EP1290108A1 - Verfahren zur herstellung eines quasi-inkompressiblen phasenwechselmaterials mit geringer thermischer leitfähigkeit und produkt erhalten aus diesem verfahren - Google Patents

Verfahren zur herstellung eines quasi-inkompressiblen phasenwechselmaterials mit geringer thermischer leitfähigkeit und produkt erhalten aus diesem verfahren

Info

Publication number
EP1290108A1
EP1290108A1 EP01929691A EP01929691A EP1290108A1 EP 1290108 A1 EP1290108 A1 EP 1290108A1 EP 01929691 A EP01929691 A EP 01929691A EP 01929691 A EP01929691 A EP 01929691A EP 1290108 A1 EP1290108 A1 EP 1290108A1
Authority
EP
European Patent Office
Prior art keywords
phase change
pcm
change material
pipes
combination
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP01929691A
Other languages
English (en)
French (fr)
Inventor
Angèle CHOMARD
Jean-Claude Hipeaux
Jacques Jarrin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
IFP Energies Nouvelles IFPEN
Saipem SA
Original Assignee
IFP Energies Nouvelles IFPEN
Bouygues Offshore SA
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 IFP Energies Nouvelles IFPEN, Bouygues Offshore SA filed Critical IFP Energies Nouvelles IFPEN
Publication of EP1290108A1 publication Critical patent/EP1290108A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B17/00—Drilling rods or pipes; Flexible drill strings; Kellies; Drill collars; Sucker rods; Cables; Casings; Tubings
    • E21B17/01—Risers
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B36/00—Heating, cooling or insulating arrangements for boreholes or wells, e.g. for use in permafrost zones
    • E21B36/003—Insulating arrangements

Definitions

  • the present invention relates to a process for manufacturing a material based on phase change materials (PCM), quasi-incompressible and having a low thermal conductivity, products obtained by the process and applications.
  • PCM phase change materials
  • the material according to the invention can be used as thermal insulator in many fields, in particular for the thermal insulation of conduits or pipes where fluids which are susceptible to significant changes of state under the influence of temperature circulate: crystallization of paraffins, deposits hydrates, ice creams, etc.
  • the thermal insulation can be carried out by various methods. On land or in low immersion, porous cellular or woolly solid materials are used blocking the convection of gases with low thermal conductivity. The compressibility of these porous materials prohibits the use of this technique at a relatively high depth.
  • Another known technique consists in wrapping the pipe with a first layer of a porous material soaked in paraffin, for example, the thermal insulation coefficient of which is lower than those obtained with the gas trapping technique mentioned above, and d 'a second layer of refractory material enhancing the effect of the first layer.
  • a solution cannot be used in water.
  • Phase change materials behave like heat accumulators. They restore this energy during their solidification (crystallization) or absorb this energy during their fusion and this, in a reversible manner. These materials can therefore make it possible to increase the duration of production stoppages without risking clogging of the pipes by premature cooling of their contents.
  • phase change materials As known examples of phase change materials, mention may be made of chemical compounds of the family of alkanes C n H 2n + 2 such as for example paraffins (C 12 to C 60 ), which exhibit a good compromise between thermal properties and thermodynamics (melting temperature, latent heat of fusion, thermal conductivity, heat capacity) and cost. These compounds are thermally stable in the range of envisaged use temperatures and they are compatible with use in a marine environment because of their insolubility in water and their very low level of toxicity. They are therefore for example well suited to the thermal insulation of pipes for deep water. The temperature of change of state of these phase change materials is linked to the number of carbons in the hydrocarbon chain and is therefore adaptable to a particular application. To obtain a phase change around 30 ° C., it is possible for example to use a mixture of predominantly C 18 paraffins such as Limpar 18-20 sold by the company CONDEA Augusta SpA.
  • waxes normal paraffins, long chain isoparaffins (C 30 - C 40 ) very weakly branched (1 or 2 branches), branched long chain alkylcycloalkanes or branched long chain alkylaromatics also weakly branched, fatty alcohols or fatty acids can also be considered.
  • phase change materials are in the liquid phase and their viscosity is low.
  • a thickening agent such as silica to solidify them and prevent leaks.
  • Phase change materials also have the disadvantage that their viscous liquid state promotes thermal losses by convection.
  • the method according to the invention makes it possible to manufacture a material or product based on quasi-incompressible phase change materials (PCM) having a low thermal conductivity at a temperature above their melting temperature Tf.
  • PCM quasi-incompressible phase change materials
  • It comprises the combination, with a phase change material, of a thickening agent chosen to very greatly reduce the thermal convection at a temperature higher than the melting temperature of the phase change material.
  • the method comprises the combination of a thickening agent dispersed in the phase change material.
  • the method comprises the combination of a thickening agent forming with the phase change material a gelled structure.
  • the product based on phase change materials (PCM) having a low thermal conductivity comprises in combination a thickening agent chosen to very strongly reduce thermal convection at a temperature higher than the melting temperature of the change material. phase.
  • the product comprises in combination a phase change material (PCM) and at least one metallic soap, this combination being obtained by the action of bases on fatty acids or fatty substances.
  • PCM phase change material
  • the product comprises in combination a phase change material (PCM) and complex soaps of aluminum, calcium or lithium obtained by in situ neutralization of asymmetric acids.
  • PCM phase change material
  • the product comprises in combination a phase change material (PCM) and at least one inorganic thickener (graphite, hydrophobic silica gel, silico-aluminates rendered oleophilic, etc.).
  • the product comprises in combination at least one organic or organometallic thickener of the aromatic polyurea type or colored pigments, dispersed in a phase change material (PCM).
  • the product may optionally include antioxidants or antibacterial agents, corrosion inhibitors or an insoluble filler intended to adjust its density or thermal conductivity, additives intended to improve its stability or a solvent intended to control viscosity.
  • the product according to the invention finds applications for thermal insulation in general. It can be applied in particular for the thermal insulation of hydrocarbon transport pipes, where it is used as a direct or interposed (injected) coating between the pipes and an external protective envelope.
  • the manufacturing process as we have seen, consists in dispersing, in a phase change material (hereinafter PCM), an insoluble thickening or gelling agent chosen to reduce both the viscosity of the PCM and the thermal convection of the PCM in the liquid state, so as to form an insulating substance with blocked convection having a semi-fluid to solid consistency.
  • PCM phase change material
  • an insoluble thickening or gelling agent chosen to reduce both the viscosity of the PCM and the thermal convection of the PCM in the liquid state, so as to form an insulating substance with blocked convection having a semi-fluid to solid consistency.
  • the liquid component constituting the continuous phase, can be a mixture of chemical compounds of the family of alkanes C n H 2n + 2 such as for example paraffins (C 12 to C 60 ) or waxes, normal paraffins, very weakly branched (1 or 2 branches) long chain isoparaffins (C 30 - C 40 ), branched long chain alkylcycloalkanes or branched long chain alkylaromatics, fatty alcohols or fatty acids.
  • the liquid component preferably represents from 70% to 99.5% of the mass of the product.
  • the thickening agent constituting the dispersed solid phase can be organic (aromatic ureas), organometallic (alkaline or alkaline earth soaps) or purely inorganic (silica, silico-aluminates (bentonite) made oleophilic by grafting an organic chain preferably comprising from 12 to 24 carbon atoms.
  • the thickeners are generally in the form of fibers, crystals or lamellar or spherical particles, of very variable dimensions according to their chemical nature and their method of production.
  • composition with a gelled or dispersed structure is obtained.
  • the elementary particles of the thickening agent form, within the product, a coherent three-dimensional network (entanglement of fibers), with the establishment of internal bonding forces.
  • the liquid phase change material (PCM) is maintained in the network by capillarity.
  • the elementary particles of the thickening agent are in suspension in the PCM.
  • the dispersion is of the colloidal type.
  • the stability of the thickener suspension depends on the dimensions and density of the particles, the viscosity of the medium and above all the inter-particle forces which keep the system in balance.
  • the effectiveness of a phase change material with blocked convection (PCM-CB) therefore depends on four main parameters: the concentration of thickening agent, the elementary dimensions of the thickener, the solvent power of the PCM vis-à-vis thickening and dispersing forces. A judicious combination of these parameters makes it possible to optimize the insulating power of the PCM-CB at temperatures above the melting temperature Tf of the PCM. Different combinations are also possible.
  • compositions according to the nature of the thickening agents are examples of compositions according to the nature of the thickening agents.
  • PCMs can be formed from metallic soaps: lithium soaps, calcium soaps, sodium soaps, aluminum soaps, or mixed lithium / calcium or calcium / sodium soaps. They are obtained in the presence of liquid PCM, either by neutralization of fatty acids, or by saponification of fatty substances with the following bases: lime, lithine, soda or aluminum hydroxide for example.
  • 2- Blocked convection PCMs can also be formed from complex soaps of aluminum, calcium or lithium, which are obtained by in situ neutralization of asymmetric acids in the presence of liquid PCM.
  • the blocked convection PCMs can also be formed without soap from:
  • 3a- inorganic thickeners such as graphite or carbon black, hydrophobic silica gel or oleophilic silico-aluminates (montmorillonite, bentonite, etc.); 3b- organic or organometallic thickeners such as sodium terephthalate or aromatic polyureas or colored pigments (indanthrene, copper phthalocyanine).
  • compositions obtained without soap are formed by dispersion of inorganic or organic compounds in the liquid PCM. These compounds are insoluble in the liquid phase (PCM) at all temperatures.
  • the following compounds can also be included in the compositions for certain applications.
  • Antioxidant additives can be added essentially when the product (PCM with blocked convection) is subjected to a rise in temperature in service.
  • the most frequently encountered are phenolic derivatives (dibutylparacresol, etc.), phenolic derivatives containing sulfur and aromatic amines (phenyl • or • naphthylamine or alkylated amino diphenyls).
  • phenolic derivatives dibutylparacresol, etc.
  • phenolic derivatives containing sulfur and aromatic amines phenyl • or • naphthylamine or alkylated amino diphenyls.
  • soluble in liquid PCM consist of polar chemical compounds which are easily adsorbed on the surface metallic forming a hydrophobic film (fatty amines, alkaline earth sulfonate, etc.)
  • polar modifying additives water, acetone, glycerol, etc. which are intended to stiffen the structure of the entanglement of soap or thickener fibers and to improve the stability of the dispersion of the gelling agent in PCM.
  • Insoluble fillers such as hollow glass microbeads, fly ash, macrobeads, hollow fibers, etc., can be added to the PCM-CB to adjust its density and / or its thermal conductivity.
  • hydrocarbons of petroleum origin such as hydrocarbon solvents, distillation cups, predominantly aromatic, naphthenic or paraffinic oils obtained by solvent extraction processes or by deep hydrotreating, solvents or sections obtained by the hydroisomerization process of paraffinic extracts of petroleum origin or of synthesis of Fischer Tropsch type, solvents and compounds obtained by synthesis, such as for example oxygenated compounds of ester type, synthetic hydrocarbons such as hydrogenated polyolefins, etc.
  • PCM with blocked convection therefore consists of a combination of 70 to 99.5% by mass of liquid PCM and 0.5 to 30% of thickener, to which additives ( ⁇ 10%), fillers (5 to 60%) and solvents (0.2 to 5%). Examples of wording:
  • the following product can be used, consisting of 90% PCM, 9.5% lithium soap and 0.5% antioxidant.
  • Another composition can comprise, for example, 90% oil, 2.5% dispersant (water, acetone, polar products), 7% oleophilic bentone and
  • the blocked convection PCMs which have been described can be used for example for the thermal insulation of subsea pipes.
  • the device comprises an outer coating composed of an almost incompressible liquid / solid phase change (PCM) material having an intermediate melting temperature between the temperature of the effluents flowing in the pipe (s) and the temperature of the outside medium, and an absorbent matrix surrounding the pipe (s) as closely as possible.
  • PCM liquid / solid phase change
  • the external coating consisting of the matrix impregnated with PCM described in the prior document can here be advantageously replaced by one of the PCMs with blocked convection which have just been described, with as a result an improvement in the thermal insulation of the pipes and a simplification of the positioning operations around the pipe or pipes, for example by pumping at a temperature above the melting temperature Tf, very appreciable when the assembly of pipes to be isolated is complex.
  • Applications of the material have been described for the thermal insulation of pipes for conveying fluids and in particular hydrocarbons. It is obvious, however, that such a material can be used in any other application where a very low thermal conductivity is sought, associated with energy restitution.

Landscapes

  • Engineering & Computer Science (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mining & Mineral Resources (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Thermal Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Thermal Insulation (AREA)
  • Lubricants (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
EP01929691A 2000-05-19 2001-04-24 Verfahren zur herstellung eines quasi-inkompressiblen phasenwechselmaterials mit geringer thermischer leitfähigkeit und produkt erhalten aus diesem verfahren Withdrawn EP1290108A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0006489A FR2809115B1 (fr) 2000-05-19 2000-05-19 Procede pour fabriquer un materiau a changement de phase quasi-incompressible et a faible conductivite thermique, et produit obtenu par le procede
FR0006489 2000-05-19
PCT/FR2001/001244 WO2001088057A1 (fr) 2000-05-19 2001-04-24 Procede pour fabriquer un materiau a changement de phase quasi-incompressible et a faible conductivite thermique, et produit obtenu par le procede

Publications (1)

Publication Number Publication Date
EP1290108A1 true EP1290108A1 (de) 2003-03-12

Family

ID=8850458

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01929691A Withdrawn EP1290108A1 (de) 2000-05-19 2001-04-24 Verfahren zur herstellung eines quasi-inkompressiblen phasenwechselmaterials mit geringer thermischer leitfähigkeit und produkt erhalten aus diesem verfahren

Country Status (10)

Country Link
US (1) US7105104B2 (de)
EP (1) EP1290108A1 (de)
CN (1) CN1295294C (de)
AU (1) AU2001256397A1 (de)
BR (1) BR0110905A (de)
CA (1) CA2409026C (de)
FR (1) FR2809115B1 (de)
MX (1) MXPA02011383A (de)
OA (1) OA12331A (de)
WO (1) WO2001088057A1 (de)

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FR2840314B1 (fr) * 2002-06-03 2004-08-20 Inst Francais Du Petrole Methode d'isolation thermique, procede de preparation d'un gel isolant et gel isolant obtenu
CN100467565C (zh) * 2005-05-26 2009-03-11 同济大学 制备有机分子合金相变储能材料的方法
CN1322091C (zh) * 2006-01-06 2007-06-20 华南理工大学 聚乙二醇/二氧化硅复合定形相变材料的制备方法
FR2937706B1 (fr) * 2008-10-29 2013-02-22 Saipem Sa Ensemble de conduites coaxiales comprenant un manchon d'isolation thermique
DE102010040829B4 (de) * 2010-09-15 2020-07-09 Bayerische Motoren Werke Aktiengesellschaft Vorrichtung zur indirekten Ladeluftkühlung sowie Verfahren zur indirekten Ladeluftkühlung
US9417013B2 (en) * 2010-11-12 2016-08-16 Toyota Motor Engineering & Manufacturing North America, Inc. Heat transfer systems including heat conducting composite materials
FR2973473B1 (fr) 2011-03-29 2014-06-13 Saipem Sa Materiau d'isolation thermique et/ou de flottabilite rigide pour conduite sous-marine
FR2973807B1 (fr) * 2011-04-08 2020-09-18 Air Liquide Melange d'un adsorbant et d'un materiau a changement de phase a densite adaptee
JP5908577B2 (ja) * 2011-04-08 2016-04-26 レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード 適合密度を有する吸着剤と相変化材料の混合物
US10590742B2 (en) 2011-07-15 2020-03-17 Exxonmobil Upstream Research Company Protecting a fluid stream from fouling using a phase change material
US9714374B2 (en) 2011-07-15 2017-07-25 Exxonmobil Upstream Research Company Protecting a fluid stream from fouling
WO2014052409A2 (en) 2012-09-25 2014-04-03 Cold Chain Technologies, Inc. Gel comprising a phase-change material, method of preparing the gel, and thermal exchange implement comprising the gel
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
CN103908912A (zh) * 2014-03-13 2014-07-09 安徽明讯新材料科技有限公司 一种相变恒温配胶容器
SG11201607806VA (en) 2014-03-26 2016-10-28 Cold Chain Technologies Inc Gel comprising a phase-change material, method of preparing the gel, thermal exchange implement comprising the gel
US10281079B2 (en) 2015-08-31 2019-05-07 General Electric Company Insulated fluid conduit
US9903525B2 (en) 2015-08-31 2018-02-27 General Electronic Company Insulated fluid conduit
US10487986B2 (en) 2017-06-16 2019-11-26 Exxonmobil Upstream Research Company Protecting a fluid stream from fouling
CN111022784B (zh) * 2019-12-20 2021-03-09 信达科创（唐山）石油设备有限公司 超长保温管道及其加工方法
CN114059974A (zh) * 2021-11-17 2022-02-18 北京大学 海域水合物藏径向井复合液固相变材料的防砂方法、装置及实验方法
CN116640366A (zh) * 2023-06-27 2023-08-25 广东力王新材料有限公司 一种橡胶相变材料及其制备工艺

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Also Published As

Publication number Publication date
CN1429261A (zh) 2003-07-09
FR2809115A1 (fr) 2001-11-23
CN1295294C (zh) 2007-01-17
CA2409026A1 (fr) 2001-11-22
CA2409026C (fr) 2009-12-08
US7105104B2 (en) 2006-09-12
WO2001088057A1 (fr) 2001-11-22
AU2001256397A1 (en) 2001-11-26
OA12331A (en) 2006-05-15
MXPA02011383A (es) 2005-06-30
FR2809115B1 (fr) 2002-07-05
US20040030016A1 (en) 2004-02-12
BR0110905A (pt) 2003-03-11

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