CN113444509B - Supercritical carbon dioxide foam system, preparation method thereof and foaming liquid - Google Patents
Supercritical carbon dioxide foam system, preparation method thereof and foaming liquid Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 278
- 238000005187 foaming Methods 0.000 title claims abstract description 173
- 239000006260 foam Substances 0.000 title claims abstract description 157
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 139
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 139
- 239000007788 liquid Substances 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 84
- 239000011780 sodium chloride Substances 0.000 claims abstract description 48
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000004088 foaming agent Substances 0.000 claims abstract description 19
- 239000003381 stabilizer Substances 0.000 claims abstract description 18
- 239000002280 amphoteric surfactant Substances 0.000 claims abstract description 10
- 239000012530 fluid Substances 0.000 claims description 59
- 239000012267 brine Substances 0.000 claims description 27
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 4
- 230000033558 biomineral tissue development Effects 0.000 description 19
- 230000001965 increasing effect Effects 0.000 description 19
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 9
- 229960003237 betaine Drugs 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000000007 visual effect Effects 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- -1 salt ions Chemical class 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—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 surfactants
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/594—Compositions used in combination with injected gas, e.g. CO2 orcarbonated gas
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/92—Compositions for stimulating production by acting on the underground formation characterised by their form or by the form of their components, e.g. encapsulated material
- C09K8/94—Foams
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
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- Gas Separation By Absorption (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a supercritical carbon dioxide foam system, a preparation method thereof and foaming liquid. The foaming liquid for the supercritical carbon dioxide foam system comprises 0.01-1wt% of foaming agent, 0.1-3wt% of foam stabilizer and the balance of saline water, wherein the mass of the foaming liquid is 100%; wherein the foaming agent is an amphoteric surfactant, and the foam stabilizer is hydrophilic silica sol. The supercritical carbon dioxide foam system comprises supercritical carbon dioxide and the foaming liquid. The foaming liquid provided by the invention can well form a supercritical carbon dioxide foam system under the action of supercritical carbon dioxide, the formed supercritical carbon dioxide foam system has good salt resistance and good foamability, and abundant foam can be generated under severe oil reservoir conditions.
Description
Technical Field
The invention belongs to the technical field of oil and gas field development and oil extraction, and particularly relates to a supercritical carbon dioxide foam system suitable for a high-salinity oil reservoir, a preparation method of the supercritical carbon dioxide foam system, and foaming liquid for the supercritical carbon dioxide foam system.
Background
In China, high-temperature high-salinity low-permeability oil reservoirs are gradually developed along with the continuous reduction of yield-increasing potential of old oil fields. Under the condition of an oil reservoir, the supercritical carbon dioxide has high-efficiency oil displacement effects of viscosity reduction, expansion and energy increase, interface tension reduction and the like, and gradually becomes an important technical means for low-permeability oil reservoir development. And CO 2 The oil displacement also becomes CCUS (CO) 2 Trapping, utilization and sealing) techniqueAn indispensable part of the oil well, can realize CO while improving the underground recovery rate 2 And (7) burying.
However, in the supercritical carbon dioxide flooding process, due to the characteristics of small gas density, low viscosity, stratum heterogeneity and the like, problems of gas channeling, overlaying, viscous fingering and the like often occur, so that the gas flooding efficiency is low, and the effect of improving the recovery ratio is poor. Therefore, to expand the gas flooding spread, supercritical CO 2 Foams have developed into an important technological means of reducing the fluidity of carbon dioxide. The conventional carbon dioxide foam has poor foaming performance and low stability under the condition of high salt, so that the foam flooding effect is reduced. For example, the commonly used anionic surfactant Sodium Dodecyl Sulfate (SDS) precipitates when it encounters inorganic salts, and the cationic surfactant cetyltrimethylammonium bromide (CTAB) has a high absorption loss in formation rock, which all contribute to poor foam properties. In order to improve the foam stability, a method of adding a polymer, inorganic particles, or the like to a foaming agent is generally employed. Although the methods can improve the foam stability, under the oil reservoir conditions of high temperature, high salinity and high pressure, the polymer is easy to degrade, the inorganic particles are easy to adsorb and settle, and finally the foam stabilizing effect is poor. For example, CN 102746841a discloses a nanoparticle-added syntactic foam system for oil and gas fields and a preparation method thereof. The composite foam system consists of anionic surfactant and hydrophobically modified silica nanoparticles, and although the composite system improves foam stability under indoor conditions, the composite foam system is especially Ca-modified under high-salt reservoir conditions 2+ 、Mg 2+ Under the condition of higher content, the anionic surfactant and the nano particles can be precipitated, so that the underground foaming effect is poor.
Disclosure of Invention
The invention aims to provide a foaming liquid for a supercritical carbon dioxide foam system, which is suitable for a high-salinity oil reservoir. The foaming liquid and the supercritical carbon dioxide act to form a supercritical carbon dioxide foam system. The formed supercritical carbon dioxide foam system has good salt resistance and good foamability, and can generate abundant foam under severe oil reservoir conditions.
In order to achieve the above object, the present invention provides a foaming liquid for a supercritical carbon dioxide foam system, wherein the foaming liquid comprises 0.01-1wt% of a foaming agent, 0.1-3wt% of a foam stabilizer, and the balance of brine, based on 100% of the mass of the foaming liquid; the foaming agent is an amphoteric surfactant, and the foam stabilizer is hydrophilic silica sol.
In the foaming liquid for the supercritical carbon dioxide foam system, the foam stabilizer hydrophilic silica sol is an aqueous solution of nano silica particles, can be well dispersed in an aqueous solution of the two-type surfactant, plays an excellent foam stabilizing role in the aqueous solution of the two-type surfactant, and forms the foaming liquid for the supercritical carbon dioxide foam system in a saline water system together with the amphoteric surfactant.
In the foaming liquid for a supercritical carbon dioxide foam system described above, preferably, the amphoteric surfactant includes at least one of tetradecyl hydroxysultaine and hexadecyl hydroxysultaine.
In the foaming liquid for a supercritical carbon dioxide foam system, the mass fraction of the active ingredient of the hydrophilic silica sol is preferably 10% to 50% based on 100% of the total mass of the hydrophilic silica sol, and more preferably the mass fraction of the active ingredient of the hydrophilic silica sol is 30% based on 100% of the total mass of the hydrophilic silica sol.
In the foaming liquid for a supercritical carbon dioxide foam system, preferably, the particle size of the silica particles in the hydrophilic silica sol is 5 to 30 μm.
In the foaming liquid for the supercritical carbon dioxide foam system, preferably, the salinity of the brine is 1 × 10 4 mg/L-25×10 4 mg/L。
In the above-mentioned foaming liquid for supercritical carbon dioxide foam system, preferably, the brine contains NaCl and CaCl 2 (ii) a More preferably, the NaCl and CaCl 2 The mass ratio is 5:1-10: 1; further preferably, the NaCl and CaCl are 2 The mass ratio is 9: 1.
In a specific embodiment, the foaming liquid contains a foaming agent, a foam stabilizer, NaCl, CaCl 2 The mass ratio of the water to the water is (0.1-1): 0.01-0.1): 1.8-22.5): 0.2-2.5): 100.
In a specific embodiment, the foaming liquid contains a foaming agent, a foam stabilizer, NaCl, CaCl 2 The mass ratio of the water to the water is (0.1-1): 0.01-0.1):1.8:0.2: 100.
In a specific embodiment, the foaming liquid contains a foaming agent, a foam stabilizer, NaCl, CaCl 2 The mass ratio of the water to the water is (0.1-1): 0.01-0.1):4.5:0.5: 100.
In a specific embodiment, the foaming liquid contains a foaming agent, a foam stabilizer, NaCl, CaCl 2 The mass ratio of the water to the water is (0.1-1): 0.01-0.1):9:1: 100.
In a specific embodiment, the foaming liquid contains a foaming agent, a foam stabilizer, NaCl, CaCl 2 The mass ratio of the water to the water is (0.1-1): 0.01-0.1):13.5:1.5: 100.
In a specific embodiment, the foaming liquid contains a foaming agent, a foam stabilizer, NaCl, CaCl 2 The mass ratio of the water to the water is (0.1-1): 0.01-0.1):18:2: 100.
In a specific embodiment, the foaming liquid contains a foaming agent, a foam stabilizer, NaCl, CaCl 2 The mass ratio of the water to the water is (0.1-1): (0.01-0.1):22.5:2.5: 100.
In a specific embodiment, the foaming liquid contains a foaming agent, a foam stabilizer, NaCl, CaCl 2 The mass ratio of the water to the water is (0.1-1): 0.01-0.1):9:1: 100.
The invention also provides a preparation method of the foaming liquid for the supercritical carbon dioxide foam system, wherein the method comprises the following steps:
preparing saline water, adding a foaming agent and a foam stabilizer into the saline water, and mixing (which can be performed by adopting a magnetic stirring mode) to obtain the foaming liquid for the supercritical carbon dioxide foam system.
The invention also provides a supercritical carbon dioxide foam system, wherein the system comprises supercritical carbon dioxide and the foaming liquid.
The invention also provides a preparation method of the supercritical carbon dioxide foam system, wherein the preparation method comprises the following steps: introducing carbon dioxide into the high-temperature high-pressure reactor filled with the bubble liquid, and stirring at 60-120 ℃ and 7.5-15MPa (preferably 70 ℃ and 8MPa) to obtain the supercritical carbon dioxide foam system.
In the above method for preparing a supercritical carbon dioxide foam system, the stirring speed is preferably 500-3000r/min, and more preferably 2000 r/min.
In the above preparation method of the supercritical carbon dioxide foam system, preferably, the stirring time is 3-10 min; more preferably, the stirring time is 5 min.
The foaming agent adopted by the foaming liquid for the supercritical carbon dioxide foam system provided by the invention is an amphoteric surfactant, and CO is generated in a high-pressure environment 2 The aqueous solution is acidic, and with the increase of the mineralization degree, the salt ions can shield the action repulsion force between the amphoteric surfactants and increase the adsorption of the surfactants on a gas-liquid interface, thereby enhancing the stability of the liquid film. The foam stabilizer is hydrophilic silica sol which is easily dispersed in water and has good compatibility with a surfactant, and nano particles in the silica sol can be directionally adsorbed on a gas-liquid interface to fill gaps left by the surfactant on the interface, so that the compactness and the foam stability of a liquid film are improved; and the silica sol is negatively charged and generates repulsion action with salt ions, and the adsorption of nano particles in the silica sol on a gas-liquid interface can be improved along with the increase of the mineralization degree, so that the silica sol and a foaming agent can play a synergistic action, and the application effect of the supercritical carbon dioxide foam system under severe oil reservoir conditions is greatly improved.
According to the supercritical carbon dioxide foam system provided by the invention, the foaming liquid containing the amphoteric surfactant, the hydrophilic silica sol and the saline water and the supercritical carbon dioxide are adopted to form the supercritical carbon dioxide foam system, and under the coordination of the amphoteric surfactant and the hydrophilic silica sol, the formed supercritical carbon dioxide foam system can show excellent foaming capacity and foam stability (the stability shows good shear stability, longer half-life period and the like) under the condition of high mineralization degree, has good salt resistance, and can be suitable for high-mineralization-degree oil reservoirs.
Drawings
FIG. 1 shows an apparatus for preparing a high temperature and high pressure supercritical carbon dioxide foam system used in example 1.
Figure 2 is a graph of the viscosity versus the supercritical carbon dioxide foam system at different shear rates provided in examples 19-24.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Description of terms:
supercritical carbon dioxide is carbon dioxide at an ambient temperature and pressure above the critical point (31 ℃, 7.38 MPa).
Example 1
The embodiment provides a foaming liquid for a supercritical carbon dioxide foam system, wherein the foaming liquid comprises 0.1g of tetradecyl dimethyl betaine, 0.01g of hydrophilic silica sol (the mass fraction of active ingredients of the hydrophilic silica sol is 30%, and the particle size of silica particles in the hydrophilic silica sol is 5-30 μm) and saline; wherein the brine comprises 1.8g NaCl, 0.2g CaCl 2 The mass was 100mL of water.
The foaming liquid for the supercritical carbon dioxide foam system is prepared by the following preparation method:
adding NaC and CaCl 2 Mixing with water to prepare saline, then adding tetradecyl dimethyl betaine and hydrophilic silica sol into the saline, and magnetically stirring for 10-15min to obtain the foaming liquid for the supercritical carbon dioxide foam system.
The embodiment also provides a supercritical carbon dioxide foam system, wherein the system comprises supercritical carbon dioxide and the foaming liquid provided by the embodiment.
The supercritical carbon dioxide foam system is prepared by a preparation method, wherein,
the preparation method adopts a device shown in figure 1 for preparation, the device comprises a carbon dioxide gas cylinder, an intermediate container and a visual reaction kettle which are connected in sequence, wherein the visual reaction kettle is a high-temperature high-pressure reaction kettle, the reaction kettle is provided with a liquid inlet for conveying foaming liquid and an exhaust port for exhausting, and the reaction kettle controls the stirring speed, the temperature and the pressure through a computer;
the preparation method comprises the following steps: 100mL of foaming liquid provided by the embodiment is input into a visual reaction kettle (with the volume of 600mL), then carbon dioxide is introduced into the visual reaction kettle to enable the pressure of the reaction kettle to reach 5MPa, the temperature is heated to 70 ℃, the pressure is regulated to 8MPa through a vent valve at constant temperature, and after the temperature and the pressure are constant, the supercritical carbon dioxide foam system is obtained by stirring at the speed of 2000r/min for 5 minutes.
The initial foam volume and the decant volume were recorded as a function of time. The lather volume and half-life are determined and are shown in Table 1.
Table 1 examples 1-6 properties of supercritical carbon dioxide foam systems
Degree of mineralization/10 4 mg·L -1 | Bubbling volume/mL | Half life/min | |
Example 1 | 2 | 560 | 8.9 |
Example 2 | 5 | 557 | 9.2 |
Example 2 | 10 | 550 | 10.6 |
Example 4 | 15 | 542 | 12.8 |
Example 5 | 20 | 540 | 13.7 |
Example 6 | 25 | 535 | 16.3 |
Example 2
This example provides a foaming liquid for a supercritical carbon dioxide foam system, which differs from example 1 only in that the brine of the foaming liquid has a NaCl mass of 4.5g and CaCl 2 The mass was 0.5g, and the rest was the same as in example 1.
This example also provides a supercritical carbon dioxide foam system that differs from example 1 only in that the foaming fluid provided in this example was used as the foaming fluid.
The lather volume and half-life measured in this example are shown in Table 1.
Example 3
This example provides a foaming liquid for supercritical carbon dioxide foaming system, which differs from example 1 only by Na in brine of the foaming liquidThe mass of Cl is 9g and CaCl 2 The mass was 1g, and the rest was the same as in example 1.
This example also provides a supercritical carbon dioxide foam system that differs from example 1 only in that the foaming fluid provided in this example was used as the foaming fluid.
The lather volume and half-life measured in this example are shown in Table 1.
Example 4
This example provides a foaming liquid for a supercritical carbon dioxide foam system, which differs from example 1 only in that the brine of the foaming liquid has a NaCl mass of 13.5g and CaCl 2 The mass was 1.5g, and the rest was the same as in example 1.
This example also provides a supercritical carbon dioxide foam system that differs from example 1 only in that the foaming fluid provided in this example was used as the foaming fluid.
The lather volume and half-life measured in this example are shown in Table 1.
Example 5
This example provides a foaming liquid for a supercritical carbon dioxide foam system, which differs from example 1 only in that the brine of the foaming liquid has a NaCl mass of 18g and CaCl 2 The mass was 2g, and the rest was the same as in example 1.
This example also provides a supercritical carbon dioxide foam system that differs from example 1 only in that the foaming fluid provided in this example was used as the foaming fluid.
The lather volume and half-life measured in this example are shown in Table 1.
Example 6
This example provides a foaming liquid for a supercritical carbon dioxide foam system, which differs from example 1 only in that the brine of the foaming liquid has a NaCl mass of 22.5g and CaCl 2 The mass was 2.5g, and the rest was the same as in example 1.
This example also provides a supercritical carbon dioxide foam system that differs from example 1 only in that the foaming fluid provided in this example was used as the foaming fluid.
The lather volume and half-life measured in this example are shown in Table 1.
As can be seen from Table 1, the foaming volume was substantially 530-560mL with increasing degree of mineralization, and the change was small. However, the half-life increases with increasing degree of mineralization, when the degree of mineralization is from 2X 10 4 The mg/L is increased to 25X 10 4 mg/L, the half-life increased from 8.9min to 16.3min, indicating that the mineralization increased the stability of the foam better.
Example 7
This example provides a foaming liquid for a supercritical carbon dioxide foam system, which is different from example 1 only in that the mass of tetradecyldimethyl betaine in the foaming liquid is 0.5g, the mass of hydrophilic silica sol is 0.05g, and the rest is the same as example 1.
This example also provides a supercritical carbon dioxide foam system that differs from example 1 only in that the foaming fluid provided in this example was used as the foaming fluid.
The lather volume and half-life measured in this example are shown in Table 2.
Table 2 examples 7-12 properties of supercritical carbon dioxide foam systems
Example 8
This example provides a foaming fluid for a supercritical carbon dioxide foam system which differs from example 7 only in that the brine of the foaming fluid has a NaCl mass of 4.5g and CaCl 2 The mass was 0.5g, and the rest was the same as in example 7.
This example also provides a supercritical carbon dioxide foam system that differs from example 7 only in that the foaming fluid provided in this example was used as the foaming fluid.
The lather volume and half-life measured in this example are shown in Table 2.
Example 9
This example provides a foaming liquid for a supercritical carbon dioxide foam system, which differs from example 7 only in that the brine of the foaming liquid has a NaCl mass of 9g and CaCl 2 The mass was 1g, and the rest was the same as in example 7.
This example also provides a supercritical carbon dioxide foam system that differs from example 7 only in that the foaming fluid provided in this example was used as the foaming fluid.
The lather volume and half-life measured in this example are shown in Table 2.
Example 10
This example provides a foaming liquid for a supercritical carbon dioxide foam system, which differs from example 7 only in that the brine of the foaming liquid has a NaCl mass of 13.5g and CaCl 2 The mass was 1.5g, and the rest was the same as in example 7.
This example also provides a supercritical carbon dioxide foam system that differs from example 7 only in that the foaming fluid provided in this example was used as the foaming fluid.
The lather volume and half-life measured in this example are shown in Table 2.
Example 11
This example provides a foaming liquid for a supercritical carbon dioxide foam system, which differs from example 7 only in that the brine of the foaming liquid has a NaCl mass of 18g and CaCl 2 The mass was 2g, and the rest was the same as in example 7.
This example also provides a supercritical carbon dioxide foam system that differs from example 7 only in that the foaming fluid provided in this example was used as the foaming fluid.
The lather volume and half-life measured in this example are shown in Table 2.
Example 12
This example provides a foaming liquid for a supercritical carbon dioxide foam system, which differs from example 7 only in that the brine of the foaming liquid has a NaCl mass of 22.5g and CaCl 2 The mass was 2.5g, and the rest was the same as in example 7.
This example also provides a supercritical carbon dioxide foam system that differs from example 7 only in that the foaming fluid provided in this example was used as the foaming fluid.
The lather volume and half-life measured in this example are shown in Table 2.
As can be seen from Table 2, the foaming volume was substantially 520-550mL with little change as the degree of mineralization increased. However, the half-life increases with increasing degree of mineralization, when the degree of mineralization is from 2X 10 4 The mg/L is increased to 25X 10 4 mg/L, half-life increased from 22.2min to 35.2min, indicating better stability of the mineralization increasing foam.
Example 13
This example provides a foaming liquid for a supercritical carbon dioxide foam system, which is different from example 1 only in that the mass of tetradecyldimethyl betaine in the foaming liquid is 1g, the mass of hydrophilic silica sol is 0.1g, and the other steps are the same as example 1.
This example also provides a supercritical carbon dioxide foam system that differs from example 1 only in that the foaming fluid provided in this example was used as the foaming fluid.
The lather volume and half-life measured in this example are shown in Table 3.
Table 3 examples 13-18 properties of supercritical carbon dioxide foam systems
Degree of mineralization/10 4 mg·L -1 | Bubbling volume/mL | Half life/min | |
Example 13 | 2 | 540 | 28.8 |
Example 14 | 5 | 536 | 29.3 |
Example 15 | 10 | 531 | 30.8 |
Example 16 | 15 | 527 | 36.7 |
Example 17 | 20 | 523 | 38.2 |
Example 18 | 25 | 510 | 40.5 |
Example 14
This example provides a foaming fluid for a supercritical carbon dioxide foam system which differs from example 13 only in that the brine of the foaming fluid has a NaCl mass of 4.5g and CaCl 2 The mass was 0.5g, and the rest was the same as in example 13.
This example also provides a supercritical carbon dioxide foaming system, which is different from example 13 only in that the foaming liquid provided by this example is used as the foaming liquid.
The lather volume and half-life measured in this example are shown in Table 3.
Example 15
This example provides a foaming fluid for a supercritical carbon dioxide foam system which differs from example 13 only in that the brine of the foaming fluid has a NaCl mass of 9g and CaCl 2 The mass was 1g, and the rest was the same as in example 13.
This example also provides a supercritical carbon dioxide foam system that differs from example 13 only in that the foaming fluid provided in this example was used as the foaming fluid.
The lather volume and half-life measured in this example are shown in Table 3.
Example 16
This example provides a foaming liquid for a supercritical carbon dioxide foam system, which differs from example 13 only in that the brine of the foaming liquid has a NaCl mass of 13.5g and CaCl 2 The mass was 1.5g, and the rest was the same as in example 13.
This example also provides a supercritical carbon dioxide foam system that differs from example 13 only in that the foaming fluid provided in this example was used as the foaming fluid.
The lather volume and half-life measured in this example are shown in Table 3.
Example 17
This example provides a foaming liquid for a supercritical carbon dioxide foam system, which differs from example 13 only in that the brine of the foaming liquid has a NaCl mass of 18g and CaCl 2 The mass was 2g, and the rest was the same as in example 13.
This example also provides a supercritical carbon dioxide foam system that differs from example 13 only in that the foaming fluid provided in this example was used as the foaming fluid.
The lather volume and half-life measured in this example are shown in Table 3.
Example 18
This example provides a foaming liquid for a supercritical carbon dioxide foaming system, which is different from example 13 only in that the foaming liquidThe mass of NaCl in the brine is 22.5g and CaCl 2 The mass was 2.5g, and the rest was the same as in example 13.
This example also provides a supercritical carbon dioxide foam system that differs from example 13 only in that the foaming fluid provided in this example was used as the foaming fluid.
The lather volume and half-life measured in this example are shown in Table 3.
As can be seen from Table 3, the foaming volume was substantially 520-550mL with little change as the degree of mineralization increased. However, the half-life increases with increasing degree of mineralization, when the degree of mineralization is from 2X 10 4 The mg/L is increased to 25X 10 4 mg/L, half-life increased from 28.8min to 40.5min, indicating better stability of the mineralization increasing foam.
Example 19
The embodiment provides a foaming liquid for a supercritical carbon dioxide foam system, wherein the foaming liquid comprises 0.5g of tetradecyl dimethyl betaine, 0.05g of hydrophilic silica sol (the mass fraction of active ingredients of the hydrophilic silica sol is 30%, and the particle size of silica particles in the hydrophilic silica sol is 5-30 μm) and saline; wherein the brine comprises 1.8g of NaCl and CaCl 2 The mass was 0.2g, and the volume of water was 100 mL.
The foaming liquid for the supercritical carbon dioxide foam system is prepared by the following preparation method:
adding NaC and CaCl 2 Mixing with water to prepare saline, then adding tetradecyl dimethyl betaine and hydrophilic silica sol into the saline, and magnetically stirring for 10-15min to obtain the foaming liquid for the supercritical carbon dioxide foam system.
The embodiment also provides a supercritical carbon dioxide foam system, wherein the system comprises supercritical carbon dioxide and the foaming liquid provided by the embodiment.
The supercritical carbon dioxide foam system is prepared by a preparation method, wherein,
the preparation method comprises the following steps: under the conditions of 70 ℃ and 8MPa, injecting the carbon dioxide and the foaming liquid gas-liquid ratio for the supercritical carbon dioxide foam system into a capillary (the length of the capillary is 8m, and the inner diameter is 0.5mm) at the total flow rate of 6mL/min, 10mL/min, 15mL/min and 20mL/min respectively according to the ratio of the carbon dioxide to the foaming liquid gas to the supercritical carbon dioxide foam system of 1:1, and obtaining the supercritical carbon dioxide foam system under the conditions of different shear rates.
The viscosity of the supercritical carbon dioxide foam system under different shear rate conditions is calculated by measuring the pressure difference at the two ends of the capillary, and the experimental result is shown in fig. 2.
The conversion relationship between the shear rate and the flow rate is shown in the following equations (1) to (5):
τ=Kγ n (3)
γ N for shear rate, S -1 ;τ N Is a shear stress Pa; n is a flow index and has no dimension; k is a consistency coefficient and has no dimension; v. of f Is CO 2 The section velocity of foam in the capillary tube flow, m/s, D capillary diameter, mm; pressure drop, Pa, across the Δ P capillary; l capillary length, mm; q is flow, mL/min; a is the cross-sectional area of the capillary tube, mm 2 。
Example 20
This example provides a foaming fluid for a supercritical carbon dioxide foam system which differs from example 19 only in that the brine of the foaming fluid has a NaCl mass of 4.5g and CaCl 2 The mass was 0.5g, and the rest was the same as in example 19.
This example also provides a supercritical carbon dioxide foam system that differs from example 19 only in that the foaming fluid provided in this example was used as the foaming fluid.
The viscosities of the supercritical carbon dioxide foam systems at different shear rates measured in this example are shown in figure 2.
Example 21
This example provides a foaming liquid for a supercritical carbon dioxide foam system, which differs from example 19 only in that the brine of the foaming liquid has a NaCl mass of 9g and CaCl 2 The mass was 1g, and the rest was the same as in example 19.
This example also provides a supercritical carbon dioxide foam system, which is different from example 19 only in that the foaming liquid provided by this example is used as the foaming liquid.
The viscosities of the supercritical carbon dioxide foam systems at different shear rates measured in this example are shown in FIG. 2
Example 22
This example provides a foaming liquid for a supercritical carbon dioxide foam system, which differs from example 19 only in that the brine of the foaming liquid has a NaCl mass of 13.5g and CaCl 2 The mass was 1.5g, and the rest was the same as in example 19.
This example also provides a supercritical carbon dioxide foam system that differs from example 19 only in that the foaming fluid provided in this example was used as the foaming fluid.
The viscosities of the supercritical carbon dioxide foam systems at different shear rates measured in this example are shown in figure 2.
Example 23
This example provides a foaming liquid for a supercritical carbon dioxide foam system, which differs from example 19 only in that the brine of the foaming liquid has a NaCl mass of 18g and CaCl 2 The mass was 2g, and the rest was the same as in example 19.
This example also provides a supercritical carbon dioxide foam system that differs from example 19 only in that the foaming fluid provided in this example was used as the foaming fluid.
The viscosities of the supercritical carbon dioxide foam systems at different shear rates measured in this example are shown in figure 2.
Example 24
This example provides a foaming liquid for a supercritical carbon dioxide foam system, which differs from example 19 only in that the brine of the foaming liquid has a NaCl mass of 22.5g and CaCl 2 The mass was 2.5g, and the rest was the same as in example 19.
This example also provides a supercritical carbon dioxide foam system that differs from example 19 only in that the foaming fluid provided in this example was used as the foaming fluid.
The viscosities of the supercritical carbon dioxide foam systems at different shear rates measured in this example are shown in figure 2.
As can be seen from FIG. 2, under the conditions of different shear rates, the higher the mineralization degree is, the higher the viscosity of the supercritical carbon dioxide foam system is, the more favorable the reduction of the fluidity of the supercritical carbon dioxide is, thereby enlarging the swept volume and improving the oil reservoir recovery ratio. The increase of the mineralization degree can enable the foam to be more stable, the salt ions can shield the action repulsion force between the surface active agents, and the adsorption of the surface active agents on a gas-liquid interface is increased, so that the stability of the liquid film is enhanced.
Example 25
This example provides a foaming liquid for a supercritical carbon dioxide foam system, which is different from example 1 only in that the mass of tetradecyldimethyl betaine in the foaming liquid is 0.5g, the mass of hydrophilic silica sol is 1g, and the other steps are the same as example 1.
This example also provides a supercritical carbon dioxide foam system that differs from example 1 only in that the foaming fluid provided in this example was used as the foaming fluid.
The lather volume and half-life measured in this example are shown in Table 4.
Table 4 examples 25-29 properties of supercritical carbon dioxide foam systems
Content of hydrophilic silica sol/%) | Bubbling volume/mL | Half life/min | |
Example 25 | 0.02 | 545 | 17.2 |
Example 26 | 0.04 | 550 | 20.3 |
Example 27 | 0.06 | 540 | 24.8 |
Example 28 | 0.08 | 535 | 26.2 |
Example 29 | 0.1 | 540 | 28.5 |
Example 26
This example provides a foaming liquid for a supercritical carbon dioxide foam system, which is different from example 25 only in that the mass of hydrophilic silica sol in the foaming liquid is 2g, and the rest is the same as example 25.
This example also provides a supercritical carbon dioxide foam system that differs from example 25 only in that the foaming fluid provided in this example was used as the foaming fluid.
The lather volume and half-life measured in this example are shown in Table 4.
Example 27
This example provides a foaming liquid for a supercritical carbon dioxide foam system, which is different from example 25 only in that the mass of hydrophilic silica sol in the foaming liquid is 3g, and the other steps are the same as example 25.
This example also provides a supercritical carbon dioxide foam system that differs from example 25 only in that the foaming fluid provided in this example was used as the foaming fluid.
The lather volume and half-life measured in this example are shown in Table 4.
Example 28
This example provides a foaming liquid for a supercritical carbon dioxide foam system, which is different from example 25 only in that the mass of hydrophilic silica sol in the foaming liquid is 4g, and the rest is the same as example 25.
This example also provides a supercritical carbon dioxide foam system that differs from example 25 only in that the foaming fluid provided in this example was used as the foaming fluid.
The lather volume and half-life measured in this example are shown in Table 4.
Example 29
This example provides a foaming liquid for a supercritical carbon dioxide foam system, which is different from example 25 only in that the mass of hydrophilic silica sol in the foaming liquid is 5g, and the other steps are the same as example 25.
This example also provides a supercritical carbon dioxide foam system that differs from example 25 only in that the foaming fluid provided in this example was used as the foaming fluid.
The lather volume and half-life measured in this example are shown in Table 4.
It can be seen from table 4 that the foam volume did not change much with increasing hydrophilic silica sol; when the hydrophilic silica sol is increased from 0.02% to 0.1%, the half-life is increased from 17.2min to 28.5min, which indicates that the hydrophilic silica sol can enhance the stability of the foam.
Although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that: modifications and equivalents may be made thereto without departing from the spirit and scope of the invention and it is intended to cover any modifications or equivalents as may fall within the scope of the invention.
Claims (13)
1. The foaming liquid for the supercritical carbon dioxide foam system comprises 0.01-1wt% of foaming agent, 0.1-3wt% of foam stabilizer and the balance of brine, wherein the mass of the foaming liquid is 100%;
wherein the foaming agent is an amphoteric surfactant, the foam stabilizer is hydrophilic silica sol, and the salinity of the saline water is 1 multiplied by 10 4 mg/L- 25×10 4 mg/L;
Wherein the amphoteric surfactant comprises at least one of tetradecyl hydroxysultaine and hexadecyl hydroxysultaine;
wherein the mass fraction of the effective components of the hydrophilic silica sol is 10-50% based on 100% of the total mass of the hydrophilic silica sol;
wherein the particle size of the silica particles in the hydrophilic silica sol is 5-30 μm.
2. The foaming liquid according to claim 1, wherein the mass fraction of the active ingredient of the hydrophilic silica sol is 30% based on 100% of the total mass of the hydrophilic silica sol.
3. Foaming liquid according to claim 1Wherein the brine comprises NaCl and CaCl 2 。
4. Foaming liquid according to claim 3, wherein the NaCl and CaCl are 2 The mass ratio is 5:1-10: 1.
5. Foaming liquid according to claim 4, wherein the NaCl and CaCl are 2 The mass ratio is 9: 1.
6. Foaming liquid according to any one of the claims 3-5, wherein the foaming liquid comprises a foaming agent, a foam stabilizer, NaCl, CaCl 2 The mass ratio of the water to the water is (0.1-1): 0.01-0.1): 1.8-22.5): 0.2-2.5): 100.
7. A supercritical carbon dioxide foam system, wherein the system comprises supercritical carbon dioxide and a foaming fluid as claimed in any one of claims 1 to 6.
8. The method of preparing a supercritical carbon dioxide foam system of claim 7, wherein the method comprises:
and introducing carbon dioxide into the high-temperature high-pressure reactor filled with the bubble liquid, and stirring at 60-120 ℃ and 7.5-15MPa to obtain the supercritical carbon dioxide foam system.
9. The method according to claim 8, wherein the stirring is carried out at 70 ℃ and 8 MPa.
10. The preparation method as claimed in claim 8, wherein the stirring speed is 500-3000 r/min.
11. The method of claim 10, wherein the stirring speed is 2000 r/min.
12. The method of claim 8, wherein the stirring time is 3-10 min.
13. The production method according to claim 12, wherein the stirring time is 5 min.
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