CN111892919A - Method for enhancing oil displacement profile control foaming by adopting hydrophobic metal organic framework material - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000005187 foaming Methods 0.000 title claims abstract description 29
- 230000002708 enhancing effect Effects 0.000 title claims description 15
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- 238000011549 displacement method Methods 0.000 claims abstract description 17
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- 238000002347 injection Methods 0.000 claims abstract description 14
- 239000007924 injection Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000004088 foaming agent Substances 0.000 claims abstract description 11
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000008398 formation water Substances 0.000 claims description 12
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
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- ALDXNLXJHWOGNT-UHFFFAOYSA-N 1h-imidazole;zinc Chemical class [Zn].C1=CNC=N1 ALDXNLXJHWOGNT-UHFFFAOYSA-N 0.000 claims 1
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- 238000005728 strengthening Methods 0.000 abstract 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 28
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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
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
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Abstract
The invention relates to a method for strengthening oil displacement, profile control and foaming by adopting a hydrophobic metal organic framework material, which comprises a direct liquid medium injection oil displacement method and a slurry-gas alternative oil displacement method. The direct liquid medium injection oil displacement method comprises the following steps: adding the hydrophobic metal organic framework material into the injected water, stirring to prepare hydrophobic metal organic framework material/water suspension slurry, and alternately injecting the suspension slurry slug and the single water slug to displace oil. The slurry-gas alternative oil displacement method comprises the following steps: adding the hydrophobic metal organic framework material into injected water or injected water-foaming agent mixed solution, stirring to prepare suspension slurry, and alternately injecting suspension slurry slug and gas slug to displace oil. The hydrophobic metal organic framework material is 2-methylimidazole zinc salt. The invention utilizes the hydrophobic metal organic framework material to give consideration to a plurality of effects of oil displacement, profile control, foaming, foam stabilization and the like, and has important significance for improving the crude oil recovery ratio of the oil reservoir with strong heterogeneity or cracks.
Description
Technical Field
The invention belongs to the field of oil and gas development, and particularly relates to a method for enhancing oil displacement, profile control and foaming by adopting a hydrophobic metal organic framework material.
Background
The crude oil is mainly generated in rock pores, the recovery rate is not high by adopting a conventional depressurization exploitation method, the recovery rate of the crude oil can be further improved by adopting water drive, gas drive or chemical drive and the like after depressurization exploitation, but for oil reservoirs with strong reservoir heterogeneity and cracks, the injected fluid rapidly flees along with a high-permeability channel, the recovery rate is improved to a limited extent, and at the moment, the fluid injection mode or the physical properties of the injected fluid need to be changed, such as injected foam slug, gas-liquid alternate injection, the viscosity of the injected fluid and the like.
The metal organic framework material is a porous material synthesized by metal atoms and organic ligands under certain conditions, has the advantages of adjustable and designed structure, small particle size (nano-micron size), large specific surface area and the like, and shows great application potential in the fields of gas storage and separation (Park, K.S. et al. empirical chemical and thermal activity of zeolitic inorganic acid structures, Proc. Natl Acad. Sci. USA,2006,103, 10186-. Part of hydrophobic metal organic framework materials cannot enter the pore canal of the material due to small opening diameter of the pore canal, and can form stable suspension slurry after being mixed with aqueous solution (ZL 201310014858.9, a separation method of ethane and ethylene in mixed gas); meanwhile, due to the hydrophobicity of the material, the material has good affinity with hydrocarbon components, and can effectively adsorb hydrocarbon molecules (main components of crude oil) in a water phase; in addition, as water molecules do not enter the pore channels of the material, when gas is dissolved in the slurry, the dissolved gas molecules in the slurry can be partially adsorbed by the metal organic framework material, and the gas-adsorbed material molecules can reduce the interfacial tension between gas and water, so that the whole system can show good foaming and foam stability characteristics.
In view of various characteristics of the hydrophobic metal organic framework material, the invention provides a method for enhancing oil displacement, profile control and foaming by adopting the hydrophobic metal organic framework material, and the method has important significance for popularizing the application of the metal organic framework material and widening the technology for improving the recovery ratio of crude oil.
Disclosure of Invention
The invention aims to provide a method for reinforcing oil displacement, profile control and foaming by adopting a hydrophobic metal organic framework material, which comprises the steps of directly adding the hydrophobic metal organic framework material into water to form slurry for oil displacement, or mixing the hydrophobic metal organic framework material with a foaming agent, injecting the mixture into an oil reservoir, and then injecting gas to realize foam oil displacement or foam profile control oil displacement. The characteristics of the partially hydrophobic metal organic framework material are utilized, multiple effects of oil displacement, profile control, foaming, foam stabilization and the like can be simultaneously considered, the method has important significance for improving the crude oil recovery ratio of the oil reservoir with strong heterogeneity or cracks, and has positive effects on expanding the application of the metal organic framework material.
In order to achieve the technical purpose, the invention adopts the following technical scheme.
After the hydrophobic metal organic framework material is added into the aqueous solution, a series of oil displacement enhancement effects can be shown: firstly, the viscosity of injected water is improved, the water-oil fluidity ratio in the water solution oil displacement process is reduced, and water breakthrough is delayed; secondly, the suspended hydrophobic metal organic framework material particles in the water have good lipophilicity and can play a role in washing oil; thirdly, the particle size of the metal organic framework material is nano-micro scale, and the metal organic framework material can stay in a place with a small throat to a certain degree in reservoir rock to play a role in blocking, so that the sweep range of the aqueous solution is enlarged, and the sweep efficiency of the displacement fluid is improved; and fourthly, when the gas-water-metal organic framework material is mixed, the whole system can generate a foaming phenomenon, particularly when the gas-water-metal organic framework material-foaming agent is mixed, the hydrophobic metal organic framework material can foam, has a high-efficiency foam stabilizing effect, can improve the foam stabilizing time by at least more than 2 times compared with the foam stabilizing time without adding the metal organic framework material, and shows excellent profile control characteristics.
A method for reinforcing oil displacement, profile control and foaming by adopting a hydrophobic metal organic framework material comprises a direct liquid medium injection oil displacement method and a slurry-gas alternative oil displacement method.
The direct liquid medium injection oil displacement method comprises the following steps:
(1) adding the hydrophobic metal organic framework material into the injected water, and stirring to prepare hydrophobic metal organic framework material/water suspension slurry;
(2) and alternately injecting the suspension slurry slug and the single water slug into the reservoir according to a set proportion to drive the reservoir oil.
The slurry-gas alternative oil displacement method comprises the following steps:
(1) adding the hydrophobic metal organic framework material into injected water or injected water-foaming agent mixed solution, and stirring to prepare suspension slurry;
(2) injecting 1 gas slug into the oil reservoir;
(3) and alternately injecting the suspension slurry slug and the gas slug into the reservoir according to a set proportion to drive the reservoir oil.
Preferably, the injected water can be formation water or laboratory prepared water, and the mineralization degree of the prepared water is not lower than the mineralization degree of the formation water.
Preferably, the diameter of the opening of the pore channel of the hydrophobic metal organic framework material is not greatly different from the diameter of water molecules, so that the water molecules are difficult to enter the pore channel of the material due to the combined action of the hydrophobic property of the material and the opening diameter of the pore channel, and the commercialized metal organic framework material 2-methylimidazole zinc salt (also called ZIF-8) is preferred.
The hydrophobic metal organic framework material ZIF-8 adopts ZnNO3.6H2Nanoporous materials synthesized with O and 2-methylimidazole under suitable experimental conditions (brave. scaled synthesis of ZIF-8 and ZIF-67 and application in separation of gas/liquid mixtures. doctrine of bosch graduate, university of china (beijing), 2016).
Preferably, the mass percentage of the hydrophobic metal organic framework material in the aqueous solution is 1-10%, preferably 1-5%.
Preferably, in the direct liquid medium injection oil displacement method, the volume ratio of the hydrophobic metal organic framework material/water suspension slurry slug to the single water slug is 1: 3.
preferably, in the slurry-gas alternative flooding method, the injected gas is one or more of nitrogen, oxygen-reduced air and natural gas without acid gas components.
Preferably, in the slurry-gas alternative flooding method, the foaming agent is a neutral or alkaline commercial foaming agent, preferably Sodium Dodecyl Sulfate (SDS), and the mass fraction is 1%.
Preferably, in the slurry-gas alternative flooding method, the gas slug is larger than the slurry slug, and the volume ratio of the suspension slurry slug to the gas slug is preferably 1: 3.
Preferably, for the oil deposit with strong intrastratal heterogeneity, suspension slurry slug-single water slug are selected to be alternately injected for oil displacement, and for the oil deposit with strong interlaminar heterogeneity or cracks, suspension slurry slug-gas slug are selected to be alternately injected for oil displacement.
The technical principle of the invention is as follows:
the hydrophobic metal organic framework material ZIF-8 adopts ZnNO3.6H2The microporous material synthesized by O and 2-methylimidazole under the appropriate experimental conditions has the pore canal inner diameter of single ZIF-8 crystal lattice of 1.16nm, and each crystal lattice passes through Zn with the diameter of 0.34nm2+The hexagonal window connected with the 2-methylimidazole ligand is connected with a quadrilateral window with smaller diameter, and the diameter of the quadrilateral window is far smaller than that of common gas molecules, so that an adsorbed medium (gas) needs to pass through Zn to enter a ZIF-8 pore channel2+And 2-methylimidazole ligand. Although the hexagonal window diameter (0.34nm) on ZIF-8 is slightly larger than the hydrokinetic diameter (. about.0.29 nm), the organic ligand-CH on 2-methylimidazole3The existence of the group enables ZIF-8 to have extremely strong hydrophobic property, so that water molecules are difficult to enter a ZIF-8 pore channel (Huang Liu, equivalent. tunable integration of adsorption memb)rane-adsorption for efficientlyseparating low boiling gas mixtures near normal temperature.ScientificReports,2016,6,21114)。
Compared with the prior art, the metal organic framework material adopted by the invention is high temperature resistant and has good suspension stability in aqueous solution. By utilizing the characteristics of hydrophobicity, oleophylicity, nano-micro scale, gas adsorption foaming, foam stabilization and the like of the metal organic framework material, the mechanisms of singly reducing the fluidity of injected fluid, providing oil washing efficiency, profile control, foaming, enhancing foam stability and the like in the traditional oil displacement process can be coupled, the crude oil recovery rate is obviously improved, and the application prospect is wide.
Drawings
FIG. 1 is a graph comparing the flooding effects of formation water and ZIF-8 slurry in example 1.
FIG. 2 is a graph showing the effect of nitrogen and SDS aqueous solution combined alternate flooding and nitrogen and ZIF-8/formation water-SDS slurry combined alternate flooding in example 2.
Detailed Description
The invention is further illustrated below with reference to the figures and examples in order to facilitate the understanding of the invention by a person skilled in the art. It is to be understood that the invention is not limited in scope to the specific embodiments, but is intended to cover various modifications within the spirit and scope of the invention as defined and defined by the appended claims, as would be apparent to one of ordinary skill in the art.
The hydrophobic metal organic framework material and the foaming agent are both selected from the existing commercial products. Wherein the hydrophobic metal organic framework material such as ZIF-8 is available from Sigma China official website (Cat: 691348), and the foaming agent is available from the Aladdin chemical reagent network. The experimental evaluation of the effect of the hydrophobic metal organic framework material for oil displacement mainly comprises the following indexes: compared with single injected water, the method has the advantages that the hydrophobic oleophilic characteristic of the hydrophobic metal organic framework material is utilized, and the hydrophobic metal organic framework material/water slurry is injected to improve the crude oil recovery degree; secondly, compared with the method that only a single foaming agent solution is added, the foaming volume of the solution is increased and the foam stabilizing time is prolonged after the hydrophobic metal organic framework material is added; and thirdly, further enhanced oil recovery after injection of the gas and the hydrophobic metal organic framework/frother slurry relative to injection of the gas and a single frother solution alone.
Example 1
A method for reinforcing oil displacement, profile control and foaming by adopting a hydrophobic metal organic framework material adopts direct injection of a liquid medium to drive. Preparing formation water in a laboratory, and preparing ZIF-8/formation water slurry according to the ZIF-8: formation water mass ratio of 2: 98; selecting a high-permeability core (permeability of 125mD, plunger sample) and a low-permeability core (permeability of 33mD, plunger sample) to be loaded into a high-low permeability parallel displacement system, and saturating the two cores at an oil reservoir temperature of 78 ℃ and a pressure of 32MPa to prepare formation crude oil (bubble point of 7.6MPa, density of 0.7663 g/cm)3). Firstly, single stratum water is adopted to displace the high-permeability core and the low-permeability core until no oil is produced, and the crude oil recovery rates of the high-permeability core and the low-permeability core are respectively measured to be 35.8 percent and 26.2 percent (see figure 1); and then according to ZIF-8/formation water slurry: the volume ratio of formation water is 1:3, the residual crude oil in the rock core is displaced by alternately injecting a displacement system, and the size of a slug is 0.05 times of the total volume of pores of the two rock cores; in the alternate injection process, the pressure difference between two ends of the high-permeability core and the low-permeability core gradually rises, and after 2 slurry slugs are alternately injected, the oil is extracted from the high-permeability core, which indicates that the slurry has an oil washing effect; after 3 slurry slugs are alternately injected, no liquid is discharged from the high-permeability core, which indicates that the ZIF-8 particles block a pore channel in the high-permeability core, the liquid discharge amount of the low-permeability core is increased, oil begins to be discharged, and after a liquid medium which is 1.5 times of the total volume of pores of the two cores is injected, no oil is discharged from the port of the low-permeability core. And finally, the oil recovery ratio of the high-low permeability pipe is measured to be 52.4 percent and 48.5 percent respectively (see figure 1), and the oil recovery ratio is obviously improved. The ZIF-8 material has the effects of washing oil and plugging a high-permeability pore channel for profile control in the whole displacement process.
Example 2
A method for reinforcing oil displacement, profile control and foaming by adopting a hydrophobic metal organic framework material adopts gas and slurry of the hydrophobic metal organic framework material to drive alternately. ZIF-8/formation water-SDS slurry is prepared according to the mass ratio of ZIF-8 to formation water to Sodium Dodecyl Sulfate (SDS) of 2:97: 1. Selecting high-permeability core (permeability of 125mD, plunger sample) and low-permeability core (permeability of 33mD, plunger sample) to be filled into high-low permeability parallel floodingIn the system, two cores are saturated to prepare formation crude oil (bubble point 7.6MPa, density: 0.7663 g/cm) at reservoir temperature 78 ℃ and pressure 32MPa3). Firstly, injecting a nitrogen slug with the volume 0.1 time of the total volume of the pores of the two cores by 1, and then maintaining the slurry slug: and the nitrogen slug is equal to 1:3, and the gas-slurry alternating driving is carried out on the crude oil in the rock core until no oil is produced. The size of the fluid slug in the alternate flooding process is 0.05 times of the total volume of the pores of the two cores. Finally, the oil recovery rates of the hypertonic rock core and the hypotonic rock core are 67.3 percent and 60.6 percent respectively (see figure 2).
For comparative analysis, a solution is prepared according to the mass ratio of formation water to Sodium Dodecyl Sulfate (SDS) of 99:1, an SDS aqueous solution is used for replacing ZIF-8/formation water-SDS slurry, and the experiment is repeated once, so that the crude oil recovery rates of the high-permeability core and the low-permeability core are respectively 59.8% and 51.2% (see figure 2), which are obviously lower than the alternating displacement effect of nitrogen and ZIF-8/formation water-SDS slurry, and the ZIF-8 material is proved to have the effect of obviously improving the crude oil recovery rate in the whole displacement process.
Example 3
ZIF-8 foaming and foam stabilizing effects of example 2 were evaluated: 10mL of an aqueous SDS-formation solution (mass fraction of SDS: 1 wt%) was mixed with high pressure nitrogen (pressure: 32MPa) in a high pressure zone visual window apparatus at a water-gas volume ratio of 1:5, and the experimental temperature was 78 ℃ at the reservoir temperature, and it was found that the volume of generated bubbles was 18.5mL, but the bubbles substantially disappeared after standing for 20 minutes (see Table 1).
Then mixing 10mL of ZIF-8/formation water-SDS slurry (the mass fraction of ZIF-8 is 2 wt%, and the mass fraction of SDS is 1 wt%) with high-pressure nitrogen (the pressure is 32MPa) in a device with a visual window in a high-pressure zone, wherein the volume ratio of the slurry to the gas is also 1:5, the experimental temperature is 78 ℃ of the reservoir temperature of the oil reservoir, and the finally generated bubble volume is 27mL, which indicates that the ZIF-8 material participates in and promotes foaming; and the volume of the bubbles is still 26mL after standing for 120 minutes (see Table 1), which proves that the ZIF-8 material has excellent foam stabilizing effect.
TABLE 1 ZIF-8 enhanced lather, foam stabilizing effect data
Claims (11)
1. A method for reinforcing oil displacement, profile control and foaming by adopting a hydrophobic metal organic framework material comprises a direct liquid medium injection oil displacement method and a slurry-gas alternative oil displacement method.
2. The method for enhancing oil displacement, profile control and foaming by adopting the hydrophobic metal organic framework material as claimed in claim 1, wherein the direct liquid medium injection oil displacement method comprises the following steps:
(1) adding the hydrophobic metal organic framework material into the injected water, and stirring to prepare hydrophobic metal organic framework material/water suspension slurry;
(2) and alternately injecting the suspension slurry slug and the single water slug into the reservoir according to a set proportion to drive the reservoir oil.
3. The method for enhancing oil displacement, profile control and foaming by adopting the hydrophobic metal organic framework material as claimed in claim 1, wherein the slurry-gas alternative oil displacement method comprises the following steps:
adding the hydrophobic metal organic framework material into injected water or injected water-foaming agent mixed solution, and stirring to prepare suspension slurry;
(2) injecting 1 gas slug into the oil reservoir;
(3) and alternately injecting the suspension slurry slug and the gas slug into the reservoir according to a set proportion to drive the reservoir oil.
4. The method for enhancing oil displacement profile control foaming by using the hydrophobic metal organic framework material as claimed in claim 2 or 3, wherein the injected water is formation water or laboratory prepared water, and the mineralization degree of the prepared water is not lower than the mineralization degree of the formation water.
5. The method for enhancing oil displacement profile control foaming by using the hydrophobic metal organic framework material as claimed in claim 2 or 3, wherein the hydrophobic metal organic framework material is 2-methylSalts of zinc imidazoles with ZnNO3.6H2And (3) a nano microporous material synthesized by O and 2-methylimidazole.
6. The method for enhancing oil displacement, profile control and foaming by adopting the hydrophobic metal organic framework material as claimed in claim 2 or 3, wherein the mass percentage of the hydrophobic metal organic framework material in the aqueous solution is 1-10%.
7. The method for enhancing oil displacement, profile control and foaming by adopting the hydrophobic metal organic framework material as claimed in claim 2, wherein in the direct liquid medium injection oil displacement method, the volume ratio of the hydrophobic metal organic framework material/water suspension slurry slug to the single water slug is 1: 3.
8. the method for enhancing oil displacement, profile control and foaming by using the hydrophobic metal organic framework material as claimed in claim 3, wherein in the slurry-gas alternative oil displacement method, the injected gas is one or a mixture of nitrogen, oxygen-reduced air and natural gas without acid gas components.
9. The method for enhancing oil displacement, profile control and foaming by adopting the hydrophobic metal organic framework material as claimed in claim 3, wherein in the slurry-gas alternative oil displacement method, the foaming agent is sodium dodecyl sulfate with the mass fraction of 1%.
10. The method for enhancing oil displacement, profile control and foaming by adopting the hydrophobic metal organic framework material as claimed in claim 3, wherein in the slurry-gas alternative oil displacement method, the volume ratio of the suspended slurry slug to the gas slug is 1: 3.
11. The method for enhancing oil displacement, profile control and foaming by adopting the hydrophobic metal organic framework material as claimed in claim 2 or 3, wherein for an oil reservoir with strong intrastratic heterogeneity, suspension slurry slug-single water slug is selected to be alternately injected for oil displacement, and for an oil reservoir with strong interlaminar heterogeneity or cracks, suspension slurry slug-gas slug is selected to be alternately injected for oil displacement.
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| CN113389533A (en) * | 2021-07-05 | 2021-09-14 | 西南石油大学 | CO (carbon monoxide)2Integrated method for collecting, reservoir reforming and extracting crude oil |
| CN113583647A (en) * | 2021-08-02 | 2021-11-02 | 南京师范大学 | surfactant-MOF composite material and preparation method thereof |
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