EP1290108A1 - Procede pour fabriquer un materiau a changement de phase quasi-incompressible et a faible conductivite thermique, et produit obtenu par le procede - Google Patents
Procede pour fabriquer un materiau a changement de phase quasi-incompressible et a faible conductivite thermique, et produit obtenu par le procedeInfo
- 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- Withdrawn
Links
- 239000012782 phase change material Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000002562 thickening agent Substances 0.000 claims abstract description 29
- 238000009413 insulation Methods 0.000 claims abstract description 18
- 239000000344 soap Substances 0.000 claims abstract description 17
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 11
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 6
- 239000000194 fatty acid Substances 0.000 claims abstract description 6
- 229930195729 fatty acid Natural products 0.000 claims abstract description 6
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 6
- 125000002524 organometallic group Chemical group 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 239000012530 fluid Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 229920002396 Polyurea Polymers 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 claims 1
- 238000002347 injection Methods 0.000 claims 1
- 239000007924 injection Substances 0.000 claims 1
- 150000002641 lithium Chemical class 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 8
- -1 aromatic ureas Chemical class 0.000 abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 3
- 239000000440 bentonite Substances 0.000 abstract description 3
- 229910000278 bentonite Inorganic materials 0.000 abstract description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002191 fatty alcohols Chemical class 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 239000001993 wax Substances 0.000 abstract description 3
- 235000013877 carbamide Nutrition 0.000 abstract description 2
- 238000002955 isolation Methods 0.000 abstract 1
- 230000008569 process Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000002135 phase contrast microscopy Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000003349 gelling agent Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- 241000612703 Augusta Species 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- VIQSRHWJEKERKR-UHFFFAOYSA-L disodium;terephthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 VIQSRHWJEKERKR-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 235000015243 ice cream Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 235000019239 indanthrene blue RS Nutrition 0.000 description 1
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0006489 | 2000-05-19 | ||
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 |
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 |
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EP1290108A1 true EP1290108A1 (fr) | 2003-03-12 |
Family
ID=8850458
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01929691A Withdrawn EP1290108A1 (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 |
Country Status (10)
Country | Link |
---|---|
US (1) | US7105104B2 (fr) |
EP (1) | EP1290108A1 (fr) |
CN (1) | CN1295294C (fr) |
AU (1) | AU2001256397A1 (fr) |
BR (1) | BR0110905A (fr) |
CA (1) | CA2409026C (fr) |
FR (1) | FR2809115B1 (fr) |
MX (1) | MXPA02011383A (fr) |
OA (1) | OA12331A (fr) |
WO (1) | WO2001088057A1 (fr) |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
US9314768B2 (en) | 2011-04-08 | 2016-04-19 | L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Mixture of an adsorbent and a phase change material with an adapted density |
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 |
US9714374B2 (en) | 2011-07-15 | 2017-07-25 | Exxonmobil Upstream Research Company | Protecting a fluid stream from fouling |
US10590742B2 (en) | 2011-07-15 | 2020-03-17 | Exxonmobil Upstream Research Company | Protecting a fluid stream from fouling using a phase change material |
WO2014052409A2 (fr) | 2012-09-25 | 2014-04-03 | Cold Chain Technologies, Inc. | Gel comprenant un matériau à changement de phase, procédé de préparation du gel, et équipement à échange thermique comprenant le 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 |
CA2943364C (fr) | 2014-03-26 | 2019-11-12 | Richard M. Formato | Gel comprenant un materiau a changement de phase, procede de preparation dudit gel, et ustensile d'echange thermique comprenant le 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 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
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CA2022683C (fr) * | 1989-08-04 | 2000-10-10 | Chiaki Momose | Materiau servant au stockage d'energie thermique latente |
CA2029611A1 (fr) * | 1989-12-04 | 1991-06-05 | Bruce A. Flora | Appareil de chauffage muni d'un regulateur de temperature de changement de phase |
US5370814A (en) * | 1990-01-09 | 1994-12-06 | The University Of Dayton | Dry powder mixes comprising phase change materials |
ZA974977B (en) * | 1996-06-12 | 1997-12-30 | Univ Dayton | Gel compositions for thermal energy storage. |
DE19813562A1 (de) * | 1997-05-21 | 1998-11-26 | Schuemann Sasol Gmbh & Co Kg | Latentwärmekörper |
US6108489A (en) * | 1997-10-17 | 2000-08-22 | Phase Change Laboratories, Inc. | Food warning device containing a rechargeable phase change material |
US6000438A (en) * | 1998-02-13 | 1999-12-14 | Mcdermott Technology, Inc. | Phase change insulation for subsea flowlines |
CA2300618C (fr) * | 1999-03-12 | 2009-10-20 | Ted J. Malach | Systeme d'emballage a temperature constante et formulation a changement de phase |
DE10023572A1 (de) * | 2000-05-15 | 2001-11-22 | Merck Patent Gmbh | Verfahren zur Herstellung eines Speicherverbundes zur Speicherung von Wärme und Kälte |
DE10102250A1 (de) * | 2000-07-21 | 2002-01-31 | Rubitherm Gmbh | Latenwärmespeichermaterial, Schallabsorber und Biofilter |
DE10250249A1 (de) * | 2002-10-28 | 2004-05-13 | Sgl Carbon Ag | Mischungen für Wärmespeicher |
-
2000
- 2000-05-19 FR FR0006489A patent/FR2809115B1/fr not_active Expired - Fee Related
-
2001
- 2001-04-24 MX MXPA02011383A patent/MXPA02011383A/es active IP Right Grant
- 2001-04-24 EP EP01929691A patent/EP1290108A1/fr not_active Withdrawn
- 2001-04-24 WO PCT/FR2001/001244 patent/WO2001088057A1/fr active Application Filing
- 2001-04-24 AU AU2001256397A patent/AU2001256397A1/en not_active Abandoned
- 2001-04-24 OA OA1200200353A patent/OA12331A/en unknown
- 2001-04-24 BR BR0110905-7A patent/BR0110905A/pt not_active Application Discontinuation
- 2001-04-24 CA CA002409026A patent/CA2409026C/fr not_active Expired - Fee Related
- 2001-04-24 US US10/276,804 patent/US7105104B2/en not_active Expired - Fee Related
- 2001-04-24 CN CNB018097219A patent/CN1295294C/zh not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO0188057A1 * |
Also Published As
Publication number | Publication date |
---|---|
MXPA02011383A (es) | 2005-06-30 |
CA2409026A1 (fr) | 2001-11-22 |
OA12331A (en) | 2006-05-15 |
CN1429261A (zh) | 2003-07-09 |
AU2001256397A1 (en) | 2001-11-26 |
CN1295294C (zh) | 2007-01-17 |
FR2809115A1 (fr) | 2001-11-23 |
US20040030016A1 (en) | 2004-02-12 |
FR2809115B1 (fr) | 2002-07-05 |
WO2001088057A1 (fr) | 2001-11-22 |
US7105104B2 (en) | 2006-09-12 |
BR0110905A (pt) | 2003-03-11 |
CA2409026C (fr) | 2009-12-08 |
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