CN114479808B - Natural gas reservoir water-unlocking locking agent and preparation method and application thereof - Google Patents
Natural gas reservoir water-unlocking locking 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 unlocking agent, a preparation method and application thereof. The natural gas reservoir water-unlocking agent comprises the following components in percentage by mass based on 100% of the total weight of the water-unlocking agent: A. 5% -20% of fluorocarbon surfactant; B. 5% -20% of a biological surfactant; C. 5% -30% of synergistic auxiliary agent; D. 30-85% of water. The water unlocking locking agent can greatly reduce the surface tension of water, regulate and control the surface of a strong water-wet matrix to be neutral wetting or even hydrophobic, and simultaneously reduce the viscosity of fluid. The technical characteristics enable the natural gas reservoir water lock injury relieving effect to be effectively achieved.
Description
Technical Field
The invention relates to the field of natural gas reservoir chemicals, in particular to a natural gas reservoir water unlocking agent, a preparation method and application thereof.
Background
Water lock damage is widely found in the development of natural gas reservoirs and oil reservoirs. In the oil and gas field drilling and production process, after the well completion fluid, the drilling fluid, the fracturing fluid and other foreign fluids enter the oil and gas field reservoir, the retained fluid cannot be completely discharged out of the reservoir under the action of the ground pressure due to the retention effect of capillary force, so that the water saturation of the reservoir is continuously increased, the permeability is continuously reduced, and water lock damage is generated. Water lock damage is a common problem in the development of natural gas reservoirs, except for the invasion of external fluids, reservoir energy is continuously attenuated during continuous exploitation of the natural gas reservoir, and water phase in an original equilibrium state in a near-wellbore zone flows to form effusion at the bottom of a gas well. When accumulated water at the bottom of the well cannot be carried out of the wellhead with the gas flow, reverse imbibition will occur to capillary channels in the low permeability formation, which is another cause of water lock damage. Once the water lock damage occurs, the productivity of the natural gas reservoir is greatly affected, and domestic and foreign data show that once the water lock effect occurs in the natural gas reservoir, the gas well yield can be reduced to below 1/3 of the original yield. Therefore, prevention and elimination of water lock damage are important subjects for realizing stable production and yield increase of natural gas fields.
The main reasons for the occurrence of water lock injury 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 raw pressure, depth of invasion of foreign fluids, etc. exacerbate the occurrence of water lock damage.
At present, the main method for removing the water lock injury of the natural gas reservoir adopts physical means such as increasing production pressure, thermal cleaning, formation fracturing and the like, and the water lock removing agent is used as the main water lock removing method. The water-locking remover is used for promoting the discharge of the blocked water in the natural gas reservoir stratum by utilizing the modes of reducing the surface tension of water, regulating and controlling the wettability of the stratum, reducing the viscosity of fluid and the like by utilizing agents such as a surfactant and the like, thereby achieving the effect of removing the water-locking injury.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a natural gas reservoir water unlocking agent. In particular to a natural gas reservoir water-unlocking agent and a preparation method and application thereof. The water unlocking locking agent can greatly reduce the surface tension of water, regulate and control the surface of a strong water-wet matrix to be neutral wetting or even hydrophobic, and simultaneously reduce the viscosity of fluid. The technical characteristics enable the natural gas reservoir water lock injury relieving effect to be effectively achieved.
The invention aims to provide a natural gas reservoir water-unlocking agent, which comprises the following components in percentage by mass based on 100% of the total mass of the water-unlocking agent:
wherein, the liquid crystal display device comprises a liquid crystal display device,
the fluorocarbon surfactant can play a role in reducing the surface tension and increasing the contact angle of a matrix (wetting regulation); the ionic type of the fluorine-containing surfactant is beneficial to the reasonable adsorption in sandstone type natural gas reservoir stratum so as to regulate and control the wettability of the stratum, and compared with the general surfactant, the fluorine-containing surfactant has stronger wettability regulating capability. The fluorocarbon surfactant may be selected from at least one of fluoroalkyl sulfonamide quaternary ammonium salts or fluoroalkyl amide quaternary ammonium salts; preferably, the method comprises the steps of,
the fluorocarbon surfactant may have a molecular formula of:
in the general formula (I) or (II),
M - any one of halogen anions; preferably M - Can be selected from Cl - 、Br - 、I - Any one of them;
R 1 、R 2 、R 3 can be independently selected from C 1 ～C 4 At least one of an alkyl group or a substituted alkyl group, the substituent preferably being a hydroxyl group;
m can be any integer from 1 to 10, preferably any integer from 1 to 6; n may be any integer from 4 to 20, preferably any integer from 4 to 10. In addition, if for biotoxicity and environmental reasons, n preferably does not contain 8.
The biosurfactant can reduce the surface tension and the dosage of the fluorine surfactant (environmental problem) under the same effect; in particular, the biosurfactant may be at least one selected from lipopeptides, rhamnolipids, sophorolipids, trehalose lipids, preferably lipopeptides. The lipopeptides are selected from among those commonly used in the art.
The synergistic agent can play a role in improving the fluidity of the system and reducing viscosity. Specifically, the synergistic auxiliary agent can be at least one of alcohols, ethers, amines and alcohol amines of small molecules; preferably small molecule alcohols. More preferably, the small molecule 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 at least one selected from methanol, ethanol, propanol; the dihydric alcohol is at least one selected from ethylene glycol and propylene glycol; the polyol is glycerol; further preferably, the alcohol is at least one selected from 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 matters; preferably, the inorganic mineral-containing water may be at least one of tap water, river water, and natural gas field formation water.
The second purpose of the invention is to provide a preparation method of the natural gas reservoir water-unlocking agent, which comprises the following steps:
mixing and dissolving the fluorocarbon surfactant, the biosurfactant and a part of water to obtain a surfactant solution; and then adding the synergistic agent and the residual water, and stirring and mixing uniformly to obtain the natural gas reservoir water-unlocking agent.
Preferably, the preparation method comprises the following steps:
mixing and dissolving the fluorocarbon surfactant, the biosurfactant and part of water to obtain a surfactant solution, adding the synergistic auxiliary agent, and stirring and uniformly mixing; optionally adding the rest water in a supplementary way, stirring and uniformly mixing to obtain the natural gas reservoir water locking agent.
The invention further aims to provide the application of the natural gas reservoir water-locking remover or the water-locking remover prepared according to the preparation method, and the application of the natural gas reservoir water-locking remover in water-locking injury removal is preferred. In the above technical solution, the application is not particularly limited, and a person skilled in the art can use the solution according to the existing solution lock process. For example, but not limiting of, the water-unlocking agent solution is prepared according to the weight percentage of the raw material components, and after the water-unlocking agent solution is diluted to the effective concentration of 0.01-10w.t%, a certain amount of the water-unlocking agent is injected into a natural gas well.
The natural gas reservoir water-unlocking agent provided by the invention adopts the combination of the fluorocarbon surfactant, the biosurfactant and the synergistic auxiliary agent, plays a good synergistic effect, the components interact with each other, the lipopeptid is used as a surfactant, belongs to anionic surfactants, the used fluorine surfactant is a cationic surfactant, and compared with the single components, the surface interface performance can be greatly improved in a proper proportion in an anionic-cationic composite mode, particularly when the dosage of the fluorocarbon surfactant is higher than that of the biosurfactant, the surface tension of water can be greatly reduced, the strong water-wetting surface can be regulated and controlled to be neutral wetting, and meanwhile, the fluid viscosity is reduced, so that the drainage of water in a stratum is promoted, and the good water-unlocking effect can be achieved.
The natural gas reservoir water unlocking agent obtained by adopting the technical scheme of the invention can be used for water unlocking construction of a natural gas reservoir, after the water unlocking agent is injected, the surface tension of water can be greatly reduced to about 15mN/m, the viscosity of water can be reduced by about 20% at most, and the strong water wetting surface can be regulated to be neutral wetting and hydrophobic, so that the drainage of blocked water in a stratum is promoted, and a better technical effect is achieved.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Raw material source
In the invention, the fluorine surfactant fluoroalkyl sulfonamide quaternary ammonium salt or fluoroalkyl amide quaternary ammonium salt is self-made, and the raw materials mainly adopt fluoroalkyl sulfonyl chloride, fluoroalkyl acyl chloride and amino quaternary ammonium salt, and the preparation method can be synthesized by referring to the steps described in 2.2.2 in the synthesis and the performance of a branch type fluorine-containing quaternary ammonium salt type cationic surfactant (university chemical engineering journal, 2014[28],1:201-205 ]): acetonitrile is selected as a solvent, fluoroalkyl sulfonyl chloride or fluoroalkyl acyl chloride (depending on a target product) is added, anhydrous potassium carbonate serving as a catalyst is added, stirring and heating are carried out until reflux is carried out, amino quaternary ammonium salt is slowly added for reflux reaction for 6 hours, after the reaction is finished, standing and cooling are carried out to room temperature, and after decolorization, the solvent is removed under reduced pressure, so that the product is obtained.
Lipopeptides were purchased from japan bell chemical corporation under the product name sodium surfactin.
Other materials or reagents are commercially available.
Example 1
The water unlocking agent for the natural gas reservoir comprises the following raw materials in percentage by weight:
A.C 4 F 9 CONH(CH 2 ) 8 N(CH 3 ) 3 Cl：5％；
B. lipopeptides: 20% of a base;
C. methanol: 5%;
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; adding methanol, stirring to dissolve completely; adding the rest deionized water, stirring and mixing uniformly.
Example 2
The water unlocking agent for the natural gas reservoir comprises the following raw materials in percentage by weight:
A.C 20 F 41 SO 2 NHCH 2 N(CH 3 ) 2 C 2 H 5 I：20％；
B. lipopeptides: 5%;
C. methanol: 30%;
D. the remaining 45% is water.
The preparation method is the same as in example 1.
Example 3
The water unlocking agent for the natural gas reservoir comprises the following raw materials in percentage by weight:
A.C 12 F 25 CONH(CH 2 ) 6 NC 4 H 9 (C 2 H 5 ) 2 I：10％；
B. lipopeptides: 5%;
C. ethanol: 20% of a base;
D. the remaining 65% is water.
The preparation method is the same as in example 1.
Example 4
The water unlocking agent for the natural gas reservoir comprises the following raw materials in percentage by weight:
A.C 17 F 35 SO 2 NH(CH 2 ) 3 NC 3 H 7 (CH 3 ) 2 Cl：15％；
B. lipopeptides: 10%;
C. ethylene glycol: 15%;
D. the remaining 60% is water.
The preparation method is the same as in example 1.
Example 5
The water unlocking agent for the natural gas reservoir comprises the following raw materials in percentage by weight:
A.C 6 F 13 SO 2 NH(CH 2 ) 9 NC 4 H 9 (CH 3 ) 2 I：20％；
B. lipopeptides: 15%;
C. propanol: 15%;
D. the rest 50% is water.
The preparation method is the same as in example 1.
Example 6
The water unlocking agent for the natural gas reservoir comprises the following raw materials in percentage by weight:
A.C 18 F 37 CONH(CH 2 ) 2 N(C 3 H 7 ) 2 CH 3 Cl：15％；
B. lipopeptides: 15%;
C. propylene glycol: 10%;
D. the remaining 60% is water.
The preparation method is the same as in example 1.
Example 7
The water unlocking agent for the natural gas reservoir comprises the following raw materials in percentage by weight:
A.C 14 F 29 SO 2 NH(CH 2 ) 5 N(C 2 H 5 ) 3 Br：10％；
B. lipopeptides: 10%;
C. glycerol: 5%;
D. the remaining 75% is water.
The preparation method is the same as in example 1.
Example 8
The water unlocking agent for the natural gas reservoir comprises the following raw materials in percentage by weight:
A.C 6 F 13 CONH(CH 2 ) 2 N(CH 3 ) 3 Cl：15％；
B. lipopeptides: 10%;
C. methanol: 10%;
D. the remaining 65% is water.
The preparation method is the same as in example 1.
Comparative example 1
The water unlocking agent for the natural gas reservoir comprises the following raw materials in percentage by weight:
A.C 6 F 13 CONH(CH 2 ) 2 N(CH 3 ) 3 Cl：15％；
B. methanol: 10%;
C. the remaining 75% is water.
The preparation method comprises the following steps: adding fluorocarbon surfactant, adding a certain amount of water, and stirring to dissolve completely; adding methanol, stirring to dissolve completely; adding the rest of the preparation water, stirring and mixing uniformly.
Comparative example 2
The water unlocking agent for the natural gas reservoir comprises the following raw materials in percentage by weight:
A. lipopeptides: 10%;
B. methanol: 10%;
C. the remaining 80% is water.
The preparation method comprises the following steps: adding lipopeptide, adding a certain amount of water, and stirring to dissolve completely; adding methanol, stirring to dissolve completely; adding the rest of the preparation water, stirring and mixing uniformly.
Example 9
The water-unlocking agents prepared in the examples 1 to 8 and the comparative examples 1 to 2 were diluted with deionized water to an effective concentration of 0.5wt%, and the surface tension results obtained by the test according to the test method of the surface tension of the surfactant GB/T22237-2008 are shown in Table 1.
TABLE 1 surface tension of water-unlocking 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 the water-unlocking chemistry to regulate formation wettability is measured by the contact angle method. Hydrophilic quartz plates were chosen as the test substrate, and the contact angle of water with the experimental quartz plates was measured at room temperature to be 21.6 °. The water-unlocking chemical agents prepared in the examples 1-8 and the comparative examples 1-2 are diluted to 0.5% of effective concentration, the quartz plate is immersed in the solution for 2 hours, the quartz plate is taken out and dried, the contact angle between water and the treated quartz plate is tested, and the results are shown in Table 2.
TABLE 2 contact angle of quartz plate with water after water unlocking treatment
| 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 unlocking agents prepared in the examples 1 to 8 and the comparative examples 1 to 2 were diluted to 0.5wt% of the effective concentration, and the viscosity results obtained by the test method according to the test of GB/T22235-2008 liquid viscosity are shown in Table 3.
TABLE 3 viscosity of the solution of the water-unlocking agent
| 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 the liquid that creates the water lock is to remove 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 surface of the formation substrate; the lower the viscosity of the liquid, the better the fluidity of the fluid, the easier the fluid is to migrate in the stratum, so that the liquid which generates water lock damage can be discharged as soon as possible.
Claims (12)
1. The natural gas reservoir water-unlocking agent comprises the following components in percentage by mass, based on 100% of the total mass of the water-unlocking agent:
the fluorocarbon surfactant is at least one of fluoroalkyl sulfonamide quaternary ammonium salt or fluoroalkyl amide quaternary ammonium salt;
the fluorocarbon surfactant has a molecular formula:
in the general formula (I) or (II),
m-is any one of halogen anions;
R 1 、R 2 、R 3 are independently selected from C 1 ～C 4 An alkyl or substituted alkyl group of (a);
m is any integer from 1 to 10, and n is any integer from 4 to 20;
the biosurfactant is selected from lipopeptides;
the synergistic agent is micromolecular alcohol.
2. The natural gas reservoir water-unlocking 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-unlocking agent:
3. a natural gas reservoir water-unlocking agent according to claim 1 or 2, characterized in that:
the M-is selected from Cl-, br - Any one of IA kind of module is assembled in the module and the module is assembled in the module.
4. A natural gas reservoir water-unlocking agent according to claim 1 or 2, characterized in that:
the biosurfactant is selected from lipopeptides.
5. The natural gas reservoir water-unlocking agent according to claim 1, wherein:
the micromolecular alcohol is at least one selected from monohydric alcohol, dihydric alcohol or polyhydric alcohol with C1-C3.
6. The natural gas reservoir water-unlocking agent according to claim 5, wherein:
the monohydric alcohol is at least one selected from methanol, ethanol and propanol; the dihydric alcohol is at least one selected from ethylene glycol and propylene glycol; the polyol is glycerol.
7. The natural gas reservoir water-unlocking agent according to claim 6, wherein:
the small molecular alcohols are at least one selected from methanol and ethanol.
8. A natural gas reservoir water-unlocking agent according to claim 1 or 2, characterized in that:
the water is deionized water or water containing inorganic mineral matters.
9. The natural gas reservoir water-unlocking agent according to claim 8, wherein:
the water containing inorganic mineral matters is at least one of tap water, river water and natural gas field formation water.
10. A process for the preparation of a natural gas reservoir water-unlocking agent according to any one of claims 1 to 9, characterized by comprising the steps of:
mixing and dissolving the fluorocarbon surfactant, the biosurfactant and part of water to obtain a surfactant solution; and then adding the synergistic agent and the residual water, and stirring and mixing uniformly to obtain the natural gas reservoir water-unlocking agent.
11. Use of a natural gas reservoir water-locking remover according to any of claims 1 to 9 or prepared according to the method of preparation of claim 10 in the removal of water-locking damage in a natural gas reservoir.
12. The use according to claim 11, wherein the water-unlocking agent is used in a concentration of 0.01-10 w.t.%.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0480297A (en) * | 1990-07-23 | 1992-03-13 | Piyuaretsukusu:Kk | Additive for cleaning fluid |
| CN103555309A (en) * | 2013-10-22 | 2014-02-05 | 赵静 | Water block damage treating agent based on biological surface active agent and preparation method thereof |
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| CN102924317A (en) * | 2012-10-11 | 2013-02-13 | 浙江工业大学 | Preparation method and application of branched fluorine-containing acylamino quaternary ammonium salt type cationic surfactant |
| GB2533518A (en) * | 2013-10-23 | 2016-06-22 | Halliburton Energy Services Inc | Volatile surfactant treatment for subterranean formations |
| CN104650824A (en) * | 2013-11-16 | 2015-05-27 | 中国石油化工股份有限公司 | Oil-gas bed well drilling anti-water blocking composition |
| CN106367054B (en) * | 2016-07-29 | 2019-09-24 | 中国石油集团川庆钻探工程有限公司工程技术研究院 | A kind of Xie Shui lock agent and preparation method |
| CA3071631A1 (en) * | 2017-07-31 | 2019-02-07 | Chevron U.S.A. Inc. | Injection fluids comprising a non-ionic surfactant for treating unconventional formations |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0480297A (en) * | 1990-07-23 | 1992-03-13 | Piyuaretsukusu:Kk | Additive for cleaning fluid |
| CN103555309A (en) * | 2013-10-22 | 2014-02-05 | 赵静 | Water block damage treating agent based on biological surface active agent and preparation method thereof |
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