CN115651622B - Novel Gemini surfactant, preparation method thereof, pollution remediation liquid and application thereof - Google Patents
Novel Gemini surfactant, preparation method thereof, pollution remediation liquid and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of oil and gas reservoir restoration, and discloses a novel Gemini surfactant and a preparation method thereof, a pollution restoration liquid and application thereof, wherein the novel Gemini surfactant has a structure shown in figure 12: wherein R is-C 12 H 25 N is 5; the novel Gemini surfactant has very low critical micelle concentration, good capability of reducing surface tension, and polydispersity, can effectively dissolve organic scales, and achieves the purposes of cleaning and repairing a reservoir.
Description
Technical Field
The invention relates to the technical field of oil and gas reservoir restoration, in particular to a novel Gemini surfactant, a preparation method thereof, a pollution restoration liquid and application thereof.
Background
At present, in domestic oil and gas fields, due to drilling, fracturing and other operations, various kinds of pollution are easily caused in positions close to a well wall zone, a shaft and the like, for example, drilling fluid is leaked and flows into a stratum, paraffin, asphalt and the like can be adsorbed and blocked in a pore throat of the close well zone, and damage is caused to a reservoir.
The existing blockage removal methods can be roughly divided into three types: mechanical unblocking, physical unblocking and chemical unblocking. The mechanical method cannot completely realize blockage removal at one time, and requires technical personnel to operate related equipment, so that the risk is high, and the cost is high. The effective period of blockage removal and repair by a physical method is short, and the method is not suitable for some deep polluted and blocked areas. The chemical method mainly aims at solving the problems that the variety and the performance of the repair liquid are single, and various pollutants cannot be repaired and removed.
Therefore, the novel Gemini surfactant has very low critical micelle concentration, good capability of reducing surface tension and polydispersity, can effectively dissolve organic scales, and achieves the purposes of cleaning and repairing a reservoir stratum.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a novel Gemini surfactant, a preparation method thereof, a pollution remediation liquid and application thereof.
The purpose of the invention is realized by the following technical scheme:
in one aspect, the present invention provides a novel Gemini surfactant having the following formula (1):
wherein R is-C 12 H 25 And n is 5.
Furthermore, the novel Gemini surfactant takes phthalic anhydride as a skeleton, and is connected with two hydrophilic tail chains through esterification reaction.
The novel Gemini surfactant is a nonionic Gemini surfactant, is not dissociated into an ionic state in water, has high stability, is not easily influenced by acid, alkali and salt, and has strong hard water resistance; and has high surface activity, low critical micelle concentration, large micelle aggregation number, strong solubilization and good detergency.
In another aspect, the invention provides a preparation method of a novel Gemini surfactant, which comprises the following steps:
A. according to a molar ratio of 1:5:0.1 weighing phthalic anhydride, fatty alcohol-polyoxyethylene ether and HFDAIL (3, 3' - (2, 2-bis (hydroxymethyl) propane-1, 3-diyl) bis (1-methyl-1-imidazol-3-ium) sulfonate);
the fatty alcohol-polyoxyethylene ether is RO (CH) 2 CH 2 O) n H, wherein R is-C 12 H 25 N is 5;
B. b, adding the phthalic anhydride and the fatty alcohol-polyoxyethylene ether weighed in the step A into a three-neck glass flask, stirring, slowly adding HFDAIL, and reacting at constant temperature to obtain a crude product;
C. and D, evaporating the crude product obtained in the step B to remove the solvent, washing the crude product with methanol for three times, and finally putting the crude product into a constant-temperature oven to dry the crude product to constant weight to obtain the novel Gemini surfactant.
HFDAIL is used as a catalyst for esterification reaction of phthalic anhydride and fatty alcohol-polyoxyethylene ether.
In one embodiment of this embodiment, in the step B, the reaction temperature is 125 ℃ and the reaction time is 10 hours. The temperature is controlled at 125 ℃ to ensure that the reaction is sufficient, and ether bonds in the fatty alcohol are not easy to break, so that byproducts are generated; the reaction time was controlled at 10h in order to achieve higher conversion.
The fatty alcohol-polyoxyethylene ether has shorter carbon chain and smaller molecular weight, and the waste liquid after reaction has small pollution and is easier to treat.
The fatty alcohol-polyoxyethylene ether is a special nonionic surfactant, has low surface interfacial tension, wetting reversal capability, easy degradation capability and good compatibility, is introduced into the novel Gemini surfactant to serve as a hydrophilic tail chain, so that the novel Gemini surfactant has excellent performances such as low surface interfacial tension, wetting reversal capability and the like, has degradability, and belongs to an environment-friendly surfactant.
In one embodiment of this embodiment, in the step C, the constant temperature drying temperature is 70 ℃.
In one embodiment of this embodiment, in step C, the solvent is removed from the crude product by evaporation using a rotary evaporator.
On the other hand, the invention provides a pollution remediation liquid, which is prepared by mixing the novel Gemini surfactant and water;
and in the pollution remediation liquid, the concentration of the novel Gemini surfactant is 30 to 80mg/L.
In a preferred embodiment of the present scheme, the concentration of the novel Gemini surfactant in the pollution remediation solution is 50mg/L.
In yet another aspect, the invention provides the use of a fluid for remediation of contamination of a reservoir in a near wellbore region.
According to the invention, the novel Gemini surfactant and water are prepared into a repair liquid, the interior of a formed micelle is formed by gathering hydrophobic tail chains, the exterior of the micelle is a connecting chain end, in the process of washing asphaltene, phenyl promotes deposited asphalt to be rapidly dissolved, and meanwhile, the novel Gemini surfactant also has alkyl, ester, ether and other groups in the molecule, has strong similar compatibility with crude oil, has obvious permeability, and further effectively dissolves various organic scales; and dissolved organic matter molecules enter the micelle through the affinity effect with hydrophobic tail chains in the micelle, so that the cleaning effect of the novel Gemini surfactant on deposited organic scales is enhanced.
The asphaltene is a complex mixture composed of various complex macromolecular hydrocarbons and non-metallic derivatives thereof, a crude oil balance system is damaged, and chemical bonds between colloids wrapping the asphaltene and the asphaltene are easily broken, so that the asphaltene is separated out and is stacked in a reservoir layer to form deposition, and serious influence is generated on development; and when underground operation is carried out, the conditions that drilling fluid leaks and flows into the ground seam and the like can occur, the stratum is polluted, the blockage is caused, and the effective permeability of the stratum is reduced.
According to the invention, the novel Gemini surfactant is phthalate, and an ester group of the novel Gemini surfactant and an asphalt molecule are easy to form hydrogen bonds, so that the hydrogen bonds among sheet structures can be damaged, and more importantly, a benzene ring is introduced into the novel Gemini surfactant, and can be adsorbed into the sheet structures formed by the asphaltene due to the principle of similarity and intermiscibility, so that the association structure of the asphaltene is damaged under various synergistic effects, and further, the scheme can thoroughly remove the deposited asphaltene without adding auxiliary components.
Further, the application of the pollution remediation liquid is to inject the pollution remediation liquid into a reservoir near the wellbore zone after pollution.
The novel Gemini surfactant has two fatty alcohol chains and has the capabilities of reducing surface interfacial tension, wetting inversion and the like, so that the novel Gemini surfactant can reduce the interfacial tension of fluid, improve the wettability of rock, improve the fluidity of formation fluid, remove substances blocked in pores to a great extent, relieve reservoir pollution and prolong the service life of an oil well.
The inventor finds that in the pollution remediation liquid prepared by the novel Gemini surfactant, the novel Gemini surfactant molecules can form micelles with different particle sizes in an aqueous solution (the micelles with different particle sizes have different dispersivity), so that in the pollution remediation liquid, the Gemini surfactant has polydispersity, the dispersion characteristic of the Gemini surfactant can be utilized, the remediation liquid can further achieve the effect of solubilizing pollutants, and the cleaning purpose is achieved.
The chain length of the introduced fatty alcohol-polyoxyethylene ether is shorter, but because the two head groups with the same charge are drawn close by the linking group, the hydrophobic interaction in molecules and among molecules is enhanced, so that the prepared pollution remediation liquid can achieve an ideal effect at a lower concentration; in the scheme, the novel Gemini surfactant is not easy to form wormlike micelles or dendritic micelles due to short chain length, and further is not easy to wind to form a net structure and to be connected in series between micelles and vesicles, so that the aqueous solution is thickened, and the using effect is influenced.
In the scheme, the connecting chain is a rigid group, which is more favorable for the molecules of the novel Gemini surfactant to form micelles with larger aggregation radius, so that the resistance of organic matters entering the micelles is smaller, and the organic pollutants with large viscosity and molecular weight are favorably dissolved.
The beneficial effects of the invention are: (1) The novel Gemini surfactant is synthesized by using fatty alcohol-polyoxyethylene ether and phthalic anhydride through an esterification reaction, has very low critical micelle concentration, has very good capability of reducing surface tension, has polydispersity, can effectively dissolve organic scales, and achieves the purposes of cleaning and repairing a reservoir without adding an auxiliary agent;
(2) According to the invention, the novel Gemini surfactant is synthesized by using the fatty alcohol-polyoxyethylene ether and phthalic anhydride through an esterification reaction, the preparation process is green and simple, the repair cost is low, the economic benefit is realized, the fatty alcohol-polyoxyethylene ether has a shorter carbon chain and a smaller molecular weight, and the waste liquid after the reaction has less pollution and is easier to treat.
Drawings
FIG. 1 is an infrared spectrum of a repair liquid of the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of the repair liquid of the present invention;
FIG. 3 is a graph of surface tension of a repair liquid according to the present invention as a function of concentration;
FIG. 4 is a graph of oil-water interfacial tension of the healing fluid of the present invention as a function of concentration;
FIG. 5 is a graph of the contact angle of the repair liquid as a function of concentration;
FIG. 6 is a Zeta potential diagram for various concentrations of the repair fluid of the present invention;
FIG. 7 is a schematic illustration of the particle size distribution of the repair fluid of the present invention;
FIG. 8 is a graph of viscosity and viscosity reduction rate as a function of strength of the remediation fluid according to the present invention;
FIG. 9 is a diagram of the oil wash process of the present invention;
FIG. 10 is a graph of LF injection pressure for the present invention;
FIG. 11 is SEM images before and after the repairing liquid cleans the core (in the images, a and c are schematic diagrams of the contaminated core, and b and d are schematic diagrams of the cleaned core);
FIG. 12 is a schematic diagram of the structural formula of the novel Gemini surfactant of the present invention.
Detailed Description
The technical solutions of the present invention are further described in detail below with reference to the accompanying drawings, but the scope of the present invention is not limited to the following. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are commercially available, and are not indicated by manufacturers.
In the following examples, example 1 is a preparation example of a novel Gemini surfactant, example 2 is an experimental example of preparing a repair solution with a concentration of 50mg/L by using the novel Gemini surfactant prepared in example 1 to simulate the pollution repair of a reservoir in a near wellbore area, and example 3 is an experimental example of simulating the pollution repair of a reservoir in a near wellbore area by using the repair solution with a concentration of 30mg/L and 70mg/L of the novel Gemini surfactant.
Example 1
A preparation method of a novel Gemini surfactant comprises the following steps:
A. weighing 1.48g of phthalic anhydride, 29.1mL of fatty alcohol-polyoxyethylene ether and 0.46g of HFDAIL according to the molar ratio;
B. b, adding the phthalic anhydride and the fatty alcohol-polyoxyethylene ether weighed in the step A into a three-neck glass flask together, stirring, slowly adding HFDAIL, and carrying out constant-temperature reaction, wherein the reaction temperature is controlled at 125 ℃, and the reaction time is controlled at 10 hours, so as to obtain a crude repair liquid product;
C. and D, evaporating the solvent of the crude product obtained in the step B by using a rotary evaporator, washing the product three times by using methanol, putting the product into a constant-temperature oven, and drying the product at 70 ℃ to constant weight to obtain the novel Gemini surfactant.
The novel Gemini surfactant prepared in this example was characterized by its red appearance and hydrogen spectrum:
infrared characterization
Taking a small amount of dried KBr, and tabletting by using an infrared tablet press; the novel Gemini surfactant prepared in the embodiment is smeared on a KBr sheet and dried; infrared spectrum scanning is carried out by a WQF-520 type infrared spectrometer, the background of an instrument is collected, and an infrared spectrogram of the novel Gemini surfactant is shown in figure 1.
FIG. 1 is an infrared spectrum of the novel Gemini surfactant, as can be obtained from FIG. 1, at 2950 cm -1 ，2900 cm -1 The nearby absorption peaks are symmetric and asymmetric stretching vibration peaks of-CH respectively; at 1730 cm -1 The nearby absorption peak is a C = O double-bond telescopic vibration seam; at 1600-1450cm -1 The nearby absorption peak band is the skeleton vibration peak of the benzene ring; 1110 cm of -1 The absorption peak in the vicinity is an ether bond stretching vibration peak.
Characterization by hydrogen spectroscopy
(1) Adding the novel Gemini surfactant prepared in the embodiment into a nuclear magnetic tube; (2) adding a solvent into the nuclear magnetic tube, and standing until the solvent is completely dissolved; (3) scanning hydrogen spectrum of the novel Gemini surfactant by liquid nuclear magnetic resonance (Bruker) with frequency of 400 Hz, wherein the hydrogen spectrum of the novel Gemini surfactant is respectively shown in figure 2, figure 2 is hydrogen spectrum of the novel Gemini surfactant, chemical shift/ppm is used as abscissa, absorption peak intensity is used as ordinate, and delta can be obtained from figure 2 a =7.68 ppm proton chemical shift on benzene ring; delta. For the preparation of a coating b =4.39 ppm is-CH 2 =CH 2 -proton chemical shift; delta. For the preparation of a coating c =3.62 ppm is-CH 2 -proton chemical shift of O-; delta d =0.92 ppm-1.64 ppm is terminal-CH 2 -CH 3 Chemical shift of protons. A novel Gemini surfactant with the structure shown in fig. 12 is obtained.
Example 2
Reservoir repair performance
In this example, a contaminated columnar homogeneous core is used to simulate reservoir contamination in a near wellbore region, and the novel Gemini surfactant prepared in example 1 and fatty alcohol-polyoxyethylene ether are used as raw materials to perform a comparative experiment for pollution remediation.
The implementation steps are as follows: preparing a repairing solution with the concentration of 50mg/L, a fatty alcohol-polyoxyethylene ether solution and a certain amount of polluted liquid (m crude oil: m oil-based drilling fluid = 1; using a columnar homogeneous core (the middle and the outer side are 2.5 multiplied by 10 cm), loading the columnar homogeneous core into a core holder, injecting water at a constant speed (0.5 mL/min) until the pressure is stable, and calculating the water phase permeability k1; and (3) injecting the polluted liquid at the same flow rate until the pressure is stable, calculating the permeability k2 after pollution, injecting the repairing liquid at the same flow rate reversely until the pressure is stable, standing the obtained rock core for 500min, and testing the permeability of the rock core to obtain the permeability k3 after cleaning. Examples, comparative examples three experiments were repeated.
And calculating the core permeability recovery rate to judge the damage effect on the stratum, wherein the core permeability recovery rate = (permeability after cleaning/initial permeability) × 100%. The results are shown in Table 1, FIG. 11.
Table 1 permeability recovery testing experiment
As can be seen from Table 1, for the cores with different permeabilities, after pollution by a pollution source, the permeability of the core is reduced from about 220 mD to about 80 mD, after cleaning solution is reversely injected, the permeability of the core is recovered to different degrees, the recovery rate of the core group injected with LF is higher than 85%, the average recovery rate reaches 88.64%, the recovery rate of the core group injected with the fatty alcohol-polyoxyethylene ether solution is only about 65%, and the average recovery rate is 66.20%, so that the recovery rate of the permeability injected with the restoration solution is improved by 28.04% compared with the recovery rate of the permeability injected with the fatty alcohol-polyoxyethylene ether.
Fig. 10 is a graph showing the LF injection pressure in the group (1), and it can be seen from fig. 10 that the pressure slowly increases to be stable during water injection, and after the injection of the contamination source starts, the injection pressure gradually increases, and after the repair liquid is finally injected, the pressure starts to decrease and finally stabilizes. The reason for this is probably that after the pollution source is injected, the pollution source forms a blockage in the pore throat of the rock core, so that the injection pressure is increased, and after the repair liquid solution is injected, the pressure is reduced, probably because the repair liquid structure contains benzene rings, organic matter components in the pollution source can be dissolved to a certain extent, and because the repair liquid can effectively reduce surface interfacial tension, the blockage processed through the pore throat of the rock core can be effectively driven to flow out of the pore throat, so that the permeability of the rock core is recovered.
(2) The contaminated and cleaned columnar cores were cut to an end face of about 0.5 cm and subjected to scanning electron microscope testing, and the surface topography of the contaminated and cleaned cores was compared, with the results shown in FIG. 11,
FIG. 11 is SEM images before and after the repairing liquid cleans the core, wherein a and c in the SEM images are schematic diagrams of the contaminated core, and b and d in the SEM images are schematic diagrams of the cleaned core;
as is clear from a and b (200 times magnification) in fig. 11, the extremely wide range of dull surface color of the core was seen in a after the core had become contaminated due to the contamination source occupying the plugged pore throat passages, which itself is darker; and after the repairing liquid solution is cleaned, the pollution source is dissolved by the surfactant and then is driven to flow out of the pore throat, so that the surface of the most part of the rock core becomes clean and bright as can be seen in step b. As can be seen from c and d (magnified 10000 times) in fig. 11, after the larger magnification, it is seen from c that some pore throats are blocked by pollution sources after the core is polluted, so that the surface color of the core is dark and the appearance is fuzzy; as seen in d, the core after washing was bright and clear in surface and clear in morphology. Therefore, the Gemini surfactant (novel Gemini surfactant) prepared by the method can effectively dissolve pollutants attached to the pore throat of the rock core, so that the rock core permeability is improved, and the effect is obvious.
Example 3
In the embodiment, the novel Gemini surfactant prepared in the embodiment 1 is adopted to prepare the pollution remediation liquid with the concentration of 30mg/L and 70mg/L, and the pollution remediation of the reservoir in the near wellbore area is simulated.
First, repair solution solutions with concentrations of 30mg/L and 70mg/L and a certain amount of contaminated fluid (m crude oil: m oil-based drilling fluid = 1.
The experimental steps are as follows: the columnar homogeneous rock cores (the middle side is 2.5 multiplied by 10 cm) are used in the two groups of experiments, the columnar homogeneous rock cores are respectively arranged in a rock core holder, water is injected at a constant speed (0.5 mL/min) until the pressure is stable, and the water phase permeability k'1 of the two groups of experiments is calculated;
then, respectively injecting the pollution liquid at the same flow rate until the pressure is stable, calculating the permeability k '2 after two groups of experiments are polluted, respectively injecting two groups of remediation liquids with different concentrations at the same flow rate in a reverse direction until the pressure is stable, standing the obtained rock core for 500min, and testing the permeability of the rock core to obtain the permeability k'3 after two groups of experiments are cleaned.
And calculating the core permeability recovery rate to judge the damage effect on the stratum, wherein the core permeability recovery rate = (permeability after cleaning/initial permeability) = 100%. The results are shown in Table 2.
TABLE 2 30mg/L, 70mg/L repair liquid permeability recovery test
| 30mg/L repairing liquid | 70mg/L repair liquid | |
| Initial permeability k'1/mD | 223.8 | 216.8 |
| Permeability k'2/mD after contamination | 74.1 | 76.5 |
| Permeability k'3/mD after cleaning | 195.0 | 206.7 |
| Permeability recovery/% | 87.15 | 95.79 |
As can be seen from Table 2, the repairing solution solutions with the concentrations of 30mg/L and 70mg/L can effectively dissolve the pollutants attached to the pore throats of the rock core, so that the permeability of the rock core is improved.
Examples of the experiments
Experimental example 1
Surface active
The novel Gemini surfactant prepared in example 1 was formulated into repair solutions of different concentrations, and surface tension test was performed at (25. + -. 0.01) ℃ C. By using an integral interface parameter measuring system, and the results are shown in FIG. 3. From FIG. 3, it can be seen that the critical micelle concentration (cmc) of the repairing solution is 26 mg/L, and the corresponding γ cmc is 30.26 mN/m, and it can be known that the surface tension of the repairing solution at the critical micelle concentration is very low, and the surface tension can be effectively reduced.
The interfacial tension of the repair solution solutions with different concentrations in kerosene was measured using an integral interfacial parameter measurement system, and the results are shown in fig. 4. It can be seen from FIG. 4 that the concentration of the repairing solution is increased, the interfacial tension is rapidly decreased, and then the dosage is continuously increased after the concentration reaches cmc, so that the interfacial tension is not greatly changed. It can be seen that the repair liquid can effectively reduce the oil-water interfacial tension.
The glass sheet is soaked in an ethanol-kerosene system for 3 days and then taken out, the glass sheet is placed in repair liquid solutions with different concentrations and soaked for 12 hours, an appearance image of liquid drops dropping on the glass sheet is obtained through an interface parameter integrated measuring system, then the contact angle is calculated by applying digital image processing, and the result is shown in figure 5. It can be seen from FIG. 5 that the oleophilic treated glass plate measured a contact angle of 113.34 at a healing liquid concentration of 0mg/L; the contact angle measured is gradually smaller along with the increase of the concentration of the repair liquid, and when the concentration reaches cmc, the measured contact angle is 61.14 degrees; with the concentration continued to increase, there was little change in the contact angle. The repair liquid has wetting capacity and can change lipophilicity of the glass sheet into weak hydrophilicity.
Experimental example 2
Zeta potential and particle size
Zeta potential: grinding quartz sand into powder, washing with deionized water, drying, soaking in 20% n-heptane-crude oil system, and aging at 75 deg.C for 14d. And (4) leaching out quartz powder after aging, washing the powder with n-heptane until the washing liquid is colorless, and drying the powder in an oven for later use. Adding a proper amount of quartz powder into a novel Gemini surfactant solution to prepare 0.1% suspension, and soaking for 24 hours. The Zeta potential was determined using a laser particle sizer with electrodes. Granularity: the particle size distribution of the surfactant was determined using a laser particle sizer. Wherein the concentration of the novel Gemini surfactant is 1g/L.
The Zeta potential is a potential existing on a sliding surface of a diffusion electric double layer and has an important influence on properties of a solid surface. As can be seen from FIG. 6, the Zeta potential of the quartz powder measured without the addition of the repair liquid was-3.8 mV. With the continuous increase of the LF concentration, the Zeta potential of the quartz powder first drops and then tends to stabilize, but the overall change is not large. This is because, when the concentration of the repair liquid is low (< cmc), surfactant molecules are adsorbed on the surface of the quartz powder by hydrophobic interaction, and the Zeta potential of the quartz powder is decreased with the increase of the LF concentration. After the LF concentration reached cmc, the Zeta potential of the quartz powder started to stabilize because the adsorption reached saturation.
As can be seen from FIG. 7, the particle size distribution of the repairing liquid surfactant in water is between 60 nm and 500 nm, and the distribution is concentrated between 150 nm and 250 nm, which indicates that the novel Gemini surfactant can form micelle micelles with different sizes in an aqueous solution, and the dispersibility of the micelle micelles with different particle sizes is different, so that the novel Gemini surfactant has polydispersity. This is because the prepared solution has a mass concentration of 1g/L which is much higher than the critical micelle concentration (cmc =26 mg/L), and therefore, at this concentration, the micelle diameter generated by the surfactant is large, and the solution has a good solubilizing effect and can improve the dissolution of organic substances such as asphalt.
Experimental example 3
Viscosity reducing ability
The repairing liquid of the mass concentration gradient prepared by the novel Gemini surfactant prepared in the embodiment 1 is mixed with crude oil (the viscosity eta 1 is 1263.4 mpa.s) 6:4 mixing, stirring at 70 deg.C for 15 min, and testing viscosity to be eta 2. The viscosity reduction rate was calculated as follows:
according to the following steps of 6:4, preparing an oil-water emulsion, measuring the viscosity reduction rate at 70 ℃, and analyzing the influence of the mass concentration of the repairing liquid on the viscosity reduction performance, wherein the result is shown in fig. 8. As can be seen from fig. 8, the repairing liquid can effectively reduce the oil-water interfacial tension, so that the emulsion is gradually changed from a water-in-oil emulsified state to a water-in-oil external phase state, and the viscosity of the thick oil can be greatly reduced. When the concentration of the repairing liquid is 15 mg/L, the viscosity of the emulsion is reduced to about 250 mPa & s, when the concentration of the repairing liquid is increased to 25 mg/L, the viscosity reduction rate reaches 93.2%, the viscosity of the emulsion is reduced to 84 mPa & s, and finally the viscosity reduction rate tends to be stable, because the concentration of the repairing liquid reaches the critical micelle concentration, the dosage is continuously increased, and the viscosity reduction rate cannot be greatly improved.
Experimental example 4
Washing oil performance
The novel Gemini surfactant prepared in example 1 is prepared, and 50mg/L of surfactant solution is prepared for standby. Weighing a proper amount of quartz sand and crude oil, and fully and uniformly mixing to form oil sand (mass m) 1 ) And aging at 70 ℃ for 24h. According to the mass ratio of agent sand to sand of 10:1, adding the repairing liquid, stirring for 30 min at 70 ℃, standing until oil sand is separated, drying the separated oil sand, and weighing the dry oil sand (mass m) 2 ) The three groups were measured in parallel and averaged. Calculating the oil washing efficiency by using a gravimetric method, which is shown as the following formula:
wherein eta is the washing oil efficiency,%; m is 1 、m 2 The quality g of the oil sand and the dry oil sand before and after the oil sand cleaning oil respectively; p is the oil content of the oil sand before the oil sand cleaning agent is used for cleaning oil, and is percent. The results are shown in table 3, fig. 9;
table 3 repair liquids wash oil test results
From table 2, it can be known that the average oil washing efficiency of the repairing liquid reaches 84.64% under the condition that the mass ratio of the agent sand to the agent sand is 10. As can be seen from fig. 9, the oil sands are dull in color before oil washing, since the crude oil is tightly adsorbed on the sand surface after the oil sands are aged; in the oil washing process, small oil droplets can be seen to float on the water surface because the wettability of the sand surface is changed due to the addition of the repair liquid, the oil sand is gradually changed from lipophilicity to neutrality or hydrophilicity, and the oil film attached to the sand is desorbed and then floats out of the water surface; after the wash oil is dried, the sand color can be seen to be obviously whitened, which shows that the repair liquid has good oil washing capability.
In the present invention, the solvent used for preparing the repair liquid is water.
The foregoing is illustrative of the preferred embodiments of the present invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and is not to be construed as limited to the exclusion of other embodiments, and that various other combinations, modifications, and environments may be used and modifications may be made within the scope of the concepts described herein, either by the above teachings or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. The repairing liquid applied to near-wellbore zone reservoir pollution repairing is characterized by being formed by mixing a novel Gemini surfactant and water;
in the pollution remediation liquid, the concentration of the novel Gemini surfactant is 30 to 80mg/L;
the novel Gemini surfactant has a structure shown in the following formula (1):
wherein R is-C 12 H 25 And n is 5.
2. The repairing liquid for repairing reservoir pollution near the wellbore area as claimed in claim 1, wherein the novel Gemini surfactant is phthalic anhydride as a skeleton, and two hydrophilic tail chains are connected through an esterification reaction.
3. The repairing liquid for the near-wellbore zone reservoir pollution repairing according to the claim 1, wherein the preparation method of the novel Gemini surfactant comprises the following steps:
A. according to a molar ratio of 1:5:0.1 weighing phthalic anhydride, fatty alcohol-polyoxyethylene ether and HFDAIL (3, 3' - (2, 2-bis (hydroxymethyl) propane-1, 3-diyl) bis (1-methyl-1-imidazol-3-ium) sulfonate);
the fatty alcohol-polyoxyethylene ether is RO (CH) 2 CH 2 O) n H, wherein R is-C 12 H 25 N is 5;
B. b, adding the phthalic anhydride and the fatty alcohol-polyoxyethylene ether weighed in the step A into a three-neck glass flask, stirring, slowly adding HFDAIL, and reacting at constant temperature to obtain a crude product;
C. and D, evaporating the crude product obtained in the step B to remove the solvent, washing the crude product with methanol for three times, and finally putting the crude product into a constant-temperature oven to dry the crude product to constant weight to obtain the novel Gemini surfactant.
4. The remediation fluid of claim 3 wherein in step B, the reaction temperature is 125 ℃ and the reaction time is 10 hours.
5. The repairing liquid for the near wellbore zone reservoir pollution repair as claimed in claim 4, wherein in the step C, the constant temperature drying temperature is 70 ℃.
6. The fluid for remediating near-wellbore reservoir contamination as recited in claim 5, wherein in step C, the solvent is removed by evaporation from the crude product using a rotary evaporator.
7. The repairing liquid for reservoir pollution repair in the near-wellbore area according to any one of claims 1 to 6, wherein the concentration of the novel Gemini surfactant in the pollution repairing liquid is 50mg/L.
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| JP2003155666A (en) * | 2001-11-20 | 2003-05-30 | Ipposha Oil Ind Co Ltd | Chemical for fiber |
| CN105769611B (en) * | 2014-12-23 | 2018-09-07 | 安徽绿微康生物科技有限公司 | With the potent dentifrice composition except plaque |
| CN104910024B (en) * | 2015-05-12 | 2017-02-22 | 四川理工学院 | Surfactant for driving oil |
| CN107629778B (en) * | 2017-11-01 | 2020-06-23 | 南阳理工学院 | Gemini composite surfactant for oil displacement and preparation method thereof |
| CN112195021B (en) * | 2020-11-16 | 2021-08-27 | 山东大明精细化工有限公司 | Gemini polyoxyethylene ether succinate surfactant for oil displacement and preparation method thereof |
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