Rosin polyether gemini sulfonate and preparation method thereof, imbibition agent composition, oil-displacing agent and application of oil-displacing agent

Abstract

The invention provides rosin polyether gemini sulfonate and a preparation method thereof, an imbibition agent composition, an oil-displacing agent and application of the oil-displacing agent. The structural formula of the rosin polyether gemini sulfonate is as shown in formula (I). In formula (1) # imgabs0 #, m is an integer from 0 to 50; m is selected from positive ions or positive ion groups enabling the molecules shown in the formula (1) to be electrically neutral; r1, R2, R3 and R4 are respectively and independently selected from C1-C4 alkyl groups. The rosin polyether gemini sulfonate provided by the invention is a bio-based anionic gemini surfactant; the rosin polyether gemini sulfonate can be compounded with an anionic-nonionic surfactant to form a composition, has superstrong interface performance and wetting change performance, greatly reduces the critical micelle concentration, and improves the oil displacement efficiency of the composition.

Description

Technical Field

[0001] The invention relates to the technical field of oil reservoir exploitation, in particular to the technical field of unconventional tight oil reservoir or shale oil reservoir exploitation in oil fields, and more particularly to a rosin polyether gemini sulfonate and a preparation method thereof, an imbibing agent composition and an oil displacement agent and applications thereof. Background Art

[0002] In recent years, with the successful exploration and development of shale oil in the United States, shale oil has become one of the hottest unconventional oil and gas fields in the world today. According to a report released by the U.S. Energy Information Administration, at the end of 2017, the proven reserves of shale oil in the United States were 27.36×108t, accounting for about 48% of the total proven reserves of crude oil and condensate in the United States that year. It is predicted that by 2040, the production of shale oil in the United States will reach 129.6×104t / d, accounting for about 67.3% of the total oil production.

[0003] After fracturing, shale oil reservoirs have high initial production, but the production declines rapidly and with a large decline. It is urgent to tackle the integration of fracturing energy enhancement and the technology of energy enhancement and stable production in the later stage of fracturing. Due to the extremely low matrix permeability and the development of natural fractures, conventional oil reservoir recovery enhancement technologies such as polymer flooding and ternary composite flooding contain large molecules in the injection system and cannot be injected into shale oil reservoirs dominated by nanopores.

[0004] The wettability of shale oil reservoirs is oil-wet to moderately wet. When injecting water, the capillary force is a resistance, which greatly reduces the injectability of shale oil reservoirs. Therefore, from the perspective of improving wettability, surfactants are the most promising technology for improving the recovery rate of tight shale oil reservoirs. They have good wettability change performance and promote water imbibition, thereby improving the recovery rate of tight shale oil reservoirs.

[0005] Rosin is a natural resin that is abundant, cheap, and naturally renewable. Its main component is rosin acid. Rosin derivatives are usually obtained by chemically modifying the carboxyl groups and double bonds in the rosin acid structure to introduce hydrophilic groups. In addition, the rigid structure of the rosin base can improve the thermal stability, chemical stability, and mechanical stability of the surfactant. Surfactants synthesized from rosin are considered to be ecological, biodegradable, and biocompatible.

[0006] Silicone surfactants are a type of surfactant that uses polydimethylsiloxane as the hydrophobic main chain with one or more polar groups connected to its middle or end positions. They have better surface activity and spreadability than ordinary surfactants and can significantly reduce the surface tension of water.

[0007] Gemini surfactants are composed of two hydrophobic alkyl chains and two hydrophilic groups connected by chemical bonds. Compared with traditional single-chain surfactants, their structure is more unique. The presence of the linking group enhances the interaction between the hydrophobic chains on the one hand, and weakens the electrostatic repulsion between the hydrophilic ion head groups on the other hand, thereby greatly improving the surface activity, which will also bring greater improvements in the performance of surfactants. Compared with different types of traditional surfactants, Gemini surfactants have lower Krafft points, stronger ability to reduce the surface tension of solutions, and better emulsification, wetting and other properties. Summary of the invention

[0008] In view of the above problems existing in the prior art, the present invention provides a rosin polyether gemini sulfonate and a preparation method thereof, an imbibing agent composition, an oil displacement agent and applications thereof; the rosin polyether gemini sulfonate provided by the present invention is a bio-based anionic gemini surfactant; the rosin polyether gemini sulfonate can be compounded with anionic-nonionic surfactants to form a composition, has super strong interface performance and wetting change performance, greatly reduces the critical micelle concentration, and improves the oil displacement efficiency of the composition. The imbibing agent composition described in the present invention can improve the volume expansion parameter, reduce the oil-water interfacial tension, and improve the recovery rate in oil displacement applications.

[0009] In order to achieve the above-mentioned object, the first aspect of the present invention provides a rosin polyether gemini sulfonate, the rosin polyether gemini sulfonate has a structural formula as shown in formula (I);

[0010]

[0011] In formula (1), m is an integer of 0-50; M is selected from a cation or a cationic group that makes the molecule represented by formula (1) electrically neutral;

[0012] R1, R2, R3, and R4 are each independently selected from a C1-C4 alkyl group.

[0013] The second aspect of the present invention provides a method for preparing the rosin polyether gemini sulfonate of the present invention, the method comprising:

[0014] (1) in the presence of a first catalyst, dehydroabietin alcohol and ethylene oxide are brought into first contact to obtain dehydroabietin alcohol polyoxyethylene ether;

[0015] (2) the dehydroabietin alcohol polyoxyethylene ether is contacted with a sulfuric acid source for a second time to obtain sulfonated dehydroabietin alcohol polyoxyethylene ether, and then neutralized with an alkaline substance to obtain sulfonate dehydroabietin alcohol polyoxyethylene ether;

[0016] (3) in the presence of an amine solvent, the sulfonate dehydroabietin alcohol polyoxyethylene ether is contacted with the disiloxane represented by formula (3) to obtain a rosin polyether gemini sulfonate;

[0017]

[0018] In formula (3), R1, R2, R3, and R4 are each independently selected from a C1-C4 alkyl group;

[0019] X1 and X2 are each independently selected from one of the halogens.

[0020] The third aspect of the present invention provides an imbibing agent composition, which comprises an anionic-nonionic surfactant and an anionic gemini surfactant;

[0021] The anionic gemini surfactant includes at least one of the rosin polyether gemini sulfonates described in the present invention.

[0022] The fourth aspect of the present invention provides a method for preparing the imbibition agent composition of the present invention, the method comprising: mixing the anionic gemini surfactant and the anionic-nonionic surfactant.

[0023] The fifth aspect of the present invention provides an oil-displacing agent, which includes: the oil-displacing agent includes the imbibition agent composition described in the present invention and water.

[0024] A sixth aspect of the present invention provides an application of the imbibition agent composition of the present invention or the oil displacement agent of the present invention in oil reservoir exploitation.

[0025] Through the above technical scheme, the rosin polyether gemini sulfonate provided by the present invention is a bio-based anionic gemini surfactant; the rosin polyether gemini sulfonate can be compounded with anionic-nonionic surfactants to form a composition with super strong interfacial properties and wetting change properties, greatly reducing the critical micelle concentration and improving the oil displacement efficiency of the composition. The imbibition agent composition of the present invention can improve the volume expansion parameter, reduce the oil-water interfacial tension, and improve the recovery rate in oil displacement applications.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] (1) The rosin polyether gemini sulfonate provided by the present invention is a new type of anionic gemini surfactant, which greatly reduces the critical micelle concentration and improves the oil displacement efficiency of the composition.

[0028] (2) The oil displacement agent provided by the present invention can ensure the solubilization performance and interfacial performance of the surfactant at a relatively low concentration, and can further improve the oil displacement efficiency.

[0029] (3) The imbibition agent composition of the present invention has good injection performance and can greatly improve the imbibition efficiency of shale oil reservoirs.

[0030] (4) The imbibition agent composition of the present invention has good high temperature stability and is adaptable to harsh conditions such as high temperature and high salt.

[0031] The inventors of the present invention believe that the above advantages may be due to:

[0032] The rigid structure of the rosin base is utilized to improve the thermal stability of the rosin polyether gemini sulfonate; the rosin is used as a hydrophobic group, and the hydroxyl groups in the rosin acid structure are chemically modified to introduce a hydrophilic group; siloxane, which has high interfacial activity and high spreadability and can significantly reduce the surface tension of water, is used as a connecting base to synthesize a sulfonated rosin alcohol polyoxyethylene ether anionic gemini surfactant with a double head base and double hydrophobic groups, which greatly reduces the critical micelle concentration, improves the interface molecular arrangement and thus improves its surface activity; an anionic-nonionic surfactant is used as a compounding agent to increase the adjustment degree of the hydrophilic-lipophilic balance of the composition. DETAILED DESCRIPTION

[0033] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0034] The first aspect of the present invention provides a rosin polyether gemini sulfonate, the rosin polyether gemini sulfonate has a structural formula as shown in formula (I);

[0035]

[0036] In formula (1), m is an integer of 0-50; M is selected from a cation or a cationic group that makes the molecule represented by formula (1) electrically neutral; R1, R2, R3, and R4 are each independently selected from a C1-C4 alkyl group.

[0037] According to a preferred embodiment of the present invention, m is an integer of 20-30.

[0038] According to a preferred embodiment of the present invention, M is selected from any one of alkali metals, alkaline earth metals or ammonium ions, preferably any one of Na, K or NH4.

[0039] According to a preferred embodiment of the present invention, R1, R2, R3 and R4 are all methyl groups.

[0040] The second aspect of the present invention provides a method for preparing the rosin polyether gemini sulfonate of the present invention, the method comprising:

[0041] (1) in the presence of a first catalyst, dehydroabietin alcohol and ethylene oxide are brought into first contact to obtain dehydroabietin alcohol polyoxyethylene ether;

[0042] (2) the dehydroabietin alcohol polyoxyethylene ether is contacted with a sulfuric acid source for a second time to obtain sulfonated dehydroabietin alcohol polyoxyethylene ether, and then neutralized with an alkaline substance to obtain sulfonate dehydroabietin alcohol polyoxyethylene ether;

[0043] (3) in the presence of an amine solvent, the sulfonate dehydroabietin alcohol polyoxyethylene ether is contacted with the disiloxane represented by formula (3) to obtain a rosin polyether gemini sulfonate;

[0044]

[0045] In formula (3), R1, R2, R3, and R4 are each independently selected from a C1-C4 alkyl group;

[0046] X1 and X2 are each independently selected from one of the halogens.

[0047] In the present invention, in step (1), ethoxy groups are added, and dehydroabietin alcohol (structural formula as shown in formula (1-1)) is reacted with ethylene oxide in the presence of a catalyst to obtain dehydroabietin alcohol polyoxyethylene ether, structural formula as shown in formula (1-2);

[0048]

[0049] In the present invention, in step (1), the optional range of the dosage ratio of dehydroabietyl alcohol to ethylene oxide is relatively wide. According to a preferred embodiment of the present invention, the molar ratio of dehydroabietyl alcohol to ethylene oxide is 1:1-50.

[0050] In the present invention, in step (1), the amount of the first catalyst can be selected in a wide range. According to a preferred embodiment of the present invention, the amount of the first catalyst is 0.001 wt%-2.0 wt% of the amount of dehydroabietyl alcohol.

[0051] In the present invention, in step (1), there is no particular limitation on the type of the first catalyst, as long as the hydroxyl group of dehydroabietyl alcohol reacts with ethylene oxide. According to a preferred embodiment of the present invention, the first catalyst is selected from at least one of an alkali metal hydroxide, a DMC bimetallic polyether catalyst and a phosphazene catalyst.

[0052] In the present invention, in step (1), the conditions for the first contacting can be selected in a wide range. According to a preferred embodiment of the present invention, the first contacting conditions include: a temperature of 140-200° C. and a pressure of 0-5 MPa.

[0053] In the present invention, in step (2), the structural formula of sulfonate dehydroabietin alcohol polyoxyethylene ether is as shown in formula (1-3);

[0054] The definition of M is the same as that of formula (1).

[0055] In the present invention, in step (2), the optional range of the dosage ratio of dehydroabietin alcohol polyoxyethylene ether to sulfuric acid is relatively wide. According to a preferred embodiment of the present invention, the molar ratio of dehydroabietin alcohol polyoxyethylene ether to sulfuric acid is 1:10-50.

[0056] In the present invention, the sulfuric acid source may be dilute sulfuric acid and / or concentrated sulfuric acid, preferably concentrated sulfuric acid, such as 75 wt % or more concentrated sulfuric acid, more preferably 98 wt % or more concentrated sulfuric acid.

[0057] In the present invention, in step (2), the conditions for the second contact can be selected in a wide range, and the degree of sulfonation of the product can be controlled by adjusting different sulfonation ratios and sulfonation times. According to a preferred embodiment of the present invention, the second contact conditions include: a temperature of -10°C to 0°C and a time of 0.1-1h.

[0058] In the present invention, in step (3), the reaction product obtained in step (2) is reacted with the disiloxane represented by formula (3) under alkaline conditions to introduce a siloxane linking group to synthesize a gemini surfactant.

[0059] According to a preferred embodiment of the present invention, in step (3), the molar ratio of sulfonate dehydroabietin alcohol polyoxyethylene ether to the disiloxane represented by formula (3) is 2-3:1.

[0060] In the present invention, the third contact conditions have a wide range of optional conditions. According to a preferred embodiment of the present invention, the third contact conditions include: a temperature of 50-70° C. and a time of 0.5-1 h.

[0061] In the present invention, the dosage of the amine solvent can be selected in a wide range. According to a preferred embodiment of the present invention, the volume ratio of the amine solvent to the sulfonate dehydroabietin alcohol polyoxyethylene ether is 1-8:1.

[0062] In the present invention, there is no particular limitation on the type of the amine solvent, as long as it is a basic amine solvent. Preferably, the amine solvent is pyridine.

[0063] The third aspect of the present invention provides an imbibition agent composition, which includes an anionic-nonionic surfactant and an anionic gemini surfactant; the anionic gemini surfactant includes at least one of the rosin polyether gemini sulfonates described in the present invention. The rosin polyether gemini sulfonate can be compounded with an anionic-nonionic surfactant to form a composition with super strong interfacial properties and wettability change properties, greatly reducing the critical micelle concentration and improving the oil displacement efficiency of the composition. The imbibition agent composition described in the present invention can improve the volume expansion parameters, reduce the oil-water interfacial tension, and improve the recovery rate in oil displacement applications.

[0064] In the present invention, the molar ratio of the anionic gemini surfactant to the anionic-nonionic surfactant can be selected in a wide range. According to a preferred embodiment of the present invention, the molar ratio of the anionic gemini surfactant to the anionic-nonionic surfactant is 1:0.01-1000; preferably 1:0.1-20, more preferably 1:1-20.

[0065] In the present invention, there is no special requirement for the type of the anionic-nonionic surfactant. The following is an exemplary description of the implementation of the present invention, but the present invention is not limited to this scope.

[0066] According to one embodiment of the present invention, the anionic-nonionic surfactant is a fatty alcohol anionic-nonionic surfactant; preferably, the anionic-nonionic surfactant is selected from at least one of the fatty alcohol polyoxyethylene / polyoxypropylene ether salts shown in formula (2);

[0067]

[0068] Wherein, in formula (2), R5 is selected from C4-C22 alkyl;

[0069] R6 is SO3M1 or COOM1, M1 is selected from a cation or a cationic group that makes the molecule represented by formula (2) electrically neutral;

[0070] a is the addition number of ethoxy groups EO, which is an integer of 0-30; b is the addition number of propoxy groups, which is an integer of 0-20; and a and b are not 0 at the same time.

[0071] According to a preferred embodiment of the present invention, in formula (2), R5 is selected from C8-C16 alkyl groups.

[0072] According to a preferred embodiment of the present invention, in formula (2), M1 is selected from any one of alkali metals, alkaline earth metals or ammonium ions, preferably any one of Na, K or NH4.

[0073] According to a preferred embodiment of the present invention, in formula (2), the sum of a and b is not higher than 50, preferably the sum of a and b is 10-30.

[0074] According to a preferred embodiment of the present invention, the anionic-nonionic surfactant is selected from at least one of the sulfonates and / or carboxylates of tridecyl alcohol polyoxyethylene ether (10EO), the sulfonates and / or carboxylates of tridecyl alcohol polyoxyethylene ether (5EO), the sulfonates and / or carboxylates of tridecyl alcohol polyoxyethylene ether (5EO) polyoxypropylene (2PO), the sulfonates and / or carboxylates of dodecyl alcohol polyoxyethylene ether (3EO), the sulfonates and / or carboxylates of dodecyl alcohol polyoxyethylene ether (3EO) polyoxypropylene (2PO), and the sulfonates and / or carboxylates of dodecyl alcohol polyoxyethylene ether (5EO).

[0075] According to a preferred embodiment of the present invention, in the absorbing agent composition, the anionic-nonionic surfactant is selected from at least one of the rosin polyether gemini sulfonates described in formula (1-4), wherein m is an integer of 10-30. Preferably, it is a mixture of rosin polyether gemini sulfonates in which m=20 and m=30 in formula (1-4), and more preferably, the molar ratio of the two is 0.5-2;

[0076]

[0077] In formula (1-4), the definitions of m and M are the same as those in formula (1).

[0078] In the present invention, it is sufficient to mix the components of the imbibition composition. According to a preferred embodiment of the present invention, the fourth aspect of the present invention provides a method for preparing the imbibition composition of the present invention, which comprises: mixing the anionic gemini surfactant and the anionic-nonionic surfactant.

[0079] The fifth aspect of the present invention provides an oil-displacing agent, which includes: the oil-displacing agent includes the imbibition agent composition described in the present invention and water.

[0080] In the present invention, in the oil-displacing agent, the mass ratio of the sorbent composition to water can be selected in a wide range. According to a preferred embodiment of the present invention, in the oil-displacing agent, the mass ratio of the sorbent composition to water is not greater than 10:100; preferably, the mass ratio of the sorbent composition to water is not greater than 1:100; more preferably, the mass ratio of the sorbent composition to water is 0.05-0.3:100.

[0081] In the present invention, the selection range of the mineralization applicable to the above-mentioned imbibing agent composition and oil displacement composition of the present invention is relatively wide. According to a preferred embodiment of the present invention, the mineralization of water is 0-25wt%, and preferably, the concentration of calcium and magnesium ions is 2000mg / L.

[0082] A sixth aspect of the present invention provides an application of the imbibition agent composition of the present invention or the oil displacement agent of the present invention in oil reservoir exploitation; preferably, an application in shale oil reservoir development.

[0083] The present invention will be described in detail below through examples.

[0084] The reagent raw materials used in the embodiments of the present invention can be obtained from commercial sources or can be prepared according to the preparation methods disclosed in the prior art. For example, the raw materials tridecyl alcohol polyoxyethylene ether (10EO), dehydroabietyl alcohol, and 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane are used to prepare the compound shown in formula (1-4).

[0085] 1. The test method of the present invention and the equipment used in the test are as follows:

[0086] (1) The oil-water interfacial tension was measured using an American TX-500C spinning drop interfacial tension meter.

[0087] (2) Imbibition experiment: A sandstone core with a diameter of 25 mm and a permeability of 10 mD was aged in crude oil for 14 days and an imbibition experiment was conducted using an Amott Cell.

[0088] (3) The determination method of the solubilization parameters is:

[0089] Phase state experiments are mainly carried out by the glass capillary method. A certain amount of surfactant solution and crude oil are added to a capillary sealed at one end according to a water-to-oil ratio (WOR) of 1:1, and the liquid levels of the surfactant solution and crude oil and the mass of each added are recorded. Then the glass capillary is sealed with an acetylene-oxygen flame or epoxy resin glue and immersed in a 10 ml oil bath glass test tube filled with silicone oil, and placed in a metal bath (Hanuo Instruments) and heated at a reservoir temperature of 52°C. The test tube must first be shaken manually or mechanically to mix the oil and water phases evenly, and then balanced in a constant temperature metal bath for several days to weeks until the oil and water levels no longer change. The solubilization parameters (SP) of the oil phase and the water phase can be calculated based on the changes in the oil-water interface level in the microemulsion:

[0090]

[0091] Where V i is the volume of the aqueous or oil phase in the microemulsion, V s is the volume of surfactant. There are three assumptions in the calculation of SP parameters: the total volume of oil and water remains unchanged after mixing; all surfactants are in the microemulsion phase; the volume of surfactant is equal to its mass.

[0092] (4) The oil washing rate determination method comprises the following steps:

[0093] 1) Preparation of standard oil solution

[0094] Weigh 0.5g (accurate to 0.0001g) of artificial oil pollution and transfer it into a 100mL volumetric flask, dissolve it in petroleum ether with a boiling range of 60℃-90℃, and dilute it to the scale. The oil concentration of this solution is 5.0mg / mL.

[0095] 2) Drawing of standard curve

[0096] Use a pipette to transfer 0.0mL, 0.2mL, 0.4mL, 0.6mL, 0.8mL, 1.0mL, 1.2mL, and 1.4mL of standard oil solution into 8 50mL clean volumetric flasks, respectively, and dilute to the scale with petroleum ether with a boiling range of 90℃-120℃. Use petroleum ether with a boiling range of 90℃-120℃ as the blank, measure the absorbance on a spectrophotometer with a wavelength of 225nm and a 1cm colorimetric dish, and draw a standard curve based on the measured absorbance values ​​and the corresponding oil content.

[0097] 3) Preparation of oil sands

[0098] Weigh 3.675g crude oil into a 250mL beaker, add 10mL petroleum ether with a boiling range of 60℃-90℃ to dissolve the artificial oil, add 156.260g quartz sand to the solution, stir evenly to mix the sand and oil, heat and stir in a water bath at 80℃-90℃ for more than 0.5h, evaporate the petroleum ether to obtain oil sand.

[0099] 4) Sample preparation

[0100] The detergent sample was prepared into distilled water solutions with mass fractions of 0.3% and 1% for later use.

[0101] 5) Weigh 3.0g of oil sand into a 50mL blue-capped bottle, add 10mL of the prepared sample, place the blue-capped bottle in a 60℃ constant temperature water bath, take out the blue-capped bottle every 15 minutes and gently rotate it 10 times, then place it in the water bath again, place it for a total of 1 hour, take it out, shake it and place it on the colorimetric stand. Carefully pour off the washing solution.

[0102] 6) Rinse the remaining detergent solution in the blue-cap bottle with distilled water until the washing liquid becomes transparent.

[0103] 7) Place the rinsed blue-capped bottle with oil sand in an oven at (105±1)℃ and dry for 4 hours. Take it out and place it in a desiccator to room temperature.

[0104] 8) Add 50 mL of petroleum ether with a boiling range of 90°C-120°C to the blue-capped bottle and shake it thoroughly. Aspirate the petroleum ether solution, measure the absorbance on a spectrophotometer, and find out the residual oil content in the blue-capped bottle on the standard curve.

[0105] 9) Calculation of oil washing rate

[0106] The oil washing rate is calculated according to the following formula:

[0107]

[0108] In the formula: X is the oil washing rate; K is the mass fraction of oil in oil sand, %; W0 is the mass of the oil sand, g; W1 is the residual oil content of the oil sand in the blue cap bottle, g.

[0109] (5) The critical micelle concentration is determined by using a Kruss 100 surface tension meter and the hanging plate method to determine the change in surface tension of the surfactant in water with concentration at room temperature, and the CMC value of the surfactant is obtained.

[0110] Preparation Example 1

[0111] (1) The molar ratio of dehydroabietin alcohol to ethylene oxide is 1:10, and dehydroabietin alcohol ethylene oxide and a sodium hydroxide catalyst (the amount used is 0.5wt% of the dehydroabietin alcohol) are mixed and reacted at a reaction temperature of 150° C. and a reaction pressure of 3 MPa to obtain alkyl dehydroabietin alcohol polyoxyethylene ether;

[0112] (2) dehydroabietin amine polyoxyethylene ether and concentrated sulfuric acid (concentration of 98 wt%) were reacted at a molar ratio of 1:20 based on sulfuric acid at -1°C for 0.8 h to obtain sulfonated dehydroabietin alcohol polyoxyethylene ether, which was then neutralized with sodium hydroxide solution to obtain sulfonate dehydroabietin alcohol polyoxyethylene ether;

[0113] (3) Pyridine and sulfonate dehydroabietin polyoxyethylene ether were added in a volume ratio of 5:1 as solvent, and the molar ratio of sulfonate dehydroabietin polyoxyethylene ether and 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane was 2:1, and the reaction was carried out at 58°C for 0.8h.

[0114] The rosin polyether gemini sulfonate represented by formula (1-4) is obtained, where m=10 and M is Na.

[0115] Preparation Example 2

[0116] (1) The molar ratio of dehydroabietin alcohol to ethylene oxide is 1:20, and dehydroabietin alcohol ethylene oxide and a sodium hydroxide catalyst (in an amount of 2 wt% of the dehydroabietin alcohol) are mixed and reacted at a reaction temperature of 140° C. and a reaction pressure of 5 MPa to obtain alkyl dehydroabietin alcohol polyoxyethylene ether;

[0117] (2) the molar ratio of dehydroabietin amine polyoxyethylene ether to concentrated sulfuric acid (concentration of 98 wt%) is 1:50, and the reaction is carried out at -10°C for 0.3 h to obtain sulfonated dehydroabietin alcohol polyoxyethylene ether, which is then neutralized with sodium hydroxide solution to obtain sulfonate dehydroabietin alcohol polyoxyethylene ether;

[0118] (3) Pyridine and sulfonate dehydroabietin polyoxyethylene ether were added in a volume ratio of 5:1 as solvent, and the molar ratio of sulfonate dehydroabietin polyoxyethylene ether and 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane was 3:1, and the reaction was carried out at 50°C for 0.5h.

[0119] The rosin polyether gemini sulfonate represented by formula (1-4) is obtained, where m=20 and M is Na.

[0120] Preparation Example 3

[0121] (1) The molar ratio of dehydroabietin alcohol to ethylene oxide is 1:30, and dehydroabietin alcohol ethylene oxide and a sodium hydroxide catalyst (the amount used is 0.1wt% of the dehydroabietin alcohol) are mixed to react at a reaction temperature of 200° C. and a reaction pressure of 1 MPa to obtain alkyl dehydroabietin alcohol polyoxyethylene ether;

[0122] (2) reacting dehydroabietin amine polyoxyethylene ether with concentrated sulfuric acid (concentration of 98 wt%) at a molar ratio of 1:10 at 0°C for 1 h to obtain sulfonated dehydroabietin alcohol polyoxyethylene ether, and then neutralizing with sodium hydroxide solution to obtain sulfonate dehydroabietin alcohol polyoxyethylene ether;

[0123] (3) Pyridine and sulfonate dehydroabietin polyoxyethylene ether were added in a volume ratio of 5:1 as solvent, and the molar ratio of sulfonate dehydroabietin polyoxyethylene ether and 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane was 2.5:1, and the reaction was carried out at 70°C for 1 hour.

[0124] The rosin polyether gemini sulfonate represented by formula (1-4) is obtained, where m=30 and M is Na.

[0125] Examples 1-3 and Comparative Example 1

[0126] Preparation of oil displacement agent composition

[0127] Example 1-3, the anionic surfactant prepared in Preparation Example 1-3, where m is 10, 20, and 30, respectively, is mixed with tridecyl alcohol polyoxyethylene ether (10EO) sulfonate in a molar ratio of 1:10 to obtain an imbibing agent composition, and the mixture is dissolved in deionized water at a temperature of 20°C to obtain an oil-displacing agent having a composite surfactant mass concentration of 0.1wt%.

[0128] Embodiment 4-5

[0129] The anionic surfactant prepared in Preparation Example 2 (m=20, M is Na; rosin-based anionic polyoxyethylene ether (20EO) sodium sulfonate) and tridecyl alcohol polyoxyethylene ether (10EO) sulfonate were mixed in a molar ratio of 9:91 and 2:98, respectively, to obtain an imbibing agent composition, and dissolved in deionized water at a temperature of 20°C to obtain an oil-displacing agent with a composite surfactant mass concentration of 0.1wt%.

[0130] Comparative Example 1

[0131] Tridecyl alcohol polyoxyethylene ether (10EO) sulfonate was dissolved in deionized water at 20° C. to obtain an oil displacement agent with a surfactant mass concentration of 0.1 wt %.

[0132] The critical micelle concentration (CMC) of the oil displacing agents of Examples 1-5 and Comparative Example 1 was measured at 20° C. The test results are shown in Table 1.

[0133] Table 1

[0134]

[0135]

[0136] The results in Table 1 show that the anionic gemini surfactants provided in Examples 1-5 have extremely low critical micelle concentrations and ultra-low surface tensions, and can reduce the critical micelle concentration of the compound system.

[0137] Embodiment 6-9

[0138] Rosin-based anionic polyoxyethylene ether (20EO) sodium sulfonate and tridecyl alcohol polyoxyethylene ether (10EO) sodium sulfonate were mixed in molar ratios of 9:91, 2:98, 5:95 and 50:50, respectively, to obtain an imbibing agent composition, and the mixture was dissolved in a 5wt% NaCl aqueous solution at a temperature of 20°C to obtain an oil-displacing agent with a mass concentration of 0.1wt%.

[0139] Comparative Examples 2-3

[0140] Rosin-based anionic polyoxyethylene ether (20EO) sodium sulfonate and tridecyl alcohol polyoxyethylene ether (10EO) sodium sulfonate were dissolved in a 5% NaCl aqueous solution at 20° C. to obtain an oil displacement agent with a mass concentration of 0.1 wt %.

[0141] At 20°C, the performance of the oil displacing agents described in Examples 6-9 and Comparative Examples 2-3 and Shengli crude oil was tested, as shown in Table 2.

[0142] At 20°C, the imbibition efficiency of the oil displacing agents described in Examples 6-9 and Comparative Examples 2-3 was tested. The imbibition test results are shown in Table 2.

[0143] The oil washing ability of the samples in Examples 6-9 was tested to further verify the wetting reversal ability of the sorbent on the oil sand surface. The results are shown in Table 2.

[0144] Table 2

[0145]

[0146]

[0147] The results in Table 2 indicate that the oil displacement agent of the present invention can improve the volume expansion parameter and reduce the oil-water interfacial tension in oil displacement applications.

[0148] The results in Table 2 indicate that the imbibition composition of the present invention can improve the imbibition efficiency relative to a single agent.

[0149] The oil washing rate results in Table 2 indicate that the oil displacement agent composition of the present invention has a strong wetting reversal ability on the surface of oil sands.

[0150] Example 10

[0151] The cationic surfactant (m=20, M is Na) represented by formula (1-4), i.e., rosin-based anionic polyoxyethylene ether (20EO) sodium sulfonate, the cationic surfactant (m=30, M is Na) represented by formula (1-4), i.e., rosin-based anionic polyoxyethylene ether (30EO) sodium sulfonate and tridecyl alcohol polyoxyethylene ether (10EO) sodium sulfonate were mixed in a molar ratio of 5:4:91 to obtain an imbibing agent composition, and dissolved in a 5wt% NaCl aqueous solution at a temperature of 20°C to obtain an oil displacement agent with a mass concentration of 0.1wt%. The test results are shown in the following table.

[0152]

[0153]

[0154] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A rosin polyether gemini sulfonate, characterized in that: The structural formula of the rosin polyether gemini sulfonate is shown in formula (I); In formula (1), m is an integer of 0-50; M is selected from a cation or a cationic group that makes the molecule represented by formula (1) electrically neutral; R1, R2, R3, and R4 are each independently selected from a C1-C4 alkyl group.

2. The rosin polyether gemini sulfonate according to claim 1, wherein m is an integer from 20 to 30; and / or M is selected from any one of alkali metal, alkaline earth metal or ammonium ion, preferably any one of Na, K or NH4; R1, R2, R3 and R4 are all methyl groups.

3. The method for preparing the rosin polyether gemini sulfonate according to claim 1 or 2, characterized in that: The method includes: (1) in the presence of a first catalyst, dehydroabietin alcohol and ethylene oxide are brought into first contact to obtain dehydroabietin alcohol polyoxyethylene ether; (2) the dehydroabietin alcohol polyoxyethylene ether is contacted with a sulfuric acid source for a second time to obtain sulfonated dehydroabietin alcohol polyoxyethylene ether, and then neutralized with an alkaline substance to obtain sulfonate dehydroabietin alcohol polyoxyethylene ether; (3) in the presence of an amine solvent, the sulfonate dehydroabietin alcohol polyoxyethylene ether is contacted with the disiloxane represented by formula (3) to obtain a rosin polyether gemini sulfonate; In formula (3), R1, R2, R3, and R4 are each independently selected from a C1-C4 alkyl group; X1 and X2 are each independently selected from one of the halogens.

4. The preparation method according to claim 3, wherein In step (1), The molar ratio of dehydroabietyl alcohol to ethylene oxide is 1:1-50, preferably 1:10-30; and / or The dosage of the first catalyst is 0.001wt%-2.0wt% of the dosage of dehydroabietyl alcohol; and / or The first catalyst is selected from at least one of an alkali metal hydroxide, a DMC bimetallic polyether catalyst and a phosphazene catalyst; and / or The first contact conditions include: a temperature of 140-200° C. and a pressure of 0-5 MPa; and / or In step (2), The molar ratio of dehydroabietin polyoxyethylene ether to sulfuric acid is 1:10-50; and / or The second contact conditions include: temperature of -10°C to 0°C, time of 0.1-1h; In step (3), The molar ratio of sulfonate dehydroabietin alcohol polyoxyethylene ether to the disiloxane represented by formula (3) is 2-3:1; and / or The volume ratio of the amine solvent to the sulfonate dehydroabietin alcohol polyoxyethylene ether is 1-8:1; and / or The amine solvent is pyridine; and / or The third contact conditions include: temperature of 50-70° C. and time of 0.5-1 h.

5. A wicking agent composition, characterized in that The imbibition agent composition comprises an anionic-nonionic surfactant and an anionic gemini surfactant; The anionic gemini surfactant comprises at least one of the rosin polyether gemini sulfonates according to claim 1 or 2.

6. The imbibing agent composition according to claim 5, wherein The molar ratio of the anionic gemini surfactant to the anionic-nonionic surfactant is 1:0.01-1000; preferably 1:0.1-20; Preferably, the anionic gemini surfactant is a mixture of a rosin polyether gemini sulfonate with m=20 in formula (1-4) and a rosin polyether gemini sulfonate with m=30 in formula (1-4), and more preferably the molar ratio of the two is 0.5-2; In formula (1-4), m and M are defined as in claim 1 or 2.

7. The imbibing agent composition according to claim 5 or 6, wherein The anionic-nonionic surfactant is a fatty alcohol anionic-nonionic surfactant; Preferably, the anionic-nonionic surfactant is selected from at least one of the fatty alcohol polyoxyethylene / polyoxypropylene ether salts shown in formula (2); Wherein, in formula (2), R5 is selected from C4-C22 alkyl; R6 is SO3M1 or COOM1, M1 is selected from a cation or a cationic group that makes the molecule represented by formula (2) electrically neutral; a is the addition number of ethoxy groups EO, which is an integer of 0-30; b is the addition number of propoxy groups, which is an integer of 0-20; and a and b are not 0 at the same time.

8. The imbibing agent composition according to claim 7, wherein R5 is selected from C8-C16 alkyl; and / or M1 is selected from any one of alkali metal, alkaline earth metal or ammonium ion, preferably any one of Na, K or NH4; and / or The sum of a and b is not higher than 50, preferably the sum of a and b is 10-30; Preferably, the anionic-nonionic surfactant is selected from at least one of sulfonates and / or carboxylates of tridecyl alcohol polyoxyethylene ether (10EO), sulfonates and / or carboxylates of tridecyl alcohol polyoxyethylene ether (5EO), sulfonates and / or carboxylates of tridecyl alcohol polyoxyethylene ether (5EO) polyoxypropylene (2PO), sulfonates and / or carboxylates of dodecyl alcohol polyoxyethylene ether (3EO), sulfonates and / or carboxylates of dodecyl alcohol polyoxyethylene ether (3EO) polyoxypropylene (2PO), and sulfonates and / or carboxylates of dodecyl alcohol polyoxyethylene ether (5EO).

9. The method for preparing the imbibition agent composition according to any one of claims 5 to 8, characterized in that: The method comprises: mixing the anionic gemini surfactant and the anionic-nonionic surfactant.

10. An oil displacing agent, characterized in that: The oil-displacing agent comprises: the oil-displacing agent comprises the imbibition agent composition according to any one of claims 5 to 8 and water.

11. The oil-displacing agent according to claim 10, wherein In the oil displacement agent, the mass ratio of the imbibition agent composition to water is not greater than 10:100; Preferably, the mass ratio of the absorbing agent composition to water is not greater than 1:100; More preferably, the mass ratio of the sorbent composition to water is 0.05-0.3:100; and / or The mineralization degree of water is 0-25 wt %, and preferably, the concentration of calcium and magnesium ions is 2000 mg / L.

12. Use of the imbibition agent composition according to any one of claims 5 to 8 or the oil displacement agent according to claim 10 or 11 in oil reservoir exploitation.

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