A hydrate kinetic inhibitor and its preparation method and application

The hydrate kinetic inhibitor prepared by the binary copolymerization reaction of N-vinyl caprolactam and vinyl n-butyl ether solves the problem of pipeline blockage caused by hydrate formation in oil and gas transportation, and achieves a low-cost and efficient hydrate inhibition effect.

CN116535571BActive Publication Date: 2025-04-08CHINA UNIV OF PETROLEUM (BEIJING) +1
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Patent Information

Application Number
CN202310618994.2
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2023-05-29
Publication Date
2025-04-08
Estimated Expiration
2043-05-29

AI Technical Summary

Technical Problem

During oil and gas transportation, pipelines are blocked due to the formation of natural gas hydrates. The existing technology inhibitors are costly, have high environmental risks, and have poor results.

Method used

A hydrate kinetic inhibitor is prepared by binary copolymerization of N-vinyl caprolactam and vinyl n-butyl ether, which has excellent properties to inhibit hydrate formation.

Benefits of technology

The amount of hydrate kinetic inhibitor is small, the cost is low, and the inhibitory effect on hydrates is better than that of existing inhibitors, and has good commercial application prospects.

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Abstract

The present invention provides a hydrate kinetic inhibitor and a preparation method and application thereof. The hydrate kinetic inhibitor is obtained by binary copolymerization of N-vinyl caprolactam and vinyl n-butyl ether, and the preparation method thereof comprises the following steps: mixing N-vinyl caprolactam and vinyl n-butyl ether with a solvent, adding an initiator, performing binary copolymerization, and then adding a terminator to obtain the hydrate kinetic inhibitor. The hydrate kinetic inhibitor has excellent performance in inhibiting hydrate formation, and can better solve the problem of pipe blockage caused by hydrate formation in oil and gas development and transportation.
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Description

Technical Field

[0001] The invention relates to a hydrate kinetic inhibitor and a preparation method and application thereof, belonging to the technical field of oil and gas exploitation and transportation. Background Art

[0002] Natural gas hydrates are usually ice-like cage compounds formed by gas molecules and water molecules under high pressure and low temperature conditions. They are found in large quantities in nature, especially in permafrost on land and in the deep sea. They also often appear in oil and gas pipelines and laboratories. Since the discovery of natural gas hydrates in natural gas pipelines, their prevention and control has always been a major challenge for the oil and gas industry. As oil and gas drilling gradually develops into deep ocean waters, the higher hydrostatic pressure and lower ambient temperature in deep waters also provide favorable conditions for the formation of hydrates. Once hydrates are formed in the pipeline, some will flow with the fluid in the pipe, and some will adhere to the pipe wall and deposit, gradually blocking the pipeline, causing the fluid to be unable to be transported normally, and even causing serious safety accidents, leading to significant economic losses.

[0003] Therefore, the research on gas hydrate risk prevention and control technology has always been valued and supported by the oil and gas industry. In response to the risk of hydrate blockage in pipelines, different mitigation measures and remedial strategies have been developed, such as pressure reduction, injection of chemical inhibitors, and heating. Among them, chemical inhibitor injection is the most commonly used method. Traditional thermodynamic inhibitors may bring high costs and environmental risks due to their large dosage. Therefore, low-dose hydrate kinetic inhibitors (LDHIs) are considered to be a potential alternative that can effectively inhibit the nucleation and growth of hydrates without changing the thermodynamic conditions for hydrate formation. At present, some gas fields have commercially applied hydrate kinetic inhibitors, such as PVP and Inhibex 501. It has been proven that these low-dose hydrate kinetic inhibitors can effectively inhibit the formation of hydrates.

[0004] In summary, it is of great commercial significance to develop efficient, environmentally friendly and low-cost hydrate kinetic inhibitors. Summary of the invention

[0005] In order to solve the above problems, the purpose of the present invention is to provide a hydrate kinetic inhibitor and a preparation method and application thereof. The hydrate kinetic inhibitor has excellent performance in inhibiting hydrate formation and can better solve the problem of pipe blockage caused by hydrate formation in oil and gas development and transportation.

[0006] In order to achieve the above object, the present invention provides a hydrate kinetic inhibitor, which is obtained by binary copolymerization of N-vinyl caprolactam and vinyl n-butyl ether.

[0007] According to a specific embodiment of the present invention, preferably, the relative molecular mass of the hydrate kinetic inhibitor is 1000-50000.

[0008] The structure of the hydrate kinetic inhibitor of the present invention is illustrated by Formula I:

[0009]

[0010] The molar ratio of the N-vinyl caprolactam structural unit to the vinyl n-butyl ether structural unit is x:y=9:1-1:1.

[0011] The present invention also provides a method for preparing the above-mentioned hydrate kinetic inhibitor, which comprises the following steps: mixing N-vinyl caprolactam and vinyl n-butyl ether with a solvent, adding an initiator, performing a binary copolymerization reaction, and then adding a terminator to obtain the hydrate kinetic inhibitor.

[0012] According to a specific embodiment of the present invention, preferably, in the above preparation method, the binary copolymerization reaction temperature is 323.15-363.15K, and the reaction time is 5-12h.

[0013] According to a specific embodiment of the present invention, preferably, in the above preparation method, the molar ratio of N-vinyl caprolactam to vinyl n-butyl ether is 9:1-1:1.

[0014] According to a specific embodiment of the present invention, preferably, in the above preparation method, the initiator includes one or a combination of two or more of azobisisobutyronitrile, dimethyl azobisisobutyrate, azobisisoheptanenitrile and tert-butyl hydroperoxide.

[0015] According to a specific embodiment of the present invention, preferably, in the above preparation method, based on the total weight of the N-vinyl caprolactam and vinyl n-butyl ether being 100%, the amount of the initiator is 0.01%-0.5%.

[0016] According to a specific embodiment of the present invention, preferably, in the above preparation method, the terminator includes one of styrene and methacrylic acid or a combination of the two.

[0017] According to a specific embodiment of the present invention, preferably, in the above preparation method, based on the total weight of the N-vinyl caprolactam and vinyl n-butyl ether being 100%, the amount of the terminator is 0.01%-0.1%.

[0018] According to a specific embodiment of the present invention, preferably, in the above preparation method, the solvent includes one or a combination of two or more of ethanol, isopropanol, N,N-dimethylformamide, and n-propanol.

[0019] According to a specific embodiment of the present invention, preferably, in the above preparation method, the weight ratio of the solvent to the sum of the N-vinyl caprolactam and the vinyl n-butyl ether is 2-10:1.

[0020] According to a specific embodiment of the present invention, the above preparation method comprises the following specific steps:

[0021] (1) adding N-vinyl caprolactam and vinyl n-butyl ether monomers into a solvent and mixing them uniformly to obtain a mixture;

[0022] (2) adding an initiator to the mixture, raising the temperature to the target reaction temperature, and reacting under the protection of a protective gas (e.g., a nitrogen atmosphere), and finally adding a terminator to terminate the reaction. After the reaction is completed, the resulting solution is vacuum dried at a drying temperature of 313.15-343.15 K to obtain the hydrate kinetic inhibitor.

[0023] The present invention also provides the use of the above hydrate kinetic inhibitor to inhibit hydrate formation during oil and gas development or transportation.

[0024] According to a specific embodiment of the present invention, preferably, the hydrate kinetic inhibitor is applied to an oil-gas-water three-phase system or a gas-water two-phase system.

[0025] According to a specific embodiment of the present invention, preferably, the pressure of the oil-gas-water three-phase system or the gas-water two-phase system is 0.2-30 MPa, and the temperature is -15°C to 30°C.

[0026] According to a specific embodiment of the present invention, preferably, the hydrate kinetic inhibitor is used alone or in combination with alcohols; when the hydrate kinetic inhibitor is used in combination with alcohols, the inhibitory effect on hydrate formation is better.

[0027] According to a specific embodiment of the present invention, preferably, the alcohol comprises ethylene glycol.

[0028] According to a specific embodiment of the present invention, preferably, when the hydrate kinetic inhibitor is used alone, the amount of the hydrate kinetic inhibitor is 0.5-5.0wt%, calculated based on the total weight of water in the system as 100%; when the hydrate kinetic inhibitor is used after being compounded with alcohols, the amount of the hydrate kinetic inhibitor is 0.5-5wt%, and the amount of the alcohol is 0.1-20wt%, calculated based on the total weight of water in the system as 100%.

[0029] The hydrate kinetic inhibitor provided by the present invention has the following beneficial technical effects:

[0030] (1) The hydrate kinetic inhibitor provided by the present invention is a binary copolymer obtained by binary copolymerization of N-vinyl caprolactam and vinyl n-butyl ether monomers, which has good water solubility and can ensure that it works in the aqueous phase;

[0031] (2) Compared with traditional thermodynamic inhibitors, the hydrate kinetic inhibitor provided by the present invention has the advantages of small dosage, low cost and significant effect;

[0032] (3) Compared with existing hydrate kinetic inhibitors, such as PVP and Inhibex 501, the hydrate kinetic inhibitor provided by the present invention has a better inhibitory effect on hydrates and has a good commercial application prospect. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 This is the infrared spectrum of the hydrate kinetics inhibitor of Example 1. DETAILED DESCRIPTION

[0034] In order to have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be construed as limiting the applicable scope of the present invention.

[0035] Unless otherwise specified, the devices and reagents used in the present invention are all conventional equipment and conventional materials, and can be obtained through commercial channels.

[0036] Example 1

[0037] This embodiment provides a hydrate kinetic inhibitor, and the preparation method thereof comprises the following steps:

[0038] (1) selecting N-vinyl caprolactam and vinyl n-butyl ether as synthetic raw materials, using isopropyl alcohol as a solvent for polymerization, and uniformly mixing the synthetic raw materials and the solvent to obtain a mixture; wherein the amounts of N-vinyl caprolactam and vinyl n-butyl ether are 5.8155 g and 4.1845 g, respectively; and the amount of isopropyl alcohol is 30 g;

[0039] (2) Add the above mixture into a three-necked round-bottom flask, wait until the temperature of the thermostatic water bath reaches 353.15K, add 0.01% of the total weight of the two monomers as the initiator azobisisobutyronitrile into the three-necked round-bottom flask, then quickly fix the three-necked round-bottom flask in the thermostatic water bath, install a condenser on the three-necked round-bottom flask, introduce nitrogen into the three-necked round-bottom flask, and start stirring. Keep the water bath temperature and stirring speed constant during the reaction. Stop heating after 10 hours of reaction, and add 0.05% of the total weight of the two monomers as the terminator styrene into the three-necked round-bottom flask;

[0040] (3) When the system temperature is cooled to room temperature, the nitrogen gas is stopped and the stirring is turned off, and the product in the three-necked round-bottom flask is transferred to a beaker to obtain a crude product of the hydrate kinetic inhibitor;

[0041] (4) The liquid in the beaker is transferred to a rotary evaporator, and the crude product of the hydrate kinetic inhibitor is purified by the rotary evaporator. The purified product is taken out and vacuum dried at a temperature of 323.15 K to obtain the hydrate kinetic inhibitor, which has a relative molecular mass of 11499. Finally, the product is sealed and stored in a dry and cool place for use.

[0042] The hydrate kinetic inhibitor obtained in this example was subjected to infrared spectroscopy analysis, and the obtained infrared spectrum is shown in FIG. Figure 1 As shown, from Figure 1 It can be seen that the binary copolymer, i.e., the hydrate kinetic inhibitor, has a peak at 912 cm -1 、993cm -1 、3080cm -1 、1682cm -1 There are no C=CH、=CH、C=C absorption peaks on the left and right, which indicates that the unsaturated hydrocarbons disappear; 1617cm -1 The strong absorption peaks on the left and right are the C=O absorption peaks on the polymer molecule caprolactam, 1430 cm -1 The absorption peaks on the left and right are strong absorption peaks of CN on the polymer molecule caprolactam; 2876cm -1 With 2853cm -1 The two strong absorption peaks on the left and right are the absorption peaks of saturated CH symmetric stretching vibration and antisymmetric stretching vibration respectively; at 1225-1200cm -1 There is no obvious absorption peak around 1150cm -1 The strong absorption peaks on the left and right are the absorption peaks of the fatty ether COC, which indicates that the vinyl ether has been polymerized with N-vinyl caprolactam to convert it into fatty ether.

[0043] In summary, Figure 1 The solid infrared data results shown indicate that N-vinyl caprolactam has been successfully polymerized with vinyl n-butyl ether monomer and has a high purity, contains no or only a trace amount of unreacted monomers, and the synthesized product is the target product.

[0044] Example 2

[0045] This embodiment provides a hydrate kinetic inhibitor, and its preparation method is basically the same as the preparation method of the hydrate kinetic inhibitor provided in Example 1, except that:

[0046] (1) In this embodiment, the amounts of N-vinyl caprolactam and vinyl n-butyl ether monomers are 6.0455 g and 4.0347 g respectively;

[0047] (2) The reaction time in this example is 8 h.

[0048] The relative molecular mass of the hydrate kinetic inhibitor obtained in this example is 28455, and the infrared spectrum is as follows: Figure 1 As shown, its infrared spectrum characteristic absorption peak is ~1617cm -1 、1430cm -1 、2876cm -1 、2853cm -1 、1150cm -1 Etc., indicating that the polymer has high purity, the system contains almost no unreacted monomers, and the polymer contains fatty ether, caprolactam and other groups.

[0049] Example 3

[0050] This embodiment provides a hydrate kinetic inhibitor, and its preparation method is basically the same as the preparation method of the hydrate kinetic inhibitor provided in Example 1, except that:

[0051] (1) In this embodiment, the amounts of N-vinyl caprolactam and vinyl n-butyl ether monomers are 7.0527 g and 3.0591 g respectively;

[0052] (2) The reaction time in this example is 6 h.

[0053] The relative molecular mass of the hydrate kinetic inhibitor obtained in this example is 32847, and the infrared spectrum is as follows: Figure 1 As shown, its infrared spectrum characteristic absorption peak is ~1617cm -1 、1430cm -1 、2876cm -1 、2853cm -1 、1150cm -1 Etc., indicating that the polymer has high purity, the system contains almost no unreacted monomers, and the polymer contains fatty ether, caprolactam and other groups.

[0054] Example 4

[0055] This embodiment provides a hydrate kinetic inhibitor, and its preparation method is basically the same as the preparation method of the hydrate kinetic inhibitor provided in Example 1, except that:

[0056] (1) In this embodiment, the amounts of N-vinyl caprolactam and vinyl n-butyl ether monomers are 8.0025 g and 2.0304 g respectively;

[0057] (2) The reaction time in this example is 7 h.

[0058] The relative molecular mass of the hydrate kinetic inhibitor obtained in this example is 22950, ​​and the infrared spectrum is as follows: Figure 1 As shown, its infrared spectrum characteristic absorption peak is ~1617cm -1 、1430cm -1 、2876cm -1 、2853cm -1 、1150cm -1 Etc., indicating that the polymer has high purity, the system contains almost no unreacted monomers, and the polymer contains fatty ether, caprolactam and other groups.

[0059] Example 5

[0060] This embodiment provides a hydrate kinetic inhibitor, and its preparation method is basically the same as the preparation method of the hydrate kinetic inhibitor provided in Example 1, except that:

[0061] (1) In this embodiment, the amounts of N-vinyl caprolactam and vinyl n-butyl ether monomers are 9.0025 g and 1.0035 g respectively;

[0062] (2) The reaction time in this example is 9 h.

[0063] The relative molecular mass of the hydrate kinetic inhibitor obtained in this example is 32652, and the infrared spectrum is as follows: Figure 1 As shown, its infrared spectrum characteristic absorption peak is ~1617cm -1 、1430cm -1 、2876cm -1 、2853cm -1 、1150cm -1 Etc., indicating that the polymer has high purity, the system contains almost no unreacted monomers, and the polymer contains fatty ether, caprolactam and other groups.

[0064] Inhibition performance test

[0065] The following is an evaluation of the inhibitory performance of the hydrate kinetic inhibitors prepared in Examples 1-5 and the existing conventional commercial inhibitors PVP (produced by Sigma-Aldrich) and Inhibex 501 (produced by Ashland Group) on the hydrate formation process. The device used in the evaluation experiment mainly consists of six parts: a visible high-pressure sapphire kettle, a temperature sensor, a pressure sensor, a data acquisition system, a constant temperature air bath and a magnetic stirring device; wherein the volume of the visible high-pressure sapphire kettle is 59 cm 3, with an inner diameter of 2.54cm, and can withstand a maximum pressure of 40MPa to ensure the safety of the evaluation experiment operation; the errors of the pressure sensor and temperature sensor are ±0.01MPa and ±0.1K respectively; the temperature error of the constant temperature air bath is also ±0.1K, and the adjustment of the experimental temperature is mainly controlled by the constant temperature air bath.

[0066] The method for evaluating the inhibitory performance of hydrate kinetic inhibitors on the hydrate formation process is as follows:

[0067] First, clean the visible high-pressure sapphire kettle by soaking it with petroleum ether and ethanol once, then clean it three times with anhydrous ethanol, then open the inlet and outlet valves of the visible high-pressure sapphire kettle, and purge it with nitrogen to make the inside completely dry;

[0068] Add the prepared test solution containing the hydrate kinetic inhibitor into the visible high-pressure sapphire kettle, and use a vacuum pump to evacuate the kettle. After the air in the kettle is pumped out, close the valve to prevent the presence of air from interfering with the experimental results;

[0069] Open the air inlet valve of the balance kettle, add sufficient experimental gas into the balance kettle, and then close the air inlet valve of the balance kettle;

[0070] Turn on the constant temperature air bath and set the temperature of the constant temperature air bath to the experimental target temperature. When the temperature in the visible high-pressure sapphire kettle is stable at the target temperature, open the air inlet valve of the visible high-pressure sapphire kettle, and pass the experimental gas from the balance kettle into the visible high-pressure sapphire kettle. After reaching the target pressure, close the air inlet valve, turn on the magnetic stirring device, and keep the stirring speed unchanged during the entire experiment;

[0071] Turn on the cold light source, observe the appearance and morphological changes of hydrates through the visual window of the constant temperature air bath, and record them with a camera. At the same time, the temperature and pressure data in the kettle are saved in real time through the data acquisition system.

[0072] The test gas used in the evaluation experiment was methane with a purity of 99.99%.

[0073] The evaluation experiment determines the strength of the hydrate kinetic inhibitor by measuring the nucleation time of hydrates. The nucleation time of hydrates is determined by real-time monitoring of the camera and real-time monitoring of the pressure change of the system by the pressure sensor. When the camera first captures the appearance of hydrate nuclei in the visible high-pressure sapphire reactor and the pressure sensor monitors that the pressure of the system begins to drop, the time at this time is the nucleation time of the hydrate in the system.

[0074] Test Example 1

[0075] 10 g of an aqueous solution containing the hydrate kinetic inhibitor provided in Example 1 of the present invention (the concentration of the hydrate kinetic inhibitor in the aqueous solution is 0.5 wt % based on the total weight of water) was added to a visible high-pressure sapphire kettle, and an evaluation experiment was carried out by introducing 6.17 MPa of experimental gas into the visible high-pressure sapphire kettle at a temperature of 275.65 K. It was found that the nucleation time of hydrates in the system was 1251 min, indicating that in this evaluation system, the formation of hydrates was significantly inhibited due to the presence of the hydrate kinetic inhibitor.

[0076] Test Example 2

[0077] 10 g of an aqueous solution containing the hydrate kinetic inhibitor provided in Example 2 of the present invention (the concentration of the hydrate kinetic inhibitor in the aqueous solution is 0.5 wt % based on the total weight of water) was added to a visible high-pressure sapphire kettle, and an evaluation experiment was carried out by introducing 6.17 MPa of experimental gas into the visible high-pressure sapphire kettle at a temperature of 275.65 K. It was found that the nucleation time of hydrates in the system was 482 min, indicating that in this evaluation system, the formation of hydrates was significantly inhibited due to the presence of the hydrate kinetic inhibitor.

[0078] Test Example 3

[0079] 10 g of an aqueous solution containing the hydrate kinetic inhibitor provided in Example 3 of the present invention (the concentration of the hydrate kinetic inhibitor in the aqueous solution is 0.5 wt % based on the total weight of water) was added to a visible high-pressure sapphire kettle, and an evaluation experiment was carried out by introducing 6.17 MPa of experimental gas into the visible high-pressure sapphire kettle at a temperature of 275.65 K. It was found that the nucleation time of hydrates in the system was 389 min, indicating that in this evaluation system, the formation of hydrates was significantly inhibited due to the presence of the hydrate kinetic inhibitor.

[0080] Test Example 4

[0081] 10 g of an aqueous solution containing the hydrate kinetic inhibitor provided in Example 4 of the present invention (the concentration of the hydrate kinetic inhibitor in the aqueous solution is 0.5 wt % based on the total weight of water) was added to a visible high-pressure sapphire kettle, and an evaluation experiment was carried out by introducing 6.17 MPa of experimental gas into the visible high-pressure sapphire kettle at a temperature of 275.65 K. It was found that the nucleation time of hydrates in the system was 94 min, indicating that in this evaluation system, due to the presence of the hydrate kinetic inhibitor, the formation of hydrates was significantly inhibited.

[0082] Test Example 5

[0083] 10 g of an aqueous solution containing the hydrate kinetic inhibitor provided in Example 5 of the present invention (the concentration of the hydrate kinetic inhibitor in the aqueous solution is 0.5 wt % based on the total weight of water) was added to a visible high-pressure sapphire kettle, and an evaluation experiment was carried out by introducing 6.17 MPa of experimental gas into the visible high-pressure sapphire kettle at a temperature of 275.65 K. It was found that the nucleation time of hydrates in the system was 199 min, indicating that in this evaluation system, the formation of hydrates was significantly inhibited due to the presence of the hydrate kinetic inhibitor.

[0084] Test Example 6

[0085] 10 g of an aqueous solution containing the hydrate kinetic inhibitor provided in Example 1 of the present invention (the concentration of the hydrate kinetic inhibitor in the aqueous solution is 1.0 wt % based on the total weight of water) was added to a visible high-pressure sapphire kettle, and an evaluation experiment was carried out by introducing 6.17 MPa of experimental gas into the visible high-pressure sapphire kettle at a temperature of 275.65 K. It was found that the nucleation time of hydrates in the system was 1862 min, indicating that in the evaluation system, the formation of hydrates was significantly inhibited due to the presence of the hydrate kinetic inhibitor.

[0086] Test Example 7

[0087] 10 g of an aqueous solution containing the hydrate kinetic inhibitor provided in Example 1 of the present invention (the concentration of the hydrate kinetic inhibitor in the aqueous solution is 5.0 wt % based on the total weight of water) was added to a visible high-pressure sapphire kettle, and an evaluation experiment was carried out by introducing 6.17 MPa of experimental gas into the visible high-pressure sapphire kettle at a temperature of 275.65 K. It was found that the nucleation time of hydrates in the system was 2800 min, indicating that in the evaluation system, due to the presence of the hydrate kinetic inhibitor, the formation of hydrates was significantly inhibited.

[0088] Test Case 8

[0089] 10 g of an aqueous solution containing the composite mixture (wherein the composite mixture is obtained by compounding the hydrate kinetic inhibitor provided in Example 1 of the present invention and ethylene glycol, and based on the total weight of water, the concentration of the hydrate kinetic inhibitor in the aqueous solution is 0.5 wt %, and the concentration of ethylene glycol is 5.0 wt %) is added to a visible high-pressure sapphire kettle, and an evaluation experiment is carried out by introducing 6.17 MPa of experimental gas into the visible high-pressure sapphire kettle at a temperature of 275.65 K. It is found that the nucleation time of hydrates in the system is 1640 min, indicating that in this system, due to the presence of the hydrate kinetic inhibitor, the formation of hydrates is significantly inhibited.

[0090] By comparing the experimental data obtained in Test Example 1 and Test Example 8, it can be seen that the hydrate kinetic inhibitor provided by the embodiment of the present invention is compounded with an alcohol reagent for use, which has a better inhibitory effect on hydrate formation.

[0091] Comparative test example 1

[0092] 10g of deionized water was added into a visible high-pressure sapphire kettle, and 6.17MPa of experimental gas was introduced into the visible high-pressure sapphire kettle at a temperature of 275.65K to carry out an evaluation experiment. It was found that the nucleation time of hydrates in the system was less than 1min, indicating that in this evaluation system, since no hydrate kinetic inhibitors were added, the formation of hydrates was very rapid.

[0093] Comparative test example 2

[0094] 10 g of an aqueous solution containing the commercial inhibitor Inhibex 501 (based on the total weight of water, the concentration of the commercial inhibitor Inhibex 501 in the aqueous solution is 0.5 wt %) is added to a visible high-pressure sapphire autoclave, and an experimental gas of 6.17 MPa is introduced into the visible high-pressure sapphire autoclave at a temperature of 275.65 K for an evaluation experiment. It is found that the nucleation time of hydrates in the system is 21 min, indicating that in this evaluation system, due to the addition of the commercial inhibitor Inhibex501, the formation of hydrates is also inhibited. However, compared with the evaluation system containing the hydrate kinetic inhibitor provided in Example 1 of the present invention in Test Example 1, the nucleation time of hydrates in Comparative Test Example 2 is still shorter, which indicates that compared with the existing hydrate kinetic inhibitor Inhibex 501, the hydrate kinetic inhibitor provided in the embodiment of the present invention has a better inhibitory effect on hydrates.

[0095] Comparative test example 3

[0096] 10 g of an aqueous solution containing the commercial inhibitor PVP (based on the total weight of water, the concentration of the commercial inhibitor PVP in the aqueous solution is 0.5 wt %) was added to a visible high-pressure sapphire kettle, and an experimental gas of 6.17 MPa was introduced into the visible high-pressure sapphire kettle at a temperature of 275.65 K for an evaluation experiment. It was found that the nucleation time of hydrates in the system was 6 min, indicating that in this evaluation system, the formation of hydrates was also inhibited due to the addition of the commercial inhibitor PVP. However, compared with the evaluation system containing the hydrate kinetic inhibitor provided in Example 1 of the present invention in Test Example 1, the nucleation time of hydrates in Test Example 3 was still shorter, which indicates that compared with the existing hydrate kinetic inhibitor PVP, the hydrate kinetic inhibitor provided in the embodiment of the present invention has a better inhibitory effect on hydrates.

[0097] Comparative test example 4

[0098] 10 g of an aqueous solution containing the commercial inhibitor Inhibex 501 (based on the total weight of water, the concentration of the commercial inhibitor Inhibex 501 in the aqueous solution is 1.0 wt%) was added to a visible high-pressure sapphire autoclave, and an experimental gas of 6.17 MPa was introduced into the visible high-pressure sapphire autoclave at a temperature of 275.65 K for an evaluation experiment. It was found that the nucleation time of hydrates in the system was 120 min, indicating that in this evaluation system, due to the addition of the commercial inhibitor Inhibex501, the formation of hydrates was also inhibited. However, compared with the evaluation system containing the hydrate kinetic inhibitor provided in Example 1 of the present invention in Test Example 6, the nucleation time of hydrates in Test Example 4 was still shorter, indicating that compared with the existing hydrate kinetic inhibitor Inhibex 501, the hydrate kinetic inhibitor provided in the embodiment of the present invention has a better inhibitory effect on hydrates.

[0099] In summary, compared with existing hydrate kinetic inhibitors, such as PVP, Inhibex 501, etc., the hydrate kinetic inhibitor provided by the present invention has a better inhibitory effect on hydrates, indicating that it has good commercial application prospects.

[0100] The above is only a specific embodiment of the present invention, and cannot be used to limit the scope of the invention. Therefore, the replacement of equivalent components, or equivalent changes and modifications made according to the protection scope of the patent of the present invention, should still fall within the scope of this patent. In addition, the technical features of the present invention can be freely combined with each other, with each other and with each other, and with each other.

Claims

1. A use of a hydrate kinetic inhibitor to inhibit hydrate formation during oil and gas development or transportation, wherein: The hydrate kinetic inhibitor is obtained by binary copolymerization of N-vinyl caprolactam and vinyl n-butyl ether, and the molar ratio of N-vinyl caprolactam to vinyl n-butyl ether is 9:1-1:

1.

2. The use according to claim 1, wherein: The relative molecular mass of the hydrate kinetic inhibitor is 1000-50000.

3. The use according to claim 1, wherein: The preparation method of the hydrate kinetic inhibitor comprises the following steps: N-vinyl caprolactam and vinyl n-butyl ether are mixed with a solvent, an initiator is added, a binary copolymerization reaction is carried out, and then a terminator is added to obtain the hydrate kinetic inhibitor.

4. The use according to claim 3, wherein: In the preparation method of the hydrate kinetic inhibitor, the binary copolymerization reaction temperature is 323.15-363.15K, and the reaction time is 5-12h.

5. The use according to claim 3, wherein: In the preparation method of the hydrate kinetic inhibitor, based on the total weight of the N-vinyl caprolactam and vinyl n-butyl ether being 100%, the amount of the initiator used is 0.01%-0.5%.

6. The use according to claim 3, wherein: In the preparation method of the hydrate kinetic inhibitor, the initiator includes one or a combination of two or more of azobisisobutyronitrile, dimethyl azobisisobutyrate, azobisisoheptanenitrile and tert-butyl hydroperoxide.

7. The use according to claim 3, wherein: In the preparation method of the hydrate kinetic inhibitor, the amount of the terminator is 0.01%-0.1%, calculated based on the total weight of the N-vinyl caprolactam and vinyl n-butyl ether as 100%.

8. The use according to claim 3, wherein: In the method for preparing the hydrate kinetic inhibitor, the terminator includes styrene, methacrylic acid or a combination of the two.

9. The use according to claim 3, wherein: In the preparation method of the hydrate kinetic inhibitor, the weight ratio of the solvent to the sum of the N-vinyl caprolactam and the vinyl n-butyl ether is 2-10:

1.

10. The use according to claim 3, wherein: In the preparation method of the hydrate kinetic inhibitor, the solvent includes one or a combination of two or more of ethanol, isopropanol, N,N-dimethylformamide, and n-propanol.

11. The use according to claim 1, wherein: The hydrate kinetic inhibitor is applied to an oil-gas-water three-phase system or a gas-water two-phase system.

12. The use according to claim 11, wherein: The oil-gas-water three-phase system or the gas-water two-phase system has a pressure of 0.2-30 MPa and a temperature of -15°C to 30°C.

13. The use according to claim 1, wherein: The hydrate kinetic inhibitor is used alone or in combination with alcohols.

14. The use according to claim 13, wherein: The alcohols include ethylene glycol.

15. The use according to claim 13, wherein: When the hydrate kinetic inhibitor is used alone, the amount of the hydrate kinetic inhibitor is 0.5-5.0 wt % based on the total weight of water in the system as 100%; When the hydrate kinetic inhibitor is compounded with alcohols for use, based on the total weight of water in the system being 100%, the amount of the hydrate kinetic inhibitor is 0.5-5wt%, and the amount of the alcohol is 0.1-20wt%.

Citation Information

Patent Citations

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    JP2021066758A