WO2002062874A1 - Gel d'isolation thermique a reticulation controlee pour les lignes de transport d'hydrocarbures petroliers - Google Patents
Gel d'isolation thermique a reticulation controlee pour les lignes de transport d'hydrocarbures petroliers Download PDFInfo
- Publication number
- WO2002062874A1 WO2002062874A1 PCT/FR2002/000406 FR0200406W WO02062874A1 WO 2002062874 A1 WO2002062874 A1 WO 2002062874A1 FR 0200406 W FR0200406 W FR 0200406W WO 02062874 A1 WO02062874 A1 WO 02062874A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymers
- product according
- reaction
- monomers
- crosslinking
- Prior art date
Links
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L59/00—Thermal insulation in general
- F16L59/14—Arrangements for the insulation of pipes or pipe systems
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
- B01J13/0065—Preparation of gels containing an organic phase
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
Definitions
- the present invention relates to the technical sector of thermal insulation of petroleum transport lines whose operating conditions from production wells are at a temperature of the order of 60 to 120 ° C and at a pressure of around 300 bars. ; the crude oil is then liquid and pumpable. Pressure and temperature drop continuously along these lines and the major drawback is the bulk of the crude oil.
- the production well In operation at sea, the production well has a production head which rests on the seabed.
- the crude oil must then be reassembled to petroleum vessels, storage barges, or storage and / or pumping platforms, by means of complex systems of risers, pipelines, and the like, below lines or "flowlines".
- Point 1 extremely complex to implement 3 ° US 5871034 and 60092557 (G.R. Summer 1999 and 2000): Mixture of bitumens with thermoplastic polymers and mineral fillers. Disadvantages: Point 1) and soft product under high pressure and high temperature.
- gels are currently the most advantageous technique because of its cost, its flexibility in the choice of materials, its ease of implementation. They essentially consist of a base and a thickener:
- base a base is chosen which is the most thermal insulating possible, in general petroleum or chemical products or derivatives of glycol
- the present invention relates to and uses, in order to prevent the crude oil from "freezing" in a "line", a thermally insulating gel with controlled crosslinking, that is to say relatively fluid at the outset and not developing gelification in located in the pipes only under certain conditions, temperature among others.
- the gels obtained are mechanically and thermally stable, at high and low temperatures, and especially in very few bases, such as pure linear paraffins, pure isoparaffins, etc. and also especially with bases of the same type exhibiting phase changes. such as crystallization.
- - vegetable oils such as rapeseed, sunflower, soybean, palm oil, etc. extracted from seeds, plants, bark, fruits
- - Synthetic bases such as polyalphaolefins (PAO), polyisobutylenes (PIB), polyalkylene glycols (PAG), "polyinternal olefins” (PIO), fatty esters, fatty alcohols, fatty ethers ...
- phase change bases form with conventional thickeners often loose gels, unstable when subjected to thermal cycles.
- block polymers di or triblock or star-shaped (radial) Any block polymer di or triblock or star-shaped (radial). This type of structure is found to be very particular, mainly by means of ionic polymerization (anionic or cationic).
- anionic or cationic A non-limiting example is the range of products known commercially as KRATON® and marketed by Shell TM. These products are distinguished by:
- the mechanical properties of the gel depend on the nature of the base used, the grade of Kraton TM used, the percentage. Depending on the desired application, there is a very “firm”, rubbery gel, extremely resistant and stable to thermal or mechanical stresses or a very “loose” gel, at the limit of flow, reversible, thixotropic and pseudoplastic.
- these physical gelling agents are advantageously combined with standard thickeners such as polyisoprene, polybutadière, natural rubber, polyisobutylene, ethylene-propylene copolymers, etc.
- the crosslinking nodes of which are phase segregation zones the KRATON® range of products from Shell TM, etc. have preferably been mentioned, without limitation.
- the bases preferably used in the examples which follow, without being limiting, as described above are: a rapeseed methyl ester, a linear paraffin (Linpar C 10 ®), "light” cut and “heavy” cut ( Linpar C16 - C18 ®), an iso paraffin (Isopar TM M), a standard diesel (diesel), “white spirit” etc.
- a composition is prepared under the conditions in the examples which will follow in a glass flask provided with a metal screw lid to obtain a gel or not.
- composition is fluid at the observation temperature if it sinks when the bottle is tilted (or inverted 180 °). Otherwise, we have a gel.
- the gelation time is the time necessary for a composition in the fluid state to pass to the gel state at the temperature of the experiment.
- Cycle 1 10h at 80 ° C / 2h at 20 ° C / 10h at 80 ° CV 14h at 20 ° C
- the gel must remain firm (no loss of mechanical properties) and must not "release" the base, that is to say existence of 2 phases, a liquid phase and a gel phase. This phenomenon is known as syneresis or penetrant testing.
- thermoplastic polymers have their applications as additives in adhesives, bitumens, blends of thermoplastics, sealants, elastomers, etc.
- the Kraton® as described above may be more or less suitable depending on the specificity of each need and the bases used.
- the following examples will illustrate these remarks, without limitation:
- mineral fillers such as clays, bentonite, baryte, calcium carbonates, and there will be mentioned very particularly as an agent lightening the use of glass microbeads, such as those marketed by the company 3M TM, which are micro beads with dimensions from 10 to 150 microns approximately, with an average dimension around 30 microns, and a double function of lightening the product and improving thermal insulation.
- Gelling agent Kraton G 1651 E vs. bentone (Thixogel® VP)
- Test temperature Cycles 1 and 2 The percentages in all the examples which follow are by mass of active material.
- Table 2 Manufacturing and implementation of products.
- the example shows the simplicity and flexibility of the implementation of a physical gel with in-situ crosslinking and with controlled triggering, for example at temperature.
- EX 3 Product packaging process if the implementation is not direct.
- EX 4 Effect of the base, the temperature, the nature and the concentration of the physical gelling agent: comparative tests with conventional polymeric thickeners.
- Table 3 Conditions for forming a gel stable at 20 or 80 ° C.
- these polymers are in the form of di or triblocks or in the shape of a star, preferably in the form of triblocks having ethylene - propylene or butadiene or isoprene blocks, preferably ethylene - propylene with styrene blocks with a styrene composition ranging from 10 to 40%, preferably from 20 to 35%, having molecular weights by weight characterized in the manufacturer's technical sheets by high, medium and low, preferably high molecular weight by weight.
- the percentage of use of these physical gelling agents depends on the bases used but, in general, varies from 1 to 30%, preferably from 2 to 20%.
- Table 5 properties of gels (1) The thermal conductivity is measured at different angles of rotation; if it is the same everywhere, there is no convection.
- Example 7 Examples of thixotropic physical gel based on associative polymers a) White spirit base: - Lixol TM alkyd resin 27%
- example "a” is replaced by the methyl ester of rapeseed.
- the gels are stable to thermal cycles and over time.
- compositions of these physical gels based on associative polymers are between 10 - 40% of alkyd resin, preferably approx. 35%, with possibly a polar solvent derived from glycol between 0.5 to 10%, preferably 1 to 3%, the rest being constituted by the base.
- the temperature and / or stirring is used to completely dissolve the macromolecular chains: the reaction begins.
- the gelation (solidification) is more or less rapid and is done over time by physical bonds or segregation phases.
- a "loose" physical gel, reversible mechanically that is to say pseudoplastic and thixotropic (fluid by shear) and becoming thermally fluid (fluid by increase in temperature).
- the starting mixture is a mixture of reactive monomers which, under the effect or not of radical initiators or not, will trigger the polymerization (or polyaddition) or crosslinking reaction (polyfunctional monomers) in the presence or not of catalysts, under well-defined temperature and stirring conditions.
- the starting mixture is a mixture of polymers having reactive functions which will react with each other or by means of a mono or polyfunctional monomer.
- the latter plays the same role of crosslinking agent as the first case.
- this reaction can start with radical initiators or not, in the presence or absence of catalysts and under well-defined temperature and stirring conditions.
- radical crosslinking the monomers have an unsaturated bond (double bond) which under the effect of an initiator radical will start the reaction.
- monomers one can think of the monomers of alkyl methacrylates or alkyl acrylates, vinyl esters, vinyl chlorides etc., as polyfunctional monomers, for example a divinylbenzene or a neopentylglycol dimethacrylate; peroxides (for example, benzoyl peroxide) or diazo compounds (for example AIBN: 2,2 'azobisisobutyronitrile, etc.) can be used as radical initiator.
- peroxides for example, benzoyl peroxide
- diazo compounds for example AIBN: 2,2 'azobisisobutyronitrile, etc.
- polyurethanes polyols reacting with polyisocyanates
- polyureas polyamines reacting with polyisocyanates
- polyesters polyacids with polyalcohols
- polyamides polyamines with polyacids
- thermosetting resins such as epoxy resin, polyimides, etc.
- the reactive monomers as well as the compounds necessary for the reaction are mixed in the chosen base and the crosslinking polymerization reaction is generally triggered by a rise in temperature.
- the gel setting time must be controlled according to the implementation process.
- polymers soluble in the chosen base having reaction functions or double bonds capable of crosslinking the polymers with one another.
- initiators of the peroxide type for example benzoyl peroxide ... etc ... or nitrogen, for example 2, 2'azobisisobutyronitrile ... with or without difunctional monomers of the type divinylbenzene or neopentylglycol dimethacrylate may be suitable.
- the gel setting time must be controlled according to the needs of the implementation process.
- composition gives a firm chemical gel after approximately 4 hours at 80 ° C.
- the freezing of the system starts either very gradually over time or is triggered by an external factor (temperature, energy supply)
- the gel is perfectly thermally stable from 0 ° C to 100 ° C, resistant to biological pollution, and is stable over time.
- the gel is perfectly compact, flexible and resistant to pressure.
- the gel always remains stable to thermal cycles between 0 and 100 ° C
- the models consist of a steel hub (M) 27mm in diameter and 50cm in length (L »d to limit side effects) filled with oil kept at constant temperature by a heating tape supplied with direct current.
- This steel tube is slid into a Plexiglas TM tube (1) with a diameter of 100mm and held in place with insulating centralizing plugs (2) made of polystyrene.
- the cavity (3) thus formed is filled with INSULATING GEL of the as homogeneous as possible.
- heating resistors (4) In the center are heating resistors (4).
- the assembly is immersed in a container of water maintained at 30 ° C by an immersion heater.
- thermocouples The models are instrumented with 6 T thermocouples:
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/466,936 US6933341B2 (en) | 2001-02-07 | 2002-02-04 | Thermal insulation gel with controlled crosslinking for petroleum hydrocarbon transmission lines |
BR0207028-6A BR0207028A (pt) | 2001-02-07 | 2002-02-04 | Gel de isolamento térmico com reticulação controlada para as linhas de transporte de hidrocarbonetos petrolìferos |
MXPA03007040A MXPA03007040A (es) | 2001-02-07 | 2002-02-04 | Gel de aislamiento termico de reticulacion controlada para lineas de transportacion de hicrocarburos de petroleo. |
EP02701390A EP1368414A1 (fr) | 2001-02-07 | 2002-02-04 | Gel d'isolation thermique a reticulation controlee pour les lignes de transport d'hydrocarbures petroliers |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0101892A FR2820426B1 (fr) | 2001-02-07 | 2001-02-07 | Gel d'isolation thermique a reticulation controlee pour les lignes de transport d'hydrocarbures petroliers |
FR01/01892 | 2001-02-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002062874A1 true WO2002062874A1 (fr) | 2002-08-15 |
Family
ID=8859916
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2002/000406 WO2002062874A1 (fr) | 2001-02-07 | 2002-02-04 | Gel d'isolation thermique a reticulation controlee pour les lignes de transport d'hydrocarbures petroliers |
Country Status (8)
Country | Link |
---|---|
US (1) | US6933341B2 (fr) |
EP (1) | EP1368414A1 (fr) |
CN (1) | CN1496383A (fr) |
BR (1) | BR0207028A (fr) |
FR (1) | FR2820426B1 (fr) |
MX (1) | MXPA03007040A (fr) |
OA (1) | OA13298A (fr) |
WO (1) | WO2002062874A1 (fr) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006512349A (ja) * | 2002-12-23 | 2006-04-13 | ジヤンセン・フアーマシユーチカ・ナームローゼ・フエンノートシヤツプ | 置換1−ピペリジン−4−イル−4−アゼチジン−3−イル−ピペラジン誘導体およびそれらのニューロキニン拮抗薬としての使用 |
JP2006512350A (ja) * | 2002-12-23 | 2006-04-13 | ジヤンセン・フアーマシユーチカ・ナームローゼ・フエンノートシヤツプ | 置換4−(4−ピペリジン−4−イル−ピペラジン−1−イル)−アゼパン誘導体およびそれらのニューロキニン拮抗薬としての使用 |
JP2006514027A (ja) * | 2002-12-23 | 2006-04-27 | ジヤンセン・フアーマシユーチカ・ナームローゼ・フエンノートシヤツプ | 置換1−ピペリジン−4−イル−4−ピロリジン−3−イル−ピペラジン誘導体およびそれらのニューロキニン拮抗薬としての使用 |
EP2365023A1 (fr) | 2010-03-10 | 2011-09-14 | IFP Energies nouvelles | Composition et méthode de gélification d'un matériau à changement de phase |
US8030389B2 (en) | 2006-09-12 | 2011-10-04 | Baker Hughes Incorporated | Thermal insulation composition |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB0312781D0 (en) * | 2003-06-04 | 2003-07-09 | Ythan Environmental Services L | Method |
US7713917B2 (en) * | 2006-05-08 | 2010-05-11 | Bj Services Company | Thermal insulation compositions containing organic solvent and gelling agent and methods of using the same |
DE602007008744D1 (de) * | 2006-09-11 | 2010-10-07 | Dsm Ip Assets Bv | Wärmeisolierendes material |
FR2917746B1 (fr) * | 2007-06-19 | 2010-11-26 | Total France | Utilisation d'une composition fluide a reticulation retardee pour le maintien d'un tubage a l'interieur d'un puits de forage et procede de consolidation d'un puits de forage |
MX364304B (es) | 2008-02-29 | 2019-04-22 | Texas United Chemical Company Llc | Métodos, sistemas y composiciones para el entrelazamiento controlado de fluidos de servicio de pozos. |
FR2937706B1 (fr) | 2008-10-29 | 2013-02-22 | Saipem Sa | Ensemble de conduites coaxiales comprenant un manchon d'isolation thermique |
FR2939178B1 (fr) | 2008-12-03 | 2013-05-03 | Saipem Sa | Conduite sous-marine de jonction comprenant une isolation thermique. |
FR2973473B1 (fr) | 2011-03-29 | 2014-06-13 | Saipem Sa | Materiau d'isolation thermique et/ou de flottabilite rigide pour conduite sous-marine |
US9598622B2 (en) * | 2012-09-25 | 2017-03-21 | Cold Chain Technologies, Inc. | Gel comprising a phase-change material, method of preparing the gel, thermal exchange implement comprising the gel, and method of preparing the thermal exchange implement |
EP3122335B1 (fr) * | 2014-03-26 | 2022-02-16 | Cold Chain Technologies, LLC | Procédé de préparation d'un gelcomprenant un matériau à changement de phase |
EP3544029B1 (fr) * | 2018-03-19 | 2020-10-14 | ABB Power Grids Switzerland AG | Douille imprégnée de gel |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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GB1523958A (en) * | 1977-06-21 | 1978-09-06 | Secr Defence | Slurry explosives |
FR2405345A1 (fr) * | 1977-05-09 | 1979-05-04 | Jackson Peter | Bassin de stockage de chaleur et generateur d'energie utilisant un tel bassin |
US4709982A (en) * | 1984-11-27 | 1987-12-01 | Bicc Public Limited Company | Gelled oil filling compounds |
US4941773A (en) * | 1988-04-07 | 1990-07-17 | Smit Offshore Contractors Bv | Method for thermal insulation of pipeline bundles under water and pipelines insulated in this way |
US5177143A (en) * | 1984-08-31 | 1993-01-05 | Raychem Corporation | Method of making heat stable polymeric gelloid composition |
US5221534A (en) * | 1989-04-26 | 1993-06-22 | Pennzoil Products Company | Health and beauty aid compositions |
-
2001
- 2001-02-07 FR FR0101892A patent/FR2820426B1/fr not_active Expired - Fee Related
-
2002
- 2002-02-04 CN CNA028045432A patent/CN1496383A/zh active Pending
- 2002-02-04 MX MXPA03007040A patent/MXPA03007040A/es active IP Right Grant
- 2002-02-04 EP EP02701390A patent/EP1368414A1/fr not_active Withdrawn
- 2002-02-04 WO PCT/FR2002/000406 patent/WO2002062874A1/fr not_active Application Discontinuation
- 2002-02-04 OA OA1200300197A patent/OA13298A/fr unknown
- 2002-02-04 BR BR0207028-6A patent/BR0207028A/pt not_active IP Right Cessation
- 2002-02-04 US US10/466,936 patent/US6933341B2/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2405345A1 (fr) * | 1977-05-09 | 1979-05-04 | Jackson Peter | Bassin de stockage de chaleur et generateur d'energie utilisant un tel bassin |
GB1523958A (en) * | 1977-06-21 | 1978-09-06 | Secr Defence | Slurry explosives |
US5177143A (en) * | 1984-08-31 | 1993-01-05 | Raychem Corporation | Method of making heat stable polymeric gelloid composition |
US4709982A (en) * | 1984-11-27 | 1987-12-01 | Bicc Public Limited Company | Gelled oil filling compounds |
US4941773A (en) * | 1988-04-07 | 1990-07-17 | Smit Offshore Contractors Bv | Method for thermal insulation of pipeline bundles under water and pipelines insulated in this way |
US5221534A (en) * | 1989-04-26 | 1993-06-22 | Pennzoil Products Company | Health and beauty aid compositions |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006512349A (ja) * | 2002-12-23 | 2006-04-13 | ジヤンセン・フアーマシユーチカ・ナームローゼ・フエンノートシヤツプ | 置換1−ピペリジン−4−イル−4−アゼチジン−3−イル−ピペラジン誘導体およびそれらのニューロキニン拮抗薬としての使用 |
JP2006512350A (ja) * | 2002-12-23 | 2006-04-13 | ジヤンセン・フアーマシユーチカ・ナームローゼ・フエンノートシヤツプ | 置換4−(4−ピペリジン−4−イル−ピペラジン−1−イル)−アゼパン誘導体およびそれらのニューロキニン拮抗薬としての使用 |
JP2006514027A (ja) * | 2002-12-23 | 2006-04-27 | ジヤンセン・フアーマシユーチカ・ナームローゼ・フエンノートシヤツプ | 置換1−ピペリジン−4−イル−4−ピロリジン−3−イル−ピペラジン誘導体およびそれらのニューロキニン拮抗薬としての使用 |
JP4660199B2 (ja) * | 2002-12-23 | 2011-03-30 | ジヤンセン・フアーマシユーチカ・ナームローゼ・フエンノートシヤツプ | 置換1−ピペリジン−4−イル−4−アゼチジン−3−イル−ピペラジン誘導体およびそれらのニューロキニン拮抗薬としての使用 |
JP4746878B2 (ja) * | 2002-12-23 | 2011-08-10 | ジヤンセン・フアーマシユーチカ・ナームローゼ・フエンノートシヤツプ | 置換1−ピペリジン−4−イル−4−ピロリジン−3−イル−ピペラジン誘導体およびそれらのニューロキニン拮抗薬としての使用 |
US8030389B2 (en) | 2006-09-12 | 2011-10-04 | Baker Hughes Incorporated | Thermal insulation composition |
EP2365023A1 (fr) | 2010-03-10 | 2011-09-14 | IFP Energies nouvelles | Composition et méthode de gélification d'un matériau à changement de phase |
Also Published As
Publication number | Publication date |
---|---|
FR2820426B1 (fr) | 2007-05-11 |
MXPA03007040A (es) | 2004-01-15 |
BR0207028A (pt) | 2004-02-17 |
US20050075437A1 (en) | 2005-04-07 |
US6933341B2 (en) | 2005-08-23 |
CN1496383A (zh) | 2004-05-12 |
EP1368414A1 (fr) | 2003-12-10 |
FR2820426A1 (fr) | 2002-08-09 |
OA13298A (fr) | 2007-04-13 |
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