CN106987241A - A kind of low dosage Compositional type hydrate inhibitor for natural gas - Google Patents

A kind of low dosage Compositional type hydrate inhibitor for natural gas Download PDF

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Publication number
CN106987241A
CN106987241A CN201710226029.5A CN201710226029A CN106987241A CN 106987241 A CN106987241 A CN 106987241A CN 201710226029 A CN201710226029 A CN 201710226029A CN 106987241 A CN106987241 A CN 106987241A
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inhibitor
natural gas
low dosage
hydrate inhibitor
compositional type
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CN106987241B (en
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王婷
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/52Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C09K8/524Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/22Hydrates inhibition by using well treatment fluids containing inhibitors of hydrate formers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/32Anticorrosion additives

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention relates to a kind of low dosage Compositional type hydrate inhibitor for natural gas.When mainly solving prevention and control gas hydrates present in prior art, thermodynamic inhibitor consumption is big, accumulating running cost is high and the problem of the poor feature of environmental protection.The inhibitor of the present invention, includes by weight percentage:5~40% APGs, 0~10% synergist, 48~95% solvents, the technical scheme of 0~2% defoamer preferably solves above mentioned problem.The inhibitor of the present invention has the features such as low adding amount, good suppression gas hydrates performance, good economy performance, environmental protection, available for gas hydrates prevention and control field.

Description

A kind of low dosage Compositional type hydrate inhibitor for natural gas
Technical field
The present invention relates to a kind of low dosage Compositional type hydrate inhibitor for natural gas.
Background technology
Gas hydrates are the crystalline materials for the species ice-like that natural gas and water are formed under low temperature and condition of high voltage, It is incendivity that outward appearance meets fire as ice, also referred to as " combustible ice ", " solid gas " or " gas ice ".Gas hydrates are in exploitation day Formed in the pipeline of right gas, line clogging can be caused, reduce the output quantity of natural gas, increase the pressure difference of pipeline, damaged pipe fitting and set It is standby, cause serious pipeline accident, or even cause gas well to stop production.Gas hydrates in pipeline are prevented and treated in gas industry at present The most effective and conventional method of embolism is injection chemical inhibitor, and it can suppress the formation of gas hydrates, can also Dissolve established gas hydrates.Current domestic each Gas Fields are mainly hydrated using methanol as chemical inhibitor come prevention and control The formation of thing, methanol is used as traditional thermodynamics hydrate inhibitor, although can effectively suppress the formation of hydrate, but there is also Methanol dosing is big, volatile, has stronger toxicity, to environment and artificial into certain injury, and is mixed with the production of methanol Sewage must be recycled, and accumulating and running cost are higher.Methanol has no longer met that gas field is safe and environment-friendly, inexpensive open The need for hair.The major research institutions of Abroad in Recent Years, such as BASF BASF, BP BP, shell SHELL, Mobil Mobile Develop the kinetic inhibitor using high-molecular compound as active component of low dosage in succession Deng company(KHI), polymerization inhibitor (AA)Deng, but can not still be used when using at the scene in the presence of such as polymer dynamics inhibitor under high supercooling degree, exist turbid Point, synthesis cost is higher, the low problem of degradation rate;Although the polymerization inhibitor based on surfactant can bear higher supercooling Degree, but used there is also needs in the oil-water coexistence pipeline of by-product condensate, cost is high, the problem of degradation rate is low so that this Only a small amount of condition compares the land gas well of mitigation and applied abroad for class inhibitor.Also there is development correlative study the country.
CN101629071B discloses a kind of efficient combined inhibitor for suppressing gas hydrate generation.The inhibitor It is according to quality proportioning 1 by polyvinylpyrrolidone, three kinds of materials of polyetheramine and butyl glycol ether:1:1 formulated in combination is formed.Suppression Total mass concentration when preparation is used is 0.2-2%.Inhibitor is applied in oilfield drilling mining system, and usage amount is small, efficiently Advantage.
CN102504786B discloses a kind of sulfur-containing natural gas hydrate inhibitor, by weight 100% meter:Dynamics is hydrated Thing inhibitor 10-30%, surfactant 10-30%, defoamer 2-5%, corrosion inhibiter 2-5% and organic solvent 50-70%, dynamics Hydrate inhibitor is N- caprolactam and 2- acrylamido -2- methyl-prop of the weight average molecular weight in 5000-20000 N vinyl pyrrolidone, N- caprolactam of the bipolymer or weight average molecular weight of sulfonate in 6000-30000 With the terpolymer of 2- acrylamide-2-methylpro panesulfonic acid salt;The hydrate inhibitor is applied to prevent high temperature, high salt Gas hydrate synthesis in sulfur-containing gas gathering system, prevents gas hydrate synthesis from blocking, and has to gathering line and ground installation Antiseptic effect.
CN104293326A discloses a kind of petroleum drilling fluid hydrate inhibitor for natural gas, is mainly used in wellbore fluid System.The hydrate inhibitor for natural gas of the invention is a kind of kinetic inhibitor, thermodynamic inhibitor, polyamine class and defoamer Mixture.The inhibitor is 5-35MPa using pressure, and temperature in use is at -10~30 DEG C.The inhibitor consumption is few, with relatively low dense Degree is mixed into drilling fluid, and reduction gas hydrates nucleation, growth, the speed of coalescence, environmental pollution are small.
In addition to above-mentioned patent, there are other functional materials to be developed to as hydrate inhibitor, but all there is conjunction Into high polymer material cost is high, difficult degradation the problems such as, being this Patent exploitation of the present invention, a kind of adding amount is low, suppress natural gas It is hydrated good physical performance, good economy performance, degradable environmentally friendly hydrate inhibitor.
The content of the invention
When the technical problems to be solved by the invention are prevention and control gas hydrates present in prior art, thermodynamics suppression Preparation consumption is big, accumulating running cost is high and the problem of the poor feature of environmental protection.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows:A kind of low dosage Compositional type gas water Compound inhibitors, it is characterised in that inhibitor includes by weight percentage:5~40% APGs, 0~10% synergist, 48~95% solvents, 0~2% defoamer.
In above-mentioned technical proposal, it is C that described APG, which is selected from alkyl number,4~C16Straight chain type or branch chain type alkyl sugar At least one of glycosides.
In above-mentioned technical proposal, described synergist is selected from sodium formate, potassium formate, calcium formate, sodium chloride, potassium chloride, chlorine Change calcium, polyetheramine, PEO, polyethylene glycol, polypropylene glycol, polyacrylamide, PVP, polyvinyl One or more in caprolactam.
In above-mentioned technical proposal, described solvent is selected from water, methanol, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, third At least one of glycol, butanediol, butyl glycol ether, ethylene glycol monobutyl ether.
In above-mentioned technical proposal, described defoamer may be selected from one kind in copolyether, polyether siloxane copolymer Or it is a variety of.
The hydrate inhibitor of the present invention is with surface-active height, ecological security and good biocompatibility, microorganism drop The excellent APG of solution property is primary functional components, the efficient hydrate inhibitor through compounding.Because APG is Amphi-pathic compound with hydrophilic group and lipophilic group, hydrophilic group can reduce the activity of water with hydrone formation hydrogen bond, lipophilic group There is alkyl chain steric hindrance natural gas molecule can be hindered to enter in water cage, reduce the interaction between natural gas and water, from And reach the purpose for suppressing gas hydrate synthesis.When using inhibitor of the present invention, synergist can be added in inhibitor solution and entered One step lifts the performance of inhibitor.Because APG can may also function as inhibition in inner-walls of duct formation diaphragm to pipeline Agent function, further improves the economy of inhibitor.Therefore, inhibitor of the present invention have adding amount it is low, suppress gas water Compound performance is good, good economy performance, environmental protection the features such as, available for gas hydrates prevention and control field.
Embodiment
Below by embodiment, the present invention is further elaborated, but the implementation of the present invention is not limited to this.
The performance test of the hydrate inhibitor for natural gas of the present invention is carried out in the reaction under high pressure handkerchief kettle independently transformed, Handkerchief kettle volume 1L, maximum pressure 10MPa, circulation deep cooling bath can make the operating temperature range of handkerchief kettle at -30~25 DEG C, by suppression to be measured Formulation samples and salt-containing solution(Simulated formation water)It is fitted into after mixing in proportion in handkerchief kettle, being filled with natural gas arrives system pressure Designated value, the time that record pressure is begun to decline under stirring is as the time for judging hydrate appearance.Test condition:It is real Test -3 DEG C of pressure 6.5MPa, experimental temperature(18 DEG C of degree of supercooling), 300 revs/min of speed of agitator, natural gas composition be shown in Table 1.
The natural gas of table 1 is constituted
Component CH4 C2H6 C3H8 C4H10 C5H12 He N2 CO2 H2S
Content % 94.50 0.47 0.06 0.01 0.01 0.03 0.21 4.70 0.01
【Embodiment 1】
By weight percentage, 30% C12APG, 10% potassium formate, the 59% ethylene glycol monobutyl ether aqueous solution(Concentration 50%), 1% polyether antifoam agent is configured to hydrate inhibitor A, in the NaCl aqueous solution for adding it to 3.5%, makes inhibitor in solution In mass percent concentration be 1%.Sample to be tested is added to progress hydrate rejection test in high pressure handkerchief kettle, test It the results are shown in Table 2.
【Embodiment 2】
By weight percentage, 30% C8APG, 10% potassium formate, the 59% ethylene glycol monobutyl ether aqueous solution(Concentration 50%), 1% Polyether antifoam agent is configured to hydrate inhibitor B, in the NaCl aqueous solution for adding it to 3.5%, makes inhibitor in the solution Mass percent concentration is 1%.Sample to be tested is added to progress hydrate rejection test, test result in high pressure handkerchief kettle It is shown in Table 2.
【Embodiment 3】
By weight percentage, 30% C12APG, 10% polyetheramine, the 59% ethylene glycol monobutyl ether aqueous solution(Concentration 50%), 1% polyether antifoam agent is configured to hydrate inhibitor C, in the NaCl aqueous solution for adding it to 3.5%, makes inhibitor in solution In mass percent concentration be 1%.Sample to be tested is added to progress hydrate rejection test in high pressure handkerchief kettle, test It the results are shown in Table 2.
【Embodiment 4】
By weight percentage, 30% C12APG, 10% polyethylene glycol, the 59% ethylene glycol monobutyl ether aqueous solution(Concentration 50%), 1% polyether antifoam agent is configured to hydrate inhibitor D, in the NaCl aqueous solution for adding it to 3.5%, inhibitor is existed Mass percent concentration in solution is 1%.Sample to be tested is added to progress hydrate rejection test in high pressure handkerchief kettle, Test result is shown in Table 2.
【Embodiment 5】
By weight percentage, 30% C12APG, 10% PVP, the 59% ethylene glycol monobutyl ether aqueous solution (Concentration 50%), 1% polyether antifoam agent is configured to hydrate inhibitor E, in the NaCl aqueous solution for adding it to 3.5%, makes suppression The mass percent concentration of preparation in the solution is 1%.Sample to be tested is added to progress hydrate rejection in high pressure handkerchief kettle Test, test result is shown in Table 2.
【Embodiment 6】
By weight percentage, 35% C12APG, the 64% ethylene glycol monobutyl ether aqueous solution(Concentration 50%), 1% polyethers froth breaking Agent is configured to hydrate inhibitor F, in the NaCl aqueous solution for adding it to 3.5%, makes the quality percentage of inhibitor in the solution Specific concentration is 1%.Sample to be tested is added to progress hydrate rejection test in high pressure handkerchief kettle, test result is shown in Table 2.
【Embodiment 7】
By weight percentage, 30% C12APG, 10% potassium formate, 59% methanol aqueous solution(Concentration 50%), 1% polyethers silicon Oxygen alkane defoamer is configured to hydrate inhibitor G, in the NaCl aqueous solution for adding it to 3.5%, makes inhibitor in the solution Mass percent concentration is 1%.Sample to be tested is added to progress hydrate rejection test, test result in high pressure handkerchief kettle It is shown in Table 2.
【Embodiment 8】
By weight percentage, 35% C12APG, 64% glycol water(Concentration 50%), the preparation of 1% polyether antifoam agent Into hydrate inhibitor H, in the NaCl aqueous solution for adding it to 3.5%, make the mass percent concentration of inhibitor in the solution For 1%.Sample to be tested is added to progress hydrate rejection test in high pressure handkerchief kettle, test result is shown in Table 2.
【Embodiment 9】
By weight percentage, 15% C8APG, 15% C12APG, 10% potassium formate, 59.8% glycol water (Concentration 50%), 0.2% polyether silicone defoamer is configured to hydrate inhibitor I, adds it to the 3.5% NaCl aqueous solution In, it is 1% to make the mass percent concentration of inhibitor in the solution.Sample to be tested is added in high pressure handkerchief kettle and carries out hydrate Rejection is tested, and test result is shown in Table 2.
【Embodiment 10】
By weight percentage, 10% C4APG, 20% C10APG, 10% potassium formate, 59% ethylene glycol monobutyl ether water Solution(Concentration 50%), 1% polyether antifoam agent is configured to hydrate inhibitor J, in the NaCl aqueous solution for adding it to 3.5%, It is 1% to make the mass percent concentration of inhibitor in the solution.Sample to be tested is added to progress hydrate suppression in high pressure handkerchief kettle Performance test, test result is shown in Table 2.
【Comparative example 1】
Without inhibitor, is directly added to progress hydrate rejection test in high pressure handkerchief kettle by the 3.5% NaCl aqueous solution, Test result is shown in Table 2.
【Comparative example 2】
Thermodynamic inhibitor methanol is added in the 3.5% NaCl aqueous solution, makes the mass percent concentration of methanol in the solution For 15%.Sample to be tested is added to progress hydrate rejection test in high pressure handkerchief kettle, test result is shown in Table 2.
【Comparative example 3】
PVP is added in the 3.5% NaCl aqueous solution, makes the matter of PVP in the solution It is 1% to measure percent concentration.Sample to be tested is added to progress hydrate rejection test in high pressure handkerchief kettle, test result is shown in Table 2.
The inhibitor the performance test results of table 2
Detect sample Pressure/MPa Temperature/DEG C Degree of supercooling/DEG C Hydrate time of occurrence/min
A 6.5 -3 18 183
B 6.5 -3 18 170
C 6.5 -3 18 190
D 6.5 -3 18 172
E 6.5 -3 18 208
F 6.5 -3 18 165
G 6.5 -3 18 173
H 6.5 -3 18 178
I 6.5 -3 18 181
J 6.5 -3 18 169
Comparative example 1 6.5 -3 18 5
Comparative example 2 6.5 -3 18 20
Comparative example 3 6.5 -3 18 45

Claims (5)

1. a kind of low dosage Compositional type hydrate inhibitor for natural gas, it is characterised in that inhibitor includes by weight percentage:5 ~40% APG, 0~10% synergist, 48~95% solvents, 0~2% defoamer.
2. low dosage Compositional type hydrate inhibitor for natural gas according to claim 1, it is characterised in that described alkyl It is C that glucosides, which is selected from alkyl number,4~C16Straight chain type or at least one of branch chain type alkyl glucosides.
3. low dosage Compositional type hydrate inhibitor for natural gas according to claim 1, it is characterised in that described synergy Agent may be selected from sodium formate, potassium formate, calcium formate, sodium chloride, potassium chloride, calcium chloride, polyetheramine, PEO, polyethylene glycol, One or more in polypropylene glycol, polyacrylamide, PVP, Vinylcaprolactam homopolymer.
4. low dosage Compositional type hydrate inhibitor for natural gas according to claim 1, it is characterised in that described solvent Selected from water, methanol, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, propane diols, butanediol, butyl glycol ether, ethylene glycol only son At least one of ether.
5. low dosage Compositional type hydrate inhibitor for natural gas according to claim 1, it is characterised in that described froth breaking Agent may be selected from the one or more in copolyether, polyether siloxane copolymer.
CN201710226029.5A 2017-04-08 2017-04-08 A kind of low dosage Compositional type hydrate inhibitor for natural gas Expired - Fee Related CN106987241B (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107795848A (en) * 2017-09-30 2018-03-13 天津大学 A kind of Compositional type hydrate inhibitor for natural gas of the amphipathic copolymer containing POSS and preparation method thereof
CN111996051A (en) * 2020-09-14 2020-11-27 扬州大学 Hydrating agent for preparing natural gas hydrate
CN112592704A (en) * 2020-12-30 2021-04-02 天津新翔油气技术有限公司 High-temperature-resistant hydrate inhibitor and preparation method thereof
CN113817443A (en) * 2020-06-18 2021-12-21 中国石油化工股份有限公司 Hydrate decomposition inhibiting composition, coupling enhanced solid hydrate and method for enhancing storage and transportation stability of solid hydrate
CN114058344A (en) * 2020-08-10 2022-02-18 中国石油天然气股份有限公司 Multi-effect additive for natural gas exploitation and preparation method and application thereof
CN114539994A (en) * 2022-04-24 2022-05-27 山东维斯特尔石油科技有限公司 Reservoir drilling fluid system and preparation method thereof
WO2023122947A1 (en) * 2021-12-28 2023-07-06 大连理工大学 Environmentally-friendly natural gas hydrate inhibitor and application

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CN103232497A (en) * 2013-04-09 2013-08-07 浙江赞宇科技股份有限公司 Alkyl glucoside preparation method
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CN103232497A (en) * 2013-04-09 2013-08-07 浙江赞宇科技股份有限公司 Alkyl glucoside preparation method
CN103865505A (en) * 2014-03-03 2014-06-18 中国石油大学(北京) Non-ionic compound gas hydrate anti-agglomerant

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107795848A (en) * 2017-09-30 2018-03-13 天津大学 A kind of Compositional type hydrate inhibitor for natural gas of the amphipathic copolymer containing POSS and preparation method thereof
CN107795848B (en) * 2017-09-30 2019-06-11 天津大学 A kind of Compositional type hydrate inhibitor for natural gas of the amphipathic copolymer containing POSS and preparation method thereof
CN113817443A (en) * 2020-06-18 2021-12-21 中国石油化工股份有限公司 Hydrate decomposition inhibiting composition, coupling enhanced solid hydrate and method for enhancing storage and transportation stability of solid hydrate
CN113817443B (en) * 2020-06-18 2022-08-30 中国石油化工股份有限公司 Hydrate decomposition inhibiting composition, coupling enhanced solid hydrate and method for enhancing storage and transportation stability of solid hydrate
CN114058344A (en) * 2020-08-10 2022-02-18 中国石油天然气股份有限公司 Multi-effect additive for natural gas exploitation and preparation method and application thereof
CN111996051A (en) * 2020-09-14 2020-11-27 扬州大学 Hydrating agent for preparing natural gas hydrate
CN112592704A (en) * 2020-12-30 2021-04-02 天津新翔油气技术有限公司 High-temperature-resistant hydrate inhibitor and preparation method thereof
CN112592704B (en) * 2020-12-30 2022-09-20 天津新翔油气技术有限公司 High-temperature-resistant hydrate inhibitor and preparation method thereof
WO2023122947A1 (en) * 2021-12-28 2023-07-06 大连理工大学 Environmentally-friendly natural gas hydrate inhibitor and application
CN114539994A (en) * 2022-04-24 2022-05-27 山东维斯特尔石油科技有限公司 Reservoir drilling fluid system and preparation method thereof
CN114539994B (en) * 2022-04-24 2022-07-15 山东维斯特尔石油科技有限公司 Reservoir drilling fluid system and preparation method thereof

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