CN111394084B - Oil displacement agent and preparation and application thereof - Google Patents
Oil displacement agent and preparation and application thereof Download PDFInfo
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- CN111394084B CN111394084B CN202010312778.1A CN202010312778A CN111394084B CN 111394084 B CN111394084 B CN 111394084B CN 202010312778 A CN202010312778 A CN 202010312778A CN 111394084 B CN111394084 B CN 111394084B
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Abstract
An oil displacement agent and preparation and application thereof, which comprises the following components by weight percent: 30-70% of alkyl alcohol polyoxyethylene polyoxypropylene ether carboxylate, 0.1-10% of quaternary ammonium salt surfactant, 0.1-1.5% of hydrophilic nano silicon dioxide particles, 0.1-2% of deoxidant, 0-30% of organic solvent and 0-69% of water. The temperature-resistant and salt-resistant oil displacement agent is injected into an oil layer along with steam, so that the oil-water interfacial tension can be reduced, the rock wettability can be changed, and the oil displacement effect of the steam can be improved.
Description
Technical Field
The invention relates to the field of oil displacement agents for oil fields and oil field thermal recovery synergistic agents, in particular to an oil displacement agent and preparation and application thereof.
Background
The steam huff and puff and the steam flooding thickened oil recovery effect are obvious, and the steam huff and puff and the steam flooding thickened oil recovery method is applied to large-scale industrialization at home and abroad. The steam greatly reduces the viscosity of the thick oil by heating the thick oil, improves the flowing capacity of the thick oil, and simultaneously, under the action of injected hot steam, oil, water and rocks in the stratum expand to drive the fluid to flow to a production well, thereby greatly reducing the saturation of residual oil and obviously increasing the recovery ratio of the steam. But the effect of exploiting the thick oil by only injecting steam is poor and the economic benefit cannot be better due to the influence of the wettability of the rock and the interface characteristic between the rock and the thick oil.
By adopting a method of combining heat and chemistry, a proper amount of high-temperature oil displacement agent is added in the heat injection exploitation process, and under the action of high-temperature heat and chemistry, the fluidity of thick oil can be further improved, the oil displacement agent and the thick oil are subjected to oil-water interaction, the oil-water interfacial energy is improved, the wettability of stratum rock is changed, and the oil-water phase permeability is changed, so that the oil washing efficiency of steam or hot fluid is improved, and the recovery ratio of the thick oil is further improved.
The temperature resistance of the high-temperature oil displacement agent researched at present is not higher than 350 ℃. At 350 ℃, most of the oil displacement agent is decomposed or fails, and cannot be used. In addition, the mineralization degree of the formation fluid of part of the oil field is as high as more than 50000mg/L, the content of calcium and magnesium ions is higher than 2000mg/L, and most oil displacement agents are mixed with the formation water to form precipitates, floccules and the like so as to be ineffective. Therefore, the search for a surface active oil displacement agent which can resist 350 ℃, has high mineralization and high calcium and magnesium ions becomes a problem which needs to be researched and cared by the current oil extraction workers.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide an oil displacement agent and preparation and application thereof, and particularly relates to a temperature-resistant and salt-resistant oil displacement agent for a thermal oil recovery process, which is applied to the field of heavy oil thermal recovery, can resist 350 ℃ high temperature, high salinity and high calcium and magnesium ions, has good water solubility, and can improve the oil displacement efficiency of steam and other hot fluids. The specific functions are as follows: steam and other hot fluids (250-350 ℃) accompany with an oil displacement agent to enter an oil reservoir in the thermal recovery process of a common oil field, the oil displacement agent can greatly reduce the tension of an oil-water interface, reduce the capillary pressure of a core hole and change the wettability of rock, and the oil displacement agent enables thick oil on the surface of the rock to be more easily stripped and recovered after being displaced by the steam, so that the recovery efficiency of the steam is improved.
The invention provides an oil displacement agent, which comprises the following components in percentage by weight:
optionally, the oil displacement agent consists of the above components;
optionally, the amount of the organic solvent and the amount of the water are not 0 at the same time;
preferably, the amount of water is 1-69%, and the amount of the organic solvent is 1-30%.
In the oil displacement agent provided by the invention, the quaternary ammonium salt surfactant is selected from one or more of alkyl trimethyl ammonium salt surfactant, dialkyl dimethyl ammonium salt surfactant and alkyl dimethyl benzyl ammonium salt surfactant;
in the oil-displacing agent provided by the present invention, optionally, the number of carbon atoms of the alkyl group is C 12 -C 18 ；
In the oil displacement agent provided by the invention, optionally, the oxygen scavenger is selected from one or two of sodium sulfite and thiourea.
In the oil displacement agent provided by the invention, the organic solvent is selected from one or more of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, propylene glycol, ethylene glycol monobutyl ether and dimethylformamide;
in the oil displacement agent provided by the invention, optionally, the water is selected from one or more of distilled water, deionized water and water with a mineralization degree lower than 50000mg/L and a total content of calcium ions and magnesium ions lower than 2000 mg/L.
In the oil displacement agent provided by the invention, the number average molecular mass of the alkyl alcohol polyoxyethylene polyoxypropylene ether carboxylate is 500-5000.
In the oil displacement agent provided by the invention, the alkyl alcohol polyoxyethylene polyoxypropylene ether carboxylate is synthesized by the following method:
(1) putting alkyl alcohol and a catalyst into a reaction container, vacuumizing and heating for the first time, adding epoxypropane into the reaction container for reaction, and preserving the temperature of the reaction container until the reaction is balanced;
optionally, the reaction temperature in the step (1) is 135-145 ℃; when the reaction is balanced, the pressure in the container is reduced to be near the pressure after the first vacuumizing before the reaction or 0.
Optionally, the catalyst is a strong alkaline substance selected from one or two of sodium hydroxide and potassium hydroxide;
(2) carrying out first cooling on the mixture obtained in the step (1), carrying out second vacuumizing, then carrying out second cooling, and adjusting the pH value to be neutral to obtain an intermediate;
optionally, the temperature of the first temperature reduction in the step (2) is reduced to 105-110 ℃; the temperature of the second cooling is reduced to 70-80 ℃;
(3) and (3) selecting a new reaction container, vacuumizing and heating for the third time, adding the intermediate prepared in the step (2) and ethylene oxide into the reaction container for reaction, and preserving the temperature of the reaction container until the reaction is balanced.
Optionally, the reaction temperature in the step (3) is 125-135 ℃; when the reaction is balanced, the pressure in the container is reduced to be near the pressure after the third vacuumizing before the reaction or 0.
(4) Cooling the mixture obtained after the reaction balance in the step (3) for the third time, vacuumizing for the fourth time, cooling for the fourth time, adjusting the pH value to be neutral, and separating to obtain the alkyl alcohol polyoxyethylene polyoxypropylene block polyether;
optionally, the third temperature reduction in the step (4) is to be performed to 105-; the fourth temperature reduction is to reduce the temperature to 60-80 ℃;
(5) heating the alkyl alcohol polyoxyethylene polyoxypropylene block polyether obtained in the step (4) to completely melt, adding an alkaline substance, uniformly stirring, adding chloroacetate, and obtaining alkyl alcohol polyoxyethylene polyoxypropylene ether carboxylate after the reaction is finished;
optionally, the reaction temperature after the chloroacetate is added in the step (5) is 60-90 ℃, and the reaction time is 5-8 h;
optionally, the cation of the alkaline substance is the same as the cation in chloroacetate, preferably, the alkaline substance is sodium hydroxide, the chloroacetate is sodium chloroacetate, or the alkaline substance is potassium hydroxide, and the chloroacetate is potassium chloroacetate.
Alternatively, the alkyl alcohol polyoxyethylene polyoxypropylene ether carboxylate is prepared by the above steps.
In the oil displacement agent provided by the invention, the weight and dosage ratio of the alkyl alcohol, the ethylene oxide and the propylene oxide is (5-10): (30-200): (10-100);
in the oil displacement agent provided by the invention, the weight and dosage ratio of the alkyl alcohol to the catalyst in the step (1) is (5-10) to (0.1-1);
in the oil displacement agent provided by the invention, the weight usage ratio of the alkyl alcohol polyoxyethylene polyoxypropylene block polyether in the step (5) to chloroacetate is (2.5-35.5) to 1;
in the oil displacement agent provided by the invention, the weight using amount ratio of the alkaline substance to the chloroacetate in the step (5) is (1) to (1-2).
In the oil displacement agent provided by the invention, the alkyl alcohol is selected from one or more of dodecyl alcohol, hexadecyl alcohol and octadecyl alcohol.
The oil displacement agent provided by the invention has the advantages of high temperature resistance, high mineralization resistance and calcium and magnesium ions, and can be used for a thermal oil recovery process.
The oil displacement agent provided by the invention can improve the oil displacement efficiency of steam, hot water and multi-element hot fluid, reduce the oil-water interfacial tension, change the rock wettability and improve the oil displacement effect of steam.
In the oil displacement agent provided by the invention, optionally, the operations of primary vacuum pumping, secondary vacuum pumping, tertiary vacuum pumping and quaternary vacuum pumping are vacuum pumping to negative pressure of-0.05 MPa;
on the other hand, the invention provides a preparation method of the oil displacement agent, which comprises the following steps: weighing the components according to the weight percentage, stirring the components in a reaction container for 2 to 5 hours at the temperature of between 20 and 60 ℃, and uniformly mixing and stirring the components.
On the other hand, the invention provides the application of the oil displacement agent in steam huff and puff, steam flooding and multi-element thermal fluid thermal oil recovery processes;
optionally, the working temperature of the oil displacement agent is 20-350 ℃, preferably 200-350 ℃, and the dosage of the oil displacement agent in the injection water is 500-5000ppm by weight.
Compared with the prior art, the heat-resistant and salt-resistant oil displacement agent provided by the invention has the following beneficial technical effects:
(1) the oil displacement agent can be used at a high temperature of 200-350 ℃, still has higher effects of reducing the oil-water interfacial tension and displacing oil, and can improve the thermal recovery effect of thick oil;
(2) the oil displacement agent product prepared by the invention passes through a high-temperature high-pressure reaction kettleAfter aging at 200-350 ℃, firstly diluting the aged oil-displacing agent to the mass concentration of 0.5% by using ionized water with the mineralization degree of 50000mg/L and the calcium-magnesium ion content of 2000mg/L respectively, and then measuring the interfacial tension between the oil-displacing agent with the concentration of 0.5% and the thick oil by using an interfacial tension meter, wherein experiments show that the oil-displacing agent aged at 200-350 ℃ can reduce the oil-water interfacial tension to 10 -3 The mN/m level; in a one-dimensional thermal displacement experiment, the steam flooding efficiency can be improved by 14-18%.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Other advantages of the invention may be realized and attained by the instrumentalities and combinations particularly pointed out in the specification.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in detail below. It should be noted that the embodiments and features of the embodiments of the present invention may be arbitrarily combined with each other without conflict.
The embodiment of the invention provides an oil displacement agent, which comprises the following components in percentage by weight:
optionally, the oil displacement agent consists of the above components;
optionally, the amount of the organic solvent and the amount of water are not 0 at the same time.
In an embodiment of the present invention, the quaternary ammonium salt surfactant is selected from one or more of alkyl trimethyl ammonium salt surfactant, dialkyl dimethyl ammonium salt surfactant and alkyl dimethyl benzyl ammonium salt surfactant;
in embodiments of the invention, optionally, the alkyl group has a carbon atom number of C 12 -C 18 ；
In an embodiment of the present invention, optionally, the oxygen scavenger is selected from one or both of sodium sulfite and thiourea.
In an embodiment of the present invention, the organic solvent is selected from one or more of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, propylene glycol, ethylene glycol monobutyl ether, and dimethylformamide;
in an embodiment of the invention, optionally, the water is selected from one or more of distilled water, deionized water, water with a mineralization degree below 50000mg/L and a total content of calcium ions and magnesium ions below 2000 mg/L.
In the embodiment of the invention, the number average molecular mass of the alkyl alcohol polyoxyethylene polyoxypropylene ether carboxylate is 500-5000.
In the examples of the present invention, the alkyl alcohol polyoxyethylene polyoxypropylene ether carboxylate is synthesized by the following method:
(1) putting alkyl alcohol and a catalyst into a reaction container, vacuumizing and heating for the first time, adding epoxypropane into the reaction container for reaction, and preserving the temperature of the reaction container until the reaction is balanced;
optionally, the reaction temperature in the step (1) is 135-145 ℃;
optionally, the catalyst is a strong alkaline substance selected from one or two of sodium hydroxide and potassium hydroxide;
(2) carrying out first cooling on the mixture obtained in the step (1), carrying out second vacuumizing, then carrying out second cooling, and adjusting the pH value to be neutral to obtain an intermediate;
optionally, the temperature of the first temperature reduction in the step (2) is reduced to 105-110 ℃; the temperature of the second temperature reduction is reduced to 70-80 ℃;
(3) and (3) selecting a new reaction container, vacuumizing and heating for the third time, adding the intermediate prepared in the step (2) and ethylene oxide into the reaction container for reaction, and preserving the temperature of the reaction container until the reaction is balanced.
Optionally, the reaction temperature in the step (3) is 125-135 ℃;
(4) cooling the mixture obtained after the reaction balance in the step (3) for the third time, vacuumizing for the fourth time, cooling for the fourth time, adjusting the pH value to be neutral, and separating to obtain the alkyl alcohol polyoxyethylene polyoxypropylene block polyether;
optionally, the third temperature reduction in the step (4) is to be performed to 105-; the fourth temperature reduction is to reduce the temperature to 60-80 ℃;
(5) heating the alkyl alcohol polyoxyethylene polyoxypropylene block polyether obtained in the step (4) to completely melt, adding an alkaline substance, uniformly stirring, adding chloroacetate, and obtaining alkyl alcohol polyoxyethylene polyoxypropylene ether carboxylate after the reaction is finished;
optionally, the reaction temperature after the chloroacetate is added in the step (5) is 60-90 ℃, and the reaction time is 5-8 h;
optionally, the cation of the alkaline substance is the same as the cation in chloroacetate, preferably, the alkaline substance is sodium hydroxide, the chloroacetate is sodium chloroacetate, or the alkaline substance is potassium hydroxide, and the chloroacetate is potassium chloroacetate.
Alternatively, the sodium alkyl alcohol polyoxyethylene polyoxypropylene ether carboxylate is prepared by the steps.
In the embodiment of the invention, the weight ratio of the alkyl alcohol, the ethylene oxide and the propylene oxide is (5-10) to (30-200) to (10-100);
in the embodiment of the invention, the weight ratio of the alkyl alcohol to the catalyst in the step (1) is (5-10) to (0.1-1);
in the embodiment of the invention, the weight ratio of the alkyl alcohol polyoxyethylene polyoxypropylene block polyether in the step (5) to the chloroacetate is (2.5-35.5): 1;
in the embodiment of the invention, the weight ratio of the alkaline substance to the chloroacetate in the step (5) is (1) to (1-2).
In embodiments of the invention, the alkyl alcohol is selected from one or more of lauryl alcohol, cetyl alcohol and stearyl alcohol.
The oil displacement agent provided by the invention has high temperature resistance, high mineralization resistance and calcium and magnesium ions, and can be used for a thermal oil recovery process.
The oil displacement agent provided by the invention can improve the oil displacement efficiency of steam, hot water and multi-element hot fluid, reduce the oil-water interfacial tension, change the rock wettability and improve the oil displacement effect of steam.
In the embodiment of the present invention, optionally, the first evacuation, the second evacuation, the third evacuation and the fourth evacuation are performed to evacuate to a negative pressure of-0.05 MPa;
on the other hand, the embodiment of the invention provides a preparation method of the oil displacement agent, which comprises the following steps: weighing the components according to the weight percentage, stirring the components in a reaction container for 2 to 5 hours at the temperature of between 20 and 60 ℃, and uniformly mixing and stirring the components.
On the other hand, the embodiment of the invention provides the application of the oil displacement agent in steam huff and puff, steam flooding and multi-element thermal fluid thermal oil recovery processes;
optionally, the working temperature of the oil displacement agent is 20-350 ℃, preferably 200-350 ℃, and the dosage of the oil displacement agent in the injection water is 500-5000ppm by weight.
In the examples of the present invention, the lauryl alcohol was purchased from Shandong Juchuan chemical Co., Ltd;
the didecyl dimethyl ammonium chloride is purchased from Zhengzhou Jiaboat chemical products, Inc., industrial grade;
cetyl dimethylbenzyl ammonium chloride was purchased from Lorsen chemical Co., Linyi, Brand: ecocare, model: 1627.
hexadecyltrimethylammonium chloride, available from linyi, lussen chemical ltd, brand: ecocare, model: 1631.
the hydrophilic nano silicon dioxide particles are purchased from Zhejiang Yuda chemical industry Co., Ltd, and the product trade name is as follows:
hydrophilic nano silicon dioxide powder;
example 1
This example was used to prepare sodium alkylol polyoxyethylene polyoxypropylene ether carboxylate. In the embodiment, the vacuumizing is to be carried out until the negative pressure is-0.05 MPa;
(1) adding 5 parts by weight of dodecyl alcohol and 0.15 part by weight of catalyst potassium hydroxide into a high-pressure reaction kettle, heating, vacuumizing for the first time to negative pressure, slowly dropwise adding 20 parts by weight of propylene oxide, and controlling the reaction temperature to be 135-145 ℃. After the addition of propylene oxide was complete, the temperature was maintained at 135 ℃ until the reaction equilibrated.
(2) And then carrying out first cooling, cooling to about 110 ℃, carrying out second vacuumizing to remove the small molecular polymer, then carrying out second cooling, cooling to 80 ℃, adjusting the pH value to be neutral by using glacial acetic acid, and discharging to obtain an intermediate.
(3) And (3) selecting a new reaction kettle, vacuumizing and heating for the third time, adding ethylene oxide and an intermediate into the reaction kettle according to the molar ratio of 4:1 of ethylene oxide to propylene oxide, and controlling the temperature to be between 125 and 135 ℃. After the addition of ethylene oxide was complete, the temperature was maintained at 130 ℃ until the reaction equilibrated.
(4) And (4) cooling the mixture obtained after the reaction balance in the step (3) for the third time to about 110 ℃, and vacuumizing for the fourth time to remove the small molecular polymer. Then the temperature is reduced to 80 ℃ for the fourth time, the pH value is adjusted to about 7 by glacial acetic acid, and the lauryl polyoxyethylene polyoxypropylene block polyether is obtained by separation.
(5) Weighing 6.15 parts by weight of lauryl alcohol polyoxyethylene polyoxypropylene block polyether and 1 part by weight of sodium chloroacetate; adding lauryl alcohol polyoxyethylene polyoxypropylene block polyether into a reaction kettle, heating until the lauryl alcohol polyoxyethylene polyoxypropylene block polyether is completely melted, adding 0.5 weight part of sodium hydroxide, and stirring for 30 min; then adding 1 weight part of sodium chloroacetate while stirring; heating and keeping the temperature at 80 ℃, and reacting for 6 hours to obtain sodium lauryl polyoxyethylene polyoxypropylene ether carboxylate;
the number average molecular weight of the prepared sodium lauryl polyoxyethylene polyoxypropylene ether carboxylate is 996.
Example 2
The example is used for preparing the temperature-resistant and salt-resistant oil displacement agent.
44 percent of sodium lauryl polyoxyethylene polyoxypropylene ether carboxylate prepared in example 1, 4 percent of ammonium didecyl chloride, 1 percent of hydrophilic nano silica particles, 0.1 percent of thiourea, 10 percent of glycol and 40.9 percent of pure water are weighed according to the following weight proportions, stirred for 5 hours in a high-temperature high-pressure reaction kettle at the temperature of 50 ℃ and mixed to obtain the temperature-resistant and salt-resistant oil displacement agent A.
Example 3
The example is used for preparing the temperature-resistant and salt-resistant oil displacement agent.
62 percent of sodium lauryl polyoxyethylene polyoxypropylene ether carboxylate prepared in example 1, 4 percent of hexadecyl trimethyl ammonium chloride, 0.5 percent of hydrophilic nano silicon dioxide particles, 0.1 percent of sodium sulfite, 26 percent of isopropanol and 7.4 percent of pure water are weighed according to the following weight proportion respectively, and the materials are stirred for 2 hours in a high-temperature high-pressure reaction kettle at the temperature of 50 ℃ to be mixed and stirred to obtain the temperature-resistant and salt-resistant oil displacement agent B.
Example 4
The example is used for preparing the temperature-resistant and salt-resistant oil displacement agent.
30% of sodium lauryl polyoxyethylene polyoxypropylene ether carboxylate prepared in example 1, 10% of hexadecyl dimethyl benzyl ammonium chloride, 1% of hydrophilic nano silica particles, 0.1% of thiourea, 8% of dimethylformamide and 50.9% of pure water are weighed according to the following weight ratio, and the materials are stirred and mixed for 5 hours at 50 ℃ in a high-temperature high-pressure reaction kettle to obtain the temperature-resistant salt-resistant oil-displacing agent C.
Comparative example 1
In the comparative example, 30% of sodium lauryl polyoxyethylene polyoxypropylene ether carboxylate prepared in example 1, 0.9% of hydrophilic nano-silica particles, 0.1% of sodium sulfite and 69% of pure water are weighed according to the following weight ratio respectively, and the materials are stirred for 2 hours in a high-temperature high-pressure reaction kettle at 50 ℃ and are mixed and stirred to obtain the temperature-resistant and salt-resistant oil displacement agent D.
Comparative example 2
This comparative example was prepared containing only the common surfactant, only the quaternary ammonium surfactant, thiourea, ethylene glycol, water, nanosilica, and no sodium lauryl polyoxyethylene polyoxypropylene ether carboxylate.
Weighing 44% of sodium dodecyl benzene sulfonate, 4% of hexadecyl trimethyl ammonium chloride, 1% of hydrophilic nano silicon dioxide particles, 0.1% of thiourea, 10% of ethylene glycol and 40.9% of water according to the following weight ratio, stirring for 5 hours in a high-temperature high-pressure reaction kettle at 50 ℃, and mixing and stirring the substances to obtain the temperature-resistant and salt-resistant oil displacement agent E.
Comparative example 3
This comparative example was prepared to contain only sodium lauryl polyoxyethylene polyoxypropylene ether carboxylate, quaternary ammonium surfactant, thiourea, ethylene glycol, water, and no nanosilica.
Weighing 44% of sodium lauryl polyoxyethylene polyoxypropylene ether carboxylate, 4% of hexadecyl trimethyl ammonium chloride, 0.1% of thiourea, 10% of ethylene glycol and 41.9% of water according to the following weight ratio, stirring for 5 hours in a high-temperature high-pressure reaction kettle at 50 ℃, and mixing and stirring the substances to obtain the temperature-resistant and salt-resistant oil displacement agent F.
Comparative example 4
10 percent of sodium lauryl polyoxyethylene polyoxypropylene ether carboxylate prepared in example 1, 0.5 percent of hexadecyl trimethyl ammonium chloride, 0.5 percent of hydrophilic nano silicon dioxide particles, 0.1 percent of sodium sulfite and 88.9 percent of pure water are weighed according to the following weight ratio respectively, and the materials are stirred for 2 hours in a high-temperature high-pressure reaction kettle at the temperature of 50 ℃ to be mixed and stirred to obtain the temperature-resistant and salt-resistant oil displacing agent G.
Test examples
In order to test the oil-water interfacial tension reduction and the oil displacement effect of the temperature-resistant and salt-resistant oil displacement agent, the oil displacement agent products obtained in the above examples 2 to 4 and the oil displacement agent products obtained in the comparative example 1, the comparative example 2, the comparative example 3 and the comparative example 4 were measured to reduce the oil-water interfacial tension and improve the oil displacement effect of steam. The experimental method is as follows:
firstly, adopting a high-temperature high-pressure reaction kettle to respectively age the oil displacement agent at the temperature of 200 ℃ and 350 ℃. Then, oil field formation water is adopted to prepare 0.5 percent of oil displacement agent, and an interfacial tension determination experiment is carried out at 80 ℃ according to the oil industry standard SY/T5370-2018 & lt & gt surface and interfacial tension determination method & gt. The ion concentration of the oil field stratum water is as follows:
table 1: oil field stratum water ion concentration meter
The experimental method for improving the oil displacement effect of steam by using the oil displacement agent is implemented according to the oil industry standard SY/T6315-2006 method for measuring high-temperature relative permeability and oil displacement efficiency of heavy oil reservoir
The test results are shown in the following table:
table 2: statistical table of experimental results of examples and comparative examples
As can be seen from the above table, 3 oil-displacing agent products prepared in the embodiment of the invention have good compatibility with formation water with high salinity and high calcium and magnesium ions, and after aging at 200 ℃, 300 ℃ and 350 ℃, the oil-water interfacial tension can be reduced to the level of ultralow interfacial tension, and the oil-water interfacial tension is 2 multiplied by 10 -3 mN/m～5×10 -3 mN/m. The oil displacement agent can effectively reduce the oil-water interfacial tension at the temperature of 200-350 ℃, and realizes the synergy of thermal recovery.
In addition, the oil-water interfacial tension value of the oil displacement agent C provided by the invention is lowest, because the content of the quaternary ammonium salt surfactant is higher compared with that of the oil displacement agent A and the oil displacement agent B, and the capacity of reducing the interfacial tension of the quaternary ammonium salt surfactant is higher than that of the sodium alkyl alcohol polyoxyethylene polyoxypropylene ether carboxylate, the oil displacement agent C is lowest in the oil-water interfacial tension value.
The oil-water interfacial tension of the oil-displacing agent D obtained in comparative example 1 can be reduced by only 10 -1 The ratio of mN/m is much larger than that of the oil-displacing agent A, the oil-displacing agent B and the oil-displacing agent C, and the oil-displacing agent D does not contain a quaternary ammonium salt surfactant, and the sodium alkyl alcohol polyoxyethylene polyoxypropylene ether carboxylate has a general capability of reducing interfacial tension, so that the oil-displacing agent D has a general capability of reducing oil-water interfacial tension.
Whereas the oil-displacing agent E obtained by comparative example 2 lowered the oil-water interfacial tension to 5.6X 10 at a steam temperature of 200 deg.C -3 mN/m, but the solution becomes turbid when sodium dodecyl benzene sulfonate is decomposed by heating at 300 ℃ and 350 ℃, so that the oil-displacing agent E is not suitable for being used as an oil-displacing agent.
The difference of the oil-water interfacial tension reducing ability of the oil-displacing agent F obtained by the comparative example 3 and the oil-displacing agent A is very small, which shows that a small amount of nano silicon dioxide hardly influences the oil-water interfacial tension reducing ability of the activator.
In order to test the oil displacement effect of the temperature-resistant and salt-resistant oil displacement agent, the oil displacement agent products obtained in the embodiments 2 to 4 and the oil displacement agent products obtained in the comparative examples 1, 2 and 3 are used for measuring the capacity of improving the oil displacement efficiency of the thermal fluid by adopting a one-dimensional thermal displacement method (see SY/T6315 + 2006 method for measuring the high-temperature relative permeability and the oil displacement efficiency of the heavy oil reservoir).
The oil displacement efficiency of the oil displacement agent for improving steam is calculated according to the formula (1).
X＝X 1 -X 2 -------------------------(1)
In the formula:
x-oil displacement agent improves the oil displacement efficiency of steam, and the unit is percentage (%).
X 1 The displacement efficiency of the steam-accompanied injection oil displacement agent is expressed in percentage (%).
X 2 The displacement efficiency of the steam is expressed in percentage (%).
The test results are shown in the following table:
table 3: statistical table of experimental results of examples and comparative examples
As can be seen from the table above, the 3 oil displacement agent products prepared in the embodiment of the invention have higher oil displacement efficiency by improving steam, and when the steam displacement temperature is 200 ℃, 300 ℃ and 350 ℃, the oil displacement agent has the oil displacement efficiency by improving steam by 14-18%. The oil displacement agent can effectively improve the oil displacement efficiency of steam and realize the efficiency improvement of thermal recovery at the temperature of 200-350 ℃. In addition, the oil displacement agent B in the oil displacement agent has the highest oil displacement efficiency, and the content of the sodium alkyl alcohol polyoxyethylene polyoxypropylene ether carboxylate is higher than that of the oil displacement agent A and the oil displacement agent C, so the oil displacement efficiency is high.
The oil displacement agent D obtained by the comparative example 1 has the oil displacement efficiency of 9.6-9.7%, the sodium alkyl alcohol polyoxyethylene polyoxypropylene ether carboxylate does not generate a synergistic effect with the quaternary ammonium salt surfactant, the interfacial tension reducing capability of the sodium alkyl alcohol polyoxyethylene polyoxypropylene ether carboxylate is general, and the low content of the sodium alkyl alcohol polyoxyethylene polyoxypropylene ether carboxylate is one of the reasons for the low oil displacement efficiency, so the oil displacement agent D has the general oil displacement efficiency.
The oil displacement agent E obtained by the comparative example 2 has 14.8% higher oil displacement efficiency at the steam temperature of 200 ℃ and is higher than the oil displacement agent A and the oil displacement agent C, mainly because the main component of the sodium dodecyl benzene sulfonate in the formula is an anionic activator, the oil displacement efficiency is higher, but the sodium dodecyl benzene sulfonate is decomposed by heating at 300 ℃ and 350 ℃, so the oil displacement efficiency of the oil displacement agent E at 300 ℃ and 350 ℃ is only about 2%.
The oil displacement efficiency of the oil displacement agent F obtained by the comparative example 3 is about 12.2-12.3%, which is lower than that of the oil displacement agent A by 14.4-14.6%, because the oil displacement agent F is lack of nano silicon dioxide components compared with the oil displacement agent A.
The oil displacement agent G has low oil displacement efficiency mainly because the contents of the sodium alkyl alcohol polyoxyethylene polyoxypropylene ether carboxylate and the quaternary ammonium salt surfactant are low, and the oil displacement efficiency is increased along with the increase of the contents of the sodium lauryl alcohol polyoxyethylene polyoxypropylene ether carboxylate and the quaternary ammonium salt surfactant.
Compared with the oil displacement agent formed by the embodiment and the comparative example, the oil displacement agent has the advantages that the components in the oil displacement agent cannot be divided, so that the oil displacement agent achieves better effects in the aspects of reducing interfacial tension, improving the stability of oil-in-water emulsion and improving the displacement efficiency of hot fluid.
Although the embodiments of the present invention have been described above, the above description is only for the convenience of understanding the present invention, and is not intended to limit the present invention. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (15)
1. The application of an oil displacement agent in steam huff and puff, steam flooding and multi-element thermal fluid thermal oil recovery processes comprises the following components in percentage by weight:
30-70% of alkyl alcohol polyoxyethylene polyoxypropylene ether carboxylate
4-10% of quaternary ammonium salt surfactant
0.1 to 1.5 percent of nano silicon dioxide particles
0.1-2% of deoxidant
8 to 30 percent of organic solvent
7.4-50.9% of water;
the quaternary ammonium salt surfactant is selected from one or more of alkyl trimethyl ammonium salt surfactant, dialkyl dimethyl ammonium salt surfactant and alkyl dimethyl benzyl ammonium salt surfactant, and the carbon atom number of the alkyl is C 12 -C 18 ；
The alkyl alcohol polyoxyethylene polyoxypropylene ether carboxylate is synthesized by the following method:
(1) putting alkyl alcohol and a catalyst into a reaction container, vacuumizing and heating for the first time, adding epoxypropane into the reaction container for reaction, and preserving the temperature of the reaction container until the reaction is balanced;
(2) carrying out first cooling on the mixture obtained in the step (1), carrying out second vacuumizing on a reaction container, then carrying out second cooling, and adjusting the pH value to be neutral to obtain an intermediate;
(3) selecting a new reaction container, vacuumizing and heating for the third time, adding the intermediate prepared in the step (2) and ethylene oxide into the reaction container for reaction, and preserving the temperature of the reaction container until the reaction is balanced;
(4) cooling the mixture obtained after the reaction balance in the step (3) for the third time, vacuumizing the reaction container for the fourth time, cooling for the fourth time, adjusting the pH value to be neutral, and separating to obtain the alkyl alcohol polyoxyethylene polyoxypropylene block polyether;
(5) heating the alkyl alcohol polyoxyethylene polyoxypropylene block polyether obtained in the step (4) to completely melt, adding an alkaline substance, uniformly stirring, adding chloroacetate, and obtaining alkyl alcohol polyoxyethylene polyoxypropylene ether carboxylate after the reaction is finished;
the weight ratio of the alkyl alcohol to the ethylene oxide to the propylene oxide is (5-10) to (30-200) to (10-100); the alkyl alcohol is one or more selected from dodecyl alcohol, hexadecyl alcohol and octadecyl alcohol.
2. The use as claimed in claim 1, wherein the oxygen scavenger is selected from one or both of sodium sulfite and thiourea.
3. Use according to claim 1, wherein the organic solvent is selected from one or more of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, propylene glycol, ethylene glycol monobutyl ether, and dimethylformamide.
4. Use as claimed in claim 3 wherein the water is selected from one or more of distilled water, deionised water, water having a degree of mineralization below 50000mg/L and a total content of calcium and magnesium ions below 2000 mg/L.
5. Use according to any one of claims 1 to 4, wherein the alkyl alcohol polyoxyethylene polyoxypropylene ether carboxylate has a number average molecular mass of 500-5000.
6. The method of claim 1, wherein the reaction temperature in step (1) is 135-145 ℃.
7. The use as claimed in claim 1, wherein the first temperature reduction in step (2) is performed at a temperature of 105 ℃ to 110 ℃; the temperature of the second temperature reduction is reduced to 70-80 ℃.
8. The use as claimed in claim 1, wherein the reaction temperature in step (3) is 125-135 ℃.
9. The use of claim 1, wherein the third temperature reduction in the step (4) is to be performed to 105-110 ℃; the fourth temperature reduction is to reduce the temperature to 60-80 ℃.
10. The use according to claim 1, wherein the reaction temperature after the chloroacetate is added in step (5) is 60-90 ℃ and the reaction time is 5-8 h.
11. Use according to claim 1, wherein the cation of the basic substance is the same as the cation in chloroacetate;
in the step (1), the weight and dosage ratio of the alkyl alcohol to the catalyst is (5-10) to (0.1-1);
in the step (5), the weight and dosage ratio of the alkaline substance to the chloroacetate is (1) to (1-2).
12. The use of claim 1, wherein the first, second, third and fourth evacuations are performed to a negative pressure of-0.05 Mpa.
13. The use of claim 1, a method for preparing the oil-displacing agent, comprising: weighing the components according to the weight percentage, stirring the components in a reaction container for 2 to 5 hours at the temperature of between 20 and 60 ℃, and uniformly mixing and stirring the components.
14. The application of claim 1, wherein the working temperature of the oil displacement agent is 200-350 ℃.
15. The use as claimed in claim 1, wherein the dosing amount of the oil displacing agent in the injection water is 500-5000ppm by weight.
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| Systematic investigation on the interaction between SiO2 nanoparticles with different surface affinity and various surfactants;HanJia等;《Journal of Molecular Liquids》;20200415;第304卷;第1-8页 * |
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