CN116535571A - 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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- CN116535571A CN116535571A CN202310618994.2A CN202310618994A CN116535571A CN 116535571 A CN116535571 A CN 116535571A CN 202310618994 A CN202310618994 A CN 202310618994A CN 116535571 A CN116535571 A CN 116535571A
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- 239000003112 inhibitor Substances 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 26
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 claims abstract description 25
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000012660 binary copolymerization Methods 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 238000011161 development Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 5
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000002401 inhibitory effect Effects 0.000 abstract description 7
- 229910052594 sapphire Inorganic materials 0.000 description 34
- 239000010980 sapphire Substances 0.000 description 34
- 230000000007 visual effect Effects 0.000 description 33
- 238000011156 evaluation Methods 0.000 description 30
- 238000002474 experimental method Methods 0.000 description 25
- 239000007789 gas Substances 0.000 description 24
- 239000007864 aqueous solution Substances 0.000 description 22
- 230000006911 nucleation Effects 0.000 description 19
- 238000010899 nucleation Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 18
- 239000000178 monomer Substances 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 13
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 238000002329 infrared spectrum Methods 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000005764 inhibitory process Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- -1 Natural gas hydrates Chemical class 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 239000013000 chemical inhibitor Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 150000002195 fatty ethers Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000004660 morphological change Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000000246 remedial effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
-
- 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
- C08F226/00—Copolymers 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
- C08F226/06—Copolymers 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
-
- 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
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a hydrate dynamics inhibitor, a preparation method and application thereof. The hydrate dynamics inhibitor is obtained by binary copolymerization of N-vinyl caprolactam and vinyl N-butyl ether, and the preparation method comprises the following steps: mixing N-vinyl caprolactam and vinyl N-butyl ether with a solvent, adding an initiator to perform binary copolymerization, and then adding a terminator to obtain the hydrate dynamics inhibitor. The hydrate dynamics inhibitor has excellent performance of inhibiting the formation of hydrate, and can better solve the problem of pipe blockage caused by the formation of the hydrate in oil gas development and transportation.
Description
Technical Field
The invention relates to a hydrate dynamics inhibitor and a preparation method and application thereof, belonging to the technical field of oil and gas exploitation and transportation.
Background
Natural gas hydrates are generally ice-like clathrates formed from gas molecules and water molecules under high pressure and low temperature conditions, and are abundantly present in nature, particularly on land, in permafrost and deep sea, as well as in oil and gas transportation pipelines and laboratories. Since natural gas hydrates were found in natural gas transportation pipelines, their control efforts have been a major challenge for the oil and gas industry. As oil and gas drilling gradually progresses to ocean deepwater areas, higher hydrostatic pressure and lower ambient temperature in the deepwater also provide favorable conditions for hydrate formation, once hydrate is formed in the pipeline, a part of the hydrate flows along with the flow of fluid in the pipeline, and a part of the hydrate adheres to the pipeline wall and deposits on the pipeline, so that the pipeline is gradually blocked, the fluid cannot be normally conveyed, even serious safety accidents are caused, and great economic loss is caused.
Thus, research on gas hydrate risk prevention and control technology has been valued and supported by the oil and gas industry. Different relief measures and remedial strategies for depressurization, injection of chemical inhibitors, heating, etc. have been formulated for the risk of hydrate blockage in pipelines, with chemical inhibitor injection being the most common method. Conventional thermodynamic inhibitors may present higher costs and environmental risks due to their large amounts, and therefore low-dose hydrate kinetic inhibitors (LDHIs) are considered as potential alternatives to effectively inhibit hydrate nucleation and growth without altering the thermodynamic conditions of hydrate formation. Hydrate kinetic inhibitors such as PVP and Inhibex501 have been commercially used in some gas fields, and it has been proved that these low-dose hydrate kinetic inhibitors can effectively inhibit hydrate formation.
In conclusion, it is of great commercial interest to develop efficient, environmentally friendly, low cost inhibitors of hydrate kinetics.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a hydrate dynamics inhibitor, a preparation method and application thereof, wherein the hydrate dynamics inhibitor has excellent performance of inhibiting the formation of hydrate, and can better solve the problem of pipe blockage caused by the formation of the hydrate in oil gas development and transportation.
In order to achieve the above object, the present invention provides a hydrate kinetic inhibitor which is obtained by binary copolymerization of N-vinylcaprolactam and vinyl N-butyl ether.
According to a specific embodiment of the present invention, preferably, the relative molecular mass of the hydrate kinetic inhibitor is 1000-50000.
The structure of the hydrate kinetic inhibitors of the present invention is illustrated by formula i:
wherein the molar ratio x of the N-vinylcaprolactam structural unit to the vinyl N-butyl ether structural unit is x:y=9:1-1:1.
The invention also provides a preparation method of the hydrate dynamics inhibitor, which comprises the following steps: mixing N-vinyl caprolactam and vinyl N-butyl ether with a solvent, adding an initiator to perform binary copolymerization, and then adding a terminator to obtain the hydrate dynamics inhibitor.
According to a specific embodiment of the present invention, preferably, in the above preparation method, the binary copolymerization reaction temperature is 323.15-363.15K, and the reaction time is 5-12h.
According to a specific embodiment of the present invention, preferably, in the above preparation method, the molar ratio of the N-vinylcaprolactam to the vinyl N-butyl ether is 9:1 to 1:1.
According to a specific embodiment of the present invention, preferably, in the above preparation method, the initiator includes one or a combination of two or more of azobisisobutyronitrile, dimethyl azobisisobutyrate, azobisisoheptonitrile, tert-butyl hydroperoxide.
According to a specific embodiment of the present invention, preferably, in the above preparation method, the initiator is used in an amount of 0.01% to 0.5% based on 100% of the total weight of the N-vinylcaprolactam and vinyl N-butyl ether.
According to a specific embodiment of the present invention, preferably, in the above preparation method, the terminator includes one or a combination of styrene and methacrylic acid.
According to a specific embodiment of the present invention, preferably, in the above preparation method, the terminator is used in an amount of 0.01% to 0.1% based on 100% of the total weight of the N-vinylcaprolactam and vinyl N-butyl ether.
According to a specific embodiment of the present invention, preferably, in the above preparation method, the solvent includes one or a combination of two or more of ethanol, isopropanol, N-dimethylformamide, and N-propanol.
According to a specific embodiment of the present invention, preferably, in the above preparation method, the weight ratio of the solvent to the sum of the N-vinylcaprolactam and vinyl N-butyl ether is 2 to 10:1.
According to a specific embodiment of the present invention, the above preparation method comprises the following specific steps:
(1) Adding N-vinyl caprolactam and vinyl N-butyl ether monomer into a solvent, and uniformly mixing to obtain a mixture;
(2) And (3) adding an initiator into the mixture, heating to a target reaction temperature, reacting under the protection of protective gas (such as nitrogen atmosphere), adding a terminator to terminate the reaction, and performing vacuum drying treatment on the obtained solution after the reaction is finished, wherein the drying temperature is 313.15-343.15K, so as to obtain the hydrate dynamics inhibitor.
The invention also provides application of the hydrate dynamics inhibitor in inhibiting formation of hydrate in the oil gas development or transportation process.
According to a specific embodiment of the present invention, preferably, the hydrate kinetic inhibitor is applied to an oil-gas-water three-phase system or a gas-water two-phase system.
According to a specific embodiment of the present invention, preferably, the pressure of the oil-gas-water three-phase system or the gas-water two-phase system is 0.2 to 30MPa and the temperature is-15 ℃ to 30 ℃.
According to a specific embodiment of the present invention, preferably, the hydrate kinetic inhibitor is used alone or after being compounded with alcohols; the hydrate kinetic inhibitor is compounded with alcohols for use, and has better inhibiting effect on the formation of hydrate.
According to a specific embodiment of the present invention, preferably, the alcohol comprises ethylene glycol.
According to a specific embodiment of the present invention, preferably, the hydrate kinetic inhibitor is used in an amount of 0.5 to 5.0wt% based on 100% of the total weight of water in the system when the hydrate kinetic inhibitor is used alone; when the hydrate dynamics inhibitor is used after being compounded with alcohols, the dosage of the hydrate dynamics inhibitor is 0.5-5wt% and the dosage of the alcohols is 0.1-20wt% calculated by taking the total weight of water in a system as 100%.
The hydrate kinetic inhibitor provided by the invention has the following beneficial technical effects:
(1) The hydrate dynamics inhibitor provided by the invention is a binary copolymer synthesized by binary copolymerization of N-vinyl caprolactam and vinyl N-butyl ether monomer, has good water solubility, and can ensure that the hydrate dynamics inhibitor plays 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 dynamics inhibitors such as PVP, inhibex501 and the like, the hydrate dynamics inhibitor provided by the invention has better hydrate inhibition effect and better commercial application prospect.
Drawings
Fig. 1 is an infrared spectrum of the hydrate kinetic inhibitor of example 1.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
The apparatus, reagents, etc. used in the present invention are conventional equipment and conventional materials, and are available commercially, unless otherwise specified.
Example 1
The embodiment provides a hydrate kinetic inhibitor, and the preparation method comprises the following steps:
(1) N-vinyl caprolactam and vinyl N-butyl ether are selected as synthesis raw materials, isopropanol is used as a solvent for polymerization reaction, and the synthesis raw materials and the solvent are uniformly mixed to obtain a mixture; wherein the dosage of the N-vinyl caprolactam and the vinyl N-butyl ether is 5.8155g and 4.1845g respectively; the dosage of the isopropanol is 30g;
(2) Adding the mixture into a three-neck round-bottom flask, adding an initiator azodiisobutyronitrile accounting for 0.01% of the total weight of two monomers into the three-neck round-bottom flask after the temperature of a constant-temperature water bath reaches 353.15K, rapidly fixing the three-neck round-bottom flask into the constant-temperature water bath, installing a condensing tube on the three-neck round-bottom flask, introducing nitrogen into the three-neck round-bottom flask, starting stirring, keeping the water bath temperature and stirring speed constant in the reaction process, stopping heating after reacting for 10 hours, and adding a terminator styrene accounting for 0.05% of the total weight of the two monomers into the three-neck round-bottom flask;
(3) After the system temperature is cooled to room temperature, stopping introducing nitrogen and closing stirring, and transferring the product in the three-neck round bottom flask into a beaker to obtain a crude product of the hydrate dynamics inhibitor;
(4) Transferring the liquid in the beaker to a rotary evaporator, purifying the crude product of the hydrate dynamics inhibitor by the rotary evaporator, taking out the purified product, and vacuum drying at the temperature of 323.15K to obtain the hydrate dynamics inhibitor, wherein the relative molecular weight of the hydrate dynamics inhibitor is 11499, and finally sealing and storing the hydrate dynamics inhibitor in a dry and cool place for later use.
The hydrate kinetic inhibitor obtained in this example was subjected to infrared spectroscopic analysis, and the obtained infrared spectrum is shown in FIG. 1, and it can be seen from FIG. 1 that the bipolymer, i.e., the hydrate kinetic inhibitor was prepared at 912cm -1 、993cm -1 、3080cm -1 、1682cm -1 No c=c-H, =c-H, C =c absorption peak on either side, indicating the disappearance of unsaturated hydrocarbons; 1617cm -1 The strong absorption peak is C=O absorption peak on caprolactam of polymer molecule, 1430cm -1 The left and right absorption peaks are strong absorption peaks of C-N on caprolactam of polymer molecules; 2876cm -1 And 2853cm -1 The left and right strong absorption peaks are respectively saturated C-H symmetrical telescopic vibration and antisymmetric telescopic vibration absorption peaks; at 1225-1200cm -1 No significant absorption peaks had been left or right, indicating that no vinyl ether had been present in the sample; 1150cm -1 The strong absorption peak around is that of the fatty ether C-O-C, which indicates that the vinyl ether has polymerized with N-vinylcaprolactam to convert it to fatty ether.
In summary, the solid infrared data result shown in fig. 1 shows that the N-vinylcaprolactam has been successfully polymerized with vinyl N-butyl ether monomer and has higher purity, and no or only a small amount of unreacted monomer is contained, and the synthesized product is the target product.
Example 2
This example provides a hydrate kinetic inhibitor prepared in substantially the same manner as the hydrate kinetic inhibitor provided in example 1, except that:
(1) In the embodiment, the dosage of the two monomers of N-vinyl caprolactam and vinyl N-butyl ether is 6.0455g and 4.0347g respectively;
(2) The reaction time in this example was 8h.
The relative molecular weight of the obtained hydrate kinetic inhibitor is 28455, the infrared spectrum is shown in figure 1, and the characteristic absorption peak of the infrared spectrum is 1617cm -1 、1430cm -1 、2876cm -1 、2853cm -1 、1150cm -1 And the like, the purity of the polymer is high, the system contains almost no unreacted monomer, and the polymer contains aliphatic ether, caprolactam and other groups.
Example 3
This example provides a hydrate kinetic inhibitor prepared in substantially the same manner as the hydrate kinetic inhibitor provided in example 1, except that:
(1) In the embodiment, the dosage of the two monomers of N-vinyl caprolactam and vinyl N-butyl ether is 7.0527g and 3.0591g respectively;
(2) The reaction time in this example was 6h.
The relative molecular weight of the obtained hydrate kinetic inhibitor is 32847, the infrared spectrum is shown in figure 1, and the characteristic absorption peak of the infrared spectrum is 1617cm -1 、1430cm -1 、2876cm -1 、2853cm -1 、1150cm -1 And the like, the purity of the polymer is high, the system contains almost no unreacted monomer, and the polymer contains aliphatic ether, caprolactam and other groups.
Example 4
This example provides a hydrate kinetic inhibitor prepared in substantially the same manner as the hydrate kinetic inhibitor provided in example 1, except that:
(1) In the embodiment, the dosage of the two monomers of N-vinyl caprolactam and vinyl N-butyl ether is 8.0025g and 2.0304g respectively;
(2) The reaction time in this example was 7h.
The relative molecular weight of the obtained hydrate kinetic inhibitor is 22950, the infrared spectrum is shown in figure 1, and the characteristic absorption peak of the infrared spectrum is 1617cm -1 、1430cm -1 、2876cm -1 、2853cm -1 、1150cm -1 And the like, the purity of the polymer is high, the system contains almost no unreacted monomer, and the polymer contains aliphatic ether, caprolactam and other groups.
Example 5
This example provides a hydrate kinetic inhibitor prepared in substantially the same manner as the hydrate kinetic inhibitor provided in example 1, except that:
(1) In the embodiment, the dosage of the two monomers of N-vinyl caprolactam and vinyl N-butyl ether is 9.0025g and 1.0035g respectively;
(2) The reaction time in this example was 9h.
The relative molecular weight of the obtained hydrate kinetic inhibitor is 32652, the infrared spectrum is shown in figure 1, and the characteristic absorption peak of the infrared spectrum is 1617cm -1 、1430cm -1 、2876cm -1 、2853cm -1 、1150cm -1 And the like, the purity of the polymer is high, the system contains almost no unreacted monomer, and the polymer contains aliphatic ether, caprolactam and other groups.
Inhibition performance test
The hydrate kinetic inhibitors prepared in examples 1 to 5 and the existing conventional commercial inhibitors PVP (manufactured by Sigma Aldrich) and Inhibex501 (manufactured by Mish group Co.) were evaluated for the inhibition performance of the hydrate formation process, and the apparatus used for the evaluation experiment consisted mainly of six parts; the device comprises a visual high-pressure sapphire kettle, a temperature sensor, a pressure sensor, a data acquisition system, a constant-temperature air bath and a magnetic stirring device; wherein, the volume of the visible high-pressure sapphire kettle is 59cm 3 The inner diameter is 2.54cm, and the highest bearing pressure can reach 40MPa, so that the safety of the evaluation experiment operation is ensured; errors of the pressure sensor and the temperature sensor are +/-0.01 MPa and +/-0.1K respectively; the temperature error of the constant temperature air bath is also +/-0.1K, and the adjustment of the experimental temperature is mainly controlled by the constant temperature air bath.
The inhibition performance of the hydrate kinetic inhibitor on the hydrate formation process was evaluated as follows:
firstly, soaking and cleaning a visual high-pressure sapphire kettle with petroleum ether and ethanol for one time, cleaning with absolute ethyl alcohol for three times, then opening an inlet valve and an outlet valve of the visual high-pressure sapphire kettle, and purging with nitrogen to completely dry the inside of the visual high-pressure sapphire kettle;
adding the prepared solution to be tested containing the hydrate kinetic inhibitor into a visual high-pressure sapphire kettle, vacuumizing the kettle by using a vacuum pump, and closing a valve after the air in the kettle is pumped out to prevent the existence of the air from interfering with experimental results;
opening an air inlet valve of the balance kettle, adding a sufficient amount of experimental air into the balance kettle, and closing the air inlet valve of the balance kettle;
opening a constant-temperature air bath, setting the temperature of the constant-temperature air bath as an experimental target temperature, opening an air inlet valve of the visual high-pressure sapphire kettle when the temperature in the visual high-pressure sapphire kettle is stabilized at the target temperature, introducing experimental gas into the visual high-pressure sapphire kettle from a balance kettle, closing the air inlet valve after the target pressure is reached, opening a magnetic stirring device, and keeping the stirring speed unchanged in the whole experimental process;
and (3) turning on a cold light source, observing the appearance and the morphological change of the hydrate through a visual window of the constant-temperature air bath, shooting and recording by using a camera, and simultaneously storing temperature and pressure data in the kettle in real time through a data acquisition system.
The test gas used in the evaluation test was methane with a purity of 99.99%.
The evaluation experiment judges the strength of the inhibition performance of the hydrate kinetic inhibitor by measuring the nucleation time of the hydrate. The nucleation time of the hydrate is determined through real-time monitoring of the camera and real-time monitoring of the pressure sensor on the system pressure change, when the camera shoots that a hydrate crystal nucleus appears in the visible high-pressure sapphire kettle for the first time, and the pressure sensor monitors that the pressure of the system begins to drop, the time at the moment is the nucleation time of the hydrate in the system.
Test example 1
10g of an aqueous solution containing the hydrate kinetic inhibitor provided in example 1 of the present invention (the concentration of the hydrate kinetic inhibitor in the aqueous solution is 0.5wt% based on the total weight of water) was added to a visual high-pressure sapphire kettle, and an evaluation experiment was conducted by introducing an experiment gas of 6.17MPa into the visual high-pressure sapphire kettle at a temperature of 275.65K, and it was found that the nucleation time of the hydrate in the system was 1251min, indicating that in the evaluation system, the formation of the hydrate was significantly inhibited due to the presence of the hydrate kinetic inhibitor.
Test example 2
10g of the aqueous solution containing the hydrate dynamics inhibitor provided in example 2 of the present invention (the concentration of the hydrate dynamics inhibitor in the aqueous solution is 0.5wt% based on the total weight of water) was added into a visual high-pressure sapphire kettle, and an evaluation experiment was performed by introducing an experiment gas of 6.17MPa into the visual high-pressure sapphire kettle at a temperature of 275.65K, and the nucleation time of the hydrate in the system was found to be 482min, indicating that in the evaluation system, the formation of the hydrate was significantly inhibited due to the presence of the hydrate dynamics inhibitor.
Test example 3
10g of an aqueous solution containing the hydrate kinetic inhibitor provided in example 3 of the present invention (the concentration of the hydrate kinetic inhibitor in the aqueous solution is 0.5wt% based on the total weight of water) was added to a visual high-pressure sapphire pot, and an evaluation experiment was conducted by introducing an experimental gas of 6.17MPa into the visual high-pressure sapphire pot at a temperature of 275.65K, and it was found that the nucleation time of the hydrate in the system was 389min, indicating that in the evaluation system, the formation of the hydrate was significantly inhibited due to the presence of the hydrate kinetic inhibitor.
Test example 4
10g 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 is 0.5wt% based on the total weight of water) was added to a visual high-pressure sapphire pot, and an evaluation experiment was conducted by introducing an experimental gas of 6.17MPa into the visual high-pressure sapphire pot at a temperature of 275.65K, and it was found that the nucleation time of the hydrate in the system was 94min, indicating that in the evaluation system, the formation of the hydrate was significantly inhibited due to the presence of the hydrate kinetic inhibitor.
Test example 5
10g of an aqueous solution containing the hydrate kinetic inhibitor provided in example 5 of the present invention (the concentration of the hydrate kinetic inhibitor in the aqueous solution is 0.5wt% based on the total weight of water) was added to a visual high-pressure sapphire pot, and an evaluation experiment was conducted by introducing an experiment gas of 6.17MPa into the visual high-pressure sapphire pot at a temperature of 275.65K, and it was found that the nucleation time of the hydrate in the system was 199min, indicating that in the evaluation system, the formation of the hydrate was significantly inhibited due to the presence of the hydrate kinetic inhibitor.
Test example 6
10g of an aqueous solution containing the hydrate kinetic inhibitor provided in example 1 of the present invention (the concentration of the hydrate kinetic inhibitor in the aqueous solution is 1.0wt% based on the total weight of water) was added to a visual high-pressure sapphire pot, and an evaluation experiment was conducted by introducing an experiment gas of 6.17MPa into the visual high-pressure sapphire pot at a temperature of 275.65K, and it was found that the nucleation time of the hydrate in the system was 1862min, indicating that in the evaluation system, the formation of the hydrate was significantly inhibited due to the presence of the hydrate kinetic inhibitor.
Test example 7
10g of an aqueous solution containing the hydrate kinetic inhibitor provided in example 1 of the present invention (the concentration of the hydrate kinetic inhibitor in the aqueous solution is 5.0wt% based on the total weight of water) was added to a visual high-pressure sapphire pot, and an evaluation experiment was conducted by introducing an experiment gas of 6.17MPa into the visual high-pressure sapphire pot at a temperature of 275.65K, and it was found that the nucleation time of the hydrate in the system was 2800min, indicating that in the evaluation system, the formation of the hydrate was significantly inhibited due to the presence of the hydrate kinetic inhibitor.
Test example 8
10g of an aqueous solution containing a compound mixture (wherein the compound mixture is obtained by compounding the hydrate dynamics inhibitor provided in the embodiment 1 of the invention and ethylene glycol, the concentration of the hydrate dynamics inhibitor in the aqueous solution is 0.5wt% and the concentration of the ethylene glycol is 5.0wt% based on the total weight of water) is added into a visual high-pressure sapphire kettle, and an experiment gas of 6.17MPa is introduced into the visual high-pressure sapphire kettle at a temperature of 275.65K for evaluation experiments, so that the nucleation time of the hydrate in the system is 1640min, which indicates that the formation of the hydrate is significantly inhibited due to the existence of the hydrate dynamics inhibitor in the system.
As is clear from the comparison of the experimental data obtained in test examples 1 and 8, the hydrate kinetic inhibitor provided in the examples of the present invention was used after being compounded with an alcohol reagent, and the effect of inhibiting the formation of hydrate was more excellent.
Comparative test example 1
10g of deionized water is added into a visual high-pressure sapphire kettle, and an experiment gas of 6.17MPa is introduced into the visual high-pressure sapphire kettle at the temperature of 275.65K for evaluation experiments, and the nucleation time of the hydrate in the system is found to be less than 1min, which indicates that the hydrate is formed very rapidly in the evaluation system because no hydrate kinetic inhibitor is added.
Comparative test example 2
10g of an aqueous solution containing a commercial inhibitor Inhibex501 (the concentration of the commercial inhibitor Inhibex501 in the aqueous solution is 0.5wt% based on the total weight of water) was added into a visual high-pressure sapphire kettle, and an evaluation experiment was performed by introducing an experiment gas of 6.17MPa into the visual high-pressure sapphire kettle at a temperature of 275.65K, and the nucleation time of the hydrate in the system was found to be 21min, which indicates that in the evaluation system, the formation of the hydrate was also inhibited due to the addition of the commercial inhibitor Inhibex501, but the nucleation time of the hydrate was still shorter in comparative test example 2 than in the evaluation system containing the hydrate dynamics inhibitor provided in example 1 of the present invention, which indicates that the hydrate dynamics inhibitor provided in the present invention has a better effect of inhibiting the hydrate than the hydrate dynamics inhibitor Inhibex 501.
Comparative test example 3
10g of an aqueous solution containing a commercial inhibitor PVP (the concentration of the commercial inhibitor PVP in the aqueous solution is 0.5wt% based on the total weight of water) is added into a visual high-pressure sapphire kettle, and an experiment gas of 6.17MPa is introduced into the visual high-pressure sapphire kettle at a temperature of 275.65K to carry out an evaluation experiment, wherein the nucleation time of the hydrate in the system is found to be 6min, which indicates that the formation of the hydrate is also inhibited due to the addition of the commercial inhibitor PVP in the evaluation system, but the nucleation time of the hydrate is still shorter in comparative test example 3 compared with the evaluation system containing the hydrate dynamics inhibitor provided in the embodiment 1 of the invention, which indicates that the hydrate dynamics inhibitor provided in the embodiment of the invention has better hydrate inhibition effect than the existing hydrate dynamics inhibitor PVP.
Comparative test example 4
10g of an aqueous solution containing a commercial inhibitor Inhibex501 (the concentration of the commercial inhibitor Inhibex501 in the aqueous solution is 1.0wt% based on the total weight of water) was added into a visual high-pressure sapphire kettle, and an evaluation experiment was performed by introducing an experiment gas of 6.17MPa into the visual high-pressure sapphire kettle at a temperature of 275.65K, and the nucleation time of the hydrate in the system was found to be 120min, which indicates that in the evaluation system, the formation of the hydrate was also inhibited due to the addition of the commercial inhibitor Inhibex501, but the nucleation time of the hydrate was still shorter in comparative test example 4 as compared with the evaluation system containing the hydrate dynamics inhibitor provided in example 1 of the present invention, which indicates that the hydrate dynamics inhibitor provided in the present invention has a better effect of inhibiting the hydrate than the hydrate dynamics inhibitor Inhibex 501.
In conclusion, compared with the existing hydrate dynamics inhibitors such as PVP, inhibex501 and the like, the hydrate dynamics inhibitor provided by the invention has better hydrate inhibition effect, and has better commercial application prospect.
The foregoing description of the embodiments of the invention is not intended to limit the scope of the invention, so that the substitution of equivalent elements or equivalent variations and modifications within the scope of the invention shall fall within the scope of the patent. In addition, the technical features and the technical features, the technical features and the technical invention can be freely combined for use.
Claims (10)
1. A hydrate kinetic inhibitor is prepared from N-vinyl caprolactam and vinyl N-butyl ether through binary copolymerization.
2. The hydrate kinetic inhibitor of claim 1, wherein the hydrate kinetic inhibitor has a relative molecular mass of 1000-50000.
3. A method of preparing the hydrate kinetic inhibitor of claim 1, comprising the steps of:
mixing N-vinyl caprolactam and vinyl N-butyl ether with a solvent, adding an initiator to perform binary copolymerization reaction, and then adding a terminator to obtain the hydrate dynamics inhibitor;
preferably, the binary copolymerization reaction temperature is 323.15-363.15K, and the reaction time is 5-12h.
4. The process according to claim 3, wherein the molar ratio of N-vinylcaprolactam to vinyl N-butyl ether is from 9:1 to 1:1.
5. The process according to claim 3, wherein the initiator is used in an amount of 0.01% to 0.5% based on 100% by weight of the total of the N-vinylcaprolactam and vinyl N-butyl ether;
preferably, the initiator comprises one or a combination of more than two of azobisisobutyronitrile, dimethyl azobisisobutyrate, azobisisoheptonitrile and tert-butyl hydroperoxide.
6. The process according to claim 3, wherein the terminator is used in an amount of 0.01% to 0.1% based on 100% by weight of the total of the N-vinylcaprolactam and vinyl N-butyl ether;
preferably, the terminator comprises one or a combination of styrene and methacrylic acid.
7. The production process according to claim 3, wherein the weight ratio of the solvent to the sum of the N-vinylcaprolactam and vinyl N-butyl ether is 2-10:1;
preferably, the solvent comprises one or a combination of more than two of ethanol, isopropanol, N-dimethylformamide and N-propanol.
8. Use of the hydrate kinetic inhibitor of claim 1 or 2 to inhibit hydrate formation during oil and gas development or transport;
preferably, the hydrate kinetic inhibitor is applied to an oil-gas-water three-phase system or a gas-water two-phase system;
preferably, the pressure of the oil-gas-water three-phase system or the gas-water two-phase system is 0.2-30MPa, and the temperature is-15 ℃ to 30 ℃.
9. The use according to claim 8, wherein the hydrate kinetic inhibitor is used alone or after compounding with alcohols;
preferably, the alcohol comprises ethylene glycol.
10. The use according to claim 9, wherein the hydrate kinetic inhibitor is used in an amount of 0.5-5.0wt% based on 100% total weight of water in the system when used alone;
when the hydrate dynamics inhibitor is used after being compounded with alcohols, the dosage of the hydrate dynamics inhibitor is 0.5-5wt% and the dosage of the alcohols is 0.1-20wt% calculated by taking the total weight of water in a system as 100%.
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