CN113025297A - Temperature-resistant salt-resistant low-tension foam oil displacement agent and preparation method and application thereof - Google Patents
Temperature-resistant salt-resistant low-tension foam oil displacement agent and preparation method and application thereof Download PDFInfo
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- CN113025297A CN113025297A CN202110280937.9A CN202110280937A CN113025297A CN 113025297 A CN113025297 A CN 113025297A CN 202110280937 A CN202110280937 A CN 202110280937A CN 113025297 A CN113025297 A CN 113025297A
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
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- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
Abstract
The invention discloses a temperature-resistant salt-resistant low-tension foam oil-displacing agent, which mainly comprises fatty alcohol-polyoxyethylene ether carboxylate; and simultaneously contains fatty alcohol-polyoxyethylene ether. The product has excellent oil-water interface property and outstanding foam performance, and is particularly suitable for the foam flooding technology in the field of tertiary oil recovery. The invention also discloses a preparation method of the foam oil displacement agent, the whole synthesis process of the method is continuously completed in a reaction kettle, any additional separation and purification process is not needed, a terminal product is directly formed, and the method has the advantages of simple process, economy, environmental friendliness and the like. The invention also discloses application of the foam oil displacement agent.
Description
Technical Field
The invention relates to the field of tertiary oil recovery. More particularly, relates to a temperature-resistant salt-resistant low-tension foam oil displacement agent, and a preparation method and application thereof.
Background
In oil and gas field development engineering, oil displacement by using a surfactant is an important method for improving the recovery rate of crude oil. However, at high temperature and high water mineralization oil reservoirs, the single anionic and nonionic surfactants can not meet the oil displacement requirements. Because anionic surfactants are not inherently salt tolerant, formation water mineralization is too high, causing the surfactant to precipitate. While the presence of the nonionic surfactant at the cloud point, formation temperatures above the cloud point will also cause the surfactant to precipitate.
In some of the prior art, there is a need for a carboxymethylation process to produce high grade ether carboxylates. In the carboxylation step, sodium hydroxide solution is used, and water in the reaction system is removed under vacuum at 100-130 ℃ to prepare the ether sodium compound (one of the raw materials is the sodium hydroxide solution) so as to improve the reaction efficiency. The vacuum operation has high energy consumption and high requirement on the sealing property of the equipment. In particular, since chloroacetic acid is extremely corrosive, general stainless steel materials are not durable. In high vacuum operation, the water evaporated carries acid mist, causing corrosion to the pipeline.
However, compared with the anionic surfactant commonly used in tertiary oil recovery in oil fields, the anionic-nonionic fatty alcohol polyoxyethylene ether carboxylate has higher price, the dosage of the tertiary oil recovery in the oil fields is large, and the exploitation cost is increased.
Therefore, it is needed to provide a low-tension foam oil displacement agent which can be used for tertiary oil recovery in an oil field, is low in exploitation cost, and has temperature resistance and salt resistance.
Disclosure of Invention
Based on the above problems, a first object of the present invention is to provide a temperature-resistant, salt-resistant, low-tension foam oil-displacing agent. The foam oil displacement agent is an alkali-free system, is suitable for tertiary oil recovery in an oil field, has low exploitation cost and use cost, and has the characteristics of temperature resistance, salt resistance, low tension, excellent foaming capacity, foam stability and the like.
The second purpose of the invention is to provide a preparation method of the temperature-resistant salt-resistant low-tension foam oil displacement agent. The preparation method is simple and low in cost, the prepared product does not need to be subjected to post-treatment steps such as purification and the like, the one-pot method green chemical synthesis process is adopted, and the method can be well used for tertiary oil recovery in an oil field and has a good effect.
The third purpose of the invention is to provide the application of the temperature-resistant salt-resistant low-tension foam oil displacement agent.
In order to achieve the first purpose, the invention adopts the following technical scheme:
a temperature-resistant salt-resistant low-tension foam oil displacement agent mainly comprises fatty alcohol polyoxyethylene ether carboxylate; and simultaneously contains fatty alcohol-polyoxyethylene ether.
In the technical scheme, the fatty alcohol-polyoxyethylene ether carboxylate has excellent temperature resistance and salt resistance, is an anionic-nonionic surfactant, contains both anionic functional groups and nonionic functional groups in the same molecular structure, integrates the advantages of the anionic functional groups and the nonionic functional groups, and overcomes the respective defects of the anionic surfactant and the nonionic surfactant; the fatty alcohol-polyoxyethylene ether is easy to dissolve in water, has strong hard water resistance and good emulsibility, has obvious synergistic effect when being compounded with fatty alcohol-polyoxyethylene ether carboxylate with good temperature resistance and salt resistance, and effectively improves the foam stability of the fatty alcohol-polyoxyethylene ether carboxylate; the combination of the two can not only reduce the cost, but also form a stable temperature-resistant salt-resistant low-tension foam agent oil displacement system, and further be used for tertiary oil recovery in oil fields.
In the invention, the foam oil displacement agent is an alkali-free system, and can generate low interfacial tension without adding alkali, thereby overcoming the problems that in a general oil displacement surfactant system, alkali (sodium bicarbonate, sodium carbonate or sodium hydroxide) is usually added to reduce the oil-water interfacial tension, and the alkali has a dissolving effect on rocks and minerals in a stratum, so that the scaling of a treatment system of a united station is serious, and the normal operation of crude oil production is influenced.
Further, in the foam oil displacement agent, the total content of the fatty alcohol-polyoxyethylene ether carboxylate and the fatty alcohol-polyoxyethylene ether is more than 55 wt%; and the mass ratio of the fatty alcohol-polyoxyethylene ether carboxylate to the fatty alcohol-polyoxyethylene ether is 13: 1-7: 1. Under the condition, the obtained foam oil displacement agent has better stability, temperature resistance, salt resistance and low tension performance.
Further preferably, the foam oil displacement agent contains 50-65 wt% of fatty alcohol-polyoxyethylene ether carboxylate by mass percentage.
Further preferably, the foam oil displacement agent contains 4-7 wt% of fatty alcohol-polyoxyethylene ether by mass percentage.
Further, the foam oil displacement agent further contains a glycolic acid salt, for example, sodium glycolate and the like.
Further preferably, the foam oil displacement agent contains 15-25 wt% of hydroxy acetate by mass percentage.
Further, the foam oil displacement agent also contains water, sodium chloride and the like.
Further preferably, the foam oil displacement agent contains 12-16 wt% of sodium chloride in percentage by mass.
Further preferably, the foam oil displacement agent contains 6-8 wt% of water in percentage by mass.
In the above technical solution, "mainly comprising" means that the mass percentage content is greater than or equal to 50% and less than 100%.
Further, the chemical formula of the fatty alcohol-polyoxyethylene ether is as follows: r1O(CH2CH2O)n1H, wherein R1Is C10～C20N1 is selected from a positive integer of 1-10.
Furthermore, in the chemical formula of the fatty alcohol-polyoxyethylene ether, R is C12～C16The alkyl group of (a) is,n is a positive integer of 3-6. For example, the fatty alcohol polyoxyethylene ether includes, but is not limited to, lauryl alcohol polyoxyethylene ether, myristyl alcohol polyoxyethylene ether, cetyl alcohol polyoxyethylene ether, and the like.
Further, the chemical formula of the fatty alcohol-polyoxyethylene ether carboxylate is as follows: r2O(CH2CH2O)n2CH2COOM wherein R2Is C10～C20N2 is selected from a positive integer of 1-10, and M is selected from metal potassium or sodium ions; wherein R is as defined above1And R2The same or different, n1 and n2 are the same or different.
Further, said R1And R2Are the same and are all C12～C16The alkyl groups, n1 and n2 are the same and are selected from positive integers of 3-6. At this time, R1And R2The foam oil displacement agent is respectively matched with n1 and n2, and the obtained foam oil displacement agent has better performance.
In order to achieve the second purpose, the invention adopts the following technical scheme:
a preparation method of a temperature-resistant salt-resistant low-tension foam oil displacement agent comprises the following steps:
in the presence of solid alkali, fatty alcohol-polyoxyethylene ether is subjected to an alkalization reaction;
and adding solid chloroacetic acid into the system obtained after the alkalization reaction, performing carboxymethylation reaction, and obtaining the whole system, namely the temperature-resistant salt-resistant low-tension foam oil displacement agent after the reaction.
And researches show that if the fatty alcohol-polyoxyethylene ether, the solid alkali and chloroacetic acid react under the equimolar condition, the yield of the fatty alcohol-polyoxyethylene ether carboxylate is low (about 60-70%), and under the condition, the performance of the obtained product cannot meet the requirement of the invention on the performance of the foam oil-displacing agent product. Further, the gram equivalent ratio of the fatty alcohol-polyoxyethylene ether to the solid alkali is 1: 2.8-4; the molar ratio of the fatty alcohol-polyoxyethylene ether to the solid chloroacetic acid is 1: 1.4-2. Under the condition, in the system obtained by the preparation method after alkalization reaction and carboxymethylation reaction, the alkyl alcohol polyoxyethylene ether can be converted into corresponding sodium alkoxide as much as possible (but not completely), and meanwhile, the yield of the alkyl alcohol polyoxyethylene ether carboxylate is improved under the strongly alkaline condition; further, the solid alkali in excess of the alkalization reaction completely reacts with the generated alkyl alcohol ether carboxylic acid to generate neutralization reaction and reacts with chloroacetic acid equivalent to generate corresponding sodium glycolate and water.
Therefore, the obtained foam oil displacement agent mainly comprises fatty alcohol polyoxyethylene ether carboxylate; and simultaneously contains a small part of completely unreacted fatty alcohol-polyoxyethylene ether. The unreacted raw material, namely the non-fatty alcohol-polyoxyethylene ether is just compatible and combined with the product, namely the fatty alcohol-polyoxyethylene ether carboxylate, and the unreacted material is fully utilized by adopting a simple and practical process preparation method and mild reaction conditions, so that the aim of cheapness of the product is fulfilled; meanwhile, the foam stability of the obtained foam oil displacement agent is improved, and the oil displacement agent is endowed with stable temperature resistance, salt resistance, low tension and other characteristics.
In addition, the chloroacetic acid is easy to generate explosion, and in addition, the chloroacetic acid has low melting point and can be liquefied, but the sodium chloroacetate cannot be liquefied, so that the carboxymethylation of the fatty alcohol-polyoxyethylene ether is not suitable for the preparation method in the invention.
In addition, in the preparation method, the alkali and chloroacetic acid in the alkalization reaction and the carboxymethylation reaction are directly added in a solid material manner, the whole synthesis process is continuously completed in a reaction kettle, any additional separation and purification process is not needed, and a terminal product is directly formed. Meanwhile, the product has excellent oil-water interface property and outstanding foam performance, and is particularly suitable for the foam flooding technology in the field of tertiary oil recovery.
Further, the solid alkali is one or more of solid sodium hydroxide and solid potassium hydroxide.
Further, the conditions of the alkalization reaction are as follows:
adding solid alkali into fatty alcohol-polyoxyethylene ether at the temperature of 50-90 ℃ under the stirring condition, heating to 70-80 ℃, and reacting for 1-2 hours at the temperature. In the step, after solid alkali is added, the alkalization reaction is severe just after the solid alkali is added, and much heat is released, so the temperature range is wide, after the alkali is added, the reaction speed is slow, the heat release is slow, the temperature of a reaction system needs to be kept stable by heating, and the heating temperature is set to be 70-80 ℃.
Further, the carboxymethylation reaction conditions are as follows:
and controlling the temperature of the system obtained after the alkalization reaction to be 50-80 ℃, adding solid chloroacetic acid under the stirring condition, heating to 75-90 ℃, and reacting at constant temperature for 2-5 hours.
In order to achieve the third purpose, the invention adopts the following technical scheme:
the temperature-resistant and salt-resistant low-tension foam oil displacement agent according to the first object or the temperature-resistant and salt-resistant low-tension foam oil displacement agent prepared by the preparation method according to the second object is applied to tertiary oil recovery in an oil field.
Further, the dosage of the temperature-resistant salt-resistant low-tension foam oil displacement agent is 1.0-0.3% of the mass of the foam displacement fluid.
Further, the application conditions include: the temperature of stratum is lower than 100 deg.C, and the degree of mineralization is lower than 3X 104ppm, and the concentration of calcium and magnesium ions is less than 1000 ppm.
The starting materials used in the present invention are commercially available or can be prepared by conventional methods known in the art, unless otherwise specified.
The invention has the following beneficial effects:
1) the foam oil displacement agent disclosed by the invention has excellent oil-water interface properties and outstanding foam performance. The invention is a process which is made according to the requirement of tertiary oil recovery on the high efficiency of the foaming agent, and completely aims at the use characteristics of the oil field. Fully pays attention to the effectiveness of the compatibility of unreacted raw materials and various byproducts as auxiliary agents. The unreacted fatty alcohol-polyoxyethylene ether in the process is an effective cosurfactant, and the surfactant is reserved in a reaction system to improve the foaming capacity and the foam stability of the foaming agent and play a good role in synergism. The process adopts mild reaction conditions: the normal pressure operation and the lower reaction temperature are 60-80 ℃, and the product performance synthesized under the condition completely meets the use requirement.
2) In the preparation method, the step of removing the vacuum operation is changed into the normal pressure operation, so that the equipment investment is reduced, the energy consumption is reduced, and the corrosion effect on pipeline equipment is reduced.
3) In the preparation method, a solid alkali feeding mode is used for replacing a sodium hydroxide aqueous solution, the bulk reaction of the raw materials is adopted, the water generated in the reaction is small, the vacuum removal is not needed, and the remained material is beneficial to hydrolyzing unreacted chloroacetic acid into harmless sodium glycolate. Therefore, the reaction mixture is non-toxic, harmless and pollution-free when being used in oil fields.
4) The product prepared by the preparation method does not contain alkali, the alkali is fully consumed in the process, and the product cannot cause formation damage when being used in an oil field.
5) Solid chloroacetic acid is used for replacing sodium chloroacetate, and compared with sodium chloroacetate, the solid chloroacetic acid has the advantages that the chloroacetic acid does not generate dust, the chloroacetic acid dust generated in the adding process is harmful to the bodies of operators, meanwhile, the sodium chloroacetate dust is easy to cause explosion, and the defects can be overcome by using the chloroacetic acid.
6) In the whole production process, no solvent is required to be added, and no separation and purification process is required to be carried out, so that all raw materials are fully utilized, the real zero emission is realized, and the prepared product has excellent oil displacement property as described above.
7) The fatty alcohol-polyoxyethylene ether carboxylate is a new species of a green surfactant which is internationally recognized, and OECD experiments prove that the average degradability of the fatty alcohol-polyoxyethylene ether carboxylate is more than 90 percent. The process and the agent are nontoxic, harmless and pollution-free, and the reaction product has zero emission, thereby realizing the concepts of atomic economic reaction, environment-friendly chemical reaction and green chemistry.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows an infrared spectrum of lauryl alcohol polyoxyethylene ether in the product system obtained in example 1.
FIG. 2 shows an infrared spectrum of sodium lauryl alcohol polyoxyethylene ether carboxylate in the product system obtained in example 1.
FIG. 3 shows an infrared spectrum of sodium glycolate in the product system obtained in example 1.
FIG. 4 shows the dodecyl alcohol polyoxyethylene ether in the product system obtained in example 11H-NMR nuclear magnetic spectrum.
FIG. 5 shows the results of the reaction of sodium lauryl alcohol polyoxyethylene ether carboxylate in the product system obtained in example 11H-NMR nuclear magnetic spectrum.
FIG. 6 shows the reaction of sodium glycolate in the product system obtained in example 11H-NMR nuclear magnetic spectrum.
FIG. 7 shows the oil-water interfacial tension of the respective products of examples 1-4 with 0.5% + 5% NaCl solution.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
In the following examples, the numerical values in parentheses of the alkyl alcohol polyoxyethylene ether represent the number of polyoxyethylene units in the alkyl alcohol polyoxyethylene ether.
Example 1
1) Alkalization reaction of lauryl alcohol polyoxyethylene ether (3):
adding 318g (1mol) of lauryl alcohol polyoxyethylene ether (3) into a reaction kettle with a heating, temperature control and electric stirring device, heating to about 70 ℃, slowly adding 120g (3.0mol) of solid sodium hydroxide into the reaction kettle by using a spiral feeder under stirring, heating to about 75 ℃ after the feeding is finished, and continuously reacting for about 2 hours at the temperature;
2) carboxymethylation reaction:
reducing the temperature of a reactant system in the reaction kettle after alkalization in the step 1) to about 55 ℃, slowly adding 141.8g (1.5mol) of solid chloroacetic acid into the reaction kettle by using a spiral feeder under continuous stirring, heating to about 80 ℃ after the feeding is finished, and continuously reacting for about 4 hours at constant temperature to obtain the temperature-resistant salt-resistant low-tension foam agent, wherein the conversion rate of the dodecyl alcohol polyoxyethylene ether (3) is 92.1%, and the reaction product is directly used for the tertiary oil recovery low-tension foam oil displacement agent without purification.
The obtained product mainly comprises the following components: sodium dodecyl alcohol polyoxyethylene ether carboxylate (3), sodium glycolate, sodium chloride, water and unreacted dodecyl alcohol polyoxyethylene ether (3), wherein the mass percentages of the sodium dodecyl alcohol polyoxyethylene ether carboxylate, the sodium glycolate, the sodium chloride, the water and the unreacted dodecyl alcohol polyoxyethylene ether (3) are respectively as follows: 54.1%, 18.7%, 15.1%, 7.8% and 4.3%.
Description of the drawings: because the product is a mixture composed of a plurality of compounds, if the existing spectral means is directly adopted to not characterize the compounds in the product, a method for qualitatively and quantitatively detecting the compounds is specially established, and a high performance liquid reverse phase chromatography is adopted, and the specific detection method is as follows: the instrument is a high performance liquid phase reverse phase chromatograph, the chromatographic column is a C18 reverse phase chromatographic separation column, the detector is an evaporation light scattering instrument, and the evaporation gas is high pressure dry air; the chromatographic condition is as follows: the mobile phase is a mixed solvent of chromatographic methanol and ultrapure water (the volume ratio is 3: 97-7: 93), the speed of the mobile phase is 2ml/min, the column temperature is 25 ℃, the sample injection amount is 20ul, the temperature of an evaporator is 60 ℃, and the air flow rate is 2.5 l/min; the operation process is as follows: the method comprises the steps of taking known alkyl alcohol polyoxyethylene ether raw materials and separated and purified alkyl alcohol polyoxyethylene ether carboxylate as standard samples, obtaining the peak-appearing time of the standard samples under certain chromatographic separation conditions, making a standard curve of the concentration of the standard samples and the peak area of the standard samples, preparing the foaming agent synthesized in the embodiment into samples with determined concentration, then performing separation and determination by a liquid chromatograph, and combining the standard curve of the standard samples to obtain the composition and corresponding content of each component in the samples.
And (3) qualitative analysis: FIGS. 1 to 6 are the spectra of the components of example 1.
Example 2
1) Alkalization reaction of tetradecyl alcohol polyoxyethylene ether (3):
adding 346g (1mol) of tetradecyl alcohol polyoxyethylene ether (3) into a reaction kettle with a heating, temperature control and electric stirring device, heating to about 70 ℃, slowly adding 112g (2.8mol) of solid sodium hydroxide into the reaction kettle by using a spiral feeder under stirring, heating to about 75 ℃ after the feeding is finished, and continuously reacting for 1-2 hours at the temperature;
2) carboxymethylation reaction:
reducing the temperature of a reactant system in the alkalized reaction kettle in the step 1) to about 55 ℃, slowly adding 132.3g (1.4mol) of solid chloroacetic acid into the reaction kettle by using a spiral feeder under the condition of continuous stirring, heating to about 85 ℃ after the feeding is finished, continuously reacting for 2-5 hours at constant temperature to obtain a temperature-resistant salt-resistant low-tension foaming agent, wherein the conversion rate of the tetradecyl alcohol polyoxyethylene ether (3) is 88.4%, and the reaction product is directly used for a low-tension foam oil displacement agent for tertiary oil recovery without purification.
The obtained product mainly comprises the following components: sodium tetradecyl alcohol polyoxyethylene ether carboxylate (3), sodium glycolate, sodium chloride, water and unreacted tetradecyl alcohol polyoxyethylene ether (3), wherein the mass percentages of the sodium tetradecyl alcohol polyoxyethylene ether carboxylate, the sodium glycolate, the sodium chloride, the water and the unreacted tetradecyl alcohol polyoxyethylene ether are respectively as follows: 55.1%, 16.9%, 13.9%, 7.3% and 6.8%.
Example 3
1) Alkalization reaction of tetradecyl alcohol polyoxyethylene ether (4):
adding 390g (1mol) of tetradecyl alcohol polyoxyethylene ether into a reaction kettle with a heating, temperature control and electric stirring device, (4) heating to about 70 ℃, slowly adding 112g (2.8mol) of solid sodium hydroxide into the reaction kettle by using a spiral feeder under stirring, after the feeding is finished, heating to about 75 ℃, and continuously reacting for 1-2 hours at the temperature;
2) carboxymethylation reaction:
reducing the temperature of a reactant system in the alkalized reaction kettle in the step 1) to about 55 ℃, slowly adding 132.3g (1.4mol) of solid chloroacetic acid into the reaction kettle by using a spiral feeder under the condition of continuous stirring, heating to about 85 ℃ after the feeding is finished, continuously reacting for 3-4 hours at constant temperature to obtain a temperature-resistant salt-resistant low-tension foaming agent, wherein the conversion rate of tetradecyl alcohol polyoxyethylene ether (4) is 89.5%, and the reaction product is directly used for a tertiary oil recovery low-tension foam oil displacement agent without purification.
The obtained product mainly comprises the following components: the cetyl alcohol polyoxyethylene ether sodium carboxylate (4), sodium glycolate, sodium chloride, water and unreacted cetyl alcohol polyoxyethylene ether (4) respectively comprise the following components in percentage by mass: 58.1%, 15.7%, 12.9%, 6.8% and 6.5%.
Example 4
1) Alkalization reaction of cetyl alcohol polyoxyethylene ether (5):
adding 462g (1.0mol) of cetyl alcohol polyoxyethylene ether (5) into a reaction kettle with a heating, temperature control and electric stirring device, heating to about 70 ℃, slowly adding 120g (3.0mol) of solid sodium hydroxide into the reaction kettle by using a spiral feeder under stirring, heating to about 75 ℃ after the feeding is finished, and continuously reacting for 2 hours at the temperature;
2) carboxymethylation reaction:
reducing the temperature of a reactant system in the reaction kettle after alkalization in the step 1) to about 65 ℃, slowly adding 141.8g (1.5mol) of solid chloroacetic acid into the reaction kettle by using a spiral feeder under continuous stirring, heating to about 85 ℃ after the feeding is finished, continuously reacting for 3-4 hours at constant temperature to obtain a temperature-resistant salt-resistant low-tension foaming agent, wherein the conversion rate of cetyl alcohol polyoxyethylene ether (5) is 92.3%, and the reaction product is directly used for a low-tension foam oil displacement agent for tertiary oil recovery without purification.
The obtained product mainly comprises the following components: the cetyl alcohol polyoxyethylene ether sodium carboxylate (5), sodium glycolate, sodium chloride, water and unreacted cetyl alcohol polyoxyethylene ether (5) respectively comprise the following components in percentage by mass: 61.7%, 15.1%, 12.1%, 6.2% and 4.9%.
Example 5
1) Alkalization reaction of cetyl alcohol polyoxyethylene ether (5):
adding 462g (1.0mol) of cetyl alcohol polyoxyethylene ether (5) into a reaction kettle with a heating, temperature control and electric stirring device, heating to about 75 ℃, slowly adding 160g (4.0mol) of solid sodium hydroxide into the reaction kettle by a spiral feeder under stirring, heating to about 80 ℃ after the feeding is finished, and continuously reacting for 2 hours at the temperature;
2) carboxymethylation reaction:
reducing the temperature of a reactant system in the reaction kettle after alkalization in the step 1) to about 70 ℃, slowly adding 189g (2.0mol) of solid chloroacetic acid into the reaction kettle by using a spiral feeder under continuous stirring, heating to about 85 ℃ after the feeding is finished, continuously reacting for 3-4 hours at constant temperature to obtain the temperature-resistant salt-resistant low-tension foaming agent, wherein the conversion rate of the cetyl alcohol polyoxyethylene ether (5) is 92.5%, and the reaction product is directly used for the low-tension foam oil displacement agent for tertiary oil recovery without purification.
The obtained product mainly comprises the following components: the cetyl alcohol polyoxyethylene ether sodium carboxylate (5), sodium glycolate, sodium chloride, water and unreacted cetyl alcohol polyoxyethylene ether (5) respectively comprise the following components in percentage by mass: 53.7%, 21.4%, 14.0%, 6.5% and 4.4%.
Example 6
1) Alkalization reaction of lauryl alcohol polyoxyethylene ether (3):
adding 318g (1mol) of lauryl alcohol polyoxyethylene ether (3) into a reaction kettle with a heating, temperature control and electric stirring device, heating to about 60 ℃, slowly adding 120g (3.0mol) of solid sodium hydroxide into the reaction kettle by using a spiral feeder under stirring, heating to about 70 ℃ after the feeding is finished, and continuously reacting for about 2 hours at the temperature;
2) carboxymethylation reaction:
reducing the temperature of a reactant system in the reaction kettle after alkalization in the step 1) to about 55 ℃, slowly adding 141.8g (1.5mol) of solid chloroacetic acid into the reaction kettle by using a spiral feeder under continuous stirring, heating to about 75 ℃ after the feeding is finished, continuously reacting for about 5 hours at constant temperature to obtain the temperature-resistant salt-resistant low-tension foam agent, wherein the conversion rate of the dodecyl alcohol polyoxyethylene ether (3) is 87.4%, and the reaction product is directly used for the low-tension foam oil displacement agent for tertiary oil recovery without purification.
The obtained product mainly comprises the following components: sodium dodecyl alcohol polyoxyethylene ether (3) carboxylate, sodium glycolate, sodium chloride, water and unreacted dodecyl alcohol polyoxyethylene ether (3), wherein the mass percentages of the sodium dodecyl alcohol polyoxyethylene ether carboxylate, the sodium glycolate, the sodium chloride, the water and the unreacted dodecyl alcohol polyoxyethylene ether (3) are respectively as follows: 51.3%, 19.2%, 15.1%, 7.5% and 6.9%.
Comparative example 1
Example 1 was repeated, with the difference that the reaction feed solid sodium hydroxide had a mass of 80g (2.0mol), solid chloroacetic acid had a mass of 94.5g (1.0mol), and the dodecyl alcohol polyoxyethylene ether (3) had a conversion of 67.3%, and the product was obtained with the following main components: sodium dodecyl alcohol polyoxyethylene ether (3) carboxylate, sodium glycolate, sodium chloride, water and unreacted dodecyl alcohol polyoxyethylene ether (3), wherein the mass percentages of the sodium dodecyl alcohol polyoxyethylene ether carboxylate, the sodium glycolate, the sodium chloride, the water and the unreacted dodecyl alcohol polyoxyethylene ether (3) are respectively as follows: 46.5%, 14.4%, 11.9%, 6.1% and 21.1%.
Comparative example 2
Example 1 was repeated, with the difference that the reaction feed solid sodium hydroxide had a mass of 160g (4.0mol), solid chloroacetic acid had a mass of 189g (2.0mol), and the dodecyl alcohol polyoxyethylene ether (3) had a conversion of 94.7%, and the product obtained had a main composition of: sodium dodecyl alcohol polyoxyethylene ether (3) carboxylate, sodium glycolate, sodium chloride, water and unreacted dodecyl alcohol polyoxyethylene ether (3), wherein the mass percentages of the sodium dodecyl alcohol polyoxyethylene ether carboxylate, the sodium glycolate, the sodium chloride, the water and the unreacted dodecyl alcohol polyoxyethylene ether (3) are respectively as follows: 48.3%, 23.6%, 17.5%, 8.1% and 2.5%.
Example 7
The oil-water interfacial tension of the NaCl solution with the mass concentration of 0.5% + 5% and the crude oil in the above examples and comparative examples is measured.
Method of solution formulation in each example: in the case of 1000g of the solution, 5g of the foaming agent prepared in one example and 50g of NaCl were weighed and poured into a reaction flask, and 945g of distilled water was weighed and poured into the reaction flask, and the solute was sufficiently dissolved by stirring or sonication, thereby obtaining a solution of 0.5% foaming agent + 5% NaCl.
The interfacial tension determination experimental method is as follows: according to the method for measuring interfacial tension of SY/T5370-2018-containing interfacial tension and the method for testing SY/T6424-containing 2014-compound oil displacement system performance, firstly, each synthetic product is prepared into a solution (relative to a foam oil displacement agent system) with the concentration of 0.5 wt% (foam oil displacement agent) and 5 wt% NaCl, the oil-water interfacial tension of the victory crude oil and the oil displacement agent solution system is measured by adopting a rotary dripping method, then, an IFT-T relation curve is made by utilizing computer software, the experiment temperature is 80 ℃, and the rotating speed is 5000 r/min.
The measurement data of examples 1 to 4 are shown in FIG. 1. As can be seen from the measurement results in FIG. 1, the synthesized product has excellent interfacial properties, and can form ultra-low oil-water interfacial tension (10) with victory crude oil without adding any auxiliary agent-3mN/m) can be directly used in tertiary oil recovery.
The difference from examples 5 and 6 is that the reaction raw materials and the proportion of the reaction raw materials are different, the conversion rate of the raw materials is also different, so the content of each component in the product is different, because the physicochemical properties of surfactants with different structures are different, generally, under the condition that the chain length of the same polyether unit is within a certain carbon chain length range, the lower the surface tension is, the stronger the foaming capacity is, but the foam stability is worse, but the oil-water interfacial tension is related to oil, the nonionic surfactant and the anionic nonionic surfactant are mixed within a certain proportion range, the oil-water interfacial tension and the foam stability are both enhanced, and the product obtained within the range required by the invention can meet the requirements of temperature resistance, salt resistance and low-tension foam performance of oil fields on site in terms of interfacial tension, foaming capacity and foam stability.
Comparing the comparative example 1 with the comparative example 2, mainly explaining that under the same reaction conditions, the higher the ratio of alkali and chloroacetic acid to alkyl alcohol polyoxyethylene ether, the higher the conversion rate of alkyl alcohol polyoxyethylene ether, the better the surface tension and foaming ability of the product, but the lower the corresponding foam stability, and the higher the salt content in the product, so the comprehensive consideration, selecting proper reaction conditions and material ratio, makes the obtained product meet the requirement of being directly used for foam flooding agent in oil field.
Example 8
The products of the above examples 1 to 5 were prepared into solutions with a mass concentration of 0.5% by using formation water in the victory oil field, and the foaming ability and foam stability data measured respectively are shown in table 1 below.
The experimental method for measuring the foam property comprises the following steps: the Bikerman method of air flow is used to generate foam by passing a gas at a certain flow rate and flow rate through a glass frit, agitating a quantitative test solution on the frit, and forming a certain amount of foam in a graduated container (graduated cylinder). And recording the foam height and the liquid discharge volume at different moments, and inspecting the maximum foaming capacity and stability of a foaming system. The experimental steps are as follows: slowly pouring 50mL of prepared surfactant solution into a 500mL bubbling tube, and keeping the temperature for a certain time by using a constant-temperature water bath until the solution is balanced; then, air was introduced at a flow rate of 10mL/s while pressing a stopwatch for 20s, then the upper end of the bubble tube was plugged with a rubber stopper, the foam volume at different times was recorded, and the foam volume and foam half-life of the foamable composition (foam half-life is the time required for the initial foam volume to decay by half, indicating the stability of the foam) were obtained; the experimental temperature was 50 ℃.
TABLE 1 foaming Capacity and foam Performance data for synthetic foam displacement Agents
According to experimental results, in the embodiment, when the conversion rate of the alkyl alcohol ether is in a certain range, the foaming capacity and the foam stability of the synthesized flooding foaming agent are excellent, the foaming volume reaches more than 200ml, and the foam half-life period is more than 85min, so that the flooding foaming agent can be used as a tertiary oil recovery technology for temperature-resistant, salt-resistant and low-tension foam flooding.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. A temperature-resistant salt-resistant low-tension foam oil displacement agent is characterized in that the foam oil displacement agent mainly comprises fatty alcohol polyoxyethylene ether carboxylate; and simultaneously contains fatty alcohol-polyoxyethylene ether.
2. The temperature-resistant salt-resistant low-tension foam oil displacement agent according to claim 1, wherein the total content of the fatty alcohol-polyoxyethylene ether carboxylate and the fatty alcohol-polyoxyethylene ether in the foam oil displacement agent is greater than 55 wt%; and is
The mass ratio of the fatty alcohol-polyoxyethylene ether carboxylate to the fatty alcohol-polyoxyethylene ether is 13: 1-7: 1.
3. The temperature-resistant salt-resistant low-tension foam oil displacement agent according to claim 1, wherein the fatty alcohol-polyoxyethylene ether has a chemical formula: r1O(CH2CH2O)n1H, wherein R1Is C10～C20N1 is selected from a positive integer of 1-10;
the chemical formula of the fatty alcohol-polyoxyethylene ether carboxylate is as follows: r2O(CH2CH2O)n2CH2COOM wherein R2Is C10～C20N2 is selected from a positive integer of 1-10, and M is selected from metal potassium or sodium ions;
wherein R is as defined above1And R2The same or different, n1 and n2 are the same or different.
4. The preparation method of the temperature-resistant salt-resistant low-tension foam oil displacement agent according to any one of claims 1 to 3, which comprises the following steps:
in the presence of solid alkali, fatty alcohol-polyoxyethylene ether is subjected to an alkalization reaction;
adding solid chloroacetic acid into the system obtained after the alkalization reaction, and performing carboxymethylation reaction to obtain the whole system, namely the temperature-resistant salt-resistant low-tension foam oil displacement agent;
preferably, the gram equivalent ratio of the fatty alcohol-polyoxyethylene ether to the solid alkali is 1: 2.8-4;
preferably, the molar ratio of the fatty alcohol-polyoxyethylene ether to the solid chloroacetic acid is 1: 1.4-2.
5. The preparation method according to claim 4, wherein the solid alkali is one or more of solid sodium hydroxide and solid potassium hydroxide.
6. The production method according to claim 4 or 5, characterized in that the conditions of the alkalization reaction are:
adding solid alkali into fatty alcohol-polyoxyethylene ether at the temperature of 50-90 ℃ under the stirring condition, heating to 70-80 ℃, and reacting for 1-2 hours at the temperature.
7. The production method according to claim 4 or 5, wherein the carboxymethylation reaction is carried out under the following conditions:
and controlling the temperature of the system obtained after the alkalization reaction to be 50-80 ℃, adding solid chloroacetic acid under the stirring condition, heating to 75-90 ℃, and reacting at constant temperature for 2-5 hours.
8. The application of the temperature-resistant and salt-resistant low-tension foam oil displacement agent according to any one of claims 1 to 3 or the temperature-resistant and salt-resistant low-tension foam oil displacement agent prepared by the preparation method according to any one of claims 4 to 7 in tertiary oil recovery in an oil field.
9. The use according to claim 8, wherein the temperature-resistant salt-resistant low-tension foam oil displacement agent is used in an amount of 1.0-0.3% of the mass of the foam displacement fluid.
10. The use according to claim 8 or 9, wherein the application condition comprises:
the temperature of stratum is lower than 100 deg.C, and the degree of mineralization is lower than 3X 104ppm, calcium and magnesium ion concentration is less than 1000 ppm.
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