CN108219762A - A kind of novel hydrates kinetic inhibitor and its preparation method and application - Google Patents
A kind of novel hydrates kinetic inhibitor and its preparation method and application Download PDFInfo
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- CN108219762A CN108219762A CN201611153269.9A CN201611153269A CN108219762A CN 108219762 A CN108219762 A CN 108219762A CN 201611153269 A CN201611153269 A CN 201611153269A CN 108219762 A CN108219762 A CN 108219762A
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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
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Abstract
The invention discloses a kind of hydrate dynamic inhibitor of structural formula as shown in formula I, inhibitory activity of the present invention is high, good inhibition can be obtained, and dosage is few, cost reduction, it can be under low dosage concentration (0.5~2wt%), effectively delay hydrate nucleation time in high supercooling degree environment, reduce hydrate generating rate, suitable for oil gas water three phase or grease or air water two-phase coexistent system, it applied to the generation for inhibiting hydrate in oil-gas mining, processing and transmission process, is not restricted by degree of supercooling and application scenario, there is the prospect of wide application.Wherein n=10~10000.
Description
Technical field：
The present invention relates to chemical technology fields, and in particular to a kind of novel hydrates kinetic inhibitor and preparation method thereof
And application.
Background technology：
The guarantee of flowing safety is one of significant problem that oil and gas industry is faced, wherein the particularly important is anti-
The only generation of gas hydrates because gas hydrates once generate will result in oil-gas mining instrument and equipment failure,
The blocking of pipeline influences normal oil-gas mining, transports and operation.Gas hydrates are by water under high pressure, cryogenic conditions
It is formed with some light gas (hydrogen, carbon dioxide, nitrogen, methane, ethane, hydrogen sulfide etc.) a kind of like ice, non-chemical
The clathrate complex of metering.
Prevent the method that hydrate generates from including following three kinds：1st, change environmental condition, the modes such as be depressured, heat up can be passed through
Make the build environment of hydrate can not meet；2nd, change gas hydrates phase balance condition, this can by add methanol,
The thermodynamic inhibitors such as ethylene glycol are realized；3rd, the nucleation of extension hydrate, growth, assemble index, make it in exploitation and pipeline
It is not blocked in transportational process, this can be realized by adding kinetic inhibitor and polymerization inhibitor.1st kind of method and the 2nd
Kind of method can prevent the generation of hydrate completely, but in view of environmental protection, it is cost-effective the problems such as, pass through temperature, pressure
Management and the method for thermodynamic inhibitor (need to usually add in 10~50wt% just effective) is added in prevent the generation of hydrate from being
It is unpractical.Kinetic inhibitor and polymerization inhibitor be commonly known as low dosage hydrate inhibitor for natural gas (add in 0.1~
2wt%, that is, effective).Because its is efficient, environmental pollution is small, it is at low cost due to widely paid close attention to.Kinetic inhibitor can
Delay the nucleation time of hydrate crystal, reduce the speed of growth, prevent the further growth of hydrate crystal；Polymerization inhibitor is
Surfactant or polymer can mix with oil phase and be adsorbed to the surface of hydrate particle, hydrate crystal grain is made to suspend
It is dispersed in condensation phase, so as to prevent hydrate aggregation caking, achievees the purpose that it is inhibited to block pipeline.Kinetic inhibitor master
To include heterocyclic polyamide class kinetic inhibitor, the polyamide-based kinetic inhibitor of chain, natural products class kinetic inhibition
Agent, ionic liquid class kinetic inhibitor；Common polymerization inhibitor has alkyl aromatic sulfonate, alkylpolyglycosides, alkylethoxy benzene
Surfactants and the polymer such as glycolylate, amides compound, quaternary quaternary ammonium salt.
At present, polyvinyl pyrrole network alkanone is a kind of more common hydrate inhibitor.But because there is water solubility in it
Difference, inhibition are not ideal enough or even (degree of supercooling be more than 7 DEG C) under conditions of compared with high supercooling degree loses inhibition the defects of,
So that its application range is restricted.This just promotes researcher constantly to explore, and makes every effort to develop that inhibition is good, is applicable in model
Enclose wide, high financial profit and environmental-friendly novel hydrates inhibitor.
Invention content：
The object of the present invention is to provide a kind of novel hydrates kinetic inhibitor and its preparation method and application, the inhibition
Agent can effectively delay the nucleation of hydrate under low dosage concentration (0.5~2wt%), in the environment of high supercooling degree, reduce hydration
Object generating rate has many advantages, such as that inhibition is good, dosage is few, applicability is wide.
The present invention is achieved by the following technical programs：
A kind of hydrate dynamic inhibitor of structural formula as shown in formula I, the hydrate dynamic inhibitor are phenyl
The poly N-vinyl pyrrole network alkanone of change is formed by ethylbenzene and N- vinylpyridine network alkanone monomer polymerizations；
Wherein n=10~10000.
The volume ratio of the ethylbenzene and N- vinylpyridine network alkanone monomers is 1:50~5:1.
Average molecular weight Mw=1000~1000000 of the hydrate dynamic inhibitor.
The preparation method of the hydrate dynamic inhibitor, includes the following steps：Weigh two isobutyl of chain initiator azo
N- vinylpyridine network alkanones monomer, ethylbenzene and N, N- dimethyl formyl is slowly added dropwise in nitrile successively in reaction bulb, under nitrogen atmosphere
Amine is reacted 2~20 hours at a temperature of 40~140 DEG C in nitrogen atmosphere；Obtained head product is tied again after being cooled to room temperature
Brilliant, filtering, drying, obtain target product；The initiator amount accounts for 0.5wt%~2wt% of N,N-dimethylformamide dosage；
N,N-dimethylformamide dosage is 1-20 times of N- vinylpyridine network alkanone monomer volumes；Ethylbenzene and N- vinylpyridine network alkanones
The volume ratio of monomer is 1:50~5:1.
The reagent of recrystallization is -20~20 DEG C of ethyl acetate.
The present invention also protects the application of the hydrate dynamic inhibitor, and the hydrate inhibitor is applied to oil gas water
The generation of hydrate in three-phase system, grease or air water two-phase system, relative in system when the hydrate inhibitor uses
A concentration of 0.1wt%~20wt% of water, it is 1~25MPa to be applicable in pressure, and temperature is -25~25 DEG C.
Relative to the concentration of water in system it is preferably 0.5wt%~2wt% during the hydrate inhibitor use.
Beneficial effects of the present invention are as follows：
(1) present invention is used as kinetic inhibitor polymer, and phenyl is added on poly N-vinyl pyrrole network alkanone polymeric chain,
Therefore the polymer has better inhibition, and dosage is few, and reagent cost substantially reduces, and has wide applicability, is applicable in
In oil gas water three phase or grease or air water two-phase coexistent system, applied to inhibition hydration in oil-gas mining, processing and transmission process
The generation of object.
(2) inhibitory activity of the present invention is high, and dosage is few, cost reduction, because the lactam polymer of five-membered cyclic is inherently
It is hydrate inhibitor, along with phenyl is the cyclic group similar to hydrate cage, easily has an effect with hydrate cage, so as to
Guest molecule is prevented to be contacted with hydrone, further improves its inhibition.
In short, inhibitory activity of the present invention is high, good inhibition can be obtained, and dosage is few, cost reduction, it can be in low dosage
Under concentration (0.5~2wt%), effectively delay hydrate nucleation time in high supercooling degree environment, reduce hydrate generating rate, fit
For oil gas water three phase or grease or air water two-phase coexistent system, applied to inhibiting water in oil-gas mining, processing and transmission process
The generation of object is closed, is not restricted by degree of supercooling and application scenario, there is the prospect of wide application.
Description of the drawings：
Fig. 1 is the nmr spectrum of the product of embodiment 1；
Fig. 2 is the FTIR spectrum figure of the product of embodiment 1；
Fig. 3 is that the hydrate inhibitor that embodiment 1 obtains adds in reaction kettle hydration by mass concentration for 1.0wt% aqueous solutions
Time-temperature in object generating process, when m- pressure curve exemplary plot.
Specific embodiment：
It is the further explanation to the present invention rather than limitation of the present invention below.
Embodiment 1：Hydrate dynamic inhibitor (abbreviation PVPC of the structural formula as shown in formula I6H5) synthesis
Synthetic method includes the following steps：Chain initiator azodiisobutyronitrile 352mg (2mmol) is weighed in 250mL eggplant shapes
Reaction bulb, vacuumizes-leads to nitrogen 3 times after being sealed with rubber stopper；N- vinylpyridine network alkanone monomers 20mL is slowly added dropwise successively
(206mmol), ethylbenzene 0.56mL (about 4.6mmol) and n,N-Dimethylformamide solvent 100mL, with liquid nitrogen frozen-pumping-liter
Temperature cycle 3 times；It is reacted 7 hours at a temperature of 80 DEG C in nitrogen atmosphere；Obtained head product is slowly dropped into after being cooled to room temperature
1000mL, -10 DEG C of ethyl acetate is recrystallized, is filtered, obtained solid obtains target product after drying.Weight average molecular weight
(Mw) it is 56752,1HNMR spectrograms (CD3CN makees solvent) as shown in Figure 1, its Fourier infrared (FTIR) spectrogram such as Fig. 2 institutes
Show, gel permeation chromatography (GPC) data are as shown in table 1：
Table 1
Embodiment 2：Inhibition is evaluated
The method of inhibition evaluation of the present invention is as follows：
Experimental facilities is visualization high-pressure stirring experimental rig, which reacts including sapphire highpressure
Kettle, magnetic stirring apparatus, Cryogenic air bath, temperature and pressure transmitter, vacuum pump, camera, gas cylinder and data collecting instrument etc..
The sapphire highpressure reaction kettle maximum working pressure 11MPa, operating temperature range -30~80 DEG C.The sapphire highpressure is anti-
Answer pressure in kettle kettle that can freely be adjusted by air valve.Cryogenic air bath can provide -30~80 for sapphire highpressure reacting kettle jacketing
DEG C steady temperature.The parameters such as pressure, temperature in data collecting system acquisition in real time and storage reaction kettle kettle.The formation of hydrate
Temperature or pressure change when can pass through reaction are judged or camera is directly observed.After reaction starts, pressure is rapid in kettle
Drop is the starting point that the point drop point that pressure downward trend deviates original trend is hydrate generation, and the corresponding temperature of this point is
The minimum temperature that can bear for solution.Constant stirring rate starts to be passed through when sapphire highpressure reactor temperature is constant
Methane gas object closes intake valve when reacting kettle inner pressure is setting value.Then, with constant rate of temperature fall (such as 1
DEG C/h) when so that the temperature in reaction kettle is dropped to the pressure below the generation temperature of hydrate.The minimum temperature that solution can bear
The generation temperature of hydrate during thus.The function and effect of new inhibitor can be according to the solution institute energy for being added to the inhibitor
The minimum temperature born quantifies.The generation temperature of hydrate is lower, and inhibition is better.
Specific implementation process：
Before experiment operation, reaction kettle is first cleaned repeatedly with deionized water three to five times, then purge reaction kettle and reality with nitrogen
Test pipe-line system, it is ensured that system is dried.Reaction kettle is vacuumized, sucking 12.0mL's (about sapphire reactor volume 1/3)
Deionized water or the hydrate inhibitor solution of preparation to exclude air in kettle, are first passed through the methane gas of 1MPa purity 99.99%
Then body vacuumizes again, so repeatedly 3 times, constant stirring rate 800rpm, when sapphire highpressure reactor temperature is 20
DEG C when start to be passed through methane gas object, until reacting kettle inner pressure it is constant be 8.0MPa when close intake valve.Then, with 1 DEG C/h
Rate of temperature fall the temperature in reaction kettle is made to drop to -10 DEG C from 20 DEG C.Changed simultaneously using camera observation and temperature, pressure
Curve graph method, judges whether hydrate generates.
Pure water is added in reaction kettle and is tested, the results showed that, the generation temperature of the hydrate under the system is 7.0
℃。
It is 3.6 × 10 by weight average molecular weight5, mass concentration is respectively 0.1%, 1%, 2% poly N-vinyl pyrrole network alkane
Ketone (abbreviation PVPK90) aqueous solution is added in reaction kettle and is tested, and the results are shown in Table 2.
The weight average molecular weight that embodiment 1 is obtained is 56752 hydrate dynamic inhibitor (abbreviation PVPC6H5) water-soluble
Liquid is respectively to be tested in 0.1%, 0.5%, 1%, 2% addition reaction kettle by mass concentration, and the results are shown in Table 2.
Table 2
As shown in Table 2, the present invention can use, energy under low dosage concentration (0.5~2wt%) in the environment of high supercooling degree
Effectively delay hydrate nucleation time, reduce hydrate generating rate, have many advantages, such as that low dosage, efficient, applicability is wide, has
Preferable inhibition.
Claims (7)
1. a kind of hydrate dynamic inhibitor of structural formula as shown in formula I, the hydrate dynamic inhibitor is phenylating
Poly N-vinyl pyrrole network alkanone, formed by ethylbenzene and N- vinylpyridine network alkanone monomer polymerizations；
Wherein n=10~10000.
2. hydrate dynamic inhibitor according to claim 1, which is characterized in that the ethylbenzene and N- vinylpyridine networks
The volume ratio of alkanone monomer is 1:50~5:1.
3. a kind of preparation method of hydrate dynamic inhibitor described in claim 1, which is characterized in that including following step
Suddenly：Chain initiator azodiisobutyronitrile is weighed in reaction bulb, N- vinylpyridine network alkanones are slowly added dropwise under nitrogen atmosphere successively
Monomer, ethylbenzene and n,N-Dimethylformamide are reacted 2~20 hours at a temperature of 40~140 DEG C in nitrogen atmosphere；What is obtained is first
Product is recrystallized after being cooled to room temperature, is filtered, is dried, and obtains target product；The initiator amount accounts for N, N- dimethyl methyls
0.5wt%~2wt% of amide dosage；N,N-dimethylformamide dosage is the 1-20 of N- vinylpyridine network alkanone monomer volumes
Times；The volume ratio of ethylbenzene and N- vinylpyridine network alkanone monomers is 1:50~5:1.
4. the preparation method of hydrate dynamic inhibitor according to claim 3, which is characterized in that the recrystallization is used
Reagent be -20~20 DEG C of ethyl acetate.
5. the application of the hydrate dynamic inhibitor described in claim 1.
6. the application of hydrate dynamic inhibitor according to claim 5, which is characterized in that the hydrate inhibitor
Applied to the generation of hydrate in oil gas water three phase system, grease or air water two-phase system, when the hydrate inhibitor uses
Relative to a concentration of 0.1wt%~20wt% of water, it is 1~25MPa to be applicable in pressure, and temperature is -25~25 DEG C.
7. the application of hydrate dynamic inhibitor according to claim 6, which is characterized in that the hydrate inhibitor
Relative to a concentration of 0.5wt%~2wt% of water during use.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611153269.9A CN108219762B (en) | 2016-12-14 | 2016-12-14 | Novel hydrate kinetic inhibitor and preparation method and application thereof |
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| CN108219762A true CN108219762A (en) | 2018-06-29 |
| CN108219762B CN108219762B (en) | 2020-04-07 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020118779A1 (en) * | 2018-12-11 | 2020-06-18 | 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 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| WO2023122947A1 (en) * | 2021-12-28 | 2023-07-06 | 大连理工大学 | Environmentally-friendly natural gas hydrate inhibitor and application |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018107609A1 (en) | 2018-06-21 |
| CN108219762B (en) | 2020-04-07 |
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