CN108219762B - Novel hydrate kinetic inhibitor and preparation method and application thereof - Google Patents
Novel hydrate kinetic inhibitor and preparation method and application thereof Download PDFInfo
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- CN108219762B CN108219762B CN201611153269.9A CN201611153269A CN108219762B CN 108219762 B CN108219762 B CN 108219762B CN 201611153269 A CN201611153269 A CN 201611153269A CN 108219762 B CN108219762 B CN 108219762B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F126/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F126/06—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F126/10—N-Vinyl-pyrrolidone
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- 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
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- 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
Abstract
The invention discloses a hydrate kinetic inhibitor with a structural formula shown as a formula I, which has high inhibition activity, good inhibition effect, small dosage and low cost, can effectively delay the nucleation time of a hydrate and reduce the generation rate of the hydrate in a high supercooling degree environment under low dosage concentration (0.5-2 wt%), is suitable for an oil-gas-water three-phase or oil-water or gas-water two-phase coexistence system, is applied to inhibiting the generation of the hydrate in the oil-gas exploitation, processing and conveying processes, is not limited by supercooling degree and application occasions, and has wide application prospect.
Wherein n is 10-10000.
Description
The technical field is as follows:
the invention relates to the technical field of chemical industry, in particular to a novel hydrate kinetic inhibitor and a preparation method and application thereof.
Background art:
the guarantee of flow safety is one of the major problems faced by the oil and gas industry, and especially important is to prevent the generation of gas hydrate, because once the gas hydrate is generated, the gas hydrate can cause the failure of oil and gas exploitation instruments and equipment, the blockage of pipelines and the influence on normal oil and gas exploitation, transportation and operation. Natural gas hydrate is an ice-like, non-stoichiometric, cage-like complex formed under high pressure, low temperature conditions from water and some light gases (hydrogen, carbon dioxide, nitrogen, methane, ethane, hydrogen sulfide, etc.).
The method for preventing the generation of the hydrate comprises the following three methods: 1. the environmental conditions are changed, and the generation environment of the hydrate can not be met by means of pressure reduction, temperature rise and the like; 2. changing the phase equilibrium condition of the natural gas hydrate, which can be realized by adding thermodynamic inhibitors such as methanol, ethylene glycol and the like; 3. the time for nucleation, growth and aggregation of the hydrate is prolonged, so that the hydrate is not blocked during the process of mining and pipeline transportation, and the dynamic inhibitor and the polymerization inhibitor are added to realize the purpose. The method 1 and the method 2 can completely prevent the generation of the hydrate, but in consideration of environmental protection, cost saving and the like, it is not practical to prevent the generation of the hydrate by temperature and pressure management and a method of adding a thermodynamic inhibitor (usually 10 to 50 wt% is added to be effective). Kinetic inhibitors and inhibitors are commonly referred to as low dose natural gas hydrate inhibitors (effective with 0.1-2 wt% addition). It has received wide attention because of its high efficiency, low environmental pollution and low cost. The kinetic inhibitor can delay the nucleation time of the hydrate crystal, reduce the growth speed and prevent the further growth of the hydrate crystal; the polymerization inhibitor is a surfactant or a polymer, can be mixed with oil phase and adsorbed on the surface of hydrate particles, so that hydrate crystal grains are suspended and dispersed in a condensed phase, thereby preventing the aggregation and agglomeration of the hydrate and achieving the purpose of inhibiting the hydrate from blocking pipelines. The kinetic inhibitor mainly comprises a heterocyclic polyamide kinetic inhibitor, a chain polyamide kinetic inhibitor, a natural product kinetic inhibitor and an ionic liquid kinetic inhibitor; common polymerization inhibitors include surfactants and polymers such as alkyl aromatic sulfonates, alkyl polyglycosides, alkyl ethoxyphenylsulfonates, amide compounds, quaternary ammonium salts, and the like.
Currently, polyvinylpyrrolidone is a relatively common hydrate inhibitor. But the application range of the super-cooling agent is limited due to the defects of poor water solubility, unsatisfactory inhibition effect, even loss of inhibition effect under the condition of higher super-cooling degree (the super-cooling degree is more than 7 ℃), and the like. Therefore, researchers are prompted to continuously explore and strive to develop a novel hydrate inhibitor which has a good inhibition effect, a wide application range, high economic benefits and environmental friendliness.
The invention content is as follows:
the invention aims to provide a novel hydrate kinetic inhibitor, a preparation method and application thereof, wherein the inhibitor can effectively delay the nucleation of a hydrate and reduce the generation rate of the hydrate in the environment with low dosage concentration (0.5-2 wt%) and high supercooling degree, and has the advantages of good inhibition effect, small dosage, wide applicability and the like.
The invention is realized by the following technical scheme:
a hydrate kinetic inhibitor with a structural formula shown as a formula I is phenylated poly N-vinyl pyrrolidone and is formed by polymerizing ethylbenzene and N-vinyl pyrrolidone monomers;
wherein n is 10-10000.
The volume ratio of the ethylbenzene to the N-vinyl pyrrolidone monomer is 1: 50-5: 1.
The hydrate kinetic inhibitor has an average molecular weight Mw of 1000-1000000.
The preparation method of the hydrate kinetic inhibitor comprises the following steps: weighing a chain initiator azobisisobutyronitrile into a reaction bottle, slowly dropwise adding an N-vinyl pyrrolidone monomer, ethylbenzene and N, N-dimethylformamide in sequence under the nitrogen atmosphere, and reacting at the temperature of 40-140 ℃ for 2-20 hours under the nitrogen atmosphere; cooling the obtained primary product to room temperature, and then recrystallizing, filtering and drying to obtain a target product; the amount of the initiator accounts for 0.5 to 2 weight percent of the amount of the N, N-dimethylformamide; the dosage of the N, N-dimethylformamide is 1 to 20 times of the volume of the N-vinyl pyrrolidone monomer; the volume ratio of the ethylbenzene to the N-vinyl pyrrolidone monomer is 1: 50-5: 1.
The reagent for recrystallization is ethyl acetate at-20 to 20 ℃.
The invention also protects the application of the hydrate kinetic inhibitor, the hydrate inhibitor is applied to the generation of hydrates in an oil-gas-water three-phase system, an oil-water or gas-water two-phase system, the concentration of the hydrate inhibitor in use relative to water in the system is 0.1-20 wt%, the applicable pressure is 1-25 MPa, and the temperature is-25 ℃.
The concentration of the hydrate inhibitor relative to water in a system when the hydrate inhibitor is used is preferably 0.5-2 wt%.
The invention has the following beneficial effects:
(1) the polymer is used as a kinetic inhibitor polymer, and phenyl is added on a poly-N-vinyl pyrrolidone polymer chain, so the polymer has better inhibition effect, less dosage, greatly reduced reagent cost and wide applicability, is suitable for an oil-gas-water three-phase or oil-water or gas-water two-phase coexistence system, and is applied to inhibiting the generation of hydrate in the oil-gas exploitation, processing and conveying processes.
(2) The invention has high inhibition activity, less dosage and reduced cost, because the five-membered cyclic lactam polymer is a hydrate inhibitor, and the phenyl is a cyclic group similar to a hydrate cage and is easy to react with the hydrate cage, thereby preventing the contact of object molecules and water molecules and further improving the inhibition effect.
In a word, the invention has high inhibition activity, can obtain good inhibition effect, has small dosage and reduced cost, can effectively delay the nucleation time of the hydrate in a high supercooling degree environment under the condition of low dosage concentration (0.5-2 wt%), reduces the generation rate of the hydrate, is suitable for an oil-gas-water three-phase or oil-water or gas-water two-phase coexistence system, is applied to inhibiting the generation of the hydrate in the oil-gas exploitation, processing and conveying processes, is not limited by supercooling degree and application occasions, and has wide application prospect.
Description of the drawings:
FIG. 1 is a nuclear magnetic resonance spectrum of the product of example 1;
FIG. 2 is a Fourier infrared spectrum of the product of example 1;
FIG. 3 is an exemplary graph of the time-temperature-time-pressure curve of the hydrate inhibitor obtained in example 1 in the form of a 1.0 wt% aqueous solution added to a reaction kettle during hydrate formation.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1: a hydrate kinetic inhibitor (PVPC for short) with a structural formula shown as formula I6H5) Synthesis of (2)
The synthesis method comprises the following steps: weighing 352mg (2mmol) of azodiisobutyronitrile serving as a chain initiator into a 250mL eggplant-shaped reaction bottle, sealing the reaction bottle by using a rubber stopper, and vacuumizing for 3 times by introducing nitrogen; slowly adding 20mL (206mmol) of N-vinyl pyrrolidone monomer, 0.56mL (about 4.6mmol) of ethylbenzene and 100mL of N, N-dimethylformamide solvent dropwise in sequence, and performing freezing-air extraction-temperature rise circulation for 3 times by using liquid nitrogen; reacting for 7 hours at the temperature of 80 ℃ in the nitrogen atmosphere; and cooling the obtained initial product to room temperature, slowly dripping 1000mL of ethyl acetate at-10 ℃ for recrystallization and suction filtration, and drying the obtained solid to obtain the target product. Weight average molecular weight (Mw) of 56752, and 1HNMR spectrum (CD)3CN as solvent) is shown in fig. 1, its fourier infrared (FTIR) spectrum is shown in fig. 2, and its Gel Permeation Chromatography (GPC) data is shown in table 1:
TABLE 1
Example 2: evaluation of inhibitory Effect
The method for evaluating the inhibition effect of the invention comprises the following steps:
the experimental equipment is a visual high-pressure stirring test device, and the main components of the device comprise a sapphire high-pressure reaction kettle, a magnetic stirrer, a low-temperature air bath, a temperature and pressure sensor, a vacuum pump, a camera, a high-pressure gas cylinder, a data acquisition instrument and the like. The highest working pressure of the sapphire high-pressure reaction kettle is 11MPa, and the working temperature range is-30-80 ℃. The pressure in the sapphire high-pressure reaction kettle can be freely adjusted through a gas valve. The low-temperature air bath can provide constant temperature of-30 to 80 ℃ for the jacket of the sapphire high-pressure reaction kettle. The data acquisition system acquires and stores parameters such as pressure and temperature in the reaction kettle in real time. The formation of the hydrate can be judged by the temperature or pressure change during the reaction or directly observed by a camera. After the reaction starts, the point of the sudden pressure drop in the kettle, i.e. the point of the pressure drop trend deviating from the original trend, is the starting point of the generation of the hydrate, and the temperature corresponding to the point is the lowest temperature which can be borne by the solution. And (3) keeping the stirring speed constant, starting to introduce methane gas when the temperature in the sapphire high-pressure reaction kettle is constant, and closing an air inlet valve until the pressure in the reaction kettle is a set value. Then, the temperature in the reaction kettle is reduced to be lower than the generation temperature of the hydrate at the pressure at a constant temperature reduction rate (for example, 1 ℃/h). The lowest temperature that the solution can withstand is the hydrate formation temperature in the process. The effect of the novel inhibitors can be quantified in terms of the lowest temperature that can be tolerated by the solution to which the inhibitor is added. The lower the hydrate formation temperature, the better the inhibiting effect.
The specific implementation process comprises the following steps:
before the experiment is operated, the reaction kettle is repeatedly cleaned by deionized water for three to five times, and then the reaction kettle and the experiment pipeline system are purged by nitrogen to ensure the dryness of the system. Vacuumizing the reaction kettle, sucking 12.0mL (about 1/3 of the volume of the sapphire reaction kettle) of deionized water or a prepared hydrate inhibitor solution, firstly introducing 1MPa of methane gas with the purity of 99.99 percent for removing air in the reaction kettle, then vacuumizing, repeating the steps for 3 times, wherein the constant stirring speed is 800rpm, introducing the methane gas when the temperature in the sapphire high-pressure reaction kettle is 20 ℃, and closing an air inlet valve until the pressure in the reaction kettle is constant to 8.0 MPa. Then, the temperature in the reaction kettle is reduced from 20 ℃ to-10 ℃ at the temperature reduction rate of 1 ℃/h. Meanwhile, whether the hydrate is generated or not is judged by adopting a camera observation method and a temperature-pressure change curve graph method.
Pure water is added into the reaction kettle for testing, and the result shows that the generation temperature of the hydrate under the system is 7.0 ℃.
The weight average molecular weight is 3.6X 105Aqueous solutions of poly-N-vinylpyrrolidone (abbreviated as PVPK90) having mass concentrations of 0.1%, 1%, and 2% were added to the reaction vessel and tested, and the results are shown in table 2.
The hydrate kinetic inhibitor (PVPC for short) with weight average molecular weight of 56752 obtained in example 16H5) The aqueous solution was added to the reaction vessel at 0.1%, 0.5%, 1%, 2% by mass concentration, respectively, and the results were shown in table 2.
TABLE 2
As can be seen from Table 2, the method can be used in the environment with low dosage concentration (0.5-2 wt%) and high supercooling degree, can effectively delay the nucleation time of the hydrate and reduce the generation rate of the hydrate, has the advantages of low dosage, high efficiency, wide applicability and the like, and has a good inhibition effect.
Claims (5)
1. A hydrate kinetic inhibitor with a structural formula shown as a formula I is phenylated poly N-vinyl pyrrolidone and is formed by polymerizing ethylbenzene and N-vinyl pyrrolidone monomers, wherein the volume ratio of the ethylbenzene to the N-vinyl pyrrolidone monomers is 1: 50-5: 1;
wherein n is 10-10000.
2. A method of preparing a hydrate kinetic inhibitor according to claim 1, comprising the steps of:
weighing a chain initiator azobisisobutyronitrile into a reaction bottle, slowly dropwise adding an N-vinyl pyrrolidone monomer, ethylbenzene and N, N-dimethylformamide in sequence under the nitrogen atmosphere, and reacting at the temperature of 40-140 ℃ for 2-20 hours under the nitrogen atmosphere; cooling the obtained primary product to room temperature, and then recrystallizing, filtering and drying to obtain a target product; the amount of the initiator accounts for 0.5 to 2 weight percent of the amount of the N, N-dimethylformamide; the dosage of the N, N-dimethylformamide is 1 to 20 times of the volume of the N-vinyl pyrrolidone monomer; the volume ratio of the ethylbenzene to the N-vinyl pyrrolidone monomer is 1: 50-5: 1.
3. The method for preparing a hydrate kinetic inhibitor according to claim 2, wherein the reagent for recrystallization is ethyl acetate at-20 to 20 ℃.
4. The application of the hydrate kinetic inhibitor as claimed in claim 1, wherein the hydrate inhibitor is applied to the generation of hydrates in an oil-gas-water three-phase system, an oil-water or an air-water two-phase system, and the hydrate inhibitor is used at a concentration of 0.1-20 wt% relative to water, an application pressure of 1-25 MPa and a temperature of-25 ℃.
5. Use of a hydrate kinetic inhibitor according to claim 4, characterized in that the hydrate inhibitor is used at a concentration of 0.5-2 wt% with respect to water.
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| CN201611153269.9A CN108219762B (en) | 2016-12-14 | 2016-12-14 | Novel hydrate kinetic inhibitor and preparation method and application thereof |
| PCT/CN2017/077769 WO2018107609A1 (en) | 2016-12-14 | 2017-03-22 | Novel kinetic hydrate inhibitor, preparation method therefor and use thereof |
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| CN109735316B (en) * | 2018-12-11 | 2020-07-03 | 中国科学院广州能源研究所 | Natural gas hydrate inhibitor |
| WO2023122947A1 (en) * | 2021-12-28 | 2023-07-06 | 大连理工大学 | Environmentally-friendly natural gas hydrate inhibitor and application |
| CN116041706A (en) * | 2022-12-30 | 2023-05-02 | 中国科学院广州能源研究所 | Microsphere hydrate inhibitor and application thereof |
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| DE10114638C1 (en) * | 2001-03-24 | 2002-05-23 | Clariant Gmbh | Use of biologically degradable modified polyether compounds of specified formula as gas hydrate inhibitors |
| CN101629071B (en) * | 2009-07-31 | 2012-12-26 | 中国科学院广州能源研究所 | Natural gas hydrate inhibitor |
| CN102161720B (en) * | 2011-02-12 | 2013-05-29 | 中国海洋石油总公司 | High-efficiency composite hydrate inhibitor as well as preparation method and application thereof |
| CN102190750B (en) * | 2011-04-21 | 2012-12-05 | 华南理工大学 | Copolymer of styrene and N-vinyl pyrrolidone, and preparation method and application thereof |
| CN102504786B (en) * | 2011-09-26 | 2013-10-16 | 中国石油天然气股份有限公司 | Sulfur-containing natural gas hydrate inhibitor |
| US9145465B2 (en) * | 2011-10-20 | 2015-09-29 | Baker Hughes Incorporated | Low dosage kinetic hydrate inhibitors for natural gas production systems |
| CN104194756B (en) * | 2014-08-12 | 2017-02-22 | 华南理工大学 | Novel hydrate kinetic inhibitor as well as preparation method and applications thereof |
| CN104830291A (en) * | 2015-04-30 | 2015-08-12 | 中国石油大学(华东) | Compound low dosage natural gas hydrate inhibitor |
| CN106190060A (en) * | 2015-05-25 | 2016-12-07 | 西北大学 | A kind of Compositional type hydrate inhibitor for natural gas |
| CN105802599A (en) * | 2016-04-19 | 2016-07-27 | 中国石油化工股份有限公司 | Efficient compound-type hydrate dynamics inhibitor |
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| 天然气水合物抑制剂研究进展;许维秀，等;《化工进展》;20061125;第25卷(第11期);第1289-1293页 * |
| 天然气水合物新型抑制剂的研究进展;吴德娟，等;《天然气工业》;20001128;第20卷(第6期);第95-98页 * |
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