WO1993025798A1 - Procede d'inhibition de la formation d'hydrates de gaz - Google Patents

Procede d'inhibition de la formation d'hydrates de gaz Download PDF

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Publication number
WO1993025798A1
WO1993025798A1 PCT/EP1993/001519 EP9301519W WO9325798A1 WO 1993025798 A1 WO1993025798 A1 WO 1993025798A1 EP 9301519 W EP9301519 W EP 9301519W WO 9325798 A1 WO9325798 A1 WO 9325798A1
Authority
WO
WIPO (PCT)
Prior art keywords
vinyl
pvp
additive
pyrrolidone
water
Prior art date
Application number
PCT/EP1993/001519
Other languages
English (en)
Inventor
Mark Joseph Anselme
Marinus Johannes Reijnhout
Herman Mathieu Muijs
Ulfert Cornelis Klomp
Original Assignee
Shell Internationale Research Maatschappij B.V.
Shell Canada Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij B.V., Shell Canada Limited filed Critical Shell Internationale Research Maatschappij B.V.
Priority to AU43259/93A priority Critical patent/AU675227B2/en
Publication of WO1993025798A1 publication Critical patent/WO1993025798A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/20—Use of additives, e.g. for stabilisation
    • 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
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/003—Additives for gaseous fuels
    • 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

Definitions

  • This invention relates to a process for inhibiting the formation of gas hydrates in systems containing low-boiling hydrocarbons and water.
  • Low-boiling hydrocarbons such as methane, ethane, propane, butane and iso-butane
  • water is also present in varying amounts, the mixture of low-boiling hydrocarbons and water (such as present in natural gas), under conditions of elevated pressure and reduced temperature, tends to form hydrate crystals (gas hydrate crystals).
  • thermodynamic measures are possible in principle: removal of free water, maintaining elevated temperatures and/or reduced pressures or the addition of melting point depressants
  • antifreeze In practice, in most cases the last-mentioned measure is applied. However, the antifreezes, such as the lower alcohols and glycols, have to be added in substantial amounts (of the order of 30 per cent by weight of the water present) to be effective. An additional disadvantage of such amounts is that recovery of the added antifreezes is usually required during further processing of the mixture.
  • Plants and poikilothermic animals such as insects and cold-water fish are known to protect themselves from freezing, both by antifreezes such as glycols and by special peptides and glycopeptides (termed Antifreeze Proteins, AFP's and Antifreeze Glycoproteins, AFGP's) which interfere with ice crystal growth (A.L. de Vries, Comp. Biochem. Physiol. 73 1982 627).
  • antifreezes such as glycols and by special peptides and glycopeptides (termed Antifreeze Proteins, AFP's and Antifreeze Glycoproteins, AFGP's) which interfere with ice crystal growth (A.L. de Vries, Comp. Biochem. Physiol. 73 1982 627).
  • the present applicants found such cold-water fish peptides and glycopeptides also to be effective in interfering with the growth of gas-hydrate crystals. However, their production and use for this purpose are currently considered to be uneconomical.
  • Polyvinyl pyrrolidone is a well-known water-soluble polymer, currently used in particular in pharmacy. PVP is known to interfere with the growth of different crystals, such as the crystal growth of several drugs in aqueous suspension (K.H. Zillerand H.H. Ruppert, Pharm. Ind. 52 1990 1017), and also with the growth of ice crystals. However, in suppressing the growth of ice crystals PVP has been noted to be much less effective than the glycoproteins isolated from dialysed blood serum of the antarctic fish Notothenia neglecta (F. Frank et al. Nature 325 1987 146).
  • PVP polyethylene glycol
  • the invention therefore relates to a method for inhibiting the formation, growth and/or agglomeration of gas hydrate crystals in a mixture containing low-boiling hydrocarbons and water, characterized by adding to the mixture an effective amount of at least one additive selected from the group of polymers and copolymers of N-vinyl-2-pyrrolidone, and mixtures thereof.
  • a preferred group of additives according to the invention are the homopolymers of N-vinyl-2-pyrrolidone (PVP). These are available commercially, e.g. from BSA under the trade name K0LID0N, in average molecular weights ranging from about 5000 daltons (K12) or less to about 400000 daltons (K90) and more. In general the present inventors found the lower molecular weight PVP's, especially those of between 5000 and 40000 daltons, to be the more effective in inhibiting the formation of gas hydrate crystals.
  • PVP N-vinyl-2-pyrrolidone
  • copolymers for use as additives according to the invention which are available commercially, are the copolymers of N-vinyl-2-pyrrolidone with 1-butene, with 1-hexene, with 1-decene, with vinyl chloride, with vinyl acetate, with ethyl acrylate, with 2-ethylhexyl acrylate, and with styrene.
  • Copolymers of N-vinyl-2-pyrrolidone with mixtures of the above can also be used.
  • the copolymers for use according to the invention will contain at least 30 mol% of the N-vinyl-2-pyrrolidone component.
  • the amount of additive according to the invention is generally between 0.05 and 4 wt%, preferably between 0.25 and 1 wt%, based on the amount of water in the hydrocarbon-containing mixture.
  • the additives according to the invention can be added to the subject mixture of low-boiling hydrocarbons and water, as their dry powder or.preferably, in concentrated aqueous solution. While the polymers and copolymers according to the invention interfere effectively with the growth of hydrate crystals, it may be advantageous also to interfere with agglomeration of any remaining crystallites and with their adhesion to the wall of the conduit. For this purpose film-formers, which are known to prevent water-wetting of metal surfaces, can be added.
  • Typical examples of such film-formers are long-chain alkyl amines, alkyl diamines and imidazolines, optionally in combination with high molecular-weight organic acids.
  • film-formers are monovalent, but preferably divalent, salts of long-chain alkarylsulphonic acids. These are subject of the present applicant's EP-A-457375.
  • an aqueous solution of tetrahydrofurane (THF) was used as a model for wet gas, since tetrahydrofurane in water is known to form hydrate (structure II) crystals at about the same temperature as wet gas, but already at atmospheric pressure - for example, an 18.9 wt% aqueous solution of THF has a hydrate melting point of 4.3 ⁇ C at atmospheric pressure (S.R. Couch and D.W. Davidson, Can. J. Chem. 49 1971 2691).
  • field conditions were simulated in an experimental set-up as schematically shown in Figure 2, comprising a two-liter stirred high-pressure autoclave 11 connected via a gear pump 12 to a coiled copper pipeline 13 of 16 m length and 6 mm internal diameter which is immersed in a thermostatically controlled bath 14.
  • the pressure difference between the inlet and outlet of the pipeline is continuously monitored by a differential pressure transmitter 15.
  • the autoclave was loaded at 13 °C with 400 ml of demineralised water (in which additives could be dissolved and with 800 ml of Shellsol D60 (trade name) , a mixture of paraffinic and naphthenic hydrocarbons mainly in the C. _ - C. publish range.
  • the autoclave was loaded with ethane until the pressure (at 13 °C) within the autoclave was 20 bara.
  • the stirred mixture was circulated through the system at a rate of 6.1 liters/hour.
  • the temperature of the bath was lowered gradually, at a rate of 5 C C per hour.
  • a piece of dry ice solid C0 deliberately was continuously held against the inlet of the coiled pipeline.
  • the pressure drop over the coiled pipeline and the temperature of the bath were continuously monitored as a function of time.
  • the temperature at which the pressure drop between the inlet and outlet of the coiled pipeline exceeded 1 bar was considered to be the blocking temperature.
  • the hydrate- temperature of the mixture which is the temperature below which hydrates will form if no hydrate inhibitor is added, was approximately 10 C C, and the mixture was transported through the pipeline at a temperature of 1 C C.
  • PVP K17 was added to the mixture at the upstream side thereof. It was found that during a period of approximately 17 hours after start of transportation through the line no significant pressure drop occurred within the pipeline along the length thereof. Thereafter hydrate formation in the line caused a gradually increasing pressure drop, until complete blocking of the line at approximately 37 hours after start of transportation. If no PVP would have been added to the mixture, hydrate formation would have caused complete blocking of the line within a much shorter period.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Procédé d'inhibition de la formation, de la croissance et/ou de l'agglomération de cristaux d'hydrate de gaz dans un mélange contenant des hydrocarbures à faible point d'ébullition et de l'eau, caractérisé par l'addition audit mélange d'une quantité efficace d'au moins un additif sélectionné dans le groupe de polymères et de copolymères de N-vinyle-2-pyrrolidone, et de mélanges de ceux-ci. Un composé filmogène peut également être ajouté facultativement.
PCT/EP1993/001519 1992-06-11 1993-06-10 Procede d'inhibition de la formation d'hydrates de gaz WO1993025798A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU43259/93A AU675227B2 (en) 1992-06-11 1993-06-10 A method for inhibiting gas hydrate formation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP92201725.6 1992-06-11
EP92201725 1992-06-11

Publications (1)

Publication Number Publication Date
WO1993025798A1 true WO1993025798A1 (fr) 1993-12-23

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1993/001519 WO1993025798A1 (fr) 1992-06-11 1993-06-10 Procede d'inhibition de la formation d'hydrates de gaz

Country Status (2)

Country Link
AU (1) AU675227B2 (fr)
WO (1) WO1993025798A1 (fr)

Cited By (67)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994012761A1 (fr) * 1992-11-20 1994-06-09 Colorado School Of Mines Procede de regulation d'hydrates de clathrate dans des systemes a fluide
WO1994024413A1 (fr) * 1993-04-08 1994-10-27 Bp Chemicals Limited Procede d'inhibition de la formation de solides et melanges utilises dans ce procede
WO1994025727A1 (fr) * 1993-05-04 1994-11-10 Bp Exploration Operating Company Limited Inhibition de l'hydrate
WO1995019408A1 (fr) * 1994-01-13 1995-07-20 Bp Exploration Operating Company Limited Inhibition de formation d'hydrates
US5460728A (en) * 1993-12-21 1995-10-24 Shell Oil Company Method for inhibiting the plugging of conduits by gas hydrates
WO1995032356A1 (fr) * 1994-05-25 1995-11-30 Colorado School Of Mines Additifs et procede de regulation d'hydrates de clathrate dans des systemes a fluides
WO1996008672A1 (fr) * 1994-09-15 1996-03-21 Exxon Production Research Company Procede d'inhibition de la formation d'hydrates
WO1996008456A1 (fr) * 1994-09-15 1996-03-21 Exxon Production Reserch Company Procede empechant la formation d'hydrates
WO1996029501A1 (fr) * 1995-03-23 1996-09-26 Bp Exploration Operating Company Limited Inhibition d'hydrates
WO1996029502A1 (fr) * 1995-03-23 1996-09-26 Bp Exploration Operating Company Limited Inhibiteurs d'hydrates
WO1996034177A1 (fr) * 1995-04-25 1996-10-31 Shell Internationale Research Maatschappij B.V. Procede destine a empecher le bouchage de conduits par des hydrates de gaz
WO1996037684A1 (fr) * 1995-05-26 1996-11-28 Nippon Shokubai Co., Ltd. Inhibiteur d'hydrates de clathrate et procede permettant d'inhiber la formation des hydrates de clathrate dans lequel il est utilise
GB2301824A (en) * 1995-10-04 1996-12-18 Exxon Production Research Co Clathrate hydrate-inhibiting polymers
GB2301836A (en) * 1995-06-08 1996-12-18 Exxon Production Research Co Inhibiting Clathrate hydrate formation
WO1996041784A1 (fr) * 1995-06-08 1996-12-27 Exxon Production Research Company Procede visant a empecher la formation d'hydrates
WO1996041786A1 (fr) * 1995-06-08 1996-12-27 Exxon Production Research Company Procede permettant d'inhiber la formation d'hydrates
WO1997007320A1 (fr) * 1995-08-16 1997-02-27 Exxon Production Research Company Procede de selection d'un polymere destine a inhiber la formation d'hydrates
US5648575A (en) * 1995-01-10 1997-07-15 Shell Oil Company Method for inhibiting the plugging of conduits by gas hydrates
EP0812977A1 (fr) * 1996-06-14 1997-12-17 Institut Francais Du Petrole Méthode pour réduire la tendance à l'agglomération des hydrates dans les effluents de production contenant des huiles paraffiniques
US5741758A (en) * 1995-10-13 1998-04-21 Bj Services Company, U.S.A. Method for controlling gas hydrates in fluid mixtures
US5841010A (en) * 1994-09-15 1998-11-24 Exxon Production Research Company Surface active agents as gas hydrate inhibitors
AU707765B2 (en) * 1993-12-21 1999-07-22 Shell Internationale Research Maatschappij B.V. Method for inhibiting the plugging of conduits by gas hydrates
US5936040A (en) * 1995-06-08 1999-08-10 Exxon Production Research Company Method for inhibiting hydrate formation using maleimide copolymers
US6015929A (en) * 1994-09-15 2000-01-18 Exxon Research And Engineering Co. Gas hydrate anti-agglomerates
US6025302A (en) * 1998-05-18 2000-02-15 Bj Services Company Quaternized polyether amines as gas hydrate inhibitors
US6028233A (en) * 1995-06-08 2000-02-22 Exxon Production Research Company Method for inhibiting hydrate formation
US6107531A (en) * 1995-06-08 2000-08-22 Exxonmobil Upstream Research Company Method for inhibiting hydrate formation
US6152993A (en) * 1997-09-09 2000-11-28 Shell Oil Company Method for inhibiting the plugging of conduits by gas hydrates
US6194622B1 (en) 1998-06-10 2001-02-27 Exxonmobil Upstream Research Company Method for inhibiting hydrate formation
US6232273B1 (en) 1995-06-02 2001-05-15 Nippon Shokubai Co., Ltd. Clathrate hydrate inhibitor and method of inhibiting the formation of clathrate hydrates using it
US6319971B1 (en) 1997-05-22 2001-11-20 Rf-Procom A/S Composition for controlling clathrate hydrates and a method for controlling clathrate hydrate formation
DE10059816C1 (de) * 2000-12-01 2002-04-18 Clariant Gmbh Verwendung von Additiven zur Inhibierung der Gashydratbildung
DE10122613C1 (de) * 2001-04-11 2002-09-05 Clariant Gmbh Additive zur Inhibierung der Gashydratbildung
WO2002074722A1 (fr) 2001-03-20 2002-09-26 Isp Investments Inc. Inhibiteur d'hydrate de gaz
US6544932B2 (en) * 1996-11-22 2003-04-08 Clariant Gmbh Additives for inhibiting gas hydrate formation
US6596911B2 (en) * 2000-02-22 2003-07-22 Baker Hughes Incorporation Composition and method for inhibition of formation of gas hydrates
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DE10163260C1 (de) * 2001-12-21 2003-08-28 Kuraray Specialities Europe Additive, Verwendung und Verfahren zur Inhibierung der Gashydratbildung
WO2004042190A2 (fr) * 2002-11-06 2004-05-21 Basf Aktiengesellschaft Copolymerisats de vinyllactame comme inhibiteurs d'hydrates de gaz
US6905605B2 (en) 2000-04-07 2005-06-14 Shell Oil Company Method for inhibiting the plugging of conduits by gas hydrates
WO2005119004A1 (fr) * 2004-06-03 2005-12-15 Backer Hughes Incorporated Additifs pour l'inhibition de la formation d'hydrates dans des fluides gelifies par tensioactifs viscoelastiques
US7033504B1 (en) 1999-11-24 2006-04-25 Shell Oil Company Method for recovering water soluble surfactants
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US7264653B2 (en) 2003-10-21 2007-09-04 Champion Technologies, Inc. Methods for inhibiting hydrate blockage in oil and gas pipelines using simple quaternary ammonium and phosphonium compounds
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EP2022781A1 (fr) 2007-08-06 2009-02-11 Clariant International Ltd. Esters d'acide 1-alkyl-5-oxo-pyrrolidine-3-carboxylique ayant une biodégrabilité améliorée
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EP2031035A1 (fr) 2007-08-06 2009-03-04 Clariant International Ltd. Utilisation de polyethylenimines en tant qu'inhibiteurs d'hydrates de gaz ayant une biodégrabilité améliorée
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US7893009B2 (en) 2005-02-12 2011-02-22 Clariant Produkte (Deutschland) Gmbh Polymers and their production and use as gas hydrate inhibitors
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RU2481375C1 (ru) * 2011-12-08 2013-05-10 Открытое акционерное общество "Газпром" Ингибитор гидратообразования кинетического действия
US8735332B2 (en) 2005-11-12 2014-05-27 Clariant Produkte (Deutschland) Gmbh Use of pyroglutamic acid esters as gas hydrate inhibitors with improved biodegradability
WO2016180745A2 (fr) 2015-05-11 2016-11-17 Akzo Nobel Chemicals International B.V. Anti-agglomérants azotés servant à maintenir la fluidité de fluides contenant des hydrates de gaz
US9790104B2 (en) 2012-02-17 2017-10-17 Hydrafact Limited Water treatment
US10189986B2 (en) 2016-05-06 2019-01-29 Saudi Arabian Oil Company Acrylamide-based copolymers, terpolymers, and use as hydrate inhibitors
US10550215B2 (en) 2016-05-06 2020-02-04 Saudi Arabian Oil Company Acryloyl-based copolymers, terpolymers, and use as hydrate inhibitors
CN111116797A (zh) * 2019-12-24 2020-05-08 中国科学院广州能源研究所 一种新型的天然气水合物抑制剂
US11060042B2 (en) 2016-05-06 2021-07-13 Saudi Arabian Oil Company Succinimide-based copolymers and use as hydrate inhibitors
US11148124B2 (en) 2019-12-04 2021-10-19 Saudi Arabian Oil Company Hierarchical zeolite Y and nano-sized zeolite beta composite
US11225416B2 (en) 2019-11-26 2022-01-18 Saudi Arabian Oil Company Dry gel synthesis of nano-sized ZSM-5
US11247196B2 (en) 2019-12-04 2022-02-15 Saudi Arabian Oil Company Zeolite with encapsulated platinum
US11753492B2 (en) 2019-12-09 2023-09-12 Saudi Arabian Oil Company Acryloyl based polymers with active end cap as corrosion inhibitors

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Cited By (101)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5639925A (en) * 1992-11-20 1997-06-17 Colorado School Of Mines Additives and method for controlling clathrate hydrates in fluid systems
WO1994012761A1 (fr) * 1992-11-20 1994-06-09 Colorado School Of Mines Procede de regulation d'hydrates de clathrate dans des systemes a fluide
US5880319A (en) * 1992-11-20 1999-03-09 Colorado School Of Mines Method for controlling clathrate hydrates in fluid systems
WO1994024413A1 (fr) * 1993-04-08 1994-10-27 Bp Chemicals Limited Procede d'inhibition de la formation de solides et melanges utilises dans ce procede
WO1994025727A1 (fr) * 1993-05-04 1994-11-10 Bp Exploration Operating Company Limited Inhibition de l'hydrate
AU707765B2 (en) * 1993-12-21 1999-07-22 Shell Internationale Research Maatschappij B.V. Method for inhibiting the plugging of conduits by gas hydrates
US5460728A (en) * 1993-12-21 1995-10-24 Shell Oil Company Method for inhibiting the plugging of conduits by gas hydrates
WO1995019408A1 (fr) * 1994-01-13 1995-07-20 Bp Exploration Operating Company Limited Inhibition de formation d'hydrates
GB2307244B (en) * 1994-05-25 1998-12-30 Colorado School Of Mines Additives and method for controlling clathrate hydrates in fluid systems
GB2307244A (en) * 1994-05-25 1997-05-21 Colorado School Of Mines Additives and method for controlling clathrate hydrates in fluid systems
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