CN101608118A - Inhibitor for preventing formation of natural gas hydrate in high-sulfur-content acid gas field - Google Patents
Inhibitor for preventing formation of natural gas hydrate in high-sulfur-content acid gas field Download PDFInfo
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- CN101608118A CN101608118A CNA2008101152133A CN200810115213A CN101608118A CN 101608118 A CN101608118 A CN 101608118A CN A2008101152133 A CNA2008101152133 A CN A2008101152133A CN 200810115213 A CN200810115213 A CN 200810115213A CN 101608118 A CN101608118 A CN 101608118A
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- 239000007789 gas Substances 0.000 title claims abstract description 35
- 239000003112 inhibitor Substances 0.000 title claims abstract description 33
- 239000002253 acid Substances 0.000 title claims abstract description 8
- 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 title abstract description 12
- 230000015572 biosynthetic process Effects 0.000 title description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000003368 amide group Chemical group 0.000 claims abstract description 5
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims abstract description 5
- 229920001577 copolymer Polymers 0.000 claims abstract description 4
- -1 alkyl alcohol amine Chemical class 0.000 claims abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 50
- 239000003345 natural gas Substances 0.000 claims description 21
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 11
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 230000009435 amidation Effects 0.000 claims description 4
- 238000007112 amidation reaction Methods 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000013530 defoamer Substances 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- 229920001897 terpolymer Polymers 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims 1
- 239000000178 monomer Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 abstract description 5
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 4
- 239000002518 antifoaming agent Substances 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- MXRGSJAOLKBZLU-UHFFFAOYSA-N 3-ethenylazepan-2-one Chemical compound C=CC1CCCCNC1=O MXRGSJAOLKBZLU-UHFFFAOYSA-N 0.000 abstract 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 abstract 1
- 125000004185 ester group Chemical group 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 229920006027 ternary co-polymer Polymers 0.000 abstract 1
- 239000000047 product Substances 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 14
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- 235000009508 confectionery Nutrition 0.000 description 7
- 238000011049 filling Methods 0.000 description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000001875 compounds Chemical group 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000003203 everyday effect Effects 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 150000002462 imidazolines Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 125000005233 alkylalcohol group Polymers 0.000 description 2
- 230000002528 anti-freeze Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention relates to an inhibitor for preventing natural gas hydrate from forming in a high-sulfur-containing acid gas field, which is composed of 5-30 wt% of a binary copolymer of vinyl pyrrolidone and vinyl caprolactam with the weight-average molecular weight range of 3000-10000 or a ternary copolymer of vinyl pyrrolidone, vinyl caprolactam and N, N-dimethylamino ethyl methacrylate with the weight-average molecular weight range of 65000-100000; 5-30% of polyesteramide or amidated product containing amide group and ester group, which is polymerized by maleic anhydride and derivatives thereof and alkyl alcohol amine, and the number average molecular weight is in the range of 1000-15000; 10-15% of a surfactant and a defoaming agent; 50-70% of methanol or a mixture of ethanol and ethylene glycol; for H2S content of 0-8%, CO20-5% of C-free2The acidic natural gas hydrate of the hydrocarbon component has better inhibiting effect.
Description
Technical field
The present invention relates to a kind of be used for the preventing exploitation of high-hydrogen sulfide sour natural gas and formation of surface gathering and transferring process hydrate or accumulative inhibitor.
Background technology
In Natural gas extraction and surface gathering and transferring process, variation along with envrionment temperature and the defeated working condition (temperature, pressure and fluidised form) of collection, acidic components such as hydrocarbons such as the methane in the Sweet natural gas, ethane and hydrogen sulfide, carbonic acid gas and water (saturation water and liquid phase water) are easy to form solid hydrate, cause downhole oil sleeve pipe, gathering line and uphole equipment to stop up, produce to the gas field and bring influence and harm.Not only have a strong impact on the ordinary production of gas well and gathering system, but also can bring serious potential safety hazard.A large amount of Sweet natural gas emptying de-pluggings not only can cause serious economy loss, but also can bring the serious environmental pollution problem, particularly in temperature lower winter.Because hydrogen sulfide sour natural gas hydrate-formation temperature is higher, along with continually developing of domestic and international high in recent years sulfur-bearing gas field, hydrate forms with the obstruction problem of preventing and treating and assaults day by day, has caused vast research and production worker's very big concern.
The method that prevents at present gas well, gas gathering pipeline and the obstruction of uphole equipment generation hydrate is both at home and abroad mainly taked gas dehydration, heat tracing and the measures such as (being commonly called as frostproofer) of filling hydrate inhibitor, and the thermodynamics inhibitor such as methyl alcohol, ethylene glycol, triglycol of wherein annotating are one of at present the most frequently used methods.Because hydrogen sulfide sour natural gas corrodibility is strong, hydrate-formation temperature is high, easily separate out elemental sulfur, add the restriction of factors such as being subjected to operational condition and envrionment conditions, gas dehydration and heat tracing can not satisfy the needs that hydrate forms and obstruction prevents in the production process of sulfur-bearing gas field fully, dosing is big, environment is unfriendly, meeting produces a large amount of sour waters and be difficult to handle and traditional hot mechanics inhibitor such as methyl alcohol, ethylene glycol exist, shortcomings such as transportation, storage and use inconvenience.Therefore, screen or study little, the eco-friendly novel hydrates inhibitor of a kind of medicament dosage, for preventing that the gas hydrate obstruction of the acid gas field of sulfur-bearing from preventing significant.For overcoming big, the disagreeableness deficiency of environment of traditional hot mechanics inhibitor consumption, abroad since the nineties in 20th century, developed multiple kinetic inhibitor (KHI) and anti polymerizer low dosage hydrate inhibitors (LDHI) such as (AA) both at home and abroad, be used widely gradually in sea and the land condensation natural gas field abroad at present.Because H
2The severe corrosive of S sour gas and toxicity problem, relevant H
2The performance evaluation of the low dosage hydrate inhibitor under the S existence condition and the application aspect the control of acid gas gas hydrate are less.
At present domestic and international many companies China and foreign application the control method and the product patent of a large amount of novel low dose hydrate inhibitors (LDHI), patent as Exxon Production Research Co: CN1157650, CN1157651, CN1187181, CN1187182, CN1190385 suppresses the method that hydrate generates; The patent of Compaynie Francaise des Petroles: CN1172848 suppresses or delays to produce in the effluent to generate or the method for aggregating hydrate; The patent of Shell Internationale Research Maatschappij B.V: CN1185191, CN1426447 prevent the method that conduits by gas hydrates stops up; Li Xiangdong: CN101097040, the inhibitor method and the device thereof of gas hydrate in a kind of natural gas pipeline; U.S. Air Prod ﹠ Chem: CN1865406A, patents such as amine-based gas hydrate inhibitors.From above-mentioned patent, mainly be that some prevent from or suppress hydrate to form the process patent that stops up, what introduce is that some have inhibition or delay gas hydrate generation or accumulative high molecular weight water soluble polymer and surfactant structure type, relatively more general, specific aim is not strong, and suitability is relatively poor.Report from data at home and abroad, above-mentioned patented product is applicable to mainly and contains oil or condensation Sweet natural gas that the hydrate that mainly forms the gas gathering and transportation system of II type water of constitution compound forms and prevents.Because it is bigger that the inhibition effect of kinetic inhibitor KHI is influenced by gas composition, some have the KHI of fine inhibition effect to II type water of constitution compound, restraining effect to I type water of constitution compound is relatively poor, therefore, for only containing methane, hydrogen sulfide, carbonic acid gas and a small amount of ethane, do not contain heavy hydrocarbon, mainly form the sour natural gas gathering system of I type water of constitution compound, above-mentioned kinetic inhibitor (KHI) and anti polymerizer (AA) patented product can not be suitable fully.Report (SPE 93450) from external low dosage hydrate inhibitor in the rig-site utilization that the acid gas gathering and transportation system water of sulfur-bearing compound prevents, all contain a large amount of condensation wet goods heavy hydrocarbon components in this gathering system, for the sour natural gas hydrate that does not contain condensate oil (dry gas), high-hydrogen sulfide and carbonic acid gas, do not see application report.
Summary of the invention
The objective of the invention is to develop a kind of being applicable to and contain methane, hydrogen sulfide, carbonic acid gas and a small amount of ethane, the sour natural gas gathering system of oil-containing or condensation gas component does not have multi-functional inhibitor such as the gas hydrate of preventing generation, gathering, inhibition and cleaning.
It is characterized in that this product is made up of following prescription:
(A), the weight average molecular weight range of 5～30% (weight) is at the vinyl pyrrolidone (PVP) of 3000-10000 and the copolymer of caprolactam (PVCap); Weight average molecular weight range is at vinyl pyrrolidone, caprolactam and the N of 65000-100000, the terpolymer of N dimethylamine ylmethyl ethyl propenoate.The said products is commercialization mostly, can obtain by directly buying or oneself synthesize from offshore company.
A agent in the formula for a product of the present invention is the water-soluble polymers with amide group, quaternary ammonium salt group and cyclic group, and it mainly acts on is by the absorption of functional group and the formation or the growth of sterically hindered effect inhibition or prevention hydrate nucleus.
(B), the polyesteramide that contains amide group and fat group or the amidation product that are polymerized by maleic anhydride and derivative and alkyl alcoholamine of 5～30% (weight), the number-average molecular weight scope is at 1000-15000, its structural formula is:
Structural formula I structural formula II
Among the structural formula I: each R is an independently H, R
1And R
2Be H or C
1-C
4Alkyl, and R
1And R
2In alkyl group can be arbitrarily by hydroxyl and amino the replacement.
In the structural formula II: R, R
1, R
2The same with the group of X representative, and Alk is C
1-C
5Alkyl chain.
Can obtain by being purchased or oneself synthesizing.Its preparation method can be referring to patent US 6369004B1 and CN 1426447A.
(C), the tensio-active agent of 10～15% (weight) and defoamer.
C agent composition in the formula for a product of the present invention mainly plays dispersion, cleaning, anticorrosion and froth breaking effect, prevents the gathering of hydrate crystal.The preferred butoxy ethanol of tensio-active agent of the present invention, polyxyethylated alkylphenol (OP-10), polyoxyethylated alkyl alcohol (JFC), imidazolines water soluble rust inhibitor; Preferred organic silicone of defoamer and mixed type product thereof.
(D), the organic solvent of 50～70% (weight).
D agent composition in the formula for a product of the present invention is an organic solvent, its objective is as carrier medicament is brought in the Sweet natural gas fluid thorough mixing and has an effect, and plays a role as a kind of thermodynamics inhibitor simultaneously, reduces the condensate depression of gathering system.Organic solvent is the mixture of methyl alcohol or ethanol and ethylene glycol.
The present invention be applicable to do not contain condensate oil (dry gas), height contains H
2S and CO
2The sour natural gas hydrate forms the inhibitor that prevents, the condensate depression that is suitable for is brought up to more than 10 ℃, thereby restrained the deficiency of existing hydrate inhibitor product.Nucleus such as the solid dirt that another characteristics of the present invention are to discharge at shaft bottom in the acid gas gathering pipeline of high sulfur-bearing, elemental sulfur are more, tube wall is coarse, cause hydrate crystal to assemble the characteristics of growth easily, in formula for a product, added tensio-active agent with matting and dissemination, by changing hydrate crystal state of aggregation and tube wall character, make the hydrate crystal of generation be difficult for taking place to assemble or adhere to tube wall, thus blocking pipe.Simultaneously,, in formula for a product, added the water soluble rust inhibitor component, thereby guaranteed preventing that hydrate from forming under the situation about stopping up, and has certain preservative effect to gathering line and uphole equipment at the strong characteristics of high sulfur-bearing sour natural gas corrodibility.
The invention effect
Compare with traditional hot mechanics inhibitor, formulation product of the present invention have dosing few, do not need to reclaim, can reduce great deal of investment, store, transportation and on-the-spot advantage such as easy to use; Compare with existing patented product, for only produce condensation water, do not contain condensate oil, height contains H
2S and CO
2Sour natural gas (dry gas) gathering system, this new inhibitor formulation product has the formation of hydrate and better prevents effect, suitable temperature condition is harsher, also has certain chemistry simultaneously and cleans and corrosion mitigating effect; Dosing is little, and use cost is low; Product viscosity is low, does not need dilution, on-the-spot filling and easy to use; Good with inhibiter preparation property, be not easy to bubble, less to gas downstream separating and dehydrating and gas sweetening influence.Inhibitor formulation product of the present invention is for H
2S content is 0～8%, CO
2Content is 0～5%, do not contain C
2The sour natural gas hydrate of above hydrocarbon component has and suppresses effect preferably, is under the condition of 5%-10% at the medicament dosage, and what be suitable for can cold Du Keda more than 10 ℃.
The indoor device for evaluating performance of hydrate inhibitor (seeing Chinese utility model patent, 200620118684.6) that utilizes autonomous design to make has carried out the performance comparison evaluation to formula for a product of the present invention.Experimental gas adopts the sour gas that simulates of indoor preparation to carry out, and gas composition sees Table 1, and experiment water quality is distilled water, and the control gas-liquid volume ratio is 60: 40, and mixing speed is 500 rev/mins.The performance evaluation comparing result of product of the present invention is shown in Table 2.
Table 1 performance evaluation experiment gas composition
Table 2 product performance comparative evaluation experimental result
Embodiment
Embodiment 1
1), composition of raw materials:
Vinyl pyrrolidone/caprolactam/N, the terpolymer of N dimethylamine ylmethyl ethyl propenoate: 20%;
The polyesteramide that maleic anhydride and alkyl alcoholamine are polymerized: 10%;
Butyl glycol ether: 10%;
Polyoxyethylated alkyl alcohol (JFC): 3%
Imidazolines water soluble rust inhibitor: 5%
Methyl alcohol: 12%;
Ethylene glycol: 39.95%;
Silicone antifoam agent: 0.05%;
2), operational condition:
Above-mentioned raw materials is joined in the reactor, under the temperature condition about 35 ℃, mix and stirred 30 minutes, can obtain faint yellow viscous liquid product.
Embodiment 2
1), composition of raw materials:
Vinyl pyrrolidone/caprolactam copolymer (effective content is 50%): 20%;
The amidation modified product of maleic anhydride polymkeric substance: 15%;
Butyl glycol ether: 5%;
Polyxyethylated alkylphenol (OP-10): 3%;
Imidazolines water soluble rust inhibitor: 5%
Ethanol: 12%;
Ethylene glycol: 39.95%
Silicone antifoam agent: 0.05%
2), operational condition:
Above-mentioned raw materials is joined in the reactor, under the temperature condition about 35 ℃, mix and stirred 30 minutes, can obtain faint yellow viscous liquid product.
Embodiment 3
Hydrate inhibitor product of the present invention is not taked at CNPC's bar to have carried out scheduling to last nearly four months test in place two winters on the high sulfur-bearing moisture transport pipeline of the measure that is incubated, and has obtained effect of field application preferably.Because high-hydrogen sulfide sour gas in this pipeline Sweet natural gas, hydrate-formation temperature is higher, and in temperature lower winter, this gathering line and downstream well station separator and valve hydrate often take place stop up, average per 3～5 days must the logical ball of pigging once.For guaranteeing gas well and pipeline ordinary production, average every day of necessary intermittent type filling 45Kg ethylene glycol antifreeze; After adopting average continous way filling every day product 8～10Kg of the present invention, the hydrate latch up phenomenon does not take place in this production flow line and well station, downstream separator, valve basically, and production run is normal, and the logical ball cycle of pigging can extend to 15～20 days.
This production flow line Sweet natural gas is formed and the defeated condition of collection:
1, makings is formed: methane content is 90.38%, and ethane content is 0.07%, and hydrogen sulfide content is 7.36%, carbon dioxide content is 1.68%, does not contain condensate gas, only produces condensation water; 7.5MPa the hydrate-formation temperature under the distribution pressure condition is 19 ℃.
2, natural gas transport condition: length of pipeline is 4.2Km, and diameter is φ 168.3 * 11; Distribution pressure is 7.0MPa～8.0MPa, and the gas transmission temperature is 10 ℃～20 ℃, and displacement is 15～20 * 10
4m
3/ d, the atmosphere medial temperature is 6 ℃～12 ℃, the lowest temperature is 3 ℃.
Embodiment 4
Hydrate inhibitor product of the present invention is not taked at CNPC's bar to have carried out scheduling to last nearly 3 months test in place 1 winter on the low sulfur-bearing moisture transport pipeline of the measure that is incubated, and has obtained effect of field application preferably.Because this pipeline gas production pipeline is located in high and cold high district, winter temperature is low especially, and the frequent hydrate that takes place stops up in this gathering line production process in winter, must lead to ball once by pigging in average per 3 days.For guaranteeing gas well and pipeline ordinary production, average every day of necessary intermittent type filling 40Kg～50Kg ethylene glycol antifreeze; After adopting average continous way filling every day product 10～12Kg of the present invention, the hydrate latch up phenomenon does not take place in this production flow line basically, and production run is normal, and the logical ball cycle of pigging can extend to more than 15 days.
This production flow line Sweet natural gas is formed and the defeated condition of collection:
1, makings is formed: methane content is 95.83%, and ethane content is 0.15%, and hydrogen sulfide content is 0.80%, carbon dioxide content is 2.73%, does not contain condensate gas, only produces condensation water; 8.0MPa the hydrate-formation temperature under the distribution pressure condition is 13.17 ℃.
2, natural gas transport condition: length of pipeline is 2.8Km, and diameter is φ 108 * 6; Distribution pressure is 7.5MPa～8.5MPa, and the gas transmission temperature is 7 ℃～19 ℃, and displacement is 23～25 * 10
4m
3/ d, the atmosphere medial temperature is 1 ℃～6 ℃, the lowest temperature is-3 ℃.
Claims (1)
1. inhibitor that prevents that natural gas hydrates of high-sulfur acid gas fields from forming is characterized in that: be made up of following ingredients by weight:
(A), 5～30% weight average molecular weight range is at the copolymer of the vinyl pyrrolidone of 3000-10000 and caprolactam or weight average molecular weight range vinyl pyrrolidone, caprolactam and the N at 65000-100000, the terpolymer of N dimethylamine ylmethyl ethyl propenoate;
(B), 5～30% the polyesteramide that contains amide group and fat group or the amidation product of maleic anhydride and generating vinyl carboxylate alicyclic monomer multipolymer, the number-average molecular weight scope is at 1000-15000;
(B), 5～30% the polyesteramide that contains amide group and fat group or the amidation product that are polymerized by maleic anhydride and derivative and alkyl alcoholamine, the number-average molecular weight scope is at 1000-15000;
(C), 10～15% tensio-active agent and defoamer;
(D), the mixture of 50～70% methyl alcohol or ethanol and ethylene glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101152133A CN101608118B (en) | 2008-06-19 | 2008-06-19 | Inhibitor for preventing formation of natural gas hydrate in high-sulfur-content acid gas field |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101152133A CN101608118B (en) | 2008-06-19 | 2008-06-19 | Inhibitor for preventing formation of natural gas hydrate in high-sulfur-content acid gas field |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101608118A true CN101608118A (en) | 2009-12-23 |
| CN101608118B CN101608118B (en) | 2012-07-18 |
Family
ID=41482028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101152133A Active CN101608118B (en) | 2008-06-19 | 2008-06-19 | Inhibitor for preventing formation of natural gas hydrate in high-sulfur-content acid gas field |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101608118B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906293A (en) * | 2010-08-18 | 2010-12-08 | 李向东 | Aid for preventing and controlling natural gas hydrate |
| CN101544817B (en) * | 2009-04-28 | 2011-04-13 | 中国石油大学(北京) | Composition for enhancing hydrate inhibition effect and method for inhibiting formation of hydrate |
| CN102504786A (en) * | 2011-09-26 | 2012-06-20 | 中国石油天然气股份有限公司 | Sulfur-containing natural gas hydrate inhibitor |
| CN104910887A (en) * | 2015-06-08 | 2015-09-16 | 成都鼎鸿石油技术有限公司 | Natural gas hydrate control agent |
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| RU2160409C2 (en) * | 1995-06-08 | 2000-12-10 | Эксонмобил Апстрим Рисерч Компани | Method of inhibiting of formation of hydrates |
| DE19803384C1 (en) * | 1998-01-29 | 1999-04-15 | Clariant Gmbh | Additive for inhibiting gas hydrates |
| US6194622B1 (en) * | 1998-06-10 | 2001-02-27 | Exxonmobil Upstream Research Company | Method for inhibiting hydrate formation |
| US6905605B2 (en) * | 2000-04-07 | 2005-06-14 | Shell Oil Company | Method for inhibiting the plugging of conduits by gas hydrates |
| DE10163260C1 (en) * | 2001-12-21 | 2003-08-28 | Kuraray Specialities Europe | Inhibition of gas hydrate formation, useful in transport in petroleum and natural gas industry and in drilling mud, uses copolymer with vinyl alcohol, olefinic comonomer and optionally vinyl or allyl ester units |
| DE60303826T2 (en) * | 2002-09-03 | 2006-11-02 | Shell Internationale Research Maatschappij B.V. | METHOD AND COMPOSITIONS FOR INHIBITING HYDROCARBONHYDRATE FORMATION |
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| RU2254459C1 (en) * | 2004-07-21 | 2005-06-20 | Открытое акционерное общество "МНКТ" | Oil formation treatment emulsion |
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Assignee: Chengdu Ringt Technology Development Co.,Ltd. Assignor: PetroChina Company Limited Contract record no.: 2011510000224 Denomination of invention: Inhibitor for preventing the formation of natural gas hydrates of high-sulfur acid gas fields License type: Exclusive License Open date: 20091223 Record date: 20110828 |
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