CN107652958A - A kind of compound hydrate inhibitor of oil-gas gathering and transportation - Google Patents
A kind of compound hydrate inhibitor of oil-gas gathering and transportation Download PDFInfo
- Publication number
- CN107652958A CN107652958A CN201711006817.XA CN201711006817A CN107652958A CN 107652958 A CN107652958 A CN 107652958A CN 201711006817 A CN201711006817 A CN 201711006817A CN 107652958 A CN107652958 A CN 107652958A
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- China
- Prior art keywords
- hydrate
- oil
- present
- inhibitor
- vinylpyrrolidone
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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
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17D—PIPE-LINE SYSTEMS; PIPE-LINES
- F17D1/00—Pipe-line systems
- F17D1/08—Pipe-line systems for liquids or viscous products
- F17D1/16—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Public Health (AREA)
- Water Supply & Treatment (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of oil-gas gathering and transportation with compound hydrate inhibitor, solves in actual use, the effect of kinetic inhibitor is simultaneously not ideal enough, it is impossible to the problem of good meet demand.The present invention includes 20~30wt% vinylpyrrolidone and dimethylaminoethyl methacrylate dimer, and 10~15wt% polyvinylpyrrolidone, 50~55wt% ethanol, remaining is water.The present invention is by critical dimension, layer resistance to mass tranfer, space and absorbs the adhesive mechanism for hindering and the aggregation stage being grown after hydrate kinetic nucleation, realizes the suppression of hydrate, inhibition is splendid；And have the advantages that cost is low, usage amount is few, there is no corrosiveness to pipe container etc..
Description
Technical field
The present invention relates to inhibitor, and in particular to a kind of compound hydrate inhibitor of oil-gas gathering and transportation.
Background technology
In oil and natural gas exploitation, processing and transportation, the micro-molecular gas in oil gas is with water in certain temperature
Interaction can form the solid hydrate like ice-like under degree and pressure condition.Pit shaft, pipeline, valve and equipment can be blocked, from
And influence gas extraction, collect defeated and processing normal operation.
(1) coarse tube wall is become due to being attached to hydrate on smooth tube wall.A part of fluid passes through another part fluid
Slide；
(2) hydrate forms unsound netted plug in pipe.In lifting process, gas passes through unsound hydrate
Netted plug, and partially liq slips automatically after running into the netted plug of hydrate, makes the hydrops in shaft bottom cumulative；
(3) hydrate forms fine and close plug in pipe, and pipe inner section is blocked completely, well can not be again produced.Much
High-pressure gas well is produced under above-mentioned first two state.Sebei Gas Field is mostly mesolow well, and situation is the third state
It is shown, to winter, often there is the problem of blocking up well and can not normally producing.
Gas hydrates are formed in pipeline, pit shaft and underlying porous media voids, and oil and gas industry is produced and stored up
Fortune causes great threat, is mainly manifested in lower three aspects：
(1) hydrate produces in the duct, then can block pipeline, increase pipeline pressure difference, damage pipe fitting etc.；
(2) hydrate is formed in underlying porous medium, then can block Oil/gas Well, reduce oil-gas reservoir porosity and ooze relatively
Saturating rate, the petroleum distribution for changing oil-gas reservoir, reduce oil gas well production；
(3) hydrate is formed in the wellbore, then can block pit shaft, damage pit shaft internals, reduce oil and gas production even
Stop production.
Therefore, one long-standing problem production of hydrocarbons and the thorny problem of transport during Hydrate Plugging, for offshore oil and gas field
Exploitation and oil gas deep-sea pipe it is defeated, Hydrate Plugging is particularly problematic, thus hydrate preventing and treating turn into hydrate science in
One problem urgently to be resolved hurrily.
It is of the prior art suppress gas hydrates forming method have it is a variety of, such as：
Evaporation：By water content control in natural gas less than 165mg/m3.Gas hydrates can effectively be suppressed
Formed.It is industrial at present that triethylene glycol device is generally filled to be dehydrated using sledge, but cost of investment is higher.
Pressure application：System pressure is kept to form pressure less than gas hydrates, this control simply theoretically can be with
A kind of method realized, in order to keep certain conveying capacity, reduction that the pressure of pipeline typically can not be random.
Inhibitor processing：Thermodynamic inhibitor must be applied under high concentration (mass fraction is more than 6%), generally
10%~60% (mass fraction)；Low concentration (1%~5%) not only thermodynamic inhibitor can not play inhibition, and
In fact the formation and growth of hydrate can be promoted.Dynamics has dosage few compared with thermodynamic inhibitor, and cost is low, and effect is good
Just progressively turning into each elephant prevents main force's medicament of hydrate.But in actual use, the effect of kinetic inhibitor
Fruit is simultaneously not ideal enough, it is impossible to good meet demand.
The content of the invention
The technical problems to be solved by the invention are：In actual use, the effect of kinetic inhibitor and inadequate
It is preferable, it is impossible to, and it is an object of the present invention to provide a kind of oil-gas gathering and transportation to solve the above problems is with compound the problem of good meet demand
Hydrate inhibitor.
The present invention is achieved through the following technical solutions：
A kind of compound hydrate inhibitor of oil-gas gathering and transportation, including：
20~30wt% vinylpyrrolidone and dimethylaminoethyl methacrylate dimer,
10~15wt% polyvinylpyrrolidone,
50~55wt% ethanol,
Remaining is water.
The growth course of hydrate can be divided into nucleation, growth and aggregation three phases.And hydrate dynamic inhibitor master
The first two stage i.e. nucleation of hydrate and growth phase are acted on, by suppressing the nucleation of hydrate and postponing hydrate
Growth is flowed safely to reach hydrocarbon fluidses.
Inhibitor of the present invention can make hydrate grain growth slowly or even stop, and postpone hydrate nucleation time and growth
Time prevents hydrate crystal grain from growing up.Hydrate particle surface is adsorbed in hydrate nucleation and early growth period, the present invention, activity
The cyclic structure of agent is combined by hydrogen bond with hydrate crystal, so as to prevent and delay the further growth of hydrate crystal.It is few
The addition of the invention of amount will change the habit of structure I I type hydrates, can then cause crystalline substance in the type of structure I addition inhibitor
The rapid branch of body.If alloing the fluid in pipeline to be flowed under less than hydrate-formation temperature mass dryness fraction (4~10 DEG C), without
Hydrate Plugging problem can be produced.
Hydrate dynamic inhibitor is by significantly reducing the nucleation rate of hydrate, delaying or even preventing critical nucleus
The modes such as generation, the preferred growth direction of interference hydrate crystal and influence hydrate crystal directional stability suppress hydrate
Generation.Be exactly particularly kinetic inhibition produces inhibitory action for some step of hydrate formation, that is, suppress or
Delay hydrate nucleus to be formed, or prevent crystal further growth, so that hydrate can not be assembled blocking and block pipeline
Or equipment.
At present the present invention hydrate inhibitor by critical dimension, layer resistance to mass tranfer, space and absorb hinder and
The adhesive mechanism in aggregation stage is grown after hydrate kinetic nucleation, realizes the suppression of hydrate, it is specific as follows：
I.e. nucleus reaches critical dimension before hydrate nucleation, and hydrate inhibitor molecule of the invention with hydrone by making
For destroying the key structure to form hydrate cage structure.The effect prevents the scattered structural growth of hydrone to gas hydrate synthesis
The cluster structure needed, and the hydrate cluster structure for forming part is unstable.There is no a cluster structure, hydrate can not be into
Core, crystal also just are difficult to be formed.
After hydrate nucleation, dynamic (dynamical) factor account for it is leading, because inhibitor is mostly that its water-soluble solubility property is much better than
Guest molecule, hydrate inhibitor of the invention form a layer after hydrate nucleation between water and guest molecule so that first
The increase of alkane molecule and hydrone resistance to mass tranfer and cause that growth is difficult, and this mechanism is exactly that layer resistance to mass tranfer is said.
The present invention hydrate inhibitor in pyrrolidone ring on oxygen and hydrate surface formed two hydrogen bonds, inhale
It has been attached on the hydrate structure or crystal in nucleation process, so as to prevent the further growth of hydrate, has passed through upset
Hydrate is nucleated and prevented it further to increase the purpose for reaching and suppressing hydrate.Hydrate is to hydrate inhibitor of the present invention
Absorb and hydrate crystal is deformed, plane of crystal activated centre is isolated, and absorbed inhibitor molecules generate sky
Between inhibition, so as to have impact on the generation of hydrate crystal, reach suppress hydrate generation effect.The active group of inhibitor
Group is absorbed into the surface of hydrate crystal in the presence of hydrogen bond, so that hydrate crystal is surrounded with less radius of curvature
Condensate grows in polymer chain.After inhibitor is absorbed to grain surface, had an effect with methane molecule, prevent first
Alkane molecule enters and fills hydrate hole.
To sum up, the present invention has reached the consistent effect of hydrate, has realized suppression jointly by many inhibiting mechanisms
The purpose of hydrate generation, effect are very notable.
Further, vinylpyrrolidone and the dimethylaminoethyl methacrylate dimer is 1: 1 by mol ratio
Vinylpyrrolidone and dimethylaminoethyl methacrylate copolymerization composition.
Preferably, the present invention includes：
25~28wt% vinylpyrrolidone and dimethylaminoethyl methacrylate dimer,
13~15wt% polyvinylpyrrolidone,
50~53wt% ethanol,
Remaining is water.
It is further preferable that the present invention includes：
27wt% vinylpyrrolidone and dimethylaminoethyl methacrylate dimer,
14wt% polyvinylpyrrolidone,
52wt% ethanol,
Remaining is water.
The present invention compared with prior art, has the following advantages and advantages：
1st, the present invention is hindered by critical dimension, layer resistance to mass tranfer, space and absorption and is nucleated in hydrate kinetic
The adhesive mechanism in aggregation stage is grown afterwards, realizes the suppression of hydrate, and inhibition is splendid.
2nd, cost of the present invention is low, usage amount is few, does not have corrosiveness to pipe container etc., is especially suitable for popularization and application.
Embodiment
For the object, technical solutions and advantages of the present invention are more clearly understood, with reference to embodiment, the present invention is made
Further to describe in detail, exemplary embodiment of the invention and its explanation are only used for explaining the present invention, are not intended as to this
The restriction of invention.
Embodiment 1
A kind of compound hydrate inhibitor of oil-gas gathering and transportation, is made up of the component of following percetage by weight：
27wt% vinylpyrrolidone and dimethylaminoethyl methacrylate dimer, 14wt% polyethylene pyrrole
Pyrrolidone, 52wt% ethanol, remaining is water.
The specific preparation method of the present invention is as follows：
First, vinylpyrrolidone and dimethylaminoethyl methacrylate that mol ratio is 1: 1 are well mixed, added
Into the ethanol of phase homogenous quantities, it is well mixed, is stirred under the conditions of 60~70 DEG C, reaction generation vinylpyrrolidone and methyl
Dimethylaminoethyl acrylate dimer and alcohol mixeding liquid；
Secondly, polyethylene pyrrole is sequentially added in vinylpyrrolidone and dimethylaminoethyl methacrylate dimer
Pyrrolidone, second alcohol and water, finished product is made in stirring reaction 1-2h under the conditions of 40~50 DEG C.
Embodiment 2
The present embodiment and the difference of embodiment 1 are that the proportioning respectively formed in the present embodiment is different, and specific setting is as follows：
28wt% vinylpyrrolidone and dimethylaminoethyl methacrylate dimer, 13wt% polyethylene pyrrole
Pyrrolidone, 53wt% ethanol, remaining is water.
Embodiment 3
The present embodiment and the difference of embodiment 1 are that the proportioning respectively formed in the present embodiment is different, and specific setting is as follows：
23wt% vinylpyrrolidone and dimethylaminoethyl methacrylate dimer, 11wt% polyethylene pyrrole
Pyrrolidone, 55wt% ethanol, remaining is water.
Embodiment 4
The present embodiment and the difference of embodiment 1 are that the proportioning respectively formed in the present embodiment is different, and specific setting is as follows：
40wt% vinylpyrrolidone and dimethylaminoethyl methacrylate dimer, 18wt% polyethylene pyrrole
Pyrrolidone, 40wt% ethanol, remaining is water.
Embodiment 5
The present embodiment and the difference of embodiment 1 are that the proportioning respectively formed in the present embodiment is different, and specific setting is as follows：
18wt% vinylpyrrolidone and dimethylaminoethyl methacrylate dimer, 20wt% polyethylene pyrrole
Pyrrolidone, 58wt% ethanol, remaining is water.
The finished product of the present invention is fitted into the reactor of gas hydrates rejection evaluation experimental device, simulated
1000m depth of water drilling environments, i.e. experimental pressure are 10MPa, and experimental temperature is 2 DEG C, mixing speed 200r/min, finished product addition
Measure as 1.5%, and count under different time that hydrate generates situation in reactor, testing result is as shown in table 1.
Table 1
| 5h | 10h | 15h | 20h | 25h | 30h | |
| Embodiment 1 | Nothing | Nothing | Nothing | Nothing | Nothing | Nothing |
| Embodiment 2 | Nothing | Nothing | Nothing | Nothing | Nothing | Have |
| Embodiment 3 | Nothing | Nothing | Nothing | Have | Have | Have |
| Embodiment 4 | Nothing | Nothing | Have | Have | Have | Have |
| Embodiment 5 | Nothing | Have | Have | Have | Have | Have |
| Blank | Have | Have | Have | Have | Have | Have |
Contrasted by the test data of above-mentioned table 1：The present invention has the effect for preferably suppressing hydrate generation, effect
Fruit is very notable.
Above-described embodiment, the purpose of the present invention, technical scheme and beneficial effect are carried out further
Describe in detail, should be understood that the embodiment that the foregoing is only the present invention, be not intended to limit the present invention
Protection domain, within the spirit and principles of the invention, any modification, equivalent substitution and improvements done etc., all should include
Within protection scope of the present invention.
Claims (4)
- A kind of 1. compound hydrate inhibitor of oil-gas gathering and transportation, it is characterised in that including：20~30wt% vinylpyrrolidone and dimethylaminoethyl methacrylate dimer,10~15wt% polyvinylpyrrolidone,50~55wt% ethanol,Remaining is water.
- A kind of 2. compound hydrate inhibitor of oil-gas gathering and transportation according to claim 1, it is characterised in that the ethene pyrrole Pyrrolidone and dimethylaminoethyl methacrylate dimer are by vinylpyrrolidone and methacrylic acid that mol ratio is 1: 1 Dimethylaminoethyl copolymerization composition.
- A kind of 3. compound hydrate inhibitor of oil-gas gathering and transportation according to claim 1, it is characterised in that including：25~28wt% vinylpyrrolidone and dimethylaminoethyl methacrylate dimer,13~15wt% polyvinylpyrrolidone,50~53wt% ethanol,Remaining is water.
- A kind of 4. compound hydrate inhibitor of oil-gas gathering and transportation according to claim 3, it is characterised in that including：27wt% vinylpyrrolidone and dimethylaminoethyl methacrylate dimer,14wt% polyvinylpyrrolidone,52wt% ethanol,Remaining is water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711006817.XA CN107652958A (en) | 2017-10-25 | 2017-10-25 | A kind of compound hydrate inhibitor of oil-gas gathering and transportation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711006817.XA CN107652958A (en) | 2017-10-25 | 2017-10-25 | A kind of compound hydrate inhibitor of oil-gas gathering and transportation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107652958A true CN107652958A (en) | 2018-02-02 |
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ID=61119401
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711006817.XA Pending CN107652958A (en) | 2017-10-25 | 2017-10-25 | A kind of compound hydrate inhibitor of oil-gas gathering and transportation |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110925599A (en) * | 2019-12-13 | 2020-03-27 | 哈尔滨茂楠科技有限公司 | Efficient drag reducer and application method thereof |
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|---|---|---|---|---|
| CN101074361A (en) * | 2007-05-25 | 2007-11-21 | 东莞理工学院 | Efficient composite hydrate inhibitor |
| CN101544817A (en) * | 2009-04-28 | 2009-09-30 | 中国石油大学(北京) | Composition for enhancing hydrate inhibition effect and method for inhibiting formation of hydrate |
| CN101629071A (en) * | 2009-07-31 | 2010-01-20 | 中国科学院广州能源研究所 | Natural gas hydrate inhibitor |
| CN104357034A (en) * | 2014-10-17 | 2015-02-18 | 中国石油化工股份有限公司华北分公司 | Environmental-friendly efficient natural gas hydrate inhibitor |
| CN104830291A (en) * | 2015-04-30 | 2015-08-12 | 中国石油大学(华东) | Compound low dosage natural gas hydrate inhibitor |
| 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 |
-
2017
- 2017-10-25 CN CN201711006817.XA patent/CN107652958A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101074361A (en) * | 2007-05-25 | 2007-11-21 | 东莞理工学院 | Efficient composite hydrate inhibitor |
| CN101544817A (en) * | 2009-04-28 | 2009-09-30 | 中国石油大学(北京) | Composition for enhancing hydrate inhibition effect and method for inhibiting formation of hydrate |
| CN101629071A (en) * | 2009-07-31 | 2010-01-20 | 中国科学院广州能源研究所 | Natural gas hydrate inhibitor |
| CN104357034A (en) * | 2014-10-17 | 2015-02-18 | 中国石油化工股份有限公司华北分公司 | Environmental-friendly efficient natural gas hydrate inhibitor |
| CN104830291A (en) * | 2015-04-30 | 2015-08-12 | 中国石油大学(华东) | Compound low dosage natural gas hydrate inhibitor |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110925599A (en) * | 2019-12-13 | 2020-03-27 | 哈尔滨茂楠科技有限公司 | Efficient drag reducer and application method thereof |
| CN110925599B (en) * | 2019-12-13 | 2021-12-31 | 哈尔滨茂楠科技有限公司 | Efficient drag reducer and application method thereof |
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| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180202 |
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