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WO2023193314A1 - Polymère d'acide aminé, son procédé de préparation et son utilisation en tant qu'inhibiteur cinétique d'hydrate de gaz naturel - Google Patents

Polymère d'acide aminé, son procédé de préparation et son utilisation en tant qu'inhibiteur cinétique d'hydrate de gaz naturel Download PDF

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WO2023193314A1
WO2023193314A1 PCT/CN2022/088673 CN2022088673W WO2023193314A1 WO 2023193314 A1 WO2023193314 A1 WO 2023193314A1 CN 2022088673 W CN2022088673 W CN 2022088673W WO 2023193314 A1 WO2023193314 A1 WO 2023193314A1
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amino acid
acid polymer
natural gas
gas hydrate
methionine
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Chinese (zh)
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张倩
卢海龙
李臻超
李媛媛
管文
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Peking University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C09K8/528—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning inorganic depositions, e.g. sulfates or carbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/22—Hydrates inhibition by using well treatment fluids containing inhibitors of hydrate formers

Definitions

  • the invention belongs to the technical field of chemical production, and specifically relates to an amino acid polymer, its preparation method and its application as a natural gas hydrate kinetic inhibitor.
  • Natural gas hydrate is a solid substance formed from water and gas (methane, ethane, carbon dioxide, hydrogen, nitrogen, hydrogen sulfide, etc.) molecules under high-pressure and low-temperature conditions.
  • gas methane, ethane, carbon dioxide, hydrogen, nitrogen, hydrogen sulfide, etc.
  • Flow safety issues caused by the formation of natural gas hydrates are one of the major issues facing the oil and gas industry. Once natural gas hydrate is generated in oil and gas pipelines, it will at least reduce the flow rate, affect production capacity and output, and cause economic losses; at worst, it will cause equipment failure and pipeline blockage, which is a serious safety hazard.
  • the secondary formation of natural gas hydrate is one of the key issues affecting the production capacity and production time of flammable ice, a new energy source. Therefore, it is necessary to prevent the formation of natural gas hydrates in the fields of oil and gas transportation and flammable ice mining.
  • Methods to prevent the formation of natural gas hydrates mainly include: (1) physical methods, such as pressure reduction, temperature raising, and water removal methods; (2) chemical methods, such as adding gas hydrate inhibitors.
  • physical methods such as pressure reduction, temperature raising, and water removal methods
  • chemical methods such as adding gas hydrate inhibitors.
  • the depressurization method, the heating method and the water removal method can completely eliminate the formation of hydrates, they have the disadvantages of high cost, limited applicable sites, and difficulty in actual operation.
  • the pressure reduction method is generally only applicable to remedial measures after natural gas hydrates block pipelines; the temperature increase method requires advance layout when laying pipelines; completely removing water from oil and gas products is neither economical nor easy to achieve.
  • the chemical method of preventing hydrate formation by adding natural gas hydrate inhibitors is a relatively efficient, fast, low-cost and reliable method.
  • Natural gas hydrate inhibitors are mainly divided into three categories: (1) thermodynamic inhibitors, (2) antipolymerization agents, and (3) kinetic inhibitors.
  • Thermodynamic inhibitors can change the phase equilibrium conditions of natural gas hydrates, allowing natural gas hydrates to be generated under higher pressure and lower temperature conditions.
  • Commonly used thermodynamic inhibitors include methanol, ethylene glycol, sodium chloride, etc.
  • thermodynamic inhibitors require high concentrations (usually as high as 10 to 50% of the water phase mass fraction) to have good inhibitory effects. Therefore, thermodynamic inhibitors are more costly and harmful to the environment.
  • Both antipolymerization agents and kinetic inhibitors are low-dose inhibitors, and the ideal hydrate inhibition effect can be achieved by adding a concentration of 0.1 to 2wt%.
  • Antipolymers are surfactants or amphiphilic polymers that cannot inhibit the nucleation of natural gas hydrates, but can be adsorbed on the surface of natural gas hydrate particles to suspend and disperse the natural gas hydrate crystals in the mobile phase. Prevent natural gas hydrate from agglomerating and clumping to inhibit pipeline obstruction.
  • Kinetic inhibitors are some water-soluble polymers, mainly including heterocyclic polyamide kinetic inhibitors, chain polyamide kinetic inhibitors, non-amide kinetic inhibitors, and natural product kinetic inhibitors.
  • Agents, etc. which can delay the nucleation time of natural gas hydrate crystals, reduce the growth rate, and prevent further growth of natural gas hydrate crystals, thereby achieving safe transportation of oil and gas products.
  • hydrate kinetic inhibitors Compared with antipolymerization agents, hydrate kinetic inhibitors have a wider range of applications. In recent years, the research on hydrate kinetic inhibitors has received widespread attention around the world due to its advantages such as high efficiency, low environmental pollution, low cost, and wide application range.
  • the present invention provides an amino acid polymer and its preparation method and its application as a natural gas hydrate kinetic inhibitor.
  • the amino acid polymer provided by the present invention has good inhibitory effect, low dosage, low cost, and applicability. Wide and easily biodegradable.
  • the present invention provides an amino acid polymer, including a first polymerization unit having a structure shown in Formula 1:
  • it also includes a second polymerized unit having the structure shown in Formula 2:
  • the percentage of the amount of the first polymerized unit to the total amount of the first polymerized unit and the second polymerized unit is ⁇ 38%.
  • the average molecular weight of the amino acid polymer is 1,000 to 1,000,000 g/mol.
  • the amino acid polymer is an amino acid homopolymer formed from the first polymerized unit, and the degree of polymerization of the amino acid homopolymer is ⁇ 10,000.
  • the present invention provides a method for preparing the amino acid polymer described in the above technical solution, which includes the following steps:
  • methionine-N-carboxylic intracyclic acid anhydride, initiator and organic solvent are mixed to undergo a ring-opening polymerization reaction to obtain a methionine polymer;
  • the methionine polymer, an oxidant and a polar solvent are mixed to undergo an oxidation reaction to obtain the amino acid polymer.
  • the initiator is an oil-soluble initiator, and the molar ratio between the initiator and methionine-N-carboxylic intracyclic acid anhydride is 1: (10-60).
  • the oxidizing agent is H 2 O 2
  • the molar ratio of the sulfur atoms in the oxidizing agent and the methionine polymer is (0.6-1.5):1.
  • the present invention provides the application of the amino acid polymer described in the above technical solution or the amino acid polymer prepared by the preparation method described in the above technical solution as a natural gas hydrate kinetic inhibitor.
  • the amino acid polymer is used in the form of an aqueous amino acid polymer solution, and the mass concentration of the aqueous amino acid polymer solution is 0.1 to 10%.
  • the applied pressure is 1 to 25 MPa, and the applied temperature is -25 to 50°C.
  • the present invention provides an amino acid polymer, including a first polymerized unit having a structure shown in Formula 1:
  • the side chains of the amino acid polymer provided by the present invention can enter the interior of the natural gas hydrate cage structure and interfere with the structure of the natural gas hydrate, affecting the stability of the natural gas hydrate structure, thereby The nucleation of natural gas hydrate cannot stably grow to a critical size, making it difficult for natural gas hydrate crystals to nucleate.
  • the main chain of the polymer unit shown in Formula 1 contains an amide group, and the N and O atoms in the amide group can be adsorbed on the surface of natural gas hydrate through hydrogen bonds, thereby inhibiting the further growth of natural gas hydrate crystals. Therefore, the amino acid polymer provided by the present invention can effectively delay the nucleation of natural gas hydrate and reduce the formation rate of natural gas hydrate under low dose concentration conditions and high supercooling environment, and has good inhibitory effect, low dosage, It has the advantages of low cost and wide applicability.
  • the amino acid polymer provided by the present invention can effectively delay the nucleation/growth of hydrates, so that oil and gas products do not generate hydrates within a certain period of time, so that they can be safely transported to their destinations.
  • the amino acid polymer provided by the invention is suitable for oil-gas-water three-phase or oil-water or gas-water two-phase coexistence systems. It can be used to inhibit the generation of natural gas hydrates during oil and gas transportation and combustible ice mining processes, and can achieve good results. The inhibitory effect is small, the cost is reduced, and it has broad application prospects.
  • the amino acid polymer provided by the invention uses a water-soluble initiator to enhance the water solubility of the amino acid polymer, so that its water-soluble form can be used as a natural gas hydrate kinetic inhibitor, which is green and environmentally friendly.
  • amino acid polymers with a main chain composed of N and O heteroatoms have greater biological potential than vinyl polymers or propylene-based polymers (the main chain is composed of pure C-C bonds). Degradability potential.
  • amino acid polymerization provided by the present invention also includes a second polymerization unit having a structure shown in Formula 2:
  • the percentage of the amount of the first polymerized unit to the total amount of the first polymerized unit and the second polymerized unit is ⁇ 38%.
  • the amino acid polymer provided by the present invention also includes a second polymerized unit having the structure shown in Formula 2, and the percentage of the amount of the first polymerized unit to the total amount of the first polymerized unit and the second polymerized unit is ⁇ 38%, on the basis of ensuring the water solubility of the amino acid polymer, minimizing the amount of oxidant used can reduce the preparation cost of the amino acid polymer.
  • Figure 1 is a hydrogen nuclear magnetic resonance spectrum of the amino acid polymer prepared in Example 1 of the present invention.
  • Figure 2 is a hydrogen nuclear magnetic resonance spectrum of the amino acid polymer prepared in Example 2 of the present invention.
  • Figure 3 is a hydrogen nuclear magnetic resonance spectrum of the amino acid polymer prepared in Example 3 of the present invention.
  • Figure 4 is a hydrogen nuclear magnetic resonance spectrum of the amino acid polymer prepared in Example 4 of the present invention.
  • Figure 5 is a hydrogen nuclear magnetic resonance spectrum of the amino acid polymer prepared in Example 5 of the present invention.
  • Figure 6 is an example diagram of the time-temperature and time-pressure curves of the system in the reaction kettle of Application Example 1 of the present invention.
  • the present invention provides an amino acid polymer, which is characterized in that it includes a first polymerization unit having a structure shown in Formula 1:
  • the amino acid polymer preferably further includes a second polymerized unit having the structure shown in Formula 2:
  • the amino acid polymer when the amino acid polymer preferably further includes a second polymerized unit having the structure shown in Formula 2, the amount of the first polymerized unit accounts for the total amount of the first polymerized unit and the second polymerized unit.
  • the percentage of the amount of substance is preferably ⁇ 38%.
  • the percentage of the amount of the first polymerized unit to the total amount of the first polymerized unit and the second polymerized unit is preferably 38%, 55%, 72%, 79 %.
  • the amino acid polymer when the amino acid polymer preferably further includes a second polymerized unit having the structure shown in Formula 2, the amino acid polymer is a random copolymer formed by the first polymerized unit and the second polymerized unit. .
  • the average molecular weight of the amino acid polymer is preferably 1,000 to 1,000,000 g/mol, more preferably 2,000 to 800,000 g/mol, and even more preferably 2,500 to 600,000 g/mol.
  • the average molecular weight of the amino acid polymer is specifically preferably 4088g/mol, 4168g/mol, 4248g/mol, 4280g/mol and 4376g/mol.
  • the degree of polymerization of the amino acid polymer is preferably ⁇ 10,000.
  • the degree of polymerization of the amino acid polymer is preferably 29.
  • the amino acid polymer provided by the invention When used as a new type of natural gas hydrate kinetic inhibitor, the amino acid polymer provided by the invention has a good inhibitory effect, and has the advantages of low dosage, low cost and wide source.
  • the added amount of the amino acid polymer provided by the present invention is much smaller than that of traditional thermodynamic inhibitors.
  • a good inhibitory effect can be achieved by adding a mass concentration of 0.1 to 10%, and the reagent cost is greatly reduced.
  • the present invention provides a method for preparing the amino acid polymer described in the above technical solution, which includes the following steps:
  • methionine-N-carboxylic intracyclic acid anhydride, an initiator and an organic solvent hereinafter referred to as the first organic solvent
  • the first organic solvent methionine-N-carboxylic intracyclic acid anhydride, an initiator and an organic solvent (hereinafter referred to as the first organic solvent) are mixed (hereinafter referred to as the first mixing) to undergo a ring-opening polymerization reaction to obtain methyl sulfide Acid polymer;
  • the methionine polymer, an oxidizing agent and a polar solvent are mixed (hereinafter referred to as the second mixing) to undergo an oxidation reaction to obtain the amino acid polymer.
  • the preparation method of the methionine-N-carboxylic intracyclic acid anhydride preferably includes the following steps:
  • Methionine, bis(trichloromethyl)carbonate (triphosgene) and a second organic solvent are mixed for a third time to perform a ring-forming reaction to obtain methionine-N-carboxy intracyclic acid anhydride.
  • the mass ratio of methionine and triphosgene is preferably 1:1.
  • the second organic solvent is specifically preferably tetrahydrofuran.
  • the ratio of the mass of methionine to the volume of the second organic solvent is preferably 10.3g:250mL.
  • the third mixing sequence is preferably: mixing the methionine, triphosgene and the second organic solvent in sequence.
  • the temperature of the ring-forming reaction is preferably 20 to 60°C, and more preferably 25 to 50°C.
  • the holding time of the ring-forming reaction is preferably 4 to 24 hours, more preferably 5 to 23 hours.
  • the cyclization reaction obtains a cyclization reaction liquid.
  • the post-treatment preferably includes sequentially removing the second organic solvent and purifying.
  • the method for removing the second organic solvent is preferably vacuum distillation, and the present invention has no special requirements on the specific implementation process of the vacuum distillation.
  • the purification is preferably column chromatography purification.
  • the eluent used in the column chromatography purification is preferably a mixed solvent of petroleum ether and ethyl acetate.
  • the eluent used in the column chromatography purification is preferably a mixed solvent of petroleum ether and ethyl acetate.
  • the volume ratio of petroleum ether and ethyl acetate is preferably 1:4.
  • the initiator is preferably an oil-soluble initiator, specifically benzylamine.
  • the molar ratio of the initiator and methionine-N-carboxylic intracyclic anhydride is preferably 1: (10-60), more preferably 1: (12-55), and further preferably 1: (15 ⁇ 50).
  • the first organic solvent is preferably N,N-dimethylformamide.
  • the first organic solvent is preferably an anhydrous solvent.
  • the present invention has no special requirements on the amount of the organic solvent, as long as the raw materials for the ring-opening polymerization reaction are completely dissolved.
  • the ratio of the mass of the methionine-N-carboxyl intracyclic acid anhydride to the volume of the organic solvent is specifically preferably 8.83g:30mL.
  • the order of the first mixing is preferably: mixing the methionine-N-carboxyl intracyclic acid anhydride, the first organic solvent and the initiator in sequence.
  • the ring-opening polymerization reaction is an N-carboxyl intracyclic acid anhydride ring-opening polymerization reaction.
  • the temperature of the ring-opening polymerization reaction is preferably 20 to 60°C, and more preferably 25 to 50°C.
  • the heat preservation time of the ring-opening polymerization reaction is preferably 8 to 48 hours, more preferably 10 to 45 hours.
  • the protective gas is preferably nitrogen or an inert gas, and more preferably nitrogen.
  • the invention before performing the ring-opening polymerization reaction, preferably repeatedly evacuates and passes protective gas through the container for the ring-opening polymerization reaction three times.
  • the ring-opening polymerization reaction obtains a polymerization reaction liquid.
  • the post-treatment preferably includes: precipitation, solid-liquid separation and drying in sequence.
  • the precipitation is preferably washed out by mixing the polymerization reaction solution and diethyl ether.
  • the present invention has no special requirements on the amount of diethyl ether, as long as the polymerization product is completely precipitated.
  • the solid-liquid separation is preferably centrifugal separation, and the present invention has no special requirements on the specific implementation of the centrifugal separation.
  • the drying temperature is preferably room temperature, and the drying time is preferably 24 hours.
  • the present invention mixes the methionine polymer, an oxidant and a polar solvent for a second time to undergo an oxidation reaction to obtain the amino acid polymer.
  • the oxidizing agent is specifically preferably H 2 O 2 .
  • the polar solvent is specifically preferably water.
  • the present invention has no special requirements on the amount of the polar solvent.
  • the molar ratio of the sulfur atoms in the oxidant and the methionine polymer is preferably (0.6 ⁇ 1.5):1, more preferably (0.6 ⁇ 1.2):1
  • the order of the second mixing is preferably: mixing the methionine polymer, the oxidizing agent and the polar solvent in sequence.
  • the oxidation reaction is preferably carried out at room temperature.
  • the holding time of the oxidation reaction is preferably 4 to 24 hours, more preferably 5 to 23 hours.
  • the oxidizing agent converts the methionine polymer into The substituent is oxidized to
  • the oxidation reaction obtains an oxidation reaction liquid.
  • the post-treatment preferably includes: water dialysis purification and freeze-drying in sequence.
  • the water dialysis purification is preferably as follows: putting the reaction solution of the alkali addition reaction into a dialysis bag, and immersing the dialysis bag containing the reaction solution in water to perform dialysis.
  • the water is preferably pure water.
  • the time for water dialysis and purification is preferably 24 to 48 hours, and more preferably 48 hours.
  • the molecular weight cutoff of the dialysis membrane used in the dialysis bag is preferably 1000 Da.
  • the freeze-drying temperature is preferably -60°C.
  • the present invention provides the application of the amino acid polymer described in the above technical solution or the amino acid polymer prepared by the preparation method described in the above technical solution as a natural gas hydrate kinetic inhibitor.
  • the amino acid polymer is preferably used in the form of an aqueous amino acid polymer solution.
  • the mass concentration of the amino acid polymer aqueous solution is preferably 0.1 to 10%, and more preferably 0.1 to 2%.
  • the applied pressure is preferably 1 to 25 MPa.
  • the applied temperature is preferably -25 to 50°C.
  • the amino acid polymer provided by the invention is suitable for oil-gas-water three-phase or oil-water or gas-water two-phase coexistence systems, and can be used to inhibit natural gas in the process of oil and gas transportation and flammable ice mining.
  • the formation of hydrates can achieve good inhibitory effect, and the dosage is small, the cost is reduced, and it has broad application prospects.
  • reaction solution obtained by the ring-opening polymerization reaction is added to diethyl ether for precipitation, centrifugal separation, and drying to obtain a methionine polymer;
  • methionine polymer and hydrogen peroxide (the molar ratio of H 2 O 2 and sulfur atoms in the methionine polymer is preferably 0.6:1), and perform an oxidation reaction at room temperature for 24 hours; put the obtained reaction liquid into into the dialysis bag, immersed the dialysis bag containing the reaction solution in pure water for dialysis for 48 hours, then took it out and freeze-dried it to obtain amino acid polymer 1.
  • the data molecular weight of amino acid polymer 1 is 4088g/mol.
  • reaction solution obtained by the ring-opening polymerization reaction is added to diethyl ether for precipitation, centrifugal separation, and drying to obtain a methionine polymer;
  • methionine polymer and hydrogen peroxide (the molar ratio of sulfur atoms in H 2 O 2 and methionine polymer is preferably 0.7:1), and perform an oxidation reaction at room temperature for 24 hours; put the obtained reaction liquid into into the dialysis bag, immersed the dialysis bag containing the reaction solution in pure water for dialysis for 48 hours, then took it out and freeze-dried it to obtain amino acid polymer 2.
  • the data molecular weight of amino acid polymer 2 is 4168g/mol.
  • reaction solution obtained by the ring-opening polymerization reaction is added to diethyl ether for precipitation, centrifugal separation, and drying to obtain a methionine polymer;
  • methionine polymer and hydrogen peroxide (the molar ratio of H 2 O 2 and sulfur atoms in the methionine polymer is preferably 0.8:1), and perform an oxidation reaction at room temperature for 24 hours; put the obtained reaction liquid into into the dialysis bag, immersed the dialysis bag containing the reaction solution in pure water for 48 hours and then dialyzed for 48 hours, then took it out and lyophilized to obtain amino acid polymer 3.
  • the data molecular weight of amino acid polymer 3 was 4248g/mol.
  • reaction solution obtained by the ring-opening polymerization reaction is added to diethyl ether for precipitation, centrifugal separation, and drying to obtain a methionine polymer;
  • the methionine polymer and hydrogen peroxide (the molar ratio of H 2 O 2 and the sulfur atoms in the methionine polymer is preferably 0.9:1), and perform an oxidation reaction at room temperature for 24 hours; put the obtained reaction liquid into into the dialysis bag, immersed the dialysis bag containing the reaction solution in pure water for dialysis for 48 hours, then took it out and freeze-dried it to obtain amino acid polymer 4.
  • the data molecular weight of amino acid polymer 4 is 4280g/mol.
  • reaction solution obtained by the ring-opening polymerization reaction is added to diethyl ether for precipitation, centrifugal separation, and drying to obtain a methionine polymer;
  • the methionine polymer and hydrogen peroxide (the molar ratio of H 2 O 2 and the sulfur atoms in the methionine polymer is preferably 1.2:1), and perform an oxidation reaction at room temperature for 24 hours; put the obtained reaction liquid into into the dialysis bag, immersed the dialysis bag containing the reaction solution in pure water and dialyzed for 48 hours, then took it out and lyophilized to obtain the amino acid polymer 5.
  • the data molecular weight of the amino acid polymer 5 is 4376g/mol.
  • the amino acid polymer prepared in the embodiment of the present invention is used as a natural gas hydrate kinetic inhibitor.
  • the experimental equipment for testing the inhibitory effect of the natural gas hydrate kinetic inhibitor provided by the present invention is a high-pressure stirring test device.
  • the main components of the high-pressure stirring test device are: Parts include stainless steel high-pressure reactors, circulating water baths, magnetic stirrers, temperature sensors, pressure sensors, high-pressure gas bottles, vacuum pumps, data acquisition instruments, etc.
  • the stainless steel high-pressure reactor has a maximum working pressure of 20MPa and a working temperature range of -20 to 80°C.
  • the pressure inside the stainless steel high-pressure reaction kettle can be freely adjusted through the air valve.
  • the circulating water bath can provide a temperature environment of -20 ⁇ 80°C for the high-pressure reactor.
  • the data acquisition system collects and stores the pressure, temperature and other parameters in the high-pressure reaction kettle in real time.
  • the formation of natural gas hydrate in the reactor can be judged by sudden changes in temperature or pressure during the reaction.
  • After filling the high-pressure reaction kettle with the aqueous amino acid polymer solution prepared in the Example introduce high-pressure gas, close the valve to seal the system in the high-pressure reaction kettle, turn on stirring, and then lower the temperature at a constant rate (1°C/h) to allow the natural gas to Hydrate formation.
  • the system in the high-pressure reactor will gradually reach the conditions for the formation of natural gas hydrate. In a closed system, the pressure decreases linearly as the temperature decreases.
  • the inhibitory effect of the natural gas hydrate kinetic inhibitor provided by the present invention is quantified based on the natural gas hydrate formation temperature at which the kinetic inhibitor aqueous solution prepared in the Example is added to the reactor system. The lower the formation temperature of natural gas hydrate in the high-pressure reactor system, the better the inhibitory effect of the kinetic inhibitor.
  • the specific implementation process is: before running the experiment, clean the high-pressure reactor with detergent, ethanol, and deionized water in sequence, and then blow dry the water in the reactor with nitrogen to ensure it is dry.
  • vacuum pass in 0.5MPa high-purity methane gas, remove the gas, and then vacuum again. Repeat this three times to remove as much air as possible from the reactor and pipelines.
  • the time-temperature and time-pressure curves measured during the experiment show that when the aqueous solution of amino acid polymer 1 prepared in Example 1 with a mass concentration of 0.15% is used as a kinetic inhibitor, the generation temperature of natural gas hydrate is 9.1°C. Has better inhibitory effect.
  • the reaction device and method are basically the same as those in Application Example 1, except that an aqueous solution of amino acid polymer 2 with a mass concentration of 0.15% is added to the reaction kettle, and the time-temperature and time-pressure curves measured during the experiment ( As shown in Figure 2), it is shown that when the aqueous solution of amino acid polymer 2 prepared in Example 2 with a mass concentration of 0.15% is used as a kinetic inhibitor, the formation temperature of natural gas hydrate is 9.1°C, which has a good inhibitory effect.
  • the reaction device and method are basically the same as those in Application Example 1. The difference is that an aqueous solution of amino acid polymer 3 with a mass concentration of 0.15% is added to the reaction kettle.
  • the time-temperature and time-pressure curves measured during the experiment show that , when the aqueous solution of amino acid polymer 3 prepared in Example 3 with a mass concentration of 0.15% is used as a kinetic inhibitor, the formation temperature of natural gas hydrate is 7.3°C, which has a good inhibitory effect.
  • the reaction device and method are basically the same as those in Application Example 1, except that an aqueous solution of amino acid polymer 4 with a mass concentration of 0.15% is added to the reaction kettle.
  • the time-temperature and time-pressure curves measured during the experiment show that , when the aqueous solution of amino acid polymer 4 prepared in Example 4 with a mass concentration of 0.15% is used as a kinetic inhibitor, the formation temperature of natural gas hydrate is 8.3°C, which has a good inhibitory effect.
  • the reaction device and method are basically the same as those in Application Example 1. The difference is that an aqueous solution of amino acid polymer 5 with a mass concentration of 0.15% is added to the reaction kettle.
  • the time-temperature and time-pressure curves measured during the experiment show that , when the aqueous solution of amino acid polymer 5 prepared in Example 5 with a mass concentration of 0.15% is used as a kinetic inhibitor, the formation temperature of natural gas hydrate is 9.2°C, which has a good inhibitory effect.
  • the reaction device and method are basically the same as those in Application Example 1. The difference is that an aqueous solution of amino acid polymer 5 with a mass concentration of 0.55% is added to the reaction kettle.
  • the time-temperature and time-pressure curves measured during the experiment show that , when the aqueous solution of amino acid polymer 5 prepared in Example 5 with a mass concentration of 0.25% is used as a kinetic inhibitor, the formation temperature of natural gas hydrate is 8.0°C, which has a good inhibitory effect.
  • the reaction device and method are basically the same as those in Application Example 1. The difference is that an aqueous solution of amino acid polymer 5 with a mass concentration of 0.5% is added to the reaction kettle.
  • the time-temperature and time-pressure curves measured during the experiment show that , when the aqueous solution of amino acid polymer 5 prepared in Example 5 with a mass concentration of 0.5% is used as a kinetic inhibitor, the formation temperature of natural gas hydrate is 7.6°C, which has a good inhibitory effect.
  • the reaction device and method are basically the same as those in Application Example 1. The difference is that pure water is added to the reaction kettle.
  • the time-temperature and time-pressure curves measured during the experiment show that when pure water is a kinetic inhibitor, , the formation temperature of natural gas hydrate is 10°C.
  • the reaction device and method are basically the same as those in Application Example 1, except that an aqueous solution of polyvinylpyrrolidone (PVP K15-K19) with a mass concentration of 0.15% and a molecular weight of 10000g/mol is added to the reaction kettle, and the The time-temperature and time-pressure curves measured during the experiment show that when an aqueous solution of polyvinylpyrrolidone (PVP K15-K19) with a mass concentration of 0.15% and a molecular weight of 10000g/mol is used as a kinetic inhibitor, natural gas
  • the formation temperature of hydrate is 8.5°C, which has a good inhibitory effect.
  • the reaction device and method are basically the same as those in Application Example 1, except that an aqueous polyvinylpyrrolidone (PVP K15-K19) solution with a mass concentration of 0.25% and a molecular weight of 10000g/mol is added to the reaction kettle, and the The time-temperature and time-pressure curves measured during the experiment show that when an aqueous solution of polyvinylpyrrolidone (PVP K15-K19) with a mass concentration of 0.15% and a molecular weight of 10000g/mol is used as a kinetic inhibitor, natural gas
  • the formation temperature of hydrate is 8.2°C, which has a good inhibitory effect.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention appartient au domaine technique de la production chimique, et concerne en particulier un polymère d'acide aminé, son procédé de préparation et son utilisation en tant qu'inhibiteur cinétique d'hydrate de gaz naturel. Une liaison S=O sur une chaîne latérale du polymère d'acide aminé fourni peut former une liaison hydrogène avec des molécules d'eau, de sorte que des molécules d'eau autour de la liaison S=O sont brouillées, et la structure d'eau en forme de cage d'un hydrate de gaz naturel n'est pas facile à former, ce qui permet d'inhiber la nucléation de l'hydrate de gaz naturel. De plus, la chaîne principale de l'unité de polymérisation telle que représentée dans la formule 1 contient un groupe amide, et les atomes N et O dans le groupe amide peuvent être adsorbés sur la surface de l'hydrate de gaz naturel au moyen de liaisons hydrogène, de sorte qu'une croissance supplémentaire de cristaux d'hydrate de gaz naturel est inhibée. Par conséquent, le polymère d'acide aminé fourni peut retarder efficacement la nucléation de l'hydrate de gaz naturel et réduire le taux de génération de l'hydrate de gaz naturel dans l'état d'une faible concentration de dosage et d'un environnement à degré de surfusion élevé, et présente les avantages d'un bon effet d'inhibition, d'un petit dosage, d'un faible coût, d'une large applicabilité, etc.
PCT/CN2022/088673 2022-04-08 2022-04-24 Polymère d'acide aminé, son procédé de préparation et son utilisation en tant qu'inhibiteur cinétique d'hydrate de gaz naturel Ceased WO2023193314A1 (fr)

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