeability sandstone reservoir, belonging to the technical field of oil-water well production and injection increasing of the oil field.
Background
Ultra-low permeability reservoirs generally have poor physical properties, and are characterized by low permeability, fine pore throat, complex structure and poor connectivity between pore throat and pores. The complicated and variable pore throat structure causes the multiphase fluid to flow in the fine and unevenly distributed pore throat structure and is influenced by various resistances, and the resistances can cause the injection pressure to be overhigh in the water injection development process.
The content of clay minerals such as illite, kaolinite, illite mixed layer and the like in the sensitive reservoir is higher. Kaolinite is easy to crack, disperse or migrate, and the kaolinite is gathered in pore throats to cause blockage and reduce permeability; the montmorillonite has better expansibility and dispersibility, and is easy to expand in water with low mineralization degree, so that the porosity and the permeability are reduced; illite exists in the sandstone pores in various crystal structures, and can change originally flowable intergranular pores in the sandstone into micro-bound pores. Sensitive minerals will cause the reservoir water injection pressure to rise and the water injection capacity to continuously decline.
The ultra-low permeability reservoir has large wettability difference, and the water lock effect and Jamin effect are easily generated in the water injection process. The water lock effect causes the injected water to drive into the large pore passage to form a thicker water film, and the injected water is difficult to enter into the smaller pore passage, so that the water injection pressure is increased; in the water flooding process, when oil drops move to pore throats, the oil drops have poor trafficability due to the Jamin effect, and water injection energy is greatly consumed.
The crude oil contains polar substances such as colloid asphaltene and the like. The colloid can not only prevent the aggregation of the asphaltene, but also enable the asphaltene to be dispersed in the crude oil in the form of particles, and the asphaltene and the colloid form a liquid interface film with low flowing strength after being adsorbed on an oil-water interface, so that the water wettability of the rock is reduced, the water phase seepage resistance is increased, and the water injection is more difficult.
The water injection well has poor water absorption capacity and constantly raised water injection pressure in the water injection development process, and a high-pressure area formed near the water injection well further reduces the water injection pressure difference and greatly reduces the water injection amount.
Taking the ultra-low permeability oil reservoir of the oil field in Changqing as an example, the pressure reduction and injection increase technology of the existing water injection well is mainly an acidification acid fracturing technology. The acidizing and acid fracturing aims at increasing production and injection by removing pollutants from well walls, acid etching minerals in rocks and corroding cracks to improve the seepage condition of the stratum, but the technology has poor general effect on sandstone stratums, small action distance and short effective period.
Disclosure of Invention
In order to solve the problems, the invention provides a wetting reversal agent for pressure reduction and injection increase of an oil field and a preparation method thereof, which improve the pressure reduction, injection increase and yield increase effects of a sensitive ultra-low permeability hydrophilic water injection high-pressure oil reservoir.
The technical scheme of the invention is realized as follows:
the invention provides a wetting reversal agent for reducing pressure and increasing injection of an ultra-low permeability oil reservoir, which is prepared from the following raw materials: cationic gemini surfactant, nonionic surfactant, high-efficiency anti-swelling and anti-swelling agent, ethanol, ethylene glycol ethyl ether and deionized water;
the cationic gemini surfactant has a structure shown as the following formula I:
wherein n is 3-18;
the nonionic surfactant is nonionic low molecular polymer surfactant, is selected from one or more of polyvinyl alcohol, polyacrylamide, ethylene oxide propylene oxide block copolymer, polyvinylpyrrolidone and polyoxyethylene condensed alkyl phenyl ether, and is preferably polyvinyl alcohol;
the high-efficiency anti-swelling and anti-swelling agent is selected from two or more of a small cationic surfactant, a cationic polymer surfactant and a fluorocarbon cationic surfactant, the molecular weight of the small cationic surfactant is not higher than 1000, and the small cationic surfactant is preferably a fluorocarbon cationic surfactant.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in percentage by weight: 0.01-0.2% of cationic gemini surfactant, 0.01-0.1% of nonionic surfactant, 0.2-0.5% of high-efficiency anti-swelling and anti-swelling agent, 10-30% of ethanol, 10-20% of ethylene glycol ether and the balance of deionized water.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in percentage by weight: 0.7% of cationic Gemini surfactant, 0.2% of nonionic surfactant, 0.35% of high-efficiency anti-swelling and anti-shrinking agent, 20% of ethanol, 15% of ethylene glycol ethyl ether and the balance of deionized water.
As a further improvement of the invention, the small cationic surfactant is selected from one or a mixture of several of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and octadecyl dimethyl benzyl ammonium chloride.
As a further improvement of the invention, the cationic polymer surfactant is selected from one or more of oxyalkyl acrylate copolymer modified polyethyleneimine, polymer of 1-dodeca-4-vinylpyridine bromide and polyvinyl benzyl trimethylamine salt.
As a further improvement of the invention, the fluorocarbon cationic surfactant is selected from one or more of YF-138, FC-8 (perfluoroalkyl ether amine oxide type cationic fluorocarbon surfactant) and quaternary ammonium salt cationic fluorocarbon surfactant.
The invention further protects a cationic Gemini surfactant shown in the formula I.
The invention further provides a preparation method of the cationic Gemini surfactant shown in the formula I, which comprises the following steps:
s1, mixing p-hydroxybenzaldehyde, alkyl alcohol, thionyl chloride and triethylamine for reaction to obtain a reaction intermediate I, wherein the intermediate I is as follows:
wherein n is 3-18;
s2, reacting the intermediate I with p-toluenesulfonyl chloride to generate an intermediate II, wherein the intermediate II is as follows:
s3, reacting the intermediate II with potassium bromide to generate an intermediate III, wherein the intermediate III is as follows:
s4, reacting N, N' -dimethyl ethylenediamine, formaldehyde and acetic acid to generate an intermediate VI:
s5, reacting the intermediate III with the intermediate VI to generate a cationic Gemini surfactant shown in a formula I;
the steps can be replaced as long as the preparation is not influenced.
As a further improvement of the present invention, the preparation method specifically comprises the following steps:
s1, dissolving p-hydroxybenzaldehyde in dichloromethane, sequentially adding thionyl chloride and triethylamine, reacting at room temperature for 2-3 hours, adding alkyl alcohol, stirring at room temperature for reacting for 2 hours to obtain an intermediate I;
s2, dissolving the intermediate I in acetonitrile, adding triethylamine and p-toluenesulfonyl chloride, heating to 60-80 ℃, and reacting for 2-4h to obtain an intermediate II;
s3, dissolving the intermediate II in acetone, adding triethylamine and potassium bromide, and reacting at room temperature for 1-2h to obtain an intermediate III;
s4, mixing N, N' -dimethyl ethylenediamine and 85 wt% formic acid, heating to 80-85 ℃, adding a formaldehyde aqueous solution, heating to 110-120 ℃, and reacting for 4-8h to obtain an intermediate VI;
s5, dissolving the intermediate VI in n-propanol, heating to 100-120 ℃, adding the intermediate III, and carrying out reflux reaction for 2-5h to obtain the cationic Gemini surfactant shown in the formula I.
The invention further provides a preparation method of the wetting reversal agent for reducing pressure and increasing injection of the ultra-low permeability reservoir, which is characterized by comprising the following steps of: uniformly mixing ethylene glycol ethyl ether and ethanol, heating to 40-60 ℃, adding a cationic gemini surfactant shown in formula I, after dissolving a homogeneous phase, adding a nonionic surfactant, stirring to a homogeneous phase, adding a high-efficiency swelling and shrinking prevention agent, stirring to a homogeneous phase, adding deionized water, uniformly stirring, stopping heating, and cooling to obtain the wetting reversal agent for reducing pressure and increasing injection of the ultra-low permeability reservoir.
The invention has the following beneficial effects:
the wetting reversal agent provided by the invention has the following characteristics:
firstly, the wettability of the rock surface of the ultra-low permeability hydrophilic oil layer can be changed, so that the rock is changed from hydrophilicity to hydrophobicity, the thickness of a hydration film is reduced, and the effective permeability of a water phase is obviously improved, thereby being beneficial to improving the injection capability of the ultra-low permeability hydrophilic oil layer and achieving the purpose of reducing pressure and increasing injection;
secondly, the interfacial tension is extremely low (the oil-water interfacial tension can be reduced to 10)-3mN/m), the purposes of improving the flow capacity of crude oil in the stratum and improving the oil displacement efficiency are achieved by reducing the tension of an oil-water interface, and meanwhile, the influence of wettability, water lock effect and Jamin effect on pressure can be better solved after the wetting reversal agent is injected into the stratum;
thirdly, the wetting reversal agent system is compounded with a high-efficiency anti-swelling shrinkage-expansion agent (when the using concentration of 0.2 percent is higher than or equal to 70 percent, the swelling shrinkage rate is higher than or equal to 25 percent), the shrinkage-expansion rate of the hydrated minerals can be effectively improved, the swelling migration and blockage of the hydrated minerals can be prevented, and therefore the purposes of reducing the injection pressure, reducing the high-pressure water injection difficulty, improving the water drive development effect of an oil reservoir and improving the crude oil recovery rate are achieved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
EXAMPLE 1 cationic Gemini surfactant of formula I
The preparation method comprises the following steps:
s1, dissolving 1mol of p-hydroxybenzaldehyde in 100mL of dichloromethane, sequentially adding 1mol of thionyl chloride and 2mol of triethylamine, reacting for 2h at room temperature, adding 1mol of alkyl alcohol (n is 12), and stirring at room temperature for reacting for 2h to obtain an intermediate I (A);
s2, dissolving the intermediate I (A) in 100mL of acetonitrile, adding 2mol of triethylamine and 1mol of p-toluenesulfonyl chloride, heating to 60 ℃, and reacting for 2h to obtain an intermediate II (B);
s3, dissolving the intermediate II (B) in 100mL of acetone, adding 2mol of triethylamine and 1mol of potassium bromide, and reacting at room temperature for 1h to obtain an intermediate III (C);
s4, mixing 1mol of N, N' -dimethylethylenediamine and 100mL of 85 wt% formic acid, heating to 80 ℃, adding 100mL of 35 wt% formaldehyde aqueous solution, heating to 110-DEG C and 120 ℃, reacting for 4h, cooling to room temperature, adding 1mol/L of NaOH solution with the same volume, standing for layering, separating an oil phase, distilling, and distilling a distillation product at 195-DEG C and 197 ℃ to obtain an intermediate VI (D);
s5, dissolving the intermediate VI (D) in 100mL of n-propanol, heating to 100 ℃, adding the intermediate III (C), and carrying out reflux reaction for 2h to obtain the cationic Gemini surfactant shown in the formula I.
The prepared cationic Gemini surfactant is subjected to FTIR detection after separation and purification, and the result is as follows: 3239 and 3543cm-12938cm as the O-H stretching vibration absorption peak-12952cm as a symmetric telescopic vibration absorption peak of methyl-12844cm as asymmetric absorption peak of stretching vibration of methylene-1Is methyleneSymmetric telescopic vibration absorption peak, 1580cm-1And 1475cm-1Is a skeleton vibration absorption peak of benzene ring, 967cm-1、922cm-1And 863cm-11410cm, which is an isolated hydrogen out-of-plane bending vibration absorption peak on the benzene ring-1And 1305cm-1Is the O-H in-plane bending vibration absorption peak, 612cm-1Is an O-H out-of-plane bending vibration absorption peak, 1232--1Is C-N stretching vibration peak and is at 3000cm-1The above shows no obvious absorption peak, which indicates that the molecule has no N-H structure, i.e. primary amine and secondary amine, and concludes that the molecule has a tertiary amine structure.
EXAMPLE 2 cationic Gemini surfactant of formula I
The preparation method comprises the following steps:
s1, dissolving 1.2mol of p-hydroxybenzaldehyde in 100mL of dichloromethane, sequentially adding 1mol of thionyl chloride and 2mol of triethylamine, reacting for 3 hours at room temperature, adding 1mol of alkyl alcohol (n is 10), and stirring for reacting for 2 hours at room temperature to obtain an intermediate I (A);
s2, dissolving the intermediate I (A) in 100mL of acetonitrile, adding 2mol of triethylamine and 1.2mol of p-toluenesulfonyl chloride, heating to 80 ℃, and reacting for 4 hours to obtain an intermediate II (B);
s3, dissolving the intermediate II (B) in 100mL of acetone, adding 2mol of triethylamine and 1.2mol of potassium bromide, and reacting at room temperature for 2h to obtain an intermediate III (C);
s4, mixing 1.2mol of N, N' -dimethylethylenediamine and 100mL of 85 wt% formic acid, heating to 85 ℃, adding 100mL of 40 wt% formaldehyde aqueous solution, heating to 120 ℃, reacting for 8 hours, cooling to room temperature, adding 1mol/L of NaOH solution with the same volume, standing for layering, separating an oil phase, distilling, and distilling at 195-197 ℃ to obtain an intermediate VI (D);
s5, dissolving the intermediate VI (D) in 100mL of n-propanol, heating to 120 ℃, adding the intermediate III (C), and carrying out reflux reaction for 5 hours to obtain the cationic Gemini surfactant shown in the formula I.
EXAMPLE 3 cationic Gemini surfactant of formula I
The preparation method comprises the following steps:
s1, dissolving 1.1mol of p-hydroxybenzaldehyde in 100mL of dichloromethane, sequentially adding 1mol of thionyl chloride and 2mol of triethylamine, reacting at room temperature for 2.5h, adding 1mol of alkyl alcohol (n is 18), and stirring at room temperature for reacting for 2h to obtain an intermediate I (A);
s2, dissolving the intermediate I (A) in 100mL of acetonitrile, adding 2mol of triethylamine and 1.1mol of p-toluenesulfonyl chloride, heating to 70 ℃, and reacting for 3h to obtain an intermediate II (B);
s3, dissolving the intermediate II (B) in 100mL of acetone, adding 2mol of triethylamine and 1.1mol of potassium bromide, and reacting at room temperature for 1.5h to obtain an intermediate III (C);
s4, mixing 1.1mol of N, N' -dimethylethylenediamine and 100mL of 85 wt% formic acid, heating to 82 ℃, adding 100mL of 35-40 wt% formaldehyde aqueous solution, heating to 115 ℃, reacting for 6h, cooling to room temperature, adding 1mol/L of NaOH solution with the same volume, standing for layering, separating an oil phase, distilling, and distilling at 195-197 ℃ to obtain an intermediate VI (D);
s5, dissolving the intermediate VI (D) in 100mL of n-propanol, heating to 110 ℃, adding the intermediate III (C), and carrying out reflux reaction for 3.5h to obtain the cationic Gemini surfactant shown in the formula I.
Example 4 wetting reversal agent for ultra-low permeability reservoir depressurization augmented injection
The raw materials comprise the following components in percentage by mass:
0.01% of the cationic gemini surfactant prepared in example 1;
the cationic gemini surfactant has a structure shown as the following formula I:
nonionic surfactant (ethylene oxide propylene oxide block copolymer) 0.01%;
0.2 percent of high-efficiency anti-swelling agent (fluorocarbon cationic surfactant YF-1380.1 percent and sodium dodecyl sulfate 0.1 percent);
10% of ethanol;
10% of ethylene glycol ethyl ether;
the balance being deionized water.
The preparation method comprises the following steps:
uniformly mixing ethylene glycol ethyl ether and ethanol, heating to 40 ℃, adding a cationic gemini surfactant shown as a formula I, adding an ethylene oxide propylene oxide block copolymer after the homogeneous phase is dissolved, stirring to the homogeneous phase, adding a high-efficiency anti-swelling and anti-shrinking agent (a fluorocarbon cationic surfactant YF-138 and sodium dodecyl sulfate are compounded), stirring to the homogeneous phase, adding deionized water, stirring uniformly, stopping heating, and cooling to obtain the wetting reversal agent for reducing pressure and increasing injection of the ultra-low permeability reservoir.
Example 5 very Low permeability reservoir wetting reversal agent for depressurization and stimulation
The raw materials comprise the following components in percentage by mass:
0.2% of the cationic gemini surfactant prepared in example 2;
the cationic gemini surfactant has a structure shown as the following formula I:
0.1% of nonionic surfactant (polyoxyethylene condensed alkyl phenyl ether);
0.5 percent of high-efficiency anti-swelling agent (0.3 percent of oxy-alkyl acrylate copolymer modified polyethyleneimine and 0.2 percent of quaternary ammonium salt cationic fluorocarbon surfactant);
30% of ethanol;
20% of ethylene glycol ethyl ether;
the balance being deionized water.
The preparation method comprises the following steps:
uniformly mixing ethylene glycol ethyl ether and ethanol, heating to 60 ℃, adding a cationic gemini surfactant shown in the formula I, adding polyoxyethylene condensed alkyl phenyl ether after the homogeneous phase is dissolved, stirring to the homogeneous phase, adding a high-efficiency anti-swelling agent (compounding oxy alkyl acrylate copolymer modified polyethyleneimine and quaternary ammonium salt cationic fluorocarbon surfactant), stirring to the homogeneous phase, adding deionized water, stirring uniformly, stopping heating, and cooling to obtain the wetting reversal agent for depressurization and injection enhancement of the ultra-low permeability reservoir.
Example 6 ultra-low permeability reservoir wetting reversal agent for depressurization and stimulation
The raw materials comprise the following components in percentage by mass:
0.7% of the cationic gemini surfactant prepared in example 3;
the cationic gemini surfactant has a structure shown as the following formula I:
0.2% of nonionic surfactant (polyvinyl alcohol);
0.35 percent of high-efficiency anti-swelling agent (0.2 percent of FC-8 (perfluoroalkyl ether amine oxide type cationic fluorocarbon surfactant) and 0.15 percent of octadecyl dimethyl benzyl quaternary ammonium chloride);
20% of ethanol;
15% of ethylene glycol ethyl ether;
the balance being deionized water.
The preparation method comprises the following steps:
uniformly mixing ethylene glycol ethyl ether and ethanol, heating to 50 ℃, adding a cationic gemini surfactant shown as a formula I, adding polyvinyl alcohol after the homogeneous phase is dissolved, stirring to the homogeneous phase, adding a high-efficiency anti-swelling agent (FC-8 (perfluoroalkyl ether amine oxide type cationic fluorocarbon surfactant) and octadecyl dimethyl benzyl quaternary ammonium chloride for compounding), stirring to the homogeneous phase, adding deionized water, uniformly stirring, stopping heating, and cooling to obtain the wetting reversal agent for reducing pressure and increasing injection of the ultra-low permeability reservoir.
Comparative example 1
Compared with the example 6, the common cationic gemini surfactant (N, N' -dodecyl dimethyl ammonium bromide, Tianjin Zhonghai oil and oil clothes chemical Co., Ltd., PF-1212) is adopted to replace the cationic gemini surfactant shown in the formula I, and other conditions are not changed.
The raw materials comprise the following components in percentage by mass:
0.7 percent of N, N' -dodecyl dimethyl ammonium bromide;
0.2% of nonionic surfactant (polyvinyl alcohol);
0.35 percent of high-efficiency anti-swelling agent (0.2 percent of FC-8 (perfluoroalkyl ether amine oxide type cationic fluorocarbon surfactant) and 0.15 percent of octadecyl dimethyl benzyl quaternary ammonium chloride);
20% of ethanol;
15% of ethylene glycol ethyl ether;
the balance being deionized water.
The preparation method comprises the following steps:
uniformly mixing ethylene glycol ethyl ether and ethanol, heating to 50 ℃, adding N, N' -dodecyl dimethyl ammonium bromide, adding polyvinyl alcohol after dissolving a homogeneous phase, stirring to a homogeneous phase, adding a high-efficiency anti-swelling agent (FC-8 (perfluoroalkyl ether amine oxide type cationic fluorocarbon surfactant) and octadecyl dimethyl benzyl quaternary ammonium chloride for compounding), stirring to a homogeneous phase, adding deionized water, stirring uniformly, stopping heating, and cooling to obtain the wetting reversal agent for reducing pressure and increasing injection of the ultra-low permeability reservoir
Comparative example 2
Compared with the embodiment 6, the single FC-8 (perfluoroalkyl ether amine oxide type cationic fluorocarbon surfactant) is adopted as the high-efficiency anti-swelling agent, and other conditions are not changed.
The raw materials comprise the following components in percentage by mass:
0.7% of the cationic gemini surfactant prepared in example 3;
the cationic gemini surfactant has a structure shown as the following formula I:
0.2% of nonionic surfactant (polyvinyl alcohol);
FC-8 (perfluoroalkyl ether amine oxide type cationic fluorocarbon surfactant) 0.35%;
20% of ethanol;
15% of ethylene glycol ethyl ether;
the balance being deionized water.
The preparation method comprises the following steps:
uniformly mixing ethylene glycol ethyl ether and ethanol, heating to 50 ℃, adding a cationic gemini surfactant shown as a formula I, adding polyvinyl alcohol after the homogeneous phase is dissolved, stirring to the homogeneous phase, adding FC-8 (perfluoroalkyl ether amine oxide type cationic fluorocarbon surfactant), stirring to the homogeneous phase, adding deionized water, uniformly stirring, stopping heating, and cooling to obtain the wetting reversal agent for reducing pressure and increasing injection of the ultra-low permeability reservoir.
Comparative example 3
Compared with the example 6, the single octadecyl dimethyl benzyl quaternary ammonium chloride is adopted as the high-efficiency anti-swelling agent, and other conditions are not changed.
The raw materials comprise the following components in percentage by mass:
0.7% of the cationic gemini surfactant prepared in example 3;
the cationic gemini surfactant has a structure shown as the following formula I:
0.2% of nonionic surfactant (polyvinyl alcohol);
0.35% of octadecyl dimethyl benzyl quaternary ammonium chloride;
20% of ethanol;
15% of ethylene glycol ethyl ether;
the balance being deionized water.
The preparation method comprises the following steps:
uniformly mixing ethylene glycol ethyl ether and ethanol, heating to 50 ℃, adding a cationic gemini surfactant shown as a formula I, adding polyvinyl alcohol after the homogeneous phase is dissolved, stirring to the homogeneous phase, adding octadecyl dimethyl benzyl quaternary ammonium chloride, stirring to the homogeneous phase, adding deionized water, uniformly stirring, stopping heating, and cooling to obtain the wetting reversal agent for reducing pressure and increasing injection of the ultra-low permeability reservoir.
Comparative example 4
Compared with example 6, the nonionic surfactant (polyvinyl alcohol) was not added, and other conditions were not changed.
The raw materials comprise the following components in percentage by mass:
0.9% of the cationic gemini surfactant prepared in example 3;
the cationic gemini surfactant has a structure shown as the following formula I:
0.35 percent of high-efficiency anti-swelling agent (0.2 percent of FC-8 (perfluoroalkyl ether amine oxide type cationic fluorocarbon surfactant) and 0.15 percent of octadecyl dimethyl benzyl quaternary ammonium chloride);
20% of ethanol;
15% of ethylene glycol ethyl ether;
the balance being deionized water.
The preparation method comprises the following steps:
uniformly mixing ethylene glycol ethyl ether and ethanol, heating to 50 ℃, adding a cationic gemini surfactant shown as a formula I, after dissolving a homogeneous phase, adding a high-efficiency anti-swelling agent (FC-8 (perfluoroalkyl ether amine oxide type cationic fluorocarbon surfactant) and octadecyl dimethyl benzyl quaternary ammonium chloride for compounding), stirring to a homogeneous phase, adding deionized water, uniformly stirring, stopping heating, and cooling to obtain the wetting reversal agent for reducing pressure and increasing injection of the ultra-low permeability reservoir.
Comparative example 5
In comparison with example 6, the cationic gemini surfactant prepared in example 3 was not added, and other conditions were not changed.
The raw materials comprise the following components in percentage by mass:
0.9% of nonionic surfactant (polyvinyl alcohol);
0.35 percent of high-efficiency anti-swelling agent (0.2 percent of FC-8 (perfluoroalkyl ether amine oxide type cationic fluorocarbon surfactant) and 0.15 percent of octadecyl dimethyl benzyl quaternary ammonium chloride);
20% of ethanol;
15% of ethylene glycol ethyl ether;
the balance being deionized water.
The preparation method comprises the following steps:
uniformly mixing ethylene glycol ethyl ether and ethanol, heating to 50 ℃, adding polyvinyl alcohol, stirring to be homogeneous, adding a high-efficiency anti-swelling agent (FC-8 (perfluoroalkyl ether amine oxide type cationic fluorocarbon surfactant) and octadecyl dimethyl benzyl quaternary ammonium chloride for compounding), stirring to be homogeneous, adding deionized water, stirring uniformly, stopping heating, and cooling to obtain the wetting reversal agent for reducing pressure and increasing injection of the ultra-low permeability reservoir.
Test example 1
The ultra-low permeability reservoir pressure-reducing and injection-increasing wetting reversal agent in examples 4-6 and comparative examples 1-5 of the invention and a commercially available wetting reversal agent (purchased from the institute of engineering and technology of oil and gas, southwest petrochemical company, oil and gas) are used for ultra-low-ultra-low permeability sandstone reservoir species with high content of sensitive minerals, low permeability and small porosity in reservoir clay minerals (14% of illite, 13% of illite and 74% of kaolinite in clay minerals) to perform performance tests, and the results are shown in table 1.
TABLE 1
As can be seen from the above table, the performance of the ultra-low permeability reservoir pressure-reducing and injection-increasing wetting reversal agent prepared in the examples 4 to 6 of the invention is obviously improved compared with the performance of the comparative examples 1 to 5 and the commercially available wetting reversal agent.
In the process of the oil field water injection well depressurization and injection increase operation, preferably, in order to reflect the effect that the wetting reversal agent is different from other depressurization and injection increase processes, the wetting reversal agent is more suitable for oil reservoirs or water injection wells with the following characteristics: the reservoir clay mineral has ultra-low-ultra-low permeability sandstone reservoir with high content of sensitive mineral, low permeability and small porosity (such as clay mineral with 14% of illite, 13% of illite-montmorillonite, 74% of kaolinite, and permeability of 0.1 × 10 ≤)-3mPa.s, porosity less than or equal to 12%, anti-swelling rate more than or equal to 70%, shrinkage-swelling rate more than or equal to 25%, and oil-water interfacial tension reduced to 10-3mN/m)。
The cationic surfactant can be adsorbed on the negatively charged rock surface, so that the wettability of the rock surface is changed; in addition, the nonionic surfactant enables the surface of the rock to be subjected to wetting reversal mainly through adsorption, has a cloud point effect, can effectively block micro cracks, and slows down the invasion of drilling fluid filtrate into a stratum.
The cationic Gemini surfactant shown in the formula I contains ammonium groups and hydroxyl groups (-OH), the cationic ammonium groups are easily and preferentially adsorbed by clay, dehydration among clay crystal layers is promoted, the expansion force is reduced, alcohol groups in amino alcohol are very active, the surface of the rock contains a plurality of silanol groups, the silanol groups react with the alcohol groups in the amino alcohol to be dehydrated and crosslinked, so that the surface of the rock is bonded with hydrocarbon groups, the surface tension is reduced, the contact angle is increased, the reverse capillary effect is realized, a hydrophobic layer is formed, the inhibitive performance of the drilling fluid is improved, the filtration loss of the drilling fluid is reduced, the nonionic low molecular polymer surfactant has a cloud point effect, and when the temperature is lower than the cloud point, the polymer alcohol is adsorbed on the surface of the rock to form a hydrophobic film, so that the hydration and; when the temperature is higher than the cloud point, the polymeric alcohol is separated out from the water phase under the phase separation action to block formation pores and prevent the drilling fluid filtrate from invading the formation, the amino silanol and the polymeric alcohol are compounded according to a certain proportion to generate a better synergistic effect, the ammonium base alcohol contains cationic ammonium groups and is preferentially adsorbed by clay with negative charges, the surface tension is increased due to the reduction of the concentration of the ammonium base alcohol, and the addition of the weakly adsorbed nonionic low-molecular polymeric alcohol can weaken the adsorption action of the ammonium base alcohol when the ammonium base alcohol is contacted with the formation and reduce the loss in the formation.
Compared with the prior art, the wetting reversal agent provided by the invention has the following characteristics:
firstly, the wettability of the rock surface of the ultra-low permeability hydrophilic oil layer can be changed, so that the rock is changed from hydrophilicity to hydrophobicity, the thickness of a hydration film is reduced, and the effective permeability of a water phase is obviously improved, thereby being beneficial to improving the injection capability of the ultra-low permeability hydrophilic oil layer and achieving the purpose of reducing pressure and increasing injection;
secondly, the interfacial tension is extremely low (the oil-water interfacial tension can be reduced to 10)-3mN/m), the oil-water interfacial tension is reduced, the purposes of improving the flow capacity of crude oil in the stratum and improving the oil displacement efficiency are achieved, and meanwhile, the wetting reversal agent can be better solved after the wetting reversal agent is injected into the stratumThe influence of wettability, water lock effect and Jamin effect on pressure is determined;
thirdly, the wetting reversal agent system is compounded with a high-efficiency anti-swelling shrinkage-expansion agent (when the using concentration of 0.2 percent is higher than or equal to 70 percent, the swelling shrinkage rate is higher than or equal to 25 percent), the shrinkage-expansion rate of the hydrated minerals can be effectively improved, the swelling migration and blockage of the hydrated minerals can be prevented, and therefore the purposes of reducing the injection pressure, reducing the high-pressure water injection difficulty, improving the water drive development effect of an oil reservoir and improving the crude oil recovery rate are achieved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The wetting reversal agent for reducing pressure and increasing injection of the ultra-low permeability oil reservoir is characterized by being prepared from the following raw materials: cationic gemini surfactant, nonionic surfactant, high-efficiency anti-swelling and anti-swelling agent, ethanol, ethylene glycol ethyl ether and deionized water;
the cationic gemini surfactant has a structure shown as the following formula I:
wherein n is 3-18;
the nonionic surfactant is nonionic low molecular polymer surfactant, is selected from one or more of polyvinyl alcohol, polyacrylamide, ethylene oxide propylene oxide block copolymer, polyvinylpyrrolidone and polyoxyethylene condensed alkyl phenyl ether, and is preferably polyvinyl alcohol;
the high-efficiency anti-swelling and anti-swelling agent is selected from two or more of a small cationic surfactant, a cationic polymer surfactant and a fluorocarbon cationic surfactant, the molecular weight of the small cationic surfactant is not higher than 1000, and the small cationic surfactant is preferably a fluorocarbon cationic surfactant.
2. The wetting reversal agent for depressurization and augmented injection of the ultra-low permeability reservoir of claim 1, which is prepared from the following raw materials in percentage by weight: 0.01-0.2% of cationic gemini surfactant, 0.01-0.1% of nonionic surfactant, 0.2-0.5% of high-efficiency anti-swelling and anti-swelling agent, 10-30% of ethanol, 10-20% of ethylene glycol ether and the balance of deionized water.
3. The wetting reversal agent for depressurization and augmented injection of the ultra-low permeability reservoir of claim 2, which is prepared from the following raw materials in percentage by weight: 0.7% of cationic Gemini surfactant, 0.2% of nonionic surfactant, 0.35% of high-efficiency anti-swelling and anti-shrinking agent, 20% of ethanol, 15% of ethylene glycol ethyl ether and the balance of deionized water.
4. The wetting reversal agent for depressurization and stimulation of an ultra-low permeability reservoir of claim 1, wherein the small cationic surfactant is selected from one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and octadecyl dimethyl benzyl ammonium chloride.
5. The wetting reversal agent for depressurization and injection stimulation of an ultra-low permeability reservoir of claim 1, wherein the cationic polymer surfactant is selected from one or more of oxyalkylacrylate copolymer modified polyethyleneimine, polymer of 1-dodeca-4-vinylpyridine bromide and polyvinyl benzyl trimethylamine salt.
6. The ultra-low permeability reservoir wetting reversal agent for depressurization and injection enhancement according to claim 1, wherein the fluorocarbon cationic surfactant is one or more selected from YF-138, FC-8 (perfluoroalkyl ether amine oxide type cationic fluorocarbon surfactant) and quaternary ammonium salt cationic fluorocarbon surfactant.
7. A cationic gemini surfactant represented by formula I.
8. A method for preparing a cationic gemini surfactant of formula i as claimed in claim 7, comprising the steps of:
s1, mixing p-hydroxybenzaldehyde, alkyl alcohol, thionyl chloride and triethylamine for reaction to obtain a reaction intermediate I, wherein the intermediate I is as follows:
wherein n is 3-18;
s2, reacting the intermediate I with p-toluenesulfonyl chloride to generate an intermediate II, wherein the intermediate II is as follows:
s3, reacting the intermediate II with potassium bromide to generate an intermediate III, wherein the intermediate III is as follows:
s4, reacting N, N' -dimethyl ethylenediamine, formaldehyde and acetic acid to generate an intermediate VI:
s5, reacting the intermediate III with the intermediate VI to generate a cationic Gemini surfactant shown in a formula I;
the steps can be replaced as long as the preparation is not influenced.
9. The method for preparing the cationic gemini surfactant as shown in claim 8, wherein the method specifically comprises the following steps:
s1, dissolving p-hydroxybenzaldehyde in dichloromethane, sequentially adding thionyl chloride and triethylamine, reacting at room temperature for 2-3 hours, adding alkyl alcohol, stirring at room temperature for reacting for 2 hours to obtain an intermediate I;
s2, dissolving the intermediate I in acetonitrile, adding triethylamine and p-toluenesulfonyl chloride, heating to 60-80 ℃, and reacting for 2-4h to obtain an intermediate II;
s3, dissolving the intermediate II in acetone, adding triethylamine and potassium bromide, and reacting at room temperature for 1-2h to obtain an intermediate III;
s4, mixing N, N' -dimethyl ethylenediamine and 85 wt% formic acid, heating to 80-85 ℃, adding a formaldehyde aqueous solution, heating to 110-120 ℃, and reacting for 4-8h to obtain an intermediate VI;
s5, dissolving the intermediate VI in n-propanol, heating to 100-120 ℃, adding the intermediate III, and carrying out reflux reaction for 2-5h to obtain the cationic Gemini surfactant shown in the formula I.
10. A method for preparing the wetting reversal agent for the depressurization and the stimulation of the ultra-low permeability reservoir as set forth in any one of claims 1 to 6, which comprises the following steps: uniformly mixing ethylene glycol ethyl ether and ethanol, heating to 40-60 ℃, adding a cationic gemini surfactant shown in formula I, after dissolving a homogeneous phase, adding a nonionic surfactant, stirring to a homogeneous phase, adding a high-efficiency swelling and shrinking prevention agent, stirring to a homogeneous phase, adding deionized water, uniformly stirring, stopping heating, and cooling to obtain the wetting reversal agent for reducing pressure and increasing injection of the ultra-low permeability reservoir.
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