EP0457375B1 - Méthode d'empêchement d'hydrates - Google Patents

Méthode d'empêchement d'hydrates Download PDF

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Publication number
EP0457375B1
EP0457375B1 EP91200272A EP91200272A EP0457375B1 EP 0457375 B1 EP0457375 B1 EP 0457375B1 EP 91200272 A EP91200272 A EP 91200272A EP 91200272 A EP91200272 A EP 91200272A EP 0457375 B1 EP0457375 B1 EP 0457375B1
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EP
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Prior art keywords
fluid
cell
hydrates
alkyl aryl
alkyl
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EP91200272A
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German (de)
English (en)
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EP0457375A1 (fr
Inventor
Herman Mathieu Muijs
Nicolaas Cornelis Maria Beers
Nico Maria Van Os
Cornelus Albertus Kind
Mark Joseph Anselme
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C10L1/328—Oil emulsions containing water or any other hydrophilic phase

Definitions

  • the invention relates to a method for preventing or retarding the formation of hydrates or for reducing the tendency of hydrates to agglomerate during the transport of a fluid through a conduit.
  • glycols e.g. ethylene glycol or diethylene glycol.
  • a disadvantage thereof is that large amounts of glycol are needed (in the order of 30% by weight calculated on the amount of water).
  • composition suitable for the prevention of hydrate formation which composition comprises diethylene glycol with a minor amount of alkyl aryl sulphonate (in a quantity of 0.3-0.5% based on the weight of the diethylene glycol).
  • alkyl aryl sulphonic acids or alkali metal- or ammonium salts thereof can be used without glycols, to control hydrate formation.
  • the invention relates to a method for preventing or retarding the formation of hydrates or for reducing the tendency of hydrates to agglomerate in a stream of fluid comprising water and hydrocarbon during transport of the fluid through a conduit, which method comprises adding to the fluid an alkyl aryl sulphonic acid or an alkali metal- or ammonium salt thereof substantially in the absence of glycol flowing in the stream.
  • the hydrocarbon may be a liquid or a gas, but is preferably a gas such as methane, ethane, propane, isopropane, butane or isobutane.
  • the fluid may be produced from oil wells as well as from gas wells.
  • the fluid may also include natural gas.
  • hydrates may be formed at temperatures well above the freezing point of water.
  • Ethane hydrates for example, are formed at pressures between 10 and 30 bar (1 and 3 MPa) and temperatures between 4 °C and 14 °C. Formation and agglomeration of hydrate crystals will thus easily occur in pipelines surrounded by a cold atmosphere.
  • the problem of formation and agglomeration of gas hydrates is not limited to gas wells, but also occurs in oil wells, if water and gas are present in the fluid.
  • the alkyl aryl sulphonic acids or their salts preferably have an aryl group derived from benzene, toluene, ortho-, meta- or para-xylene.
  • the alkyl group is preferably a long chain alkyl group, which may be branched or straight.
  • the alkyl group may be e.g. a C8-C22-alkyl group.
  • Preferred compounds are those of the chemical formula wherein X is H, Na or K and R is a C8-C22 alkyl group.
  • More preferred compounds are those wherein R is a C13 and/or C14 alkyl or a C18-alkyl group, such as those known under the trade name DOBANAX-320, DOBANAX-313 and DOBANAX-205.
  • dialkyl benzene sulphonates of the chemical structure wherein X is an alkali metal and R1 and R2 are the same or different C2-C20-alkyl groups, preferably C6-C14-alkyl groups.
  • the alkyl aryl sulphonates are added in quantities from 0.1 per cent to 3 per cent by weight, calculated on the weight of the water present in the fluid.
  • a preferred range is from 0.2 to 1 percent, more preferred in the range of from 0.3 to 0.6 per cent.
  • the cell was made of stainless steel and had a cooling jacket to allow a good and easy temperature control of the cell. Two sapphire windows allowed visual observation of the cell content.
  • the cell was provided with two valves one for the introduction of liquid and one for gas.
  • a stirring bar cared for good mixing of the cell content.
  • the inner volume of the cell was 66.4 ml and dead volumes were reduced to a minimum.
  • the cell was further tested together with its loading system at a pressure of 100 bar over a period of 80 hours without any pressure drop being observed. The cell usually worked at a pressure of below 30 bar.
  • the cell was located in a plexiglass cage.
  • a personal computer based data acquisition system allowed the measurement of the temperature and pressure inside the cell once per minute.
  • a steel well went deeply inside the cell in which a platinum resistance thermometer was introduced.
  • On the cell was mounted a pressure transducer, with a very small temperature hysteresis and a high accuracy.
  • the cell was rinsed with demineralized water, rinsed with ethanol and vacuum dried, all without dismounting the cell.
  • demineralized water and decane were introduced as liquid into the cell.
  • the water contained 0.5% per cent by weight of alkyl aryl sulphonic acid or salt thereof, if desired.
  • Ethane was introduced as a gas into the cell.
  • the run started at 20 °C and the temperature in the cell was dropped, via the jacket connected to the thermostatic bath by lowering its temperature.
  • the amounts of water, decane and ethane were 25, 5.8 and 4.7 grams respectively.
  • the pressure was 25 bar at 20 °C, and no ethane hydrates were formed.
  • thermometer sent a digital signal, the pressure meter an analog signal, to the computer.
  • the computer could also send a set point command to the thermostatic bath.
  • the temperature and the pressure of the cell were recorded, together with the time, at every minute.
  • a temperature-time and a pressure-time curve could be made.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (9)

  1. Une méthode pour empêcher ou retarder la formation d'hydrates ou pour réduire la tendance d'hydrates à s'agglomérer dans un courant d'un fluide comprenant de l'eau et des hydrocarbures durant le transport du fluide par une canalisation, cette méthode comprenant l'addition au fluide d'un acide alcoyl aryl sulfonique ou d'un sel de métal alcalin ou d'ammonium d'un tel acide en l'absence de glycol dans le courant.
  2. Une méthode selon la revendication 1, dans laquelle le fluide comprend un ou plusieurs hydrocarbures choisis dans le groupe constitué par le méthane, l'éthane, le propane, l'isopropane, le butane et l'isobutane.
  3. Une méthode selon la revendication 1 ou 2, dans laquelle le fluide comprend du gaz naturel.
  4. Une méthode selon une ou plusieurs des revendications 1-3, dans laquelle on ajoute au fluide un acide C₈-C₂₂-alcoyl aryl sulfonique ou un sel de métal alcalin ou d'ammonium d'un tel acide.
  5. Une méthode selon la revendication 4, dans laquelle on utilise un composé de la structure chimique
    Figure imgb0007
     où X est H, Na ou K et R est un groupe alcoyle en C₈-C₂₂.
  6. Une méthode selon la revendication 1, dans laquelle on utilise un composé de la structure chimique
    Figure imgb0008
     où X est un métal alcalin et R₁ et R₂ sont des groupes alcoyle en C₂₋₂₀ identiques ou différents, de préférence des groupes alcoyle en C₆-C₁₄.
  7. Une méthode selon une ou plusieurs des revendications 1-6, dans laquelle la quantité d'alcoyl aryl sulfonate est comprise entre 0,1 pour cent et 3 pour cent en poids, par rapport au poids de l'eau présente dans le fluide.
  8. Une méthode selon la revendication 7, dans laquelle la quantité d'alcoyl aryl sulfonate est comprise entre 0,2 et 1 pour cent.
  9. Une méthode selon une ou plusieurs des revendications 1-8, caractérisée par l'absence d'un glycol.
EP91200272A 1990-02-16 1991-02-08 Méthode d'empêchement d'hydrates Expired - Lifetime EP0457375B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9003617 1990-02-16
GB909003617A GB9003617D0 (en) 1990-02-16 1990-02-16 A method for preventing hydrates

Publications (2)

Publication Number Publication Date
EP0457375A1 EP0457375A1 (fr) 1991-11-21
EP0457375B1 true EP0457375B1 (fr) 1993-07-28

Family

ID=10671171

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91200272A Expired - Lifetime EP0457375B1 (fr) 1990-02-16 1991-02-08 Méthode d'empêchement d'hydrates

Country Status (7)

Country Link
EP (1) EP0457375B1 (fr)
CA (1) CA2036084A1 (fr)
DE (1) DE69100197T2 (fr)
DK (1) DK0457375T3 (fr)
GB (1) GB9003617D0 (fr)
NO (1) NO180783C (fr)
NZ (1) NZ237020A (fr)

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2110730T3 (es) * 1992-07-06 1998-02-16 Eniricerche Spa Procedimiento para la recuperacion de petroleo de alta viscosidad y provocar el flujo de este.
US5432292A (en) * 1992-11-20 1995-07-11 Colorado School Of Mines Method for controlling clathrate hydrates in fluid systems
US5420370A (en) * 1992-11-20 1995-05-30 Colorado School Of Mines Method for controlling clathrate hydrates in fluid systems
US5600044A (en) * 1994-09-15 1997-02-04 Exxon Production Research Company Method for inhibiting hydrate formation
US6015929A (en) * 1994-09-15 2000-01-18 Exxon Research And Engineering Co. Gas hydrate anti-agglomerates
US5491269A (en) * 1994-09-15 1996-02-13 Exxon Production Research Company Method for inhibiting hydrate formation
USH1749H (en) * 1994-09-15 1998-09-01 Exxon Production Research Company Method for inhibiting hydrate formation
US5583273A (en) * 1994-09-15 1996-12-10 Exxon Production Research Company Method for inhibiting hydrate formation
US5841010A (en) * 1994-09-15 1998-11-24 Exxon Production Research Company Surface active agents as gas hydrate inhibitors
US5744665A (en) * 1995-06-08 1998-04-28 Exxon Production Research Company Maleimide copolymers and method for inhibiting hydrate formation
US5936040A (en) * 1995-06-08 1999-08-10 Exxon Production Research Company Method for inhibiting hydrate formation using maleimide copolymers
US6194622B1 (en) 1998-06-10 2001-02-27 Exxonmobil Upstream Research Company Method for inhibiting hydrate formation
US6359047B1 (en) 2001-03-20 2002-03-19 Isp Investments Inc. Gas hydrate inhibitor
NO316295B1 (no) 2002-05-07 2004-01-05 Agr Group As Fremgangsmåte og anordning for fjerning av en hydratplugg
WO2005005567A1 (fr) 2003-07-02 2005-01-20 Exxonmobil Upstream Research Company Procede d'inhibition de formation d'hydrates
FR2879189B1 (fr) * 2004-12-13 2007-03-30 Inst Francais Du Petrole Methode pour transporter des hydrates en suspension dans des effluents de production utilisant un additif non-polluant
CA2645486A1 (fr) 2006-03-15 2007-08-23 Exxonmobil Upstream Research Company Procede de production d'une boue hydratee non obstruante
WO2007111789A2 (fr) 2006-03-24 2007-10-04 Exxonmobil Upstream Research Company Composition et procédé de production d'une boue d'hydrates d'hydrocarbures pompable avec une forte proportion d'eau
US8430169B2 (en) 2007-09-25 2013-04-30 Exxonmobil Upstream Research Company Method for managing hydrates in subsea production line
US9988568B2 (en) 2015-01-30 2018-06-05 Ecolab Usa Inc. Use of anti-agglomerants in high gas to oil ratio formations
EP3071785A1 (fr) 2015-02-16 2016-09-28 Osman Zühtü GÖKSEL Système et procédé d'exploitation de gaz issu de formations d'hydrate de gaz
FR3092331A1 (fr) 2019-02-06 2020-08-07 Arkema France Composition pour prévenir l'agglomération d'hydrates de gaz

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU697696A1 (ru) * 1977-12-01 1979-11-15 Всесоюзный Научно-Исследовательский И Проектный Институт По Подготовке К Транспортировке И Переработки Природного Газа Состав дл предотвращени парафиногидратных отложений
JPS5935960B2 (ja) * 1982-02-25 1984-08-31 株式会社 柏化学工業 配管類の洗浄剤
FR2625548B1 (fr) * 1987-12-30 1990-06-22 Inst Francais Du Petrole Procede pour retarder la formation et/ou reduire la tendance a l'agglomeration des hydrates

Also Published As

Publication number Publication date
EP0457375A1 (fr) 1991-11-21
NO180783B (no) 1997-03-10
GB9003617D0 (en) 1990-04-11
NO180783C (no) 1997-06-18
NO910619L (no) 1991-08-19
NZ237020A (en) 1992-11-25
CA2036084A1 (fr) 1991-08-17
DE69100197D1 (de) 1993-09-02
NO910619D0 (no) 1991-02-15
DK0457375T3 (da) 1993-12-27
DE69100197T2 (de) 1993-12-02

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