CN113388379B - Hydrate kinetic inhibitor and preparation method and application thereof - Google Patents
Hydrate kinetic inhibitor and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a hydrate kinetic inhibitor and a preparation method and application thereof, wherein the hydrate kinetic inhibitor has a structural formula shown as a formula I:
in the formula I, R is C1-C7 alkyl; the hydrate kinetic inhibitor comprises the following structural units in a molar ratio: x, y, z-8: 1:1-6:3: 2. The hydrate kinetic inhibitor provided by the invention has the characteristics of obvious hydrate formation inhibition effect, good water solubility, low cost and the like, and can solve the problem of pipeline blockage caused by hydrate formation in the oil gas generation and/or transportation process.
Description
Technical Field
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
The hydrate is an ice-like and non-stoichiometric clathrate crystal compound formed by water and hydrocarbon micromolecules such as methane, ethane and the like under the conditions of high pressure and low temperature, and has the characteristics of high density, high heat value, wide distribution, large reserve and the like. In the process of oil and gas development and transportation, the normal and stable transportation of fluid is vital to the safe and effective operation of the oil and gas industry. However, in most cases, because the fluid in the production facility and the transportation pipeline contains water, under high-pressure and low-temperature environments, water and small hydrocarbon molecules (such as methane, ethane, propane, and the like) are easy to form hydrates to accumulate inside the device, the accumulation of the hydrates can affect the flow of the fluid, when the hydrates accumulate to a certain degree, even the hydrates can directly cause the blockage of the production facility and the transportation pipeline, once the blockage is formed, the pipeline is in failure, the upstream device has the situation that the pressure is too high, the fluid cannot be normally transported, and further, the unexpected production halt and the economic loss which is difficult to bear can be caused.
Thus, hydrates are generally considered to be one of the most serious and challenging problems in flow assurance. The oil and gas industry is constantly researching how to prevent hydrates from forming in pipelines, otherwise, the hydrates form blockage, which not only can block oil and gas flow, but also can cause serious potential safety hazards. Researchers have proposed many solutions to this problem. At present, the traditional approach to this problem is to inject high concentrations of thermodynamic inhibitors into the pipeline, which is effective, but costly and can cause environmental pollution. Another approach is to inject Low Doses of Hydrate Inhibitors (LDHIs) into the pipeline, which hardly affects the hydrate phase equilibrium conditions. The hydrate kinetic inhibitor serving as one of LDHIs can effectively inhibit the nucleation and growth process of hydrates without changing the thermodynamic conditions for forming the hydrates. To date, a variety of kinetic inhibitors have been demonstrated to have excellent inhibitory effects on hydrate formation and have been commercially developed and utilized, such as PVP and Inhibex501, among others.
In conclusion, the hydrate kinetic inhibitor has a very good commercial application prospect, and the development of a novel high-performance hydrate kinetic inhibitor has a very important significance.
Disclosure of Invention
In order to solve the above disadvantages and shortcomings, it is an object of the present invention to provide a hydrate kinetic inhibitor. The hydrate kinetic inhibitor provided by the invention has excellent performance of inhibiting the formation of hydrates, can better inhibit the formation of hydrates, and further can solve the problem of blockage caused by the formation of hydrates in the processes of oil and gas development and transportation.
It is also an object of the present invention to provide a process for the preparation of the above-described hydrate kinetic inhibitors.
It is also an object of the present invention to provide the use of the above hydrate kinetic inhibitors in the inhibition of hydrate formation during oil and gas development and/or transportation.
It is also an object of the present invention to provide a method for inhibiting hydrate formation during oil and gas development and/or transportation, wherein the method utilizes the hydrate kinetic inhibitor described above.
In order to achieve the above objects, in one aspect, the present invention provides a hydrate kinetic inhibitor, wherein the hydrate kinetic inhibitor has a structural formula shown in formula i:
in the formula I, R is C1-C7 alkyl;
the hydrate kinetic inhibitor has a molar ratio of each structural unit of x: y: z ═ 8:1:1-6:3: 2.
As a specific embodiment of the above-mentioned hydrate kinetic inhibitor of the present invention, the relative molecular mass of the hydrate kinetic inhibitor is 1000-50000.
In another aspect, the present invention also provides a preparation method of the above hydrate kinetic inhibitor, wherein the preparation method comprises: carrying out ternary polymerization reaction on the monomer mixture to obtain the hydrate kinetic inhibitor;
the monomer mixture comprises vinyl pyrrolidone, cyclohexyl vinyl ether and acrylate monomers, wherein the molar ratio of the vinyl pyrrolidone to the cyclohexyl vinyl ether to the acrylate monomers is 8:1:1-6:3: 2.
In a specific embodiment of the above preparation method of the present invention, the acrylate monomer is selected from alkyl acrylates, and the alkyl is a C1-C7 alkyl. As in one embodiment of the present invention, the acrylate monomers include butyl acrylate, heptyl acrylate, propyl acrylate, and methyl acrylate, among others.
As a specific embodiment of the above preparation method of the present invention, the preparation method comprises: and carrying out ternary polymerization reaction on the monomer mixture in the presence of a solvent, an initiator and a terminator to obtain the hydrate kinetic inhibitor.
As a specific embodiment of the above preparation method of the present invention, wherein the initiator comprises one or a combination of several of azobisisobutyronitrile, dimethyl azobisisobutyrate, azobisisoheptonitrile, tert-butyl hydroperoxide or sodium metabisulfite; the amount of the initiator is 0.01-0.5% by total weight of the monomer mixture as 100%.
As a specific embodiment of the above production method of the present invention, wherein the terminator comprises styrene and/or methacrylic acid; the amount of the terminating agent is 0.05-0.1% by total weight of the monomer mixture as 100%.
As a specific embodiment of the above preparation method of the present invention, wherein the terpolymerization reaction temperature is 323.15-363.15K, and the reaction time is 2-12 h.
As a specific embodiment of the above preparation method of the present invention, wherein the solvent includes one or a combination of any several of ethanol, ethylene glycol, isoamyl alcohol, and n-propanol; the weight ratio of the solvent to the monomer mixture is 2-10: 1.
As a specific embodiment of the above preparation method of the present invention, the preparation method specifically comprises the following steps:
(1) adding vinyl pyrrolidone, cyclohexyl vinyl ether and an acrylate monomer into a solvent, and uniformly mixing to obtain a mixture;
(2) and adding an initiator into the mixture, heating to the reaction temperature, reacting at the reaction temperature in an inert atmosphere, adding a terminator to terminate the reaction, and obtaining the hydrate kinetic inhibitor after the reaction is finished.
As a specific embodiment of the above preparation method of the present invention, wherein the inert gas atmosphere comprises a nitrogen gas atmosphere.
In another aspect, the present invention also provides the use of a hydrate kinetic inhibitor as described above for inhibiting hydrate formation during oil and gas development and/or transportation.
As a specific embodiment of the above application of the present invention, wherein the hydrate kinetic inhibitor is suitable for an oil-gas-water three-phase system or a gas-water two-phase system.
As a specific embodiment of the above application of the present invention, wherein the pressure of the system is 0.2-30MPa, and the temperature is-15 to 30 ℃.
As a specific embodiment of the above application of the present invention, in the application process, the hydrate kinetic inhibitor is used alone or after being compounded with an alcohol or an ether reagent (wherein the alcohol reagent may be, for example, ethylene glycol, and the ether reagent may be, for example, butyl cellosolve, and the like).
The hydrate kinetic inhibitor provided by the invention can be used alone or in combination with an alcohol or ether reagent, and the hydrate kinetic inhibitor is compounded with the alcohol or ether reagent for use, so that the hydrate formation inhibition effect is better.
As a specific embodiment of the above application of the present invention, in the application process, when the hydrate kinetic inhibitor is used alone, the dosage of the hydrate kinetic inhibitor is 0.5 to 10 wt% based on the total weight of water in the system;
preferably, when the hydrate kinetic inhibitor is compounded with an alcohol or ether reagent and then used, the dosage of the hydrate kinetic inhibitor is 0.5-10 wt% and the dosage of the alcohol or ether reagent is 0.1-20 wt% based on the total weight of water in the system.
In yet another aspect, the present invention also provides a method of inhibiting hydrate formation during oil and gas development and/or transportation, wherein the method utilizes the hydrate kinetic inhibitor described above.
The hydrate kinetic inhibitor provided by the invention has the following beneficial technical effects:
(1) the hydrate kinetic inhibitor provided by the invention is a terpolymer obtained by copolymerizing vinyl pyrrolidone, cyclohexyl vinyl ether and acrylate monomers, and has better water solubility so as to ensure that the hydrate kinetic inhibitor can play a role in a water phase;
(2) compared with the traditional thermodynamic inhibitor, the hydrate kinetic inhibitor provided by the invention has the advantages of small dosage, low cost, obvious effect and the like;
(3) compared with the existing hydrate kinetic inhibitors such as the Inhibex501 and the like, the hydrate kinetic inhibitor provided by the invention has a better inhibiting effect on the hydrate, and has a better commercial application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an infrared spectrum of a hydrate kinetic inhibitor provided in example 1 of the present invention.
Detailed Description
In order to clearly understand the technical features, objects and advantages of the present invention, the following detailed description of the technical solutions of the present invention will be made with reference to the following specific examples, which should not be construed as limiting the implementable scope of the present invention.
Unless otherwise specified, the apparatus, reagents and the like used in the present invention are conventional apparatuses and conventional substances, and are commercially available.
Example 1
This example provides a hydrate kinetic inhibitor prepared by a process comprising the steps of:
1) selecting three monomers of vinyl pyrrolidone, cyclohexyl vinyl ether and butyl acrylate as synthetic raw materials, taking alcohols such as ethanol as a solvent for polymerization reaction, and uniformly mixing the synthetic raw materials and the solvent to obtain a mixture;
wherein the dosage of the three monomers of the vinyl pyrrolidone, the cyclohexyl vinyl ether and the butyl acrylate is 7.7795g, 1.1016g and 1.1189g respectively; the dosage of ethanol is 30 g;
2) adding the mixture into a three-neck round-bottom flask, adding azodiisobutyronitrile serving as an initiator accounting for 0.01 percent of the total weight of the mixture into the three-neck round-bottom flask after the temperature of a constant-temperature water bath reaches 333.15K, quickly fixing the three-neck round-bottom flask in the constant-temperature water bath, installing a condenser pipe on the three-neck round-bottom flask, introducing nitrogen into the three-neck round-bottom flask, starting stirring, keeping the temperature of the water bath and the stirring speed constant in the reaction process, stopping heating after 6 hours of reaction, and adding styrene serving as a terminator accounting for 0.05 percent of the total weight of the mixture into the three-neck round-bottom flask;
3) stopping introducing nitrogen and stopping stirring when the temperature of the system is cooled to room temperature, and transferring a product in the three-neck round-bottom flask to a beaker to obtain a crude product of the hydrate kinetic inhibitor;
4) transferring the liquid in the beaker to a purification device (such as a rotary evaporator), purifying a crude product of the hydrate kinetic inhibitor by the rotary evaporator, taking out the purified product, drying at the temperature of 323.15K to obtain the hydrate kinetic inhibitor, wherein the relative molecular mass of the hydrate kinetic inhibitor is 19370, and finally sealing and storing the hydrate kinetic inhibitor in a cool and dry place for later use.
The infrared spectrum analysis of the hydrate kinetic inhibitor obtained in the example is carried out, the obtained infrared spectrum is shown in figure 1, and the terpolymer, namely the hydrate kinetic inhibitor is arranged at 3010cm-1There is no distinct peak, indicating that the polymer isThe purity of (A) is higher, and almost no unreacted monomer is contained; since the terpolymer contains a pyrrolidone ring, it is at-1650 cm as PVP-1An obvious peak position exists nearby, and the peak position is a stretching vibration peak of-C ═ O on a pyrrolidone ring; in addition, there is a certain misalignment between the-C ═ O peak in the ester group and the-C ═ O peak in the pyrrolidone ring, and as can be seen from fig. 1, the terpolymer was found to be at-1729 cm-1A small peak appears, which is the-C ═ O peak in the ester group; in addition, the terpolymer is at-1075 cm-1There is a distinct peak position, which is the stretching vibration peak of the ether group C-O-C in the terpolymer.
In summary, the solid infrared data result shown in fig. 1 indicates that the terpolymer synthesized by the embodiment of the present invention contains three functional groups, i.e., a pyrrolidone group, an ether group, and an ester group, and the synthesized product is a target product.
Example 2
This example provides a hydrate kinetic inhibitor prepared substantially the same as the hydrate kinetic inhibitor provided in example 1, except that:
1) in the embodiment, three monomers of vinyl pyrrolidone, cyclohexyl vinyl ether and heptyl acrylate are selected as monomers for synthesizing a hydrate kinetic inhibitor;
2) the reaction time in this example was 8 h.
The hydrate kinetic inhibitor obtained in the embodiment has the relative molecular mass of 39370, and the infrared spectrum characteristic absorption peak of-3010 cm-1、～1650cm-1、～1729cm-1、～1075cm-1And the like, which shows that the purity of the polymer is high, the system hardly contains unreacted monomers, and the polymer contains groups such as pyrrolidone ring, ester group, ether group and the like.
Example 3
This example provides a hydrate kinetic inhibitor prepared substantially the same as the hydrate kinetic inhibitor provided in example 1, except that:
1) in the embodiment, three monomers of vinyl pyrrolidone, cyclohexyl vinyl ether and propyl acrylate are selected as monomers for synthesizing a hydrate kinetic inhibitor;
2) the reaction time in this example was 12 h.
The hydrate kinetic inhibitor obtained in the embodiment has the relative molecular mass of 42370, and the infrared spectrum characteristic absorption peak of-3010 cm-1、～1650cm-1、～1729cm-1、～1075cm-1And the like, which shows that the purity of the polymer is high, the system hardly contains unreacted monomers, and the polymer contains groups such as pyrrolidone ring, ester group, ether group and the like.
Example 4
This example provides a hydrate kinetic inhibitor prepared substantially the same as the hydrate kinetic inhibitor provided in example 1, except that:
1) in the embodiment, three monomers of vinyl pyrrolidone, cyclohexyl vinyl ether and methyl acrylate are selected as monomers for synthesizing a hydrate kinetic inhibitor;
2) the reaction time was 6 h.
The hydrate kinetic inhibitor obtained in the embodiment has the relative molecular mass of 22370, and the infrared spectrum characteristic absorption peak of 3010cm-1、～1650cm-1、～1729cm-1、～1075cm-1And the like, which shows that the purity of the polymer is high, the system hardly contains unreacted monomers, and the polymer contains groups such as pyrrolidone ring, ester group, ether group and the like.
Test example
This test example shows the Kinetic inhibitors of hydrates prepared in examples 1 to 4, as well as the conventional commercial inhibitors Inhibex501 (manufactured by Islands group Co.) and the Kinetic inhibitor PVP-A (see: Hui-Bo Qin, Zhen-Feng Sun, Xiao-Qin Wang. Synthesis and Evaluation of Two New Kinetic Hydrate inhibitors&fuels.2015,29,7135-7141) was evaluated for the inhibition of the hydrate formation process, and the apparatus used for the evaluation experiments was mainly composed of six sections: visual high-pressure sapphire kettle and temperature sensorThe device comprises a device, 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 59cm3The inner diameter is 2.54cm, and the highest pressure borne by the device can reach 40MPa, so that the safety of the experimental operation is ensured to be evaluated; the errors of the pressure sensor and the temperature sensor are respectively +/-0.01 MPa and +/-0.1K; the temperature error of the thermostatic air bath was also ± 0.1K, and the adjustment of the experimental temperature was mainly controlled by the thermostatic air bath.
The method for evaluating the hydrate kinetic inhibitor's inhibition performance on the hydrate formation process is as follows:
firstly, sequentially soaking and cleaning a visible high-pressure sapphire kettle by absolute ethyl alcohol and petroleum ether, cleaning for three times by the absolute ethyl alcohol, then opening an inlet and outlet valve of the visible high-pressure sapphire kettle, and purging the visible high-pressure sapphire kettle by using nitrogen to completely dry the interior of the visible high-pressure sapphire kettle so as to prevent the influence of ethanol residue on an experimental result;
adding the prepared solution to be tested containing the hydrate kinetic inhibitor into a visible high-pressure sapphire kettle, vacuumizing by using a vacuum pump, completely pumping out air in the kettle, and preventing the air in the kettle from interfering with the composition of experimental air, thereby reducing experimental errors;
opening an air inlet valve of the balance kettle, and closing the air inlet valve of the balance kettle after sufficient experimental gas is added into the balance kettle;
opening the constant-temperature air bath, setting the temperature of the constant-temperature air bath as an experimental set temperature value, opening an air inlet valve of the visible high-pressure sapphire kettle after the temperature in the visible high-pressure sapphire kettle is stabilized at the experimental set temperature value, introducing experimental gas into the visible high-pressure sapphire kettle from the balance kettle, closing the air inlet valve of the visible high-pressure sapphire kettle, then opening the magnetic stirring device, and keeping the rotating speed of the magnetic stirring device constant in the whole experimental process;
and (3) turning on a cold light source, observing the morphological change of the generated hydrate through a visible window of the constant-temperature air bath, shooting and recording by using a Canon digital camera, and simultaneously collecting the experimental data in real time by using a data collection system.
The experimental gas used for the evaluation experiment was pure methane gas.
Evaluation experiment the strength of the inhibition performance of the hydrate kinetic inhibitor is judged by measuring the nucleation time of the hydrate. The method comprises the steps that the nucleation time of the hydrate is determined through the real-time monitoring of a digital camera and the real-time monitoring of the pressure sensor on the pressure change of a system, the digital camera shoots that hydrate crystal nuclei appear in a visible high-pressure sapphire kettle for the first time, the pressure sensor monitors that the pressure of the system begins to fall, and the time at the moment is the nucleation time of the hydrate in the system.
Test example 1
An appropriate amount of the 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 was 0.5 wt% based on the total weight of water) was added to a visible high-pressure sapphire kettle, and an experimental gas of 6.1MPa was introduced into the visible high-pressure sapphire kettle at a temperature of 275.65K to perform an evaluation experiment, and it was found that the nucleation time of hydrate in the system was 143min, indicating that the formation of hydrate was significantly inhibited in the evaluation system due to the presence of the hydrate kinetic inhibitor.
Test example 2
An appropriate amount of the 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 was 0.5 wt% based on the total weight of water) was added to a visible high-pressure sapphire kettle, and an experimental gas of 6.1MPa was introduced into the visible high-pressure sapphire kettle at a temperature of 275.65K to perform an evaluation experiment, and it was found that the nucleation time of hydrate in the system was 121min, indicating that the formation of hydrate due to the presence of the hydrate kinetic inhibitor was significantly inhibited in the evaluation system.
Test example 3
An appropriate amount of the 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 was 0.5 wt% based on the total weight of water) was added to a visible high-pressure sapphire kettle, and an experimental gas of 6.1MPa was introduced into the visible high-pressure sapphire kettle at a temperature of 275.65K to perform an evaluation experiment, and it was found that the nucleation time of hydrate in the system was 105min, indicating that the formation of hydrate was significantly inhibited in the evaluation system due to the presence of the hydrate kinetic inhibitor.
Test example 4
An appropriate amount of the 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 was 0.5 wt% based on the total weight of water) was added to a visible high-pressure sapphire kettle, and an experimental gas of 6.1MPa was introduced into the visible high-pressure sapphire kettle at a temperature of 275.65K to perform an evaluation experiment, and it was found that the nucleation time of hydrate in the system was 98min, indicating that the formation of hydrate was significantly inhibited in the evaluation system due to the presence of the hydrate kinetic inhibitor.
Test example 5
An appropriate amount of the 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 was 1.0 wt% based on the total weight of water) was added to a visible high-pressure sapphire kettle, and an experimental gas of 6.1MPa was introduced into the visible high-pressure sapphire kettle at a temperature of 275.65K to perform an evaluation experiment, and it was found that the nucleation time of hydrate in the system was 332min, indicating that the formation of hydrate was significantly inhibited in the evaluation system due to the presence of the hydrate kinetic inhibitor.
Test example 6
An appropriate amount of the 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 into a visible high-pressure sapphire kettle, and an experimental gas of 6.1MPa was introduced into the visible high-pressure sapphire kettle at a temperature of 275.65K to perform an evaluation experiment, and it was found that the nucleation time of the hydrate in the system was 523min, indicating that the formation of the hydrate in the evaluation system was significantly inhibited due to the presence of the hydrate kinetic inhibitor.
Test example 7
An appropriate amount of the 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 was 10.0 wt% based on the total weight of water) was added to a visible high-pressure sapphire kettle, and an experimental gas of 6.1MPa was introduced into the visible high-pressure sapphire kettle at a temperature of 275.65K to perform an evaluation experiment, and it was found that the nucleation time of the hydrate in the system was 603min, indicating that the formation of the hydrate was significantly inhibited in the evaluation system due to the presence of the hydrate kinetic inhibitor.
Test example 8
Adding a proper amount of aqueous solution containing a compound mixture (wherein the compound mixture is obtained by compounding the hydrate kinetic inhibitor provided by the embodiment 1 of the invention with ethylene glycol, and the concentration of the hydrate kinetic inhibitor in the aqueous solution is 0.5 wt% and the concentration of the ethylene glycol is 3.5 wt% based on the total weight of water) into a visible high-pressure sapphire kettle, introducing 6.1MPa of experimental gas into the visible high-pressure sapphire kettle at the temperature of 275.65K to perform an evaluation experiment, and finding that the nucleation time of hydrate in the system is 410min, which indicates that the formation of hydrate is remarkably inhibited due to the existence of the hydrate kinetic inhibitor in the evaluation system;
in addition, the experimental data obtained by comparing test example 1 with test example 8 show that the hydrate kinetic inhibitor provided by the embodiment of the invention has better inhibiting effect on hydrate formation when used after being compounded with an alcohol reagent.
Comparative test example 1
Adding a proper amount of deionized water into a visible high-pressure sapphire kettle, introducing 6.1MPa of experimental gas into the visible high-pressure sapphire kettle at the temperature of 275.65K to perform an evaluation experiment, and finding that the nucleation time of hydrate in the system is less than 1min, which indicates that the hydrate is very rapidly formed in the evaluation system because no hydrate kinetic inhibitor is added.
Comparative test example 2
An appropriate amount of an aqueous solution containing commercial inhibitor Inhibex501 (the concentration of commercial inhibitor Inhibex501 in the aqueous solution is 0.5 wt% based on the total weight of water) was added to a visible high pressure sapphire kettle, an evaluation experiment is carried out by introducing 6.1MPa of experimental gas into the visible high-pressure sapphire kettle at the temperature of 275.65K, and the nucleation time of hydrate in the system is found to be 60min, which indicates that in the evaluation system, due to the addition of the commercial inhibitor Inhibex501, the formation of hydrate is also inhibited, but compared with the evaluation system containing the hydrate kinetic inhibitor provided by the invention in the example 1 in the test example 1, in comparative test example 2, the nucleation time of the hydrate is still shorter, which indicates that the hydrate kinetic inhibitor provided by the embodiment of the invention has a better hydrate inhibition effect than the existing hydrate kinetic inhibitor Inhibex 501.
Comparative test example 3
Adding ｃA proper amount of aqueous solution containing kinetic inhibitor PVP-A (the concentration of the kinetic inhibitor PVP-A in the aqueous solution is 0.5 wt% based on the total weight of water) into ｃA visible high-pressure sapphire kettle, an evaluation experiment was conducted by introducing an experimental gas of 6.1MPa into the visible high-pressure sapphire kettle at a temperature of 275.65K, and it was found that the nucleation time of hydrates in the system was 23min, indicating that in the evaluation system, because of the addition of the kinetic inhibitor PVP-A, the formation of hydrate is also inhibited, but compared with the evaluation system containing the hydrate kinetic inhibitor provided by the invention in the example 1 in the test example 1, in comparative test example 3, the nucleation time of the hydrate is still short, which indicates that the hydrate kinetic inhibitor provided by the embodiment of the invention has better hydrate inhibition effect than that of the conventional hydrate kinetic inhibitor PVP-A.
Comparative test example 4
An appropriate amount of an aqueous solution containing commercial inhibitor Inhibex501 (the concentration of commercial inhibitor Inhibex501 in the aqueous solution is 1.0 wt% based on the total weight of water) was added to a visible high pressure sapphire kettle, an evaluation experiment is carried out by introducing 6.1MPa of experimental gas into the visible high-pressure sapphire kettle at the temperature of 275.65K, and the nucleation time of hydrate in the system is found to be 200min, which indicates that in the evaluation system, because the commercial inhibitor Inhibex501 is added, the formation of the hydrate is also inhibited to a certain extent, but compared with the evaluation system containing the hydrate kinetic inhibitor provided by the invention in the example 1 in the test example 5, in comparative test example 4, the nucleation time of the hydrate is still shorter, which indicates that the hydrate kinetic inhibitor provided by the embodiment of the invention has a better hydrate inhibition effect than the existing hydrate kinetic inhibitor Inhibex 501.
In summary, compared with the existing hydrate kinetic inhibitors such as Inhibex501 and the like, the hydrate kinetic inhibitor provided by the invention has a better hydrate inhibition effect, and has a better commercial application prospect.
The above description is only exemplary of the invention and should not be taken as limiting the scope of the invention, so that the invention is intended to cover all modifications and equivalents of the embodiments described herein. In addition, the technical features and the technical inventions of the present invention, the technical features and the technical inventions, and the technical inventions can be freely combined and used.
Claims (16)
1. A hydrate kinetic inhibitor having a structural formula as shown in formula i:
in the formula I, R is C1-C7 alkyl;
the hydrate kinetic inhibitor has a molar ratio of each structural unit of x: y: z ═ 8:1:1-6:3: 2.
2. The hydrate kinetic inhibitor according to claim 1, characterized in that the hydrate kinetic inhibitor has a relative molecular mass of 1000-50000.
3. A process for the preparation of a hydrate kinetic inhibitor according to claim 1 or 2, characterized in that the process comprises: carrying out ternary polymerization reaction on the monomer mixture to obtain the hydrate kinetic inhibitor;
the monomer mixture comprises vinyl pyrrolidone, cyclohexyl vinyl ether and acrylate monomers, wherein the molar ratio of the vinyl pyrrolidone to the cyclohexyl vinyl ether to the acrylate monomers is 8:1:1-6:3: 2.
4. The production method according to claim 3, characterized by comprising: and carrying out ternary polymerization reaction on the monomer mixture in the presence of a solvent, an initiator and a terminator to obtain the hydrate kinetic inhibitor.
5. The preparation method according to claim 4, comprising the following steps:
(1) adding vinyl pyrrolidone, cyclohexyl vinyl ether and an acrylate monomer into a solvent, and uniformly mixing to obtain a mixture;
(2) and adding an initiator into the mixture, heating to the reaction temperature, reacting at the reaction temperature in an inert atmosphere, adding a terminator to terminate the reaction, and obtaining the hydrate kinetic inhibitor after the reaction is finished.
6. The preparation method according to claim 4 or 5, wherein the initiator comprises one or more of azodiisobutyronitrile, dimethyl azodiisobutyrate, azodiisoheptonitrile, tert-butyl hydroperoxide or sodium metabisulfite; the amount of the initiator is 0.01-0.5% by total weight of the monomer mixture as 100%.
7. The preparation method according to claim 4 or 5, wherein the solvent comprises one or a combination of any of ethanol, ethylene glycol, isoamyl alcohol and n-propanol; the weight ratio of the solvent to the monomer mixture is 2-10: 1.
8. The production method according to claim 4 or 5, wherein the terminator comprises styrene and/or methacrylic acid; the amount of the terminating agent is 0.05-0.1% by total weight of the monomer mixture as 100%.
9. The preparation method according to claim 4 or 5, wherein the terpolymerization temperature is 323.15-363.15K, and the reaction time is 2-12 h.
10. Use of the hydrate kinetic inhibitor of claim 1 or 2 to inhibit hydrate formation during oil and gas development and/or transportation.
11. Use according to claim 10, wherein the hydrate kinetic inhibitor is suitable for use in an oil-gas-water three-phase system or a gas-water two-phase system.
12. Use according to claim 11, wherein the system has a pressure of 0.2-30MPa and a temperature of-15 to 30 ℃.
13. The use according to any one of claims 10 to 12, wherein, during use, the hydrate kinetic inhibitor is used alone or after being compounded with an alcohol or ether reagent.
14. The use according to any one of claims 10 to 12, wherein the hydrate kinetic inhibitor is used in an amount of 0.5 to 10 wt% based on the total weight of water in the system when the hydrate kinetic inhibitor is used alone during use.
15. The use according to claim 13, wherein, in the application process, when the hydrate kinetic inhibitor is used after being compounded with an alcohol or ether reagent, the dosage of the hydrate kinetic inhibitor is 0.5-10 wt% and the dosage of the alcohol or ether reagent is 0.1-20 wt% based on the total weight of water in the system.
16. A method of inhibiting hydrate formation during oil and gas development and/or transportation, wherein the method utilises the hydrate kinetic inhibitor of claim 1 or 2.
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| US5874660A (en) * | 1995-10-04 | 1999-02-23 | Exxon Production Research Company | Method for inhibiting hydrate formation |
| CN101074361A (en) * | 2007-05-25 | 2007-11-21 | 东莞理工学院 | Efficient composite hydrate inhibitor |
| CN101544817A (en) * | 2009-04-28 | 2009-09-30 | 中国石油大学(北京) | Composition for enhancing hydrate inhibition effect and method for inhibiting formation of hydrate |
| CN101817909A (en) * | 2010-03-19 | 2010-09-01 | 西南石油大学 | Hydrate inhibitor polymer and preparation method |
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| GB2454139B (en) * | 2006-08-03 | 2011-03-16 | Baker Hughes Inc | Kinetic gas hydrate inhibitors in completion fluids |
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| US5874660A (en) * | 1995-10-04 | 1999-02-23 | Exxon Production Research Company | Method for inhibiting hydrate formation |
| CN101074361A (en) * | 2007-05-25 | 2007-11-21 | 东莞理工学院 | Efficient composite hydrate inhibitor |
| CN101544817A (en) * | 2009-04-28 | 2009-09-30 | 中国石油大学(北京) | Composition for enhancing hydrate inhibition effect and method for inhibiting formation of hydrate |
| CN101817909A (en) * | 2010-03-19 | 2010-09-01 | 西南石油大学 | Hydrate inhibitor polymer and preparation method |
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