CN115651619B - Shear strength response intelligent profile control gel for oil field and preparation method thereof - Google Patents
Shear strength response intelligent profile control gel for oil field and preparation method thereof Download PDFInfo
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- 230000004044 response Effects 0.000 title abstract description 4
- 229920001661 Chitosan Polymers 0.000 claims abstract description 56
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims abstract description 54
- 229910000271 hectorite Inorganic materials 0.000 claims abstract description 54
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- 238000000034 method Methods 0.000 claims description 7
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- 239000003921 oil Substances 0.000 description 23
- 229940094522 laponite Drugs 0.000 description 13
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
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Abstract
The invention discloses an intelligent profile control gel with shear strength responsiveness for an oil field and a preparation method thereof. The shear strength response profile control gel for the oil field is prepared by co-assembling organic gel factors in a solvent, wherein the organic gel factors comprise hectorite and chitosan, and the solvent is water; in a solvent, the mass fraction of the hectorite is 0.5-5%, and the mass fraction of the chitosan is 0.5-5%; according to the invention, chitosan is doped into the hectorite matrix, and the electrostatic interaction between the chitosan and the hectorite matrix is utilized to enhance the mechanical strength and the temperature and salt resistance of the hectorite matrix hydrogel, so that the hectorite matrix hydrogel can be suitable for an oil layer environment. The thixotropic properties of the hectorite-based hydrogels enable them to perform very well in heterogeneous oil layers. The hectorite-based hydrogel with thixotropic property has lower viscosity and strength under high flow rate and high shear strength, smoothly enters a hypertonic layer, and has higher viscosity and strength after the flow rate of the deep oil reservoir is obviously reduced.
Description
Technical Field
The invention relates to an intelligent profile control gel with shear strength responsiveness for an oil field and a preparation method thereof, belonging to the technical field of profile control agents for oil fields.
Background
The offshore oil is an important component of the energy system of China, and the realization of the efficient development of the offshore oil is important to the guarantee of the energy safety of China and the promotion of the national economy development. Increasing the recovery of low permeability layers is one of the current concerns for enhanced oil recovery. In order to improve the heterogeneity of oil layer, the water absorption profile of crude oil reservoir is adjusted, and profile control agents are widely studied and applied. The most widely used profile control agent at present is a polymer gel profile control agent, but the polymer gel profile control agent has the problems of easiness in hydrolysis in water, small profile control radius, short effective period, poor scouring resistance, poor stability and the like.
With the development of intelligent materials, a new thought is provided for the development of profile control agents, and the aim of intelligently adjusting the water absorption profile is achieved by introducing groups with different stimulus responsivity into the plugging agent and then utilizing stratum conditions or changing injection conditions. The intelligent profile control agent can change the property of the intelligent profile control agent by receiving external stimulus, so that the intelligent profile control agent can selectively block the large-aperture channel in a directional manner. The hectorite has good gel forming performance under the conditions of high temperature and high salt and good thixotropic property, which provides possibility for the application of the hectorite-based gel in an offshore oil field profile control system. The hectorite has strong gel forming performance, but the mechanical performance and the severe environment resistance of the formed gel are still insufficient to meet the requirements of an ocean oil field profile control system.
Chitosan is the only natural polycationic polysaccharide discovered so far, and its unique role in enhancing self-healing and temperature/ionic strength resistance through synergistic co-assembly with hectorite has not been revealed. Therefore, it is necessary to study the synergy of hectorite and chitosan.
Disclosure of Invention
The invention aims to provide shear strength response profile control gel for oil fields, which is prepared by doping chitosan into a hectorite matrix, and enhancing the mechanical strength and the temperature and salt resistance of the hectorite-based hydrogel by utilizing electrostatic interaction between the chitosan and the hectorite matrix, so that the gel can be suitable for an oil layer environment; the thixotropic properties of the hectorite-based hydrogels enable them to perform very well in heterogeneous oil layers.
The profile control gel provided by the invention has lower viscosity and strength under high flow rate and high shear strength, smoothly enters a hypertonic layer, and has higher viscosity and strength after the flow rate of the deep oil reservoir is obviously reduced.
The shear strength responsive profile control gel for the oil field is prepared by co-assembling organic gel factors in a solvent;
the organogel factor includes laponite and chitosan.
Preferably, the solvent is water.
In the solvent, the mass fraction of the hectorite is 0.5-5%, preferably 0.5-2%, 0.5-1.5%, 0.5-1%, 0.5%, 1%, 1.5% or 2%;
the mass fraction of the chitosan is 0.5-5%, preferably 0.5-2%, 0.5-1.5%, 0.5-1%, 0.5%, 1%, 1.5% or 2%;
the deacetylation degree of the chitosan is 80.0-95.0, and the viscosity is 50-800 mPas.
Preferably, the mass ratio of the hectorite to the chitosan is 1:0 to 1, both preferably 1:1.
the invention also provides a preparation method of the profile control gel, which comprises the following steps:
preparing a solution of the hectorite, adding the chitosan, and standing to form gel, thus obtaining the profile control gel;
the laponite is commercially available;
the chitosan is commercially available.
The invention has the following beneficial technical effects:
the hydrogel formed by the hectorite has good high-temperature high-salt gel forming performance, and the application of the hectorite-based hydrogel in a marine oil field profile control system is possible. The hectorite-based hydrogel has excellent thixotropic properties, which allows it to have good injection properties, reduces plateau injection pressure, and forms a gel with higher strength at a site with less shear strength by self-assembly with a polymer,
according to the invention, chitosan is doped into the hectorite matrix, and the electrostatic interaction between the chitosan and the hectorite matrix is utilized to enhance the mechanical strength and the temperature and salt resistance of the hectorite matrix hydrogel, so that the hectorite matrix hydrogel can be suitable for an oil layer environment. The thixotropic properties of the hectorite-based hydrogels enable them to perform very well in heterogeneous oil layers. The hectorite-based hydrogel with thixotropic property has lower viscosity and strength under high flow rate and high shear strength, smoothly enters a hypertonic layer, and has higher viscosity and strength after the flow rate of the deep oil reservoir is obviously reduced.
Drawings
FIG. 1 is a phase diagram of a hectorite chitosan binary co-assembly system in deionized water
FIG. 2 is an XRD spectrum of the co-assembled hydrogels prepared in example 1 of the present invention at different mass concentrations.
Fig. 3 is an SEM image of the profile control gel of different mass ratios prepared in example 1 according to the present invention.
Fig. 4 shows the rheological properties of the formulated gel prepared in example 1 of the present invention at different temperatures.
Fig. 5 is a graph showing the rheological properties of the formulated gel prepared in example 1 of the present invention at different shear rates.
FIG. 6 is a graph showing the mechanical strength test of various hydrogels prepared in example 1 of the present invention.
FIG. 7 is a time-scanning plot of the alternating strain values of the different hydrogels prepared in example 1 of the present invention.
FIG. 8 is a chart showing temperature swing scanning test and dynamic strain scanning under the action of NaCl at different concentrations for different hydrogels prepared in example 1 of the present invention.
Detailed Description
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Hectorite used in the examples described below was purchased from Shanghai national pharmaceutical chemical Co., ltd.
The chitosan used in the following examples was purchased from Shanghai national pharmaceutical chemical Co., ltd, and had a degree of deacetylation of 80.0 to 95.0 and a viscosity of 50 to 800 mPas.
Example 1 preparation of shear Strength responsive Intelligent Profile control gel for oil field
200mg of hectorite is added into 10ml of water, and the mixture is fully mixed and dissolved by ultrasonic to obtain transparent colorless hectorite solution; 200mg of chitosan is added into the hectorite solution, the solution is uniformly shaken and then is kept stand for 1h, and the intelligent gel with adjustable profile is obtained after the solution forms gel, wherein the mass fraction of the hectorite in water is 2%, and the mass fraction of the chitosan is 2%.
Preparing profile control gel with different proportions according to the above, and obtaining the weight ratio of hectorite to chitosan as 2:0.5, 2:1. 2:1.5, wherein the mass fraction of hectorite in water is 2%.
FIG. 1 is the effect on phase behavior when the weight ratio of hectorite to chitosan. When the concentration of laponite is less than 1wt%, precipitation occurs as the concentration of chitosan increases, and the middle region of the phase diagram is a liquid phase due to the complexation of laponite with the host and guest of chitosan. When the chitosan concentration is more than 1wt%, a hydrogel is formed. These results indicate that there is a synergistic effect between the components that forms a precipitate phase, a liquid phase and a gel phase, respectively, and thus fine control of complexation between binary components will provide the desired colloidal material.
Fig. 2 is a trend of XRD spectrum evolution when the concentration of hectorite nanoplatelets was fixed to 2.0wt% and the chitosan concentration was increased from 0wt% to 2 wt%. The individual hectorite hydrogels exhibited several diffraction peaks at 7.1, 14.6, 19.3 and 27.7 2 theta angles with corresponding distances of 1.3, 0.61, 0.46 and 0.32nm, respectively, according to the bragg equation. The interplanar spacing ratio was approximately 1:2:3:4, and it was considered to be a lamellar phase with a lattice spacing of 1.3nm. After the addition of 0.5wt% chitosan, there was no significant shift or disappearance of the main peak, indicating that the system remained lamellar structure with lower concentrations of the second component. However, when the chitosan concentration was 1% wt%, the peak at 14.6 ° labeled (002) disappeared, and several peaks appeared at 35 °, 61 ° and 72 °, respectively. Meanwhile, the original peaks of (001), (003) and (004) are not disturbed. Residual peaks and emerging peaks can also be divided into lamellar phases, shown as (001) - (008) planes. Indicating that the newly formed lamellar phase has a clearer structure and a higher phase purity than the original single phase of laponite. The polymer chains of chitosan may be embedded in the interlayer of hectorite flakes, however, there is no significant change in peak position due to the larger lattice parameter (1.3 nm).
FIG. 3 is an SEM image when the concentration of hectorite nanosheets was fixed to 2.0wt%, and chitosan concentrations were 0wt%, 1wt%, and 2 wt%. The surface of the single hectorite hydrogel was smooth and wrinkled, indicating tight aggregation between the nano-platelets of the hectorite material. The mechanism by which laponite fixes water depends on interlayer hydration, and water is adsorbed to the interlayer space. The large surface area of nano hectorite can form high solid content hydrogel with a critical gel concentration of 2.0wt%. The polymer chitosan was added to the laponite matrix and the gel morphology was transformed into a pleated network as shown in fig. 3b, c. Such a crosslinked network results from the cooperative assembly between the two components (fig. 3 d), and since chitosan itself has a slight dispersibility in water, the polymer chains can be mixed on a molecular scale without microphase separation when co-assembly occurs, thereby improving the immobilization effect. This assumption is consistent with the observed networks, which are able to develop stronger capillary forces.
Example 2 rheological Performance test of Profile control gels at different temperatures
The rheological properties of the profile control gel prepared in example 1 (2:2) were tested according to the following procedure:
the profile control gel was passed through a Thermo Haake RS6000 rheometer with conical plates (diameter 35mm, cone gap 0.105 mm) to observe the phase change of the gel by changes in the macroscopic morphology of the gel.
FIG. 4 is a graph showing rheological properties of the gel prepared in example 1 of the present invention at different temperatures and corresponding different shear rates, wherein the plot is 2.0wt% hectorite and 2.0wt% chitosan in order from top to bottom at reservoir temperature (65 ℃ C.) for 10s -1 Viscosity curve at shear rate, 2.0wt% laponite and 2.0wt% chitosan concentration at dosing temperature (45 ℃) for 1000s -1 ShearingViscosity profile of rate. From the graph, 2.0wt% laponite and chitosan at a concentration of 2.0wt% at reservoir temperature for 10s -1 Viscosity at shear Rate vs. dispensing temperature 1000s -1 The shear rate is higher by more than one order of magnitude, and the method can be practically applied to profile control of oil field wells.
Example 3 rheological Performance test of Profile control gels at different shear Rate
The rheological properties of the profile control gel prepared in example 1 (2:2) were tested according to the following procedure:
the profile control gel was passed through a Thermo Haake RS6000 rheometer with conical plates (diameter 35mm, cone gap 0.105 mm) to observe the phase change of the gel by changes in the macroscopic morphology of the gel.
FIG. 5 is a graph showing rheological properties of the gel prepared in example 1 according to the present invention at different shear rates, wherein the curves are 2.0wt% laponite and 2.0wt% chitosan in order from top to bottom at reservoir temperature (65 ℃ C.) for 10s -1 Viscosity profile at shear rate at 1000s at formulation temperature (45 ℃) -1 Gel at reservoir temperature (65 ℃ C.) for 10s after 5min of shear rate shearing -1 Viscosity profile at shear rate. From the graph, at the injection allocation temperature, 1000s -1 Gel at reservoir temperature for 10s after 5min of shear rate -1 The viscosity at the shearing rate is more than 80% before non-shearing, and the method can be practically applied to profile control of oil field wells.
Example 4 mechanical Strength test of Profile control gel
FIG. 6 is a graph showing the mechanical strength test of the gel prepared in example 1 of the present invention.
In fig. 6, a-d are strain scan curves of hydrogel formed by hectorite and chitosan, and e-h are frequency scan curves of gel in a linear viscoelastic region. The hydrogels formed by laponite itself have G' and G "in the linear viscoelastic region of around 35 and 3.3 Pa. After 0.5wt% of chitosan is added, the storage modulus and the loss modulus are respectively improved by several times to reach 126Pa and 16Pa, which shows that the mechanical strength of the gel is greatly improved. However, the ratio of G 'to G' shrinks simultaneously with the yield stress (82 Pa). The same trend was also exhibited by increasing chitosan to 1.5wt% and 2wt%, respectively, and the addition of chitosan significantly reduced stress/strain resistance. The frequency scanning curve also proves that the phenomenon is weak in dependence of modulus on frequency in the range of 0.01-100 Hz, and shows that the hydrogel after chitosan is added has good stability. In fig. 6, i is the G' value of the binary co-assembly system (gamma=1%) and when the chitosan has the same concentration (2wt%) as hectorite, the mechanical strength is obviously improved by 13 times, so that the practical application of oil field well profile control can be performed.
Example 5 alternate Strain of Profile control gels
The self-healing property of the chitosan is obviously improved after the chitosan is introduced into a hectorite network. As shown in fig. 7 a, three samples with 0, 1 and 2wt% chitosan added showed different self-healing periods. The hydrogel with the chitosan addition amount of 2wt% was restored to the hydrogel immediately within 5 seconds after severe shaking. A hydrogel sample with a chitosan addition of 1.5wt% required a longer time of 15 seconds, whereas a simple laponite gel required 220 seconds to reform the hydrogel. The co-assembly of chitosan and hectorite network can shorten the self-healing period and improve the performance.
The time sweep strain for the alternating strain values of b-d in fig. 7 was 1% and 105%, respectively, with a frequency of 1Hz, with a sweep time interval of 30 seconds. After 2wt percent of chitosan is added, the self-repairing time is shortened from 220s to 5s, the strain recovery capacity can reach 100 percent, and the method can be applied to the practical profile control of oil field wells.
Example 6 temperature Change Scan test of Profile control gel and dynamic Strain test under the action of different concentrations of NaCl
FIG. 8 is a graph of temperature swing scan test of the gel prepared in example 1 of the present invention and dynamic strain scan under the action of NaCl at different concentrations.
In FIG. 8, a-c are the results of temperature swing scans of hydrogels of different ratios of gel factors, with a strain of 5% and a frequency of 1Hz.
In FIG. 8, d-f are dynamic strain scans of hydrogels of 2.0wt% laponite with 2.0wt% chitosan at different concentrations of NaCl, with a strain of 5% and a frequency of 1Hz.
As can be seen from FIG. 8, the G' of the gel is enhanced when the temperature is increased from room temperature to 80 ℃, indicating that the gel has better high temperature resistance. When the mass fraction of chitosan is 1.5%, the mechanical strength thereof is improved several times at a relatively high temperature. Under the action of the ultra-high concentration NaCl (10 wt%) the mechanical strength of the hydrogel is reduced, and the elastic modulus of the hydrogel is reduced. The method can be applied to the practical profile control of the oilfield well.
Claims (3)
1. A shear strength responsive profile control gel for oil fields is prepared by co-assembling organic gel factors in water;
the organogel factor consists of hectorite and chitosan;
in the water, the mass fraction of the hectorite is 0.5-5%, and the mass fraction of the chitosan is 0.5-5%;
the deacetylation degree of the chitosan is 80.0-95.0, and the viscosity is 50-800 mPas;
the mass ratio of the hectorite to the chitosan is 1:1.
2. the method for preparing the profile control gel according to claim 1, comprising the following steps:
preparing a solution of the hectorite, adding the chitosan, and standing to form gel, thus obtaining the profile control gel.
3. Use of the profile control gel of claim 1 as a profile control gel for oil fields.
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| CN106479465A (en) * | 2015-08-31 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of profile-controlling and plugging agent and its preparation method and application |
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| CN106479465A (en) * | 2015-08-31 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of profile-controlling and plugging agent and its preparation method and application |
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| "一锅法"制备壳聚糖/锂皂石互穿网络水凝胶;李云秋;李迎博;樊晓敏;刘瑞雪;;郑州师范教育(06);第25-29页 * |
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