CN114479808A - Natural gas reservoir water-lock releasing agent and preparation method and application thereof - Google Patents
Natural gas reservoir water-lock releasing agent and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of natural gas reservoir chemicals, in particular to a natural gas reservoir water-lock releasing agent and a preparation method and application thereof. The natural gas reservoir water-lock breaking agent comprises the following components in percentage by mass based on 100% of the total mass of the water-lock breaking agent: A. 5% -20% of fluorocarbon surfactant; B. 5% -20% of biosurfactant; C. 5% -30% of synergistic auxiliary agent; D. 30 to 85 percent of water. The water-releasing locking agent can greatly reduce the surface tension of water, regulate the surface of a strong water-wet substrate to be neutral wetting or even hydrophobic, and simultaneously reduce the viscosity of fluid. The technical characteristics can effectively realize the effect of relieving the water lock injury of the natural gas reservoir.
Description
Technical Field
The invention relates to the field of natural gas reservoir chemicals, in particular to a natural gas reservoir water-lock releasing agent and a preparation method and application thereof.
Background
Water lock damage is widely present in the development of natural gas and oil reservoirs. In the drilling and production process of an oil and gas field, after external fluids such as completion fluid, drilling fluid, fracturing fluid and the like enter an oil and gas field reservoir, due to the retention effect of capillary force, the retained fluid cannot be completely discharged out of the reservoir under the action of the formation pressure, so that the water saturation of the reservoir is continuously increased, the permeability is continuously reduced, and water lock damage is caused. Water lock damage is a common problem in natural gas reservoir development, except for invasion of foreign fluids, in the continuous exploitation process of a natural gas reservoir, reservoir energy is attenuated continuously, water phase in an original equilibrium state of a near well zone flows, and accumulated liquid is formed at the bottom of a gas well. When the accumulated water at the bottom of the well can not be carried out of the well head along with the airflow, reverse osmosis suction is generated to the capillary hole in the low-permeability stratum, and the reverse osmosis suction is also another reason for generating water-lock damage. Once water lock damage occurs, the capacity of the natural gas reservoir is greatly influenced, and domestic and foreign data show that once the water lock effect occurs to the natural gas reservoir, the yield of the gas well can be reduced to below 1/3. Therefore, prevention and elimination of water lock damage are important issues for achieving stable yield and increased yield in natural gas fields.
The main causes of water lock damage are capillary self-priming and liquid phase retention, which are directly influenced by fluid surface tension, capillary wetting angle, fluid viscosity, and pore throat radius. In addition, formation initial pressure, depth of invasion of foreign fluids, etc. exacerbate the occurrence of water lock damage.
At present, the water lock releasing damage of the natural gas reservoir adopts physical means such as production pressure increase, thermal cleaning, formation fracturing and the like, and the most main water lock releasing method is to use a water lock releasing agent. The water-lock releasing agent is used for promoting the discharge of blocking water in the natural gas reservoir stratum by using the modes of reducing the surface tension of water, regulating the wettability of the stratum, reducing the viscosity of fluid and the like by using the agents such as a surfactant and the like, so that the effect of releasing water-lock damage is achieved.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a natural gas reservoir water-locking releasing agent. In particular to a natural gas reservoir water-lock releasing agent and a preparation method and application thereof. The water-releasing locking agent can greatly reduce the surface tension of water, regulate the surface of a strong water-wet substrate to be neutral wetting or even hydrophobic, and simultaneously reduce the viscosity of fluid. The technical characteristics can effectively realize the effect of relieving the water lock injury of the natural gas reservoir.
One of the purposes of the invention is to provide a natural gas reservoir water-lock breaking agent, which comprises the following components in percentage by mass based on 100% of the total mass of the water-lock breaking agent:
wherein the content of the first and second substances,
the fluorocarbon surfactant can play a role in reducing surface tension and increasing a substrate contact angle (wetting regulation); the ionic type of the fluorine-containing surfactant is beneficial to regulating and controlling formation wettability in a sandstone-type natural gas reservoir formation through reasonable adsorption, and compared with the common surfactant, the fluorine-containing surfactant has stronger wettability regulating and controlling capability. The fluorocarbon surfactant can be selected from at least one of fluoroalkyl sulfonamide quaternary ammonium salt or fluoroalkyl amido quaternary ammonium salt; preferably, the first and second electrodes are formed of a metal,
the general molecular formula of the fluorocarbon surfactant can be:
in the general formula (I) or (II),
M-can be any one of halogen anions; preferably, M-Can be selected from Cl-、Br-、I-Any one of the above;
R1、R2、R3may be respectively and independently selected from C1~C4Preferably, the substituent is hydroxyl;
m can be any integer from 1 to 10, preferably any integer from 1 to 6; n can be any integer from 4 to 20, and is preferably any integer from 4 to 10. In addition, it is preferred that n not comprise 8 for bio-toxicity and environmental reasons.
The biosurfactant can reduce the surface tension and reduce the dosage of the fluorine surfactant (environmental problem) under the same effect; specifically, the biosurfactant may be at least one selected from lipopeptide, rhamnolipid, sophorolipid and seaweed glycolipid, preferably lipopeptide. The lipopeptide is selected from lipopeptides commonly used in the art.
The synergistic auxiliary agent can play a role in improving the fluidity of a system and reducing viscosity. Specifically, the synergist can be at least one of small molecular alcohols, ethers, amines and alcohol amines; small molecule alcohols are preferred. More preferably, the small molecular alcohol chemical agent is selected from at least one of monohydric alcohol, dihydric alcohol or polyhydric alcohol of C1-C3; further preferably, the monohydric alcohol is selected from at least one of methanol, ethanol, propanol; the dihydric alcohol is at least one of ethylene glycol and propylene glycol; the polyol is glycerol; further preferably, the alcohol is selected from at least one of methanol and ethanol.
In the technical scheme, the water-unlocking agent has no special requirement on water during preparation, and the water can be deionized water or water containing inorganic mineral substances; preferably, the water containing inorganic minerals may be at least one of tap water, river water, natural gas field formation water.
The invention also aims to provide a preparation method of the natural gas reservoir water-lock removal agent, which comprises the following steps:
mixing and dissolving the fluorocarbon surfactant, the biological surfactant and part of water to obtain a surfactant solution; and then adding the synergistic assistant and the residual water, and stirring and mixing uniformly to obtain the natural gas reservoir water-lock-releasing agent.
Preferably, the preparation method comprises the following steps:
mixing and dissolving the fluorocarbon surfactant, the biological surfactant and part of water to obtain a surfactant solution, then adding the synergistic assistant, stirring and uniformly mixing; and optionally, supplementing the rest water, and stirring and mixing uniformly to obtain the natural gas reservoir water-lock-releasing agent.
The invention also aims to provide the application of the natural gas reservoir water-lock release agent or the water-lock release agent prepared by the preparation method, preferably the application in water-lock damage release of the natural gas reservoir. In the above technical solutions, the application is not particularly limited, and those skilled in the art can utilize the existing water-lock-releasing process. For example, but not limited to, a water-lock breaking agent solution is prepared according to the weight percentage of the raw material components, and after the water-lock breaking agent solution is diluted to an effective concentration of 0.01-10 w.t.%, a certain amount of the water-lock breaking agent is injected into a natural gas well.
According to the natural gas reservoir water-lock releasing agent, the fluorocarbon surfactant, the biological surfactant and the synergistic auxiliary agent are combined to play a good synergistic effect, the components interact with each other, lipopeptide is taken as a surfactant and belongs to an anionic surfactant, the used fluorine surfactant is a cationic surfactant, the surface interface performance can be greatly improved compared with a single component in an anion-cation composite mode with proper proportion, especially when the using amount of the fluorocarbon surfactant is higher than that of the biological surfactant, the surface tension of water can be greatly reduced, the strong water wet surface can be regulated and controlled to be neutral wet, the fluid viscosity is reduced, the discharge of blocking water in a stratum is promoted, and a good water-lock releasing effect can be played.
By adopting the technical scheme of the invention, the obtained natural gas reservoir water-lock releasing agent can be used for water-lock releasing construction of a natural gas reservoir, after the water-lock releasing agent is injected, the surface tension of water can be greatly reduced to about 15mN/m, the viscosity of the water can be reduced by about 20% at most, and the strong water-wet surface can be regulated to be neutral, wet and partially hydrophobic, so that the discharge of blocking water in a stratum is promoted, and a better technical effect is obtained.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Source of raw materials
In the invention, the fluorine surfactant fluoroalkyl sulfonamide quaternary ammonium salt or fluoroalkyl amido quaternary ammonium salt is self-made, the raw materials mainly adopt fluoroalkyl sulfonyl chloride, fluoroalkyl acyl chloride and amido quaternary ammonium salt, and the preparation method can be synthesized according to the steps of 2.2.2 in the synthesis and the performance of a branch type fluorine-containing quaternary ammonium salt cationic surfactant (the report of college chemical engineering, 2014[28],1: 201-: selecting acetonitrile as a solvent, adding fluoroalkyl sulfonyl chloride or fluoroalkyl acyl chloride (determined according to a target product), adding anhydrous potassium carbonate as a catalyst, stirring and heating to reflux, slowly adding amino quaternary ammonium salt, carrying out reflux reaction for 6 hours, standing and cooling to room temperature after the reaction is finished, and removing the solvent under reduced pressure after decoloration to obtain the product.
Lipopeptides were purchased from Bell-chemical, Japan, under the product name sodium surfactin.
Other starting materials or reagents are commercially available.
Example 1
The water-lock release agent for the natural gas reservoir comprises the following raw materials in percentage by weight:
A.C4F9CONH(CH2)8N(CH3)3Cl:5%;
B. lipopeptides: 20 percent;
C. methanol: 5 percent;
D. the remaining 70% is water (deionized water).
The preparation method comprises the following steps: adding fluorocarbon surfactant and lipopeptide, adding a certain amount of deionized water, and stirring to dissolve completely; supplementing and adding methanol, and stirring to completely dissolve the methanol; and supplementing and adding the rest deionized water, and stirring and mixing uniformly.
Example 2
The water-lock release agent for the natural gas reservoir comprises the following raw materials in percentage by weight:
A.C20F41SO2NHCH2 N(CH3)2C2H5I:20%;
B. lipopeptides: 5 percent;
C. methanol: 30 percent;
D. the remaining 45% is water.
The preparation method is the same as example 1.
Example 3
The water-lock release agent for the natural gas reservoir comprises the following raw materials in percentage by weight:
A.C12F25CONH(CH2)6NC4H9(C2H5)2I:10%;
B. lipopeptides: 5 percent;
C. ethanol: 20 percent;
D. the remaining 65% is water.
The preparation method is the same as example 1.
Example 4
The water-lock release agent for the natural gas reservoir comprises the following raw materials in percentage by weight:
A.C17F35SO2NH(CH2)3NC3H7(CH3)2Cl:15%;
B. lipopeptides: 10 percent;
C. ethylene glycol: 15 percent;
D. the remaining 60% is water.
The preparation method is the same as example 1.
Example 5
The water-lock release agent for the natural gas reservoir comprises the following raw materials in percentage by weight:
A.C6F13SO2NH(CH2)9NC4H9(CH3)2I:20%;
B. lipopeptides: 15 percent;
C. propanol: 15 percent;
D. the remaining 50% is water.
The preparation method is the same as example 1.
Example 6
The water-lock release agent for the natural gas reservoir comprises the following raw materials in percentage by weight:
A.C18F37CONH(CH2)2N(C3H7)2CH3Cl:15%;
B. lipopeptides: 15 percent;
C. propylene glycol: 10 percent;
D. the remaining 60% is water.
The preparation method is the same as example 1.
Example 7
The water-lock release agent for the natural gas reservoir comprises the following raw materials in percentage by weight:
A.C14F29SO2NH(CH2)5N(C2H5)3Br:10%;
B. lipopeptides: 10 percent;
C. glycerol: 5 percent;
D. the remaining 75% is water.
The preparation method is the same as example 1.
Example 8
The water-lock release agent for the natural gas reservoir comprises the following raw materials in percentage by weight:
A.C6F13CONH(CH2)2N(CH3)3Cl:15%;
B. lipopeptides: 10 percent;
C. methanol: 10 percent;
D. the remaining 65% is water.
The preparation method is the same as example 1.
Comparative example 1
The water-lock release agent for the natural gas reservoir comprises the following raw materials in percentage by weight:
A.C6F13CONH(CH2)2N(CH3)3Cl:15%;
B. methanol: 10 percent;
C. the remaining 75% is water.
The preparation method comprises the following steps: adding fluorocarbon surfactant, adding a certain amount of preparation water, and stirring to completely dissolve the fluorocarbon surfactant; supplementing and adding methanol, and stirring to completely dissolve the methanol; and adding the rest of the preparation water, and stirring and mixing uniformly.
Comparative example 2
The water-lock release agent for the natural gas reservoir comprises the following raw materials in percentage by weight:
A. lipopeptides: 10 percent;
B. methanol: 10 percent;
C. the remaining 80% is water.
The preparation method comprises the following steps: adding lipopeptide, adding a certain amount of preparation water, and stirring to dissolve completely; supplementing and adding methanol, and stirring to completely dissolve the methanol; and adding the rest of the preparation water, and stirring and mixing uniformly.
Example 9
The water-release lock agent prepared in the above examples 1-8 and comparative examples 1-2 is diluted to 0.5 wt% effective concentration with deionized water, and the surface tension results obtained by the test according to GB/T22237-2008 surfactant surface tension determination are shown in Table 1.
TABLE 1 surface tension of water-lock releasing agent
Examples | Surface tension (mN/m) |
1 | 15.8 |
2 | 17.2 |
3 | 16.2 |
4 | 18.1 |
5 | 17.9 |
6 | 17.3 |
7 | 16.8 |
8 | 15.1 |
Comparative example 1 | 19.9 |
Comparative example 2 | 26.4 |
Example 10
The ability of a water-lock breaking chemical to modulate the wettability of the formation is measured by the contact angle method. A hydrophilic quartz plate was selected as the test substrate, and the contact angle between water and the quartz plate for experiments was 21.6 ℃ as measured at room temperature. The water-lock release chemical prepared in examples 1-8 and comparative examples 1-2 was diluted to 0.5% effective concentration, the quartz plate was immersed in the solution for 2 hours, taken out and dried, and the contact angle between water and the treated quartz plate was measured, and the results are shown in table 2.
TABLE 2 contact angle of quartz plate with water after treatment with water-releasing agent
Examples | Contact angle (°) |
1 | 128.7 |
2 | 123.5 |
3 | 131.0 |
4 | 119.5 |
5 | 128.4 |
6 | 126.9 |
7 | 123.9 |
8 | 139.1 |
Comparative example 1 | 104.4 |
Comparative example 2 | 87.3 |
Example 11
The water-release lock release agents prepared in the above examples 1-8 and comparative examples 1-2 were diluted to 0.5 wt% effective concentration, and the viscosity results obtained by the test method according to GB/T22235-2008 determination of liquid viscosity are shown in Table 3.
TABLE 3 viscosity of the water-lock releasing agent solution
Examples | Interfacial tension (mPa. s) |
1 | 0.88 |
2 | 0.86 |
3 | 0.83 |
4 | 0.92 |
5 | 0.91 |
6 | 0.90 |
7 | 0.95 |
8 | 0.81 |
Comparative example 1 | 1.12 |
Comparative example 2 | 0.99 |
The lower the surface tension, the easier it is for the liquid that creates the water lock to be removed from the capillary channels created by the injury; the more hydrophobic the formation wettability, i.e. the greater the contact angle of water with the substrate, the less likely the water will adhere to the formation substrate surface; the lower the viscosity of the liquid, the better the fluidity of the fluid, and the easier the fluid is to move in the stratum, so that the liquid which generates water lock damage can be discharged as soon as possible.
Claims (10)
1. A natural gas reservoir water-lock breaking agent comprises the following components in percentage by mass based on 100% of the total mass of the water-lock breaking agent:
A. fluorocarbon surfactant: 5% -20%;
B. biosurfactant: 5% -20%;
C. and (3) synergistic auxiliary agent: 5% -30%;
D. water: 30 to 85 percent.
2. The natural gas reservoir water-lock breaking agent according to claim 1, characterized by comprising the following components in percentage by mass based on 100% of the total mass of the water-lock breaking agent:
A. fluorocarbon surfactant: 5% -20%;
B. biosurfactant: 5% -20%;
C. and (3) synergistic auxiliary agent: 5% -30%;
D. water: and the balance.
3. The natural gas reservoir water-lock breaking agent according to claim 1 or 2, wherein:
the fluorocarbon surfactant is selected from at least one of fluoroalkyl sulfonamide quaternary ammonium salt or fluoroalkyl amido quaternary ammonium salt; preferably, the first and second electrodes are formed of a metal,
the molecular general formula of the fluorocarbon surfactant is as follows:
in the general formula (I) or (II),
M-is any one of halogen anions; preferably, M-Selected from Cl-、Br-、I-Any one of the above;
R1、R2、R3are each independently selected from C1~C4Alkyl or substituted alkyl of (a);
m is any integer from 1 to 10, and n is any integer from 4 to 20.
4. The natural gas reservoir water-lock breaking agent according to claim 1 or 2, wherein:
the biosurfactant is at least one selected from lipopeptide, rhamnolipid, sophorolipid and seaweed glycolipid, and is preferably lipopeptide.
5. The natural gas reservoir water-lock breaking agent according to claim 1 or 2, wherein:
the synergistic auxiliary agent is at least one of micromolecular alcohols, ethers, amines and alcohol amines.
6. The natural gas reservoir water-lock breaking agent as claimed in claim 5, wherein:
the synergistic auxiliary agent is micromolecular alcohol;
preferably, the first and second electrodes are formed of a metal,
the small molecular alcohol is selected from at least one of monohydric alcohol, dihydric alcohol or polyhydric alcohol of C1-C3;
preferably, the monohydric alcohol is selected from at least one of methanol, ethanol, propanol; the dihydric alcohol is at least one of ethylene glycol and propylene glycol; the polyol is glycerol; further preferably, the alcohol is selected from at least one of methanol and ethanol.
7. The natural gas reservoir water-lock breaking agent according to claim 1 or 2, wherein:
the water is deionized water or water containing inorganic mineral substances; preferably, the water containing inorganic minerals is at least one of tap water, river water, natural gas field formation water.
8. A method for preparing the natural gas reservoir water-locking release agent according to any one of claims 1 to 7, which is characterized by comprising the following steps:
mixing and dissolving the fluorocarbon surfactant, the biological surfactant and part of water to obtain a surfactant solution; and then adding the synergistic assistant and the residual water, and stirring and mixing uniformly to obtain the natural gas reservoir water-lock-releasing agent.
9. Use of the natural gas reservoir water-lock release agent according to any one of claims 1 to 7 or the water-lock release agent prepared by the preparation method according to claim 8, preferably in water-lock damage release of natural gas reservoirs.
10. Use according to claim 9, wherein the water-locking agent is used in a concentration of 0.01% to 10 w.t.%.
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