CN112266777A - Foam discharging foaming agent for shale gas development - Google Patents
Foam discharging foaming agent for shale gas development Download PDFInfo
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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
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- 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
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing 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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
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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
- C09K8/84—Compositions based on water or polar solvents
- C09K8/845—Compositions based on water or polar solvents containing inorganic compounds
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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
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
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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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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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Abstract
The invention relates to the technical field of shale gas development chemical agents, and particularly relates to a foam discharging foaming agent for shale gas development, which comprises the following components in percentage by mass: 35-50% of betaine surfactant, 20-35% of alpha-olefin sulfonate, 15-20% of ammonium salt, 2-5% of ionic liquid and 2-5% of urea. The betaine surfactant and the alpha-olefin sulfonate in the foaming agent are used together, so that the salt resistance and temperature resistance of the foaming agent can be enhanced, the ammonium salt can promote the foaming agent to have good foaming capacity and liquid carrying capacity, and the ionic liquid improves the foam stability; by optimizing the components of the foaming agent for foam discharging and cooperatively matching the components, the liquid carrying capacity and the foam stabilizing performance of the foaming agent are enhanced, and meanwhile, the temperature resistance of the foaming agent is cooperatively enhanced.
Description
Technical Field
The invention relates to the technical field of shale gas development chemical agents, and particularly relates to a foam discharging foaming agent for shale gas development.
Background
Shale gas is a natural gas resource which is stored in a shale layer and can be exploited, and the formation and enrichment of the shale gas have unique characteristics and are often distributed in shale hydrocarbon source rock strata with large thickness and wide distribution in a basin. Compared with the conventional natural gas, the shale gas development has the advantages of long mining life and long production period, most of produced shale gas has wide distribution range and large thickness and generally contains gas, so that the shale gas well can produce gas at a stable rate for a long time. Under the influence of a special seepage mechanism of shale gas, the yield of the gas well has the characteristics of fast early-stage decline, slow middle-stage decline and stable later-stage low yield. The bottom hole effusion is a common problem faced by shale gas well production, and the foam drainage method becomes one of effective measures for solving the bottom hole effusion due to the advantages of small investment, quick effect, simple and convenient operation and the like. The foam drainage gas technology is characterized in that foam drainage foaming agents are injected into a gas well, and after bottom liquid contacts with the foam drainage foaming agents, a large amount of water-containing foam is generated by stirring natural gas flow and is carried to the ground along with the gas flow from the bottom, so that the purposes of increasing yield, stabilizing yield and prolonging the self-blowing period of the foam drainage foaming agents are achieved. The key of foam drainage gas recovery lies in the performance of foam drainage foaming agent, namely under certain methanol content, formation temperature and condensate oil content, the foam drainage agent is required to have foaming capacity and liquid carrying capacity as high as possible. Patent CN102020981A discloses a temperature-resistant salt-resistant low-tension foam oil displacement agent and a preparation method thereof, wherein the main agent of the foaming agent is alkanolamide and a bipolar surfactant, the temperature resistance is relatively poor, and the foaming agent is easy to lose efficacy in the stratum; methanol is usually added when the foaming agent is used, and the methanol can greatly reduce the foaming effect and the foam stabilizing performance of the foaming agent. Therefore, a novel foam discharging and foaming agent for shale gas, which has good temperature resistance and strong methanol resistance, needs to be provided.
Disclosure of Invention
Aiming at the problems of poor temperature resistance and poor methanol resistance of the traditional foam removing foaming agent for shale gas, the invention provides the foam removing foaming agent for shale gas development, which has good temperature resistance, strong methanol resistance, good gas condensate resistance and good compatibility with formation water.
The invention provides a foam discharging and foaming agent for development of shale gas, which comprises the following components in percentage by mass:
35 to 50 percent of betaine type surfactant
20-35% of alpha-olefin sulfonate
15 to 20 percent of ammonium salt
2 to 5 percent of ionic liquid
2 to 5 percent of urea.
Preferably, the foam discharging and foaming agent for shale gas development comprises the following components in percentage by mass:
40-45% of betaine surfactant
27% -35% of alpha-olefin sulfonate
15 to 20 percent of ammonium salt
3 to 5 percent of ionic liquid
3 to 4 percent of urea.
Further preferably, the foam discharging foaming agent for shale gas shale development comprises the following components in percentage by mass:
betaine type surfactant 42%
Alpha-olefin sulfonate 31%
20% of ammonium salt
4 percent of ionic liquid
3 percent of urea.
The betaine surfactant is one or more of coco oleylamine, propyl betaine or hexadecyl betaine; preferably, the betaine surfactant is a mixture of coco oleylamine and propyl betaine, and the mass ratio of coco oleylamine: propyl betaine ═ 2: 1. The combined use of the betaine surfactant and the alpha-olefin sulfonate can enhance the salt resistance and temperature resistance of the foaming agent, and the verification proves that when the betaine surfactant is coconut oil amine: when the propyl betaine is 2:1, the complex performance of the alpha-olefin sulfonate is the best.
The alpha-olefin sulfonate is C14-C18Sodium olefin sulfonates or C14-C18One or two kinds of olefin sulfonic acid potassium; preferably, the alpha-olefin sulfonate is C14-C18Sodium olefin sulfonate. The alpha-olefin sulfonate has the advantages of easy water solubility and good foaming performance, and enhances the foaming performance and the dissolving performance of the foaming agent.
The ammonium salt is one or more of ammonium nitrate, ammonium sulfate, ammonium bisulfate, ammonium carbonate and ammonium bicarbonate; preferably, the ammonium salt is a mixture of ammonium bisulfate and ammonium bicarbonate, and the mass percentage of the ammonium bisulfate is as follows: ammonium bicarbonate 1: 1. The ammonium salt can promote the foaming agent to have good foaming capacity and liquid carrying capacity.
The ionic liquid is [ Bmin]BF4、[Bmin][SO4]、[Bmin][HCOO]One or more of; preferably, the ionic liquid is [ Bmin]BF4. The ionic liquid not only obviously reduces the interfacial tension of the surfactant solution, but also can slow down the trend that repulsive force between liquid films is weakened when the temperature is higher, so that the strength of the liquid films is improved, the foam stability is improved, and the temperature resistance is improved.
The beneficial effect of the invention is that,
(1) the betaine surfactant and the alpha-olefin sulfonate are used together, so that the salt resistance and temperature resistance of the foaming agent can be enhanced, the ammonium salt can promote the foaming agent to have good foaming capacity and liquid carrying capacity, and the ionic liquid improves the foam stability; by optimizing the components of the foaming agent for foam discharging and cooperatively matching the components, the liquid carrying capacity and the foam stabilizing performance of the foaming agent are enhanced, and meanwhile, the temperature resistance of the foaming agent is cooperatively enhanced;
(2) the foam performance test of the foam discharging and foaming agent has good salt resistance, and the salt resistance can reach 25 multiplied by 104mg/L; the anti-methanol injection liquid has good anti-methanol capacity, and the liquid carrying capacity is more than 150mL when 40% methanol is injected; has good bubble foaming capacity and foam stabilizing capacity, the foam amount is up to 100mL, and the foam preservation rate is more than 87 percent after the foam is placed for 7 days.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A foam discharging foaming agent for shale gas development comprises the following components:
42Kg of betaine type surfactant
31Kg of alpha-olefin sulfonate
Ammonium salt 20Kg
4Kg of ionic liquid
3Kg of urea;
the betaine surfactant is a mixture of cocoamine and propyl betaine (the mass ratio of cocoamine to propyl betaine is 2: 1); alpha-olefin sulfonates C14Sodium olefin sulfonate; the ammonium salt is a mixture of ammonium bisulfate and ammonium bicarbonate (in percentage by mass, ammonium bisulfate: ammonium bicarbonate: 1); the ionic liquid is [ Bmin]BF4；
Adding 30Kg of water into a reaction kettle, heating, controlling the temperature at 30 ℃, adding the betaine type surfactant, the alpha-alkenyl sodium sulfonate and the urea, and stirring; adding ammonium salt, stirring, dissolving, and adding ionic liquid Bmim]BF4And stirring and uniformly mixing to obtain the foam discharging foaming agent S1 for shale gas.
Example 2
A foam discharging foaming agent for shale gas development comprises the following components:
betaine type surfactant 45Kg
27Kg of alpha-olefin sulfonate
Ammonium salt 20Kg
5Kg of ionic liquid
3Kg of urea;
the betaine surfactant is coconut oil oleylamine; alpha-olefin sulfonates C16Sodium olefin sulfonate; the ammonium salt is ammonium bisulfate;
adding 40Kg of water into a reaction kettle, heating, controlling the temperature at 30 ℃, adding the betaine type surfactant, the alpha-alkenyl sodium sulfonate and the urea, and stirring; adding ammonium salt, stirring, dissolving, and adding ionic liquid Bmim]BF4And stirring and uniformly mixing to obtain the foam discharging foaming agent S2 for shale gas.
Example 3
A foam discharging foaming agent for shale gas development comprises the following components:
50Kg of betaine type surfactant
25Kg of alpha-olefin sulfonate
Ammonium salt 20Kg
Ionic liquid 3Kg
2Kg of urea;
the betaine type surfactant is propyl betaine; alpha-olefin sulfonates C14Potassium alkene sulfonate; the ammonium salt is ammonium nitrate; the ionic liquid is [ Bmin][HCOO]；
Adding water into a reaction kettle, heating, controlling the temperature to be 35 ℃, adding a betaine type surfactant, alpha-alkenyl sodium sulfonate and urea, and stirring; adding ammonium salt, stirring, dissolving, and adding ionic liquid Bmim]BF4And stirring and uniformly mixing to obtain the foam discharging foaming agent S3 for shale gas.
Example 4
A foam discharging foaming agent for shale gas development comprises the following components:
42Kg of betaine type surfactant
31Kg of alpha-olefin sulfonate
Ammonium salt 20Kg
4Kg of ionic liquid
3Kg of urea;
the betaine surfactant is a mixture of cocoamine and propyl betaine (the mass ratio of cocoamine to propyl betaine is 1: 1); alpha-olefin sulfonates C14Sodium olefin sulfonate; the ammonium salt is a mixture of ammonium bisulfate and ammonium bicarbonate (by mass percentage, ammonium bisulfate: ammonium bicarbonate: 1); the ionic liquid is [ Bmin][HCOO]；
47Kg of water was added toHeating in a reaction kettle, controlling the temperature to be 33 ℃, adding the betaine type surfactant, the alpha-alkenyl sodium sulfonate and the urea, and stirring; adding ammonium salt, stirring, dissolving, and adding ionic liquid Bmim]BF4And stirring and uniformly mixing to obtain the foam discharging foaming agent S4 for shale gas.
Comparative example 1
A foam discharging foaming agent for shale gas development comprises the following components:
50Kg of betaine type surfactant
35Kg of alpha-olefin sulfonate
Ammonium salt 20Kg
3Kg of urea;
the betaine surfactant is a mixture of cocoamine and propyl betaine (the mass ratio of cocoamine to propyl betaine is 2: 1); alpha-olefin sulfonates C14Sodium olefin sulfonate; the ammonium salt is a mixture of ammonium bisulfate and ammonium bicarbonate (in percentage by mass, ammonium bisulfate: ammonium bicarbonate: 1);
adding 30Kg of water into a reaction kettle, heating, controlling the temperature at 30 ℃, adding the betaine type surfactant, the alpha-alkenyl sodium sulfonate and the urea, and stirring; adding ammonium salt, continuously stirring and uniformly mixing to obtain the foam discharging foaming agent D1 for shale gas.
Comparative example 2
A foam discharging foaming agent for shale gas development comprises the following components:
50Kg of betaine type surfactant
Alpha-olefin sulfonate 45Kg
Ionic liquid 3Kg
2Kg of urea;
the betaine surfactant is a mixture of cocoamine and propyl betaine (the mass ratio of cocoamine to propyl betaine is 2: 1); alpha-olefin sulfonates C14Sodium olefin sulfonate; the ammonium salt is a mixture of ammonium bisulfate and ammonium bicarbonate (in percentage by mass, ammonium bisulfate: ammonium bicarbonate: 1); the ionic liquid is [ Bmin]BF4；
Adding 30Kg of water into a reaction kettle, heating, controlling the temperature at 30 ℃, and adding sweetStirring the vegetable alkali type surfactant, the alpha-alkenyl sulfonic acid sodium salt and the urea; adding ammonium salt, stirring, dissolving, and adding ionic liquid Bmim]BF4And stirring and uniformly mixing to obtain the foam discharging foaming agent D2 for shale gas.
Comparative example 3
A foam discharging foaming agent for shale gas development comprises the following components:
63Kg of betaine type surfactant
Ammonium salt 20Kg
4Kg of ionic liquid
3Kg of urea;
the betaine surfactant is a mixture of cocoamine and propyl betaine (the mass ratio of cocoamine to propyl betaine is 2: 1); alpha-olefin sulfonates C14Sodium olefin sulfonate; the ammonium salt is a mixture of ammonium bisulfate and ammonium bicarbonate (in percentage by mass, ammonium bisulfate: ammonium bicarbonate: 1); the ionic liquid is [ Bmin]BF4；
Adding 30Kg of water into a reaction kettle, heating, controlling the temperature to be 40 ℃, adding the betaine type surfactant, the alpha-alkenyl sodium sulfonate and the urea, and stirring; adding ammonium salt, stirring, dissolving, and adding ionic liquid Bmim]BF4And stirring and uniformly mixing to obtain the foam discharging foaming agent D3 for shale gas.
Test example 1
The foaming capacity and the liquid carrying capacity of the foam discharging and foaming agent are evaluated according to the standard SY/T6465-2000 evaluation method for foam discharging and air collecting foaming agent and GB/T7462-1994 evaluation method for foaming plum.
1. Salt tolerance test of S1-S4 and D1-D3
Formulating 15X 10 according to API standards4mg/L、20×104mg/L and 25X 104mg/L brine (NaCl and CaCl in brine)2In a mass ratio of 4: 1). The solubility properties at room temperature and 90 ℃ in brines of different degrees of mineralization are shown in Table 1
TABLE 1 salt resistance of the products at room temperature and 90 deg.C
2. Foaming ability and foam stabilizing property of each product at room temperature
By 25X 10410mL of 0.25% of S1-S4 and D1-D3 are prepared from mg/L of mineralization water, the mixture is poured into a 100mL measuring cylinder, then gas is uniformly injected into the measuring cylinder, the height of foam is measured, the measuring cylinder is sealed, and after the foam is placed for 5 days and 7 days at room temperature, the foam preservation rate (the foam preservation rate is the foam height at the time of measurement/the original foam height 100%) is respectively calculated, and the results are shown in Table 2.
TABLE 2 foaming and foam stabilizing results for different products
3. Methanol resistance
By 25X 10410 mL0.25% of S1-S4 and D1-D3 are prepared from mg/L of mineralization water, 40% of methanol is added, and the height (0S) of Roche foam and the amount of liquid carried by the Roche foam are measured. The results are shown in Table 3.
TABLE 3 results of methanol resistance of various products
Through the optimized formula and the synergistic cooperation of the components, the foaming capacity, the foam stabilizing capacity, the methanol resistance and the temperature resistance of the S1-S4 provided by the application are all superior to those of the D1-D3, wherein the S1 has the best effect.
Although the present invention has been described in detail by way of preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The foam discharging and foaming agent for shale gas development is characterized by comprising the following components in percentage by mass:
35 to 50 percent of betaine type surfactant
20-35% of alpha-olefin sulfonate
15 to 20 percent of ammonium salt
2 to 5 percent of ionic liquid
2 to 5 percent of urea.
2. The foam discharging and foaming agent for shale gas development as claimed in claim 1, wherein the foam discharging and foaming agent comprises the following components by mass percent:
40-45% of betaine surfactant
27% -35% of alpha-olefin sulfonate
15 to 20 percent of ammonium salt
3 to 5 percent of ionic liquid
3 to 4 percent of urea.
3. The foam discharging and foaming agent for shale gas development as claimed in claim 2, wherein the foam discharging and foaming agent comprises the following components by mass percent:
betaine type surfactant 42%
Alpha-olefin sulfonate 31%
20% of ammonium salt
4 percent of ionic liquid
3 percent of urea.
4. The foam ejection agent for shale gas development according to any one of claims 1 to 3, wherein the betaine type surfactant is one or more of coco oleylamine, propyl betaine or cetyl betaine.
5. The foam discharging agent for shale gas development according to claim 4, wherein the betaine type surfactant is a mixture of coco oleylamine and propyl betaine, and the mass ratio of coco oleylamine: propyl betaine ═ 2: 1.
6. The shale gas development foam drainage agent of any of claims 1-3, wherein the alpha olefin sulfonate is C14-C18Sodium olefin sulfonates or C14-C18One or two kinds of olefin sulfonic acid potassium.
7. The foam discharging and foaming agent for shale gas development according to any one of claims 1 to 3, wherein the ammonium salt is one or more of ammonium nitrate, ammonium sulfate, ammonium bisulfate, ammonium carbonate and ammonium bicarbonate.
8. The foam discharging and foaming agent for shale gas development as claimed in claim 7, wherein the ammonium salt is a mixture of ammonium bisulfate and ammonium bicarbonate, and the mass percentage of the ammonium bisulfate is as follows: ammonium bicarbonate 1: 1.
9. The shale gas development foam ejection agent of any of claims 1-3, wherein the ionic liquid is [ Bmin [ ]]BF4、[Bmin][SO4]、[Bmin][HCOO]One or more of (a).
10. The foam-ejection foam-remover for shale gas development of claim 9, wherein the ionic liquid is [ Bmin [ ]]BF4。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113265233A (en) * | 2021-05-24 | 2021-08-17 | 中石化重庆页岩气有限公司 | Foaming agent for foam drainage for normal-pressure shale gas development and preparation method thereof |
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| US20150126417A1 (en) * | 2012-05-25 | 2015-05-07 | Rhodia Operations | Surfactant composition |
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2020
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| US20150126417A1 (en) * | 2012-05-25 | 2015-05-07 | Rhodia Operations | Surfactant composition |
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| CN113265233A (en) * | 2021-05-24 | 2021-08-17 | 中石化重庆页岩气有限公司 | Foaming agent for foam drainage for normal-pressure shale gas development and preparation method thereof |
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Effective date of registration: 20220128 Address after: 100000 22 Chaoyangmen North Street, Chaoyang District, Beijing. Applicant after: CHINA PETROLEUM & CHEMICAL Corp. Applicant after: SINOPEC CHONGQING FULING SHALE GAS EXPLORATION AND DEVELOPMENT Co.,Ltd. Applicant after: Binzhou Guangyou Chemical Co.,Ltd. Address before: 408000 No.6 Hefeng Avenue, Fuling District, Chongqing Applicant before: SINOPEC CHONGQING FULING SHALE GAS EXPLORATION AND DEVELOPMENT Co.,Ltd. Applicant before: Binzhou Guangyou Chemical Co.,Ltd. |
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Application publication date: 20210126 |