CN116355604A - Hollow core-shell TiO 2 Polymer oil-displacing agent and its prepn - Google Patents
Hollow core-shell TiO 2 Polymer oil-displacing agent and its prepn Download PDFInfo
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
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- 238000003756 stirring Methods 0.000 claims abstract description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 10
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- 238000000034 method Methods 0.000 claims abstract description 8
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- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 claims abstract description 5
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
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- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—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 polymers
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Abstract
The invention discloses a hollow core-shell TiO 2 The polymer oil-displacing agent is prepared through distillation and precipitation process, preparing polyacrylamide microsphere in acetonitrile system, adding 3.492g hexadecylamine and 1.6mL potassium chloride solution into 400.00mL absolute alcohol at room temperature, stirring until the solution is clear, adding 8.6mL isobutyl titanate, fast stirring until it is milky white, standing for 24 hr, centrifuging, washing with alcohol, drying, calcining in muffle furnace to eliminate polyacrylamide microsphere and obtain hollow titania microsphere. In a dry three-necked flask, add0.20g of hollow titanium dioxide particles and 80mL of acetonitrile, fully stirring, adding acrylamide, N, N' -methylene bisacrylamide and azodiisobutyronitrile, and carrying out distillation treatment on the reaction liquid; and (3) performing ultrasonic dispersion and centrifugation on the obtained white solid in ethanol, and drying and grinding to obtain the white solid. The polymer oil displacement agent prepared by the invention has good dispersibility, uniform particle size, swelling-swelling performance and temperature and salt resistance.
Description
Technical Field
The invention relates to the technical field of oilfield chemical additives and high molecular polymerization, in particular to a hollow core-shell TiO 2 Preparation method of polymer oil displacement agent and hollow core-shell TiO prepared by adopting preparation method 2 Polymer oil-displacing agent.
Background
In recent years, nanotechnology has become a hotspot for research in oilfield applications. The nano/micron polymer ball is an effective water shutoff method, can improve the heterogeneity of fluid and enhance the displacement capability of the oil and gas reservoir. The nano/micron polymer has large specific surface area and surface energy, so that the oil-water interfacial tension can be reduced, and simultaneously, the nano/micron particles have temporary blocking effect on small pore canals and can be used for profile control of an oil layer. While a large number of capped nano/micro polymer spheres are widely used in oil fields, the overall effect is poor. For example, the movable weak gel has poor crosslinking controllability as profile control and oil displacement and higher cost; the polymer plugging agent is easy to precipitate and can not enter deep plugging. The expandable particulate polymer gel deforms severely as a profile control agent and an oil displacement agent, resulting in a discrepancy between injection depth and seal strength, leading to rapid failure in the low permeability layer.
Aiming at the problems, the novel profile control oil displacement agent of the nano-micron organic/inorganic composite material achieves better effect. Compared with the traditional profile control agent and oil displacement agent, the organic/inorganic composite material has the advantages of high molecular weight, controllable grain diameter, high water absorption, strong water shearing resistance, suitability for severe reservoir conditions and the like. However, the addition of the inorganic core deteriorates the deformability of the organic/inorganic composite microsphere, resulting in clogging of the near well region and poor deep profile control effect.
Based on the above, an inorganic/organic material with a hollow structure is designed, and deep profile control can be performed due to the large specific surface area, high permeability and swelling-swelling performance. At the same time, nano TiO is introduced 2 The particles have the characteristics of stronger surface activity, stronger adsorptivity, photocatalytic degradation of greasy dirt and the like.
Herein, nano TiO with a hollow structure and a particle size of about 500nm is synthesized 2 The polymer microsphere is examined for the hydration expansion performance, the temperature resistance and salt resistance, the photocatalysis performance and the oil displacement performance, and the analysis result shows that the hollow TiO is 2 The polymer nano polymer oil displacement agent has swelling-imbibition performance, good temperature resistance and salt resistance and catalysisPerformance. With the increase of hydration time, the increase of recovery ratio is firstly increased, then decreased, and hollow TiO 2 The polymer may be subjected to deep profile control.
Disclosure of Invention
The invention is realized by the following technical means:
hollow core-shell TiO 2 The preparation method of the polymer oil-displacing agent comprises the following steps:
(1) Preparing polyacrylamide microspheres:
preparing polyacrylamide microspheres under an acetonitrile system by adopting a distillation precipitation method;
(2) Preparation of hollow titanium dioxide microspheres:
taking 0.5g of polyacrylamide microspheres, adding 3.492g of HAD (hexadecylamine) solution and 1.6mL of KCl (potassium chloride) solution into 400.00mL of absolute ethyl alcohol at room temperature, stirring until the solution is clear, adding 8.6mL of TIP (isobutyl titanate) and rapidly stirring to be milky white, standing, centrifuging (6000 r/min) and washing with ethanol for 3 times, drying at 60 ℃ for 6 hours, and calcining at 550 ℃ for 7 hours to obtain hollow titanium dioxide microspheres;
(3) Preparation of hollow titanium dioxide/polymer microspheres:
adding 0.20g of hollow titanium dioxide particles and 80mL of acetonitrile into a dry three-port bottle, fully stirring, adding AM (acrylamide), MBAAm (N, N' -methylene bisacrylamide) and AIBN (azodiisobutyronitrile), distilling the obtained reaction liquid, dispersing white solid in ethanol by ultrasonic waves after the distillation treatment, centrifuging (5000 r/min), drying at 60 ℃ for 6 hours, and grinding to obtain the titanium dioxide.
Further, the mass ratio of the polyacrylamide to the acetonitrile in the step (1) is 1:1.
further, the concentration of the KCl (Potassium chloride) solution in the step (2) is 0.1M; the standing time is 24 hours.
Further, the muffle furnace calcining temperature in the step (2) is 550 ℃, and the calcining time is 7h.
Further, the mass ratio of AM (acrylamide) to MBAAm (N, N' -methylenebisacrylamide) in the step (3) is 3:1.
Further, the AM (acrylamide) and MBAAm (N, N' -methylenebisacrylamide) account for 0.25wt% of the total reaction system.
Further, the AIBN of step (3) is 0.004g by weight relative to the mass of the monomer.
The invention also discloses a hollow core-shell TiO prepared by any one of the preparation methods 2 Polymer oil-displacing agent.
The invention has the beneficial effects that:
(1) The hollow TiO with good dispersibility and uniform particle size is synthesized 2 Polymer nano-polymer;
(2) Synthesized hollow TiO 2 The polymer nano polymer has swelling-debulking performance and temperature and salt resistance, the temperature is increased from 60 ℃ to 90 ℃, the maximum expansion multiplying power is 7, 7.5 and 8.3 respectively when the hydration time is less than 288 hours, the hydration time is 312 hours, and the maximum expansion multiplying power is reduced to 6.8, 7.3 and 8;
(3) Synthesized hollow TiO 2 The polymer nano polymer has the temperature resistance and salt resistance, the concentration of NaCl (sodium chloride) solution is increased from 500mg/L to 3000mg/L, the viscosity retention rate is reduced from 74% to 30%, and under the same salt solution concentration, the hollow TiO is formed 2 Polymer viscosity decreases with increasing concentration. When the NaCl solution concentration was 3000mg/L and the temperature was increased from 60℃to 90℃the viscosity retention was decreased from 76% to 33%.
(4) Hollow TiO 2 The polymer has catalytic performance, the catalytic time is prolonged, and the catalytic degradation rate is increased. When hollow TiO 2 The photocatalytic degradation efficiency gradually decreases when the concentration of the polymer increases from 0.5mg/L to 2.0 mg/L;
(5) With the increase of hydration time, the increase degree of recovery ratio is reduced and then increased, and hollow TiO 2 The polymer may be subjected to deep profile control.
Drawings
FIG. 1 is SEM (scanning electron microscope) and TEM (transmission electron microscope) characterization of nanoparticles prepared in example 1 (a) PAM, (b) hollow TiO 2 (c) hollow TiO 2 A polymer;
FIG. 2 is a schematic diagram of the process of example 1(a) XED, (b) IR Spectroscopy, (c) hollow TiO 2 N of polymer 2 Adsorption-desorption curves, (d) hollow TiO 2 Pore structure distribution of the polymer;
FIG. 3 is a graph showing the relationship between hydration time and swelling power of the sample prepared in example 1;
FIG. 4 is a graph showing the temperature and salt resistance of the sample prepared in example 1;
FIG. 5 is a graph showing the photocatalytic degradation rate of the sample prepared in example 1.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by persons of ordinary skill in the art without making creative efforts based on the embodiments of the present invention are all within the scope of protection of the present invention.
The medicine and the instrument used in the invention are as follows:
medicine: deionized water (resistance greater than 7mΩ); sodium chloride (analytically pure, chinese chemical reagent NaCl), potassium chloride (analytically pure, chinese chemical reagent NaCl), ethanol (analytically pure, chinese chemical reagent NaCl), isobutyl titanate (analytically pure, ala Ding Huaxue reagent Tip), hexadecylamine (analytically pure, tianjin optical complex HDA), acrylamide (analytically pure, chinese chemical reagent), N' -methylenebisacrylamide (analytically pure, chinese chemical reagent), azobisisobutyronitrile (analytically pure, chinese chemical reagent AIBN), acetonitrile (analytically pure, chinese chemical reagent).
Instrument: s-360 Scanning Electron Microscope (SEM); JEM-200CX Transmission Electron Microscope (TEM); nicolet NEXUS 670 Fourier transform Infrared spectrometer (FTIR); rigaku D/max-rA X-ray diffractometer (X-ray powder diffractometer, XRD), core displacement device; high speed centrifuge (Hitachi Himac CR21F, maximum speed 2000 r/min).
Example 1
Hollow core-shell TiO 2 PolymerThe preparation method of the oil displacement agent comprises the following steps:
(1) Preparing polyacrylamide microspheres: the polyacrylamide microsphere is prepared under an acetonitrile system by adopting a distillation precipitation method, and the mass ratio of polyacrylamide to acetonitrile is 1:1, a step of;
(2) Preparation of hollow titanium dioxide microspheres: taking 0.5g of prepared polyacrylamide microspheres, adding 3.492g HAD,1.6mLKCl solution (0.1M) into 400.00mL of absolute ethyl alcohol at room temperature, stirring until the solution is clear, adding 8.6mLTIP, rapidly stirring until the solution is milky white, standing for 24h, centrifuging, washing with ethanol, drying, and calcining in a muffle furnace at 550 ℃ for 7h to remove the polyacrylamide microspheres, thereby obtaining the hollow titanium dioxide microspheres.
(3) Preparation of hollow titanium dioxide/polymer microspheres: into a dry 100mL three-necked flask, 0.20g of hollow titanium dioxide (TiO 2 ) Pellets, 80mL of acetonitrile, and AM, MBAAm (N, N' -methylenebisacrylamide) (mass ratio: 3:1, total 0.25wt% of the reaction system) and AIBN (0.04 g,2wt% relative) were added thereto with stirring. Distilling the reaction liquid until the solvent in the round bottom flask is almost completely distilled; and (3) ultrasonically dispersing the white solid of the round-bottomed flask in ethanol, centrifuging, drying and grinding to obtain the solid.
Test example 1
Characterization of the nano-microparticles on the samples prepared in example 1
According to the scanning electron microscope of nano PAM (polyacrylamide) as shown in FIG. 1 (a), the synthesized nano microsphere has good dispersibility, and the average particle size is about 150 nm. FIG. 1 (b) is a hollow TiO 2 The hollow structure is apparent from the transmission electron microscope image of (a), and the average particle diameter is about 280 nm. FIG. 1 (c) is a hollow TiO 2 As can be seen from the SEM image of the polymer, the synthesized nano-microspheres have good dispersibility and the size distribution of the nano-microspheres is about 340 nm. FIG. 2 (a) is an XRD characterization of nanoparticles, by XRD analysis, uncalcined PAM/TiO 2 Is an amorphous structure. After calcination, hollow TiO 2 The XRD corresponding characteristic peaks of (101), (004), (200), (105) are all shown as hollow TiO after calcination 2 Having anataseStructure is as follows. When hollow TiO 2 After the shell layer coats the polymer, the hollow TiO 2 The polymer still has an anatase structure due to the growth of anatase crystals and the enhancement of crystallization upon high temperature calcination. Fig. 2 (b) is an infrared characterization of nanoparticles. As can be seen from the figure, 3424cm -1 、3208cm -1 Respectively is-NH in amide groups corresponding to PAM 2 Characteristic peaks; 1539cm -1 The absorption peak of N-H bending vibration in MBAA is an important characteristic of secondary amide structure, and the characteristic peak is 1630-1687cm -1 And 3400-3600cm -1 From H-O-H flexural vibrations and TiO 2 Tensile vibration of (C) indicating TiO 2 And (3) forming a shell. From the above analysis results, it was shown that hollow TiO 2 Polymer composite microspheres have been successfully synthesized. FIG. 2 (c) is a hollow TiO 2 N of polymer 2 Adsorption-desorption isotherms, which are consistent with IUPAC specified isotherms of type iv, calculated by BJH method, hollow TiO 2 The pore size of the polymer was about 3.4nm.
Test example 2
The sample obtained in example 1 was subjected to the measurement of the hydration swelling property
FIG. 3 is a hollow TiO 2 Polymer particle concentration was 1.5g/L, its rate of hydration expansion versus time at different temperatures. From the graph data, the polymer shows swelling-swelling phenomenon, namely: the hydration time is lower than 288 hours, the temperature is increased from 60 ℃ to 90 ℃, the expansion ratio of the polymer is in a linear increasing trend along with the increase of the hydration time, and the expansion ratio of the nano polymer microsphere is increased along with the increase of the temperature under the same hydration time. At 312h hydration time, the temperature was increased from 60 ℃ to 90 ℃, the rate of the nano-polymer microspheres was reduced and then remained unchanged. This is because during expansion, the water needs to continuously overcome the osmotic pressure inside the sphere. At the beginning of the swelling process, the osmotic pressure of the microspheres is low and therefore the swelling rate is high. As hydration progresses, the expansion of the microspheres gradually increases and more water enters the polymer network, so that the water needs to overcome the greater osmotic pressure and the expansion rate of the microspheres decreases with increasing osmotic pressure. According to thermodynamics and molecular expansionTheory of dispersion due to hollow TiO 2 The pore size of the @ polymer microspheres is large and there is a small amount of polymer that can enter the cavity, resulting in polymer de-swelling. At the same time, the cavity not only provides more space for containing liquid but also can make the hollow TiO 2 The @ polymer microspheres have a longer equilibrium amount.
Test example 3
Temperature and salt resistance measurement of the sample obtained in example 1
FIG. 4 (a) is a hollow TiO 2 The influence of different mineralization conditions on the viscosity of the polymer at a temperature of 80 ℃. As can be seen from the graph, the NaCl solution concentration increases and the polymer viscosity decreases. As the concentration of NaCl solution is increased from 500mg/L to 3000mg/L, the viscosity retention rate is reduced from 74% to 30%, and the result shows that the hollow TiO is hollow 2 The polymer solution can still maintain higher apparent viscosity under higher salt concentration, and shows better salt resistance. FIG. 4 (b) shows hollow TiO at different temperatures 2 Polymer viscosity versus salt concentration. As can be seen from the figure, at the same salt solution concentration, the temperature rises and the hollow TiO 2 Polymer viscosity decreases. When the concentration of NaCl solution is 3000mg/L and the temperature is increased from 60 ℃ to 90 ℃, the viscosity retention rate is reduced from 76% to 33%, and the result shows that the hollow TiO 2 The polymer solution can still keep higher apparent viscosity at high salt concentration/high temperature, and shows better temperature resistance. This is because the electrostatic repulsive force is reduced after the cations enter the polymer molecule adsorption layer. An increase in the degree of polymer molecular chain crimp results in a decrease in viscosity.
Test example 4
Catalytic stability study on the samples prepared in example 1
FIG. 5 is a graph of hollow TiO of varying concentrations 2 Graph of photodegradation rate versus time for polymer. The reaction system teaches rhodamine B at a concentration of 100mg/L and a volume of 100 ml. Firstly, the reaction system is wrapped, so that the reaction system is invisible, and the reaction system is stirred for 0.5h. Then, the light is irradiated. It can be seen from the figure that under the same experimental conditions, the time is increased, and the hollow TiO 2 Polymer catalytic degradation rate increases. When hollow TiO 2 AggregationWhen the concentration of the compound is increased from 0.5mg/L to 2.0mg/L, the photocatalytic degradation efficiency gradually decreases, which indicates hollow TiO 2 Polymer concentration has a certain influence on the photocatalytic degradation. This is probably due to the fact that the higher the concentration of the solution, the worse the light transmittance, and the more photon energy is absorbed by the solution, the lower the light utilization efficiency of the catalyst, resulting in a decrease in the number of photons participating in the photocatalytic reaction and a decrease in the photocatalytic performance.
Test example 5
Evaluation of oil-displacing Effect on the sample obtained in example 1
Hollow TiO with concentration of 2.0mg/L and different hydration time when NaCl concentration is 1000mg/L 2 The oil displacement effect of the polymer nano polymer dispersion system is shown in table 1.
Relation between permeability, porosity and average pore throat radius of rock:
k is rock permeability, μm 2 ；
Porosity of rock,%; r is the average pore throat radius of the rock, μm.
TABLE 1 influence of different hydration times on recovery ratio experimental results
As can be seen from Table 1, the hydration time is prolonged from 72h to 192h, and the recovery efficiency is increased from 7.03% to 7.91%; when the hydration time is 288 hours, the total recovery ratio is reduced, and the recovery ratio improvement degree is reduced; when the hydration time is increased to 312 hours, the total recovery ratio is increased, and the recovery ratio is improved to the greatest extent. This is probably because as the hydration time increases, the expansion rate of the polymer increases, and when the hydration time is less than 288 hours, the nano polymer does not completely plug the core; when the hydration time is 288h, the catalyst consists ofIn hollow TiO 2 The polymer nano polymer has overlarge particle size, the front end pore channel of the rock core is totally plugged, and polymer particles cannot reach the deep part of the rock core, so that the recovery ratio is too low, and when the hydration time is 312h, the hollow TiO is used 2 The polymer nano polymer has the advantages of reduced particle size, plugging of the core and increased recovery ratio. From the experimental results, it is known that hollow TiO 2 The polymer nano polymer can be subjected to deep profile control.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. Hollow core-shell TiO 2 The preparation method of the polymer oil-displacing agent comprises the following steps:
adding the hollow titanium dioxide microspheres into acetonitrile solution, and fully stirring to obtain a first solution;
adding acrylamide, N' -methylene bisacrylamide and azodiisobutyronitrile into the first solution to obtain a second solution;
distilling the second solution to obtain a third solid;
and (3) dispersing the third solid in ethanol by ultrasonic waves, and centrifuging, drying and grinding to obtain the product.
2. The method of manufacturing according to claim 1, wherein:
the hollow titanium dioxide microsphere is 0.2g;
the acetonitrile solution is 80ml;
the acrylamide and the N, N' -methylene bisacrylamide account for 0.25 weight percent of the total reaction system;
the azodiisobutyronitrile is 0.004g.
3. The preparation method according to claim 2, wherein:
the mass ratio of the acrylamide to the N, N' -methylene bisacrylamide is 3:1.
4. The method of manufacturing according to claim 1, wherein:
the hollow titanium dioxide microsphere is prepared by the following method:
mixing and stirring polyacrylamide microspheres, hexadecylamine, KCl solution and absolute ethyl alcohol to obtain a first solution;
adding isobutyl titanate into the first solution, stirring, standing and centrifuging to obtain a second substance;
and washing the second substance by ethanol, drying, and calcining in a muffle furnace to obtain the hollow titanium dioxide microspheres.
5. The method of manufacturing according to claim 4, wherein:
the polyacrylamide microsphere is 0.5g;
hexadecylamine was 3.492g;
KCl solution was 1.6mL;
the absolute ethanol is 400mL;
isobutyl titanate was 8.6mL.
6. The method of manufacturing according to claim 5, wherein:
the concentration of the KCl solution was 0.1M.
7. The method of manufacturing according to claim 4, wherein:
the standing time is 24 hours;
the centrifugation speed is 6000r/min.
8. The method of manufacturing according to claim 4, wherein:
the drying temperature is 60 ℃, and the drying time is 6 hours;
the calcination temperature is 550 ℃, and the calcination time is 7h.
9. Hollow core-shell TiO prepared by any one of the preparation methods of claims 1-8 2 Polymer oil-displacing agent.
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