CN1635006A - Application of vinyl pyrrolidone and acetic acid ethyenyl ester copolymer as hydrate growth inhibitor - Google Patents
Application of vinyl pyrrolidone and acetic acid ethyenyl ester copolymer as hydrate growth inhibitor Download PDFInfo
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- CN1635006A CN1635006A CN 200310117636 CN200310117636A CN1635006A CN 1635006 A CN1635006 A CN 1635006A CN 200310117636 CN200310117636 CN 200310117636 CN 200310117636 A CN200310117636 A CN 200310117636A CN 1635006 A CN1635006 A CN 1635006A
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Abstract
The invention relates to the application of a copolymer of N-Vinyl-2-Pyrrolidone and vinyl acetate as a hydrate growth inhibitor. By the N-Vinyl-2-Pyrrolidone reacting with the vinyl acetate in volumetric ratio of 1:9~9:1 under the existence of the initiator capable of generating free radicals, a random copolymer with 1000~5000000 average relative molecular mass can be obtained and used in the natural gas or petroleum to inhibit hydrate growth. The working concentration of the copolymer as the hydrate growth inhibitor is low, and the mass fraction is between 0.01% and 6% in the petroleum or natural gas pipeline, the working pressure is 0.1~20MPa, and the inhibition effect is excellent.
Description
Technical field
The present invention relates to of the application of the multipolymer of vinyl pyrrolidone and vinyl-acetic ester as hydrate growth inhibitor in Sweet natural gas or the oil.
Background technology
Various lower boiling hydrocarbons such as methane, ethane, propane and carbonic acid gas, hydrogen sulfide etc. are present in Sweet natural gas and other petroleum fluids, and water also mixes with these petroleum fluids components with different amounts simultaneously.Under cryogenic high pressure, when such petroleum fluids composition or other hydrates form thing and mix with water, can form gas hydrate, this gas hydrate is the cage type crystal of micro-molecular gas formation such as water and lighter hydrocarbons.These clathrate hydrates possibility blocking pipelines bring difficulty for the exploitation or the conveying of oil and natural gas in exploitation and transport gas and other petroleum fluids processes.For example under the pressure of about 1MPa, ethane can form hydrate being lower than under 4 ℃ the temperature, is being lower than under 14 ℃ the temperature at ethane under the pressure of 3MPa to form hydrate.And these temperature and pressures are not to be of little use for many operating environments of production and transport gas and other petroleum fluids.
It is to avoid and prevent the hydrate generation by the temperature and pressure degree condition that changes the hydrate generation that tradition is used inhibitor such as methyl alcohol, ethylene glycol.But this type of inhibitor has concentration height (massfraction 10～60%), consumption is big, cost is high and shortcoming such as strong toxicity contaminate environment, can not satisfy such as requirements such as offshore oil and gas mining operations.Begin one's study both at home and abroad from the nineties in 20th century and to replace the use of inhibitor such as methyl alcohol with the kinetic inhibitor of low dosage.
The hydrate generative process can be divided into dissolving, induces, four periods of nucleation, growth, and kinetic inhibitor mainly works in inductive phase, nucleation period and vegetative period.Can play a part its inductive phase, nucleation period certain, but the inhibitor that mainly works in vegetative period is called growth inhibitor, promptly it allows the generation of hydrate particle in the regular hour scope, but it can stop hydrate particle to be assembled to lump.
The multipolymer of vinyl pyrrolidone and vinyl-acetic ester early has sintetics both at home and abroad, be mainly used in the stablizer of food, medicine, makeup, thickening material etc., but do not see so far as the hydrate growth inhibitor and (see document: Cui Yingde, Yi Guobin, Liao Liewen. the synthetic and application of polyvinylpyrrolidone. Science Press, 2001.140-145; Feng Rongyin, Lu Dan, Liang Guomei etc. the research of vinyl-acetic ester and vinylpyrrolidone copolymer. Zhongshan University's journal, 1995,134:52-59; Chinese patent application number: 99121738.1).
Summary of the invention
The objective of the invention is to develop the new purposes of the multipolymer of vinyl pyrrolidone and vinyl-acetic ester, as the hydrate growth inhibitor.
Author of the present invention finds that the multipolymer of vinyl pyrrolidone and vinyl-acetic ester can play certain restraining effect to inductive phase, the nucleation period of hydrate, but mainly play restraining effect in vegetative period, and only need low dosage just can obtain the good restraining effect, realized purpose of the present invention.
The present invention is that vinyl pyrrolidone and vinyl-acetic ester reacted in the presence of the initiator that can generate free radical with volume ratio in 1: 9～9: 1, the random copolymers of the average molecular mass 1000～5000000 that obtains is as the application of hydrate growth inhibitor in Sweet natural gas or the oil.
The synthetic method of the multipolymer of vinyl pyrrolidone of the present invention and vinyl-acetic ester is a routine techniques, the synthetic catalyzer is the initiator that can generate free radical, Diisopropyl azodicarboxylate etc. for example, catalyst levels be the monomer total amount 0.01%～1% between; Synthesize and carry out in the presence of solvent usually, for example methyl alcohol, ethanol, ethylene glycol etc. contain 1～6 carbon atom monobasic or binary solubility alcohol equal solvent; 10 ℃～90 ℃ of synthesis temperatures; 0.5～8 hour synthetic reaction times.
Multipolymer of the present invention is applied to suppress the device that hydrate is grown in Sweet natural gas or the oil and mainly comprises reactor, constant temperature air bath, stirring and volume adjustment means, pressure and temperature measuring system, vacuum pump, data collecting system and chromatograph etc.Reactor is the bright sapphire still of the full impregnated of a variable volume, maximum effectively working volume 100cm
3, minimum volume 13.6cm
3, maximum working pressure generally can reach 40MPa, temperature working range-20～120 ℃.Material can mix by agitator or recycle pump in the reactor.Temperature in the reactor is measured by RTD, and pressure precision is the determination of pressure sensor of 0.06% (being 24kPa).Volumetrical changes makes the reactor inner carrier move up and down realization by a direct current motor.Parameters such as parameter (pressure, temperature, volume), airbath temperature, circular flow and stir speed (S.S.) in the reactor can be gathered automatically and be stored by computer data acquisition system.
Multipolymer of the present invention is low as hydrate growth inhibitor working concentration in Sweet natural gas or the oil, joins in oil or the natural gas line massfraction between 0.01%～6%, between applying pressure 0.1～20MPa.
Embodiment
Embodiment 1:
Vinyl pyrrolidone and vinyl-acetic ester were blended in about 5 times of volume of ethanol in 1: 1 by volume, the Diisopropyl azodicarboxylate that adds total monomer weight 0.09% is then made catalyzer, mix, 60 ℃ of heating in water bath for reaction 4 hours, the product precipitation, separate, and to be made into massfraction after being further purified be 1% solution, pack into and have the reactor of stirring, experimental pressure is 7MPa, the gas mixture that experimental gas provides for Foshan Gas Plant (methane 91.98%, ethane 5.02% and propane 3%), temperature of reaction maintains 0.5 ℃, and no hydrate generates after 24 hours.
Embodiment 2:
Vinyl pyrrolidone and vinyl-acetic ester were mixed in 1: 7 by volume, repeat the experimental implementation of embodiment 1 then, it is 1% solution that the synthetic of gained is made into massfraction, pack into and have the reactor of stirring, experimental pressure is 7MPa, the gas mixture that experimental gas provides for Foshan Gas Plant (methane 91.98%, ethane 5.02% and propane 3%), temperature of reaction maintains 0.5 ℃, and no hydrate generates after 24 hours.
Embodiment 3:
Vinyl pyrrolidone and vinyl-acetic ester were mixed in 7: 1 by volume, repeat the experimental implementation of embodiment 1 then, it is 1% solution that the synthetic of gained is made into massfraction, pack into and have the reactor of stirring, experimental pressure is 7MPa, the gas mixture that experimental gas provides for Foshan Gas Plant (methane 91.98%, ethane 5.02% and propane 3%), temperature of reaction maintains 0.5 ℃, and no hydrate generates after 24 hours.
Claims (1)
1. vinyl pyrrolidone and vinyl-acetic ester are with volume ratio reaction in the presence of the initiator that can generate free radical in 1: 9～9: 1, the random copolymers of the average molecular mass 1000～5000000 that obtains is as the application of hydrate growth inhibitor in Sweet natural gas or the oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310117636 CN1635006A (en) | 2003-12-31 | 2003-12-31 | Application of vinyl pyrrolidone and acetic acid ethyenyl ester copolymer as hydrate growth inhibitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310117636 CN1635006A (en) | 2003-12-31 | 2003-12-31 | Application of vinyl pyrrolidone and acetic acid ethyenyl ester copolymer as hydrate growth inhibitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1635006A true CN1635006A (en) | 2005-07-06 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310117636 Pending CN1635006A (en) | 2003-12-31 | 2003-12-31 | Application of vinyl pyrrolidone and acetic acid ethyenyl ester copolymer as hydrate growth inhibitor |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453591C (en) * | 2007-07-09 | 2009-01-21 | 中国科学院广州能源研究所 | Hydrate formation inhibitor |
| CN102181275A (en) * | 2011-02-15 | 2011-09-14 | 中国海洋石油总公司 | Composite hydrate inhibitor and application thereof |
| CN101608118B (en) * | 2008-06-19 | 2012-07-18 | 中国石油天然气股份有限公司 | Inhibitor for preventing the formation of natural gas hydrates of high-sulfur acid gas fields |
| CN101007857B (en) * | 2005-12-23 | 2013-01-02 | 巴斯福股份公司 | Production of vinyl-lactam copolymers from water-soluble n-vinyl-lactam and hydrophobic comonomer for use e.g. in cosmetic or pharmaceutical formulation uses pressure high enough to prevent vaporizati |
| CN109735316A (en) * | 2018-12-11 | 2019-05-10 | 中国科学院广州能源研究所 | A kind of hydrate inhibitor for natural gas |
-
2003
- 2003-12-31 CN CN 200310117636 patent/CN1635006A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101007857B (en) * | 2005-12-23 | 2013-01-02 | 巴斯福股份公司 | Production of vinyl-lactam copolymers from water-soluble n-vinyl-lactam and hydrophobic comonomer for use e.g. in cosmetic or pharmaceutical formulation uses pressure high enough to prevent vaporizati |
| CN100453591C (en) * | 2007-07-09 | 2009-01-21 | 中国科学院广州能源研究所 | Hydrate formation inhibitor |
| CN101608118B (en) * | 2008-06-19 | 2012-07-18 | 中国石油天然气股份有限公司 | Inhibitor for preventing the formation of natural gas hydrates of high-sulfur acid gas fields |
| CN102181275A (en) * | 2011-02-15 | 2011-09-14 | 中国海洋石油总公司 | Composite hydrate inhibitor and application thereof |
| CN102181275B (en) * | 2011-02-15 | 2013-04-24 | 中国海洋石油总公司 | Composite hydrate inhibitor and application thereof |
| CN109735316A (en) * | 2018-12-11 | 2019-05-10 | 中国科学院广州能源研究所 | A kind of hydrate inhibitor for natural gas |
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