Cryogenic Liquid Containment And Transfer

Abstract

Vessels, wall structures, transfer hoses and systems for storing and transferring liquid cryogens are provided and are based on an elastic layer comprised of a polymer fabric impregnated with a cured resin. The elastic layer is substantially impervious to liquid cryogen, for example LNG, and retains elastic properties at typical cryogenic temperatures.

Claims

1-22. (canceled)

23. A cryogenic liquid storage vessel comprising a composite wall structure, said wall structure comprising the following layers: (a) an elastic inner layer comprising a polymer fabric impregnated with a cured resin; (b) a structural layer; and (c) an insulating layer disposed between the elastic inner layer and the structural layer; wherein the storage vessel is a Full Containment LNG vessel or a Membrane LNG vessel in which the metal walls of said Full Containment LNG vessel or Membrane LNG vessel are replaced by the elastic inner layer; wherein the elastic inner layer has an elasticity of at least 100%; and wherein, in use, the elastic inner layer is in direct contact with a cryogenic liquid.

24. The cryogenic storage vessel according to claim 23, wherein the structural layer comprises one or more of concrete, reinforced concrete, carbon fibre, metals, alloys or combinations thereof.

25. The cryogenic storage vessel according to claim 23, wherein the insulating materials comprise one or more of perlite, vermiculite, glass fibres and ceramic fibres.

26. The cryogenic storage vessel according to claim 23, wherein the elastic inner layer provides an impervious or substantially impervious barrier to liquid cryogen.

27. The cryogenic storage vessel according to claim 23, wherein the elastic inner layer has an elasticity of at least 200%, or at least 400%, or at least 600% or at least 800%.

28. The cryogenic storage vessel according to claim 23, wherein the elastic inner layer has an elasticity of at least 100%, or at least 200% at 196 C.

29. The cryogenic storage vessel according to claim 23, wherein the polymer fabric is one or more of spandex (elastane), Lycra, block copolymers of polyurethane and polyethylene glycol, silicone rubber, segmented urea/urethane/ether copolymers, fluorinated resins such as perfluoroalkoxy alkanes (PFA), fluorinated ethylene propylene (FEP), or polytetrafluoroethylene (PTFE) optionally in combination with one or more synthetic or natural fibres, for example, nylon, polypropylene or polyethylene.

30. A cryogenic liquid storage vessel according to claim 23, wherein the cured resin comprises polyurethanes, polyureas, acrylic resins, polyester resins, silicone resins, fluorinated resins, for example polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), fluorinated silicone resins, epoxy resins or combinations thereof.

31. A cryogenic liquid storage vessel according to claim 23, wherein the structural layer comprises concrete.

32. A cryogenic liquid storage vessel according to claim 23, wherein the structural layer comprises carbon fibre.

33. A cryogenic liquid storage vessel according to claim 23, wherein the cured resin comprises a polyurethane.

34. A cryogenic liquid storage vessel according to claim 23, wherein the polymer fabric comprises one or more of spandex, Lycra or elastane.

35. A cryogenic liquid storage vessel according to claim 23, wherein the polymer fabric comprises nylon and one or more of spandex, Lycra or elastane.

36. A cryogenic liquid storage vessel according to claim 23, wherein the elastic inner layer has a thickness of less than 5000 microns.

37. A cryogenic liquid storage vessel according to claim 23, wherein the elastic inner layer has a thickness from 100 to 5000 microns.

38. A cryogenic liquid storage vessel according to claim 23, wherein the elastic inner layer has a thickness from 100 to 1000 microns.

39. A cryogenic liquid storage vessel according to claim 23, wherein the elastic inner layer is in direct contact with the insulating layer.

40. A cryogenic liquid storage vessel according to claim 23, wherein the vessel further comprises a liquid cryogen, such as LNG.

41. A cryogenic liquid storage system, said storage system comprising a plurality of cryogenic liquid storage vessels according to claim 23.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0092] FIG. 1 illustrates the wall structure of an exemplary prior art Full Containment LNG storage tank.

[0093] FIG. 2 illustrates the wall structure of an exemplary prior art Membrane LNG storage tank.

[0094] FIG. 3 illustrates a wall structure of a cryogenic liquid containment vessel according to an embodiment of the present disclosure.

[0095] FIG. 4 illustrates a cryogenic liquid transfer hose according to an embodiment of the present disclosure.

[0096] FIG. 5 illustrates a cryogenic liquid transfer hose according to another embodiment of the present disclosure.

DESCRIPTION OF EXEMPLARY EMBODIMENTS

[0097] Throughout this specification, use of the terms comprises or comprising or grammatical variations thereon shall be taken to specify the presence of stated features, integers, steps or components but does not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof not specifically mentioned.

[0098] Before the present structures, components, systems and/or methods are disclosed and described, it is to be understood that unless otherwise indicated this invention is not limited to specific structures, components, methods, or the like, as such may vary, unless otherwise specified. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0099] It must also be noted that, as used in the specification and the appended claims, the singular forms a, an and the include plural referents unless otherwise specified. Thus, for example, reference to an insulating layer may include more than one insulating layer, and the like.

[0100] Disclosed herein are advantageous structures, systems and methods for storing and transferring cryogenic liquids, particularly LNG. The structures, systems and methods are based on an elastic layer which is flexible, impervious or substantially impervious to cryogens Accordingly, advantageous cryogenic liquid storage systems may be constructed at a lower cost.

[0101] In an exemplary embodiment, there is provided a composite wall structure for a cryogenic liquid storage vessel, said wall structure comprising the following layers: [0102] (a) an elastic inner layer comprising a polymer fabric impregnated with a cured resin; [0103] (b) a structural layer comprising concrete; and [0104] (c) an insulating layer disposed between the elastic inner layer and the structural layer;
said insulating layer comprising one or more of perlite, vermiculite, glass fibres and ceramic fibres;
wherein, in use, the elastic inner layer is in direct contact with a cryogenic liquid.

[0105] In another exemplary embodiment, there is provided a composite wall structure for a cryogenic liquid storage vessel, said wall structure comprising the following layers: [0106] (a) an elastic inner layer comprising a polymer fabric impregnated with a cured resin; [0107] (b) a structural layer comprising carbon fibre; and [0108] (c) an insulating layer disposed between the elastic inner layer and the structural layer;
said insulating layer comprising one or more of perlite, vermiculite, glass fibres and ceramic fibres;
wherein, in use, the elastic inner layer is in direct contact with a cryogenic liquid.

[0109] In another exemplary embodiment, there is provided a composite wall structure for a cryogenic liquid storage vessel, said wall structure comprising the following layers: [0110] (a) an elastic inner layer comprising a polymer fabric impregnated with a cured resin; [0111] (b) a structural layer; and [0112] (c) an insulating layer disposed between the elastic inner layer and the structural layer;
wherein the polymer fabric comprises spandex (elastane), Lycra, block copolymers of polyurethane and polyethylene glycol, silicone rubber, segmented urea/urethane/ether copolymers, fluorinated resins such as perfluoroalkoxy alkanes (PFA), fluorinated ethylene propylene (FEP), polytetrafluoroethylene (PTFE) or combinations thereof optionally combined with one or more synthetic or natural fibres, for example, nylon, polypropylene or polyethylene; wherein the cured resin comprises polyurethanes, polyureas, acrylic resins, polyester resins, silicone resins, fluorinated resins, for example polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), fluorinated silicone resins, epoxy resins or combinations thereof; and
wherein, in use, the elastic inner layer is in direct contact with a cryogenic liquid.

[0113] In another exemplary embodiment, there is provided a composite wall structure for a cryogenic liquid storage vessel, said wall structure comprising the following layers: [0114] (a) an elastic inner layer comprising a polymer fabric impregnated with a cured resin; [0115] (b) a structural layer comprising one or more of concrete, reinforced concrete, carbon fibre, metals and alloys; and [0116] (c) an insulating layer disposed between the elastic inner layer and the structural layer, said insulating layer comprising one or more of perlite, vermiculite, glass fibre and ceramic fibre;
wherein the polymer fabric comprises spandex (elastane), Lycra, block copolymers of polyurethane and polyethylene glycol, silicone rubber, segmented urea/urethane/ether copolymers, fluorinated resins such as perfluoroalkoxy alkanes (PFA), fluorinated ethylene propylene (FEP), polytetrafluoroethylene (PTFE) or combinations thereof optionally combined with one or more synthetic or natural fibres, for example, nylon, polypropylene or polyethylene; wherein the cured resin comprises polyurethanes, polyureas, acrylic resins, polyester resins, silicone resins, fluorinated resins, for example polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), fluorinated silicone resins, epoxy resins or combinations thereof; and
wherein, in use, the elastic inner layer is in direct contact with a cryogenic liquid.

[0117] In another exemplary embodiment, there is provided a cryogenic liquid storage vessel said storage vessel having a composite wall structure, said wall structure comprising the following layers: [0118] (a) an elastic inner layer comprising a polymer fabric impregnated with a cured resin; [0119] (b) a structural layer comprising concrete; and [0120] (c) an insulating layer disposed between the elastic inner layer and the structural layer;
said insulating layer comprising one or more of perlite, vermiculite, glass fibres and ceramic fibres;
wherein, in use, the elastic inner layer is in direct contact with a cryogenic liquid.

[0121] In another exemplary embodiment, there is provided a cryogenic liquid storage vessel said storage vessel having a composite wall structure, said wall structure comprising the following layers: [0122] (a) an elastic inner layer comprising a polymer fabric impregnated with a cured resin; [0123] (b) a structural layer comprising carbon fibre; and [0124] (c) an insulating layer disposed between the elastic inner layer and the structural layer;
said insulating layer comprising one or more of perlite, vermiculite, glass fibres and ceramic fibres;
wherein, in use, the elastic inner layer is in direct contact with a cryogenic liquid.

[0125] In another exemplary embodiment, there is provided a cryogenic liquid storage vessel, said storage vessel having a composite wall structure, said wall structure comprising the following layers: [0126] (a) an elastic inner layer comprising a polymer fabric impregnated with a cured resin; [0127] (b) a structural layer; and [0128] (c) an insulating layer disposed between the elastic inner layer and the structural layer;
wherein the polymer fabric comprises spandex (elastane), Lycra, block copolymers of polyurethane and polyethylene glycol, silicone rubber, segmented urea/urethane/ether copolymers, fluorinated resins such as perfluoroalkoxy alkanes (PFA), fluorinated ethylene propylene (FEP), polytetrafluoroethylene (PTFE) or combinations thereof optionally combined with one or more synthetic or natural fibres, for example, nylon, polypropylene or polyethylene; wherein the cured resin comprises polyurethanes, polyureas, acrylic resins, polyester resins, silicone resins, fluorinated resins, for example polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), fluorinated silicone resins, epoxy resins or combinations thereof; and
wherein, in use, the elastic inner layer is in direct contact with a cryogenic liquid.

[0129] In another exemplary embodiment, there is provided a cryogenic liquid storage vessel, said storage vessel having a composite wall structure, said wall structure comprising the following layers: [0130] (a) an elastic inner layer comprising a polymer fabric impregnated with a cured resin; [0131] (b) a structural layer comprising one or more of concrete, reinforced concrete, carbon fibre, metals and alloys; and [0132] (c) an insulating layer disposed between the elastic inner layer and the structural layer,
said insulating layer comprising one or more of perlite, vermiculite, glass fibre and ceramic fibre;
wherein the polymer fabric comprises spandex (elastane), Lycra, block copolymers of polyurethane and polyethylene glycol, silicone rubber, segmented urea/urethane/ether copolymers, fluorinated resins such as perfluoroalkoxy alkanes (PFA), fluorinated ethylene propylene (FEP), polytetrafluoroethylene (PTFE) or combinations thereof optionally combined with one or more synthetic or natural fibres, for example, nylon, polypropylene or polyethylene; wherein the cured resin comprises polyurethanes, polyureas, acrylic resins, polyester resins, silicone resins, fluorinated resins, for example polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), fluorinated silicone resins, epoxy resins or combinations thereof; and
wherein, in use, the elastic inner layer is in direct contact with a cryogenic liquid.

[0133] In any of the above disclosed exemplary embodiments the cryogenic liquid storage vessel further comprises one or more liquid cryogens.

[0134] In another exemplary embodiment there is provided a cryogenic liquid storage system comprising a plurality of cryogenic storage vessels as disclosed in the above exemplary embodiments.

[0135] In another exemplary embodiment there is provided a cryogenic liquid transfer hose, said transfer hose comprising a wall structure, said wall structure comprising the following layers: [0136] (a) an elastic inner layer comprising a polymer fabric impregnated with a cured resin; and [0137] (b) at least one insulating layer, wherein, in use, the elastic layer is in direct contact with a cryogenic liquid; and
wherein the polymer fabric comprises spandex (elastane), Lycra, block copolymers of polyurethane and polyethylene glycol, silicone rubber, segmented urea/urethane/ether copolymers, fluorinated resins such as perfluoroalkoxy alkanes (PFA), fluorinated ethylene propylene (FEP), polytetrafluoroethylene (PTFE) or combinations thereof optionally combined with one or more synthetic or natural fibres, for example, nylon, polypropylene or polyethylene; and wherein the cured resin comprises polyurethanes, polyureas, acrylic resins, polyester resins, silicone resins, fluorinated resins, for example polyvinylidene fluoride (PVDF) and polytetrafluoroethyiene (PTFE), fluorinated silicone resins, epoxy resins or combinations thereof.

[0138] In another exemplary embodiment there is provided a method of lining a cryogenic liquid transfer hose comprising: [0139] a) introducing a cured in place layer into said hose; said layer comprising: [0140] i. an elastic polymer fabric; and [0141] ii. a resin; and [0142] b) allowing the resin to cure;
wherein the polymer fabric comprises spandex (elastane), Lycra, block copolymers of polyurethane and polyethylene glycol, silicone rubber, segmented urea/urethane/ether copolymers, fluorinated resins such as perfluoroalkoxy alkanes (PFA), fluorinated ethylene propylene (FEP), polytetrafluoroethylene (PTFE) or combinations thereof optionally combined with one or more synthetic or natural fibres, for example, nylon, polypropylene or polyethylene; and wherein the cured resin comprises polyurethanes, polyureas, acrylic resins, polyester resins, silicone resins, fluorinated resins, for example polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), fluorinated silicone resins, epoxy resins or combinations thereof.

[0143] In another exemplary embodiment there is provided a cryogenic liquid transfer hose, said transfer hose comprising a wall structure, said wall structure comprising the following layers: [0144] (a) an elastic outer layer comprising a polymer fabric impregnated with a cured resin; and [0145] (b) at least one insulating layer, wherein, in use, the elastic layer protects other layers of the wall structure from moisture;
wherein the polymer fabric comprises spandex (elastane), Lycra, block copolymers of polyurethane and polyethylene glycol, silicone rubber, segmented urea/urethane/ether copolymers, fluorinated resins such as perfluoroalkoxy alkanes (PFA), fluorinated ethylene propylene (FEP), polytetrafluoroethylene (PTFE) or combinations thereof optionally combined with one or more synthetic or natural fibres, for example, nylon, polypropylene or polyethylene; and wherein the cured resin comprises polyurethanes, polyureas, acrylic resins, polyester resins, silicone resins, fluorinated resins, for example polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), fluorinated silicone resins, epoxy resins or combinations thereof.

[0146] In another exemplary embodiment there is provided a cryogenic liquid transfer hose, said transfer hose comprising a wall structure, said wall structure comprising the following layers: [0147] (i) an elastic inner layer comprising a polymer fabric impregnated with a cured resin; [0148] (ii) at least one insulating layer; and [0149] (iii) an elastic outer layer comprising a polymer fabric impregnated with a cured resin,
wherein, in use, the elastic inner layer is in direct contact with a cryogenic liquid and the elastic outer layer protects other layers of the wall structure from moisture; and
wherein the polymer fabric comprises spandex (elastane), Lycra, block copolymers of polyurethane and polyethylene glycol, silicone rubber, segmented urea/urethane/ether copolymers, fluorinated resins such as perfluoroalkoxy alkanes (PFA), fluorinated ethylene propylene (FEP), polytetrafluoroethylene (PTFE) or combinations thereof optionally combined with one or more synthetic or natural fibres, for example, nylon, polypropylene or polyethylene; and wherein the cured resin comprises polyurethanes, polyureas, acrylic resins, polyester resins, silicone resins, fluorinated resins, for example polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), fluorinated silicone resins, epoxy resins or combinations thereof.

[0150] In another exemplary embodiment there is provided a system for storing and transferring liquid cryogen comprising: [0151] (a) one or more cryogenic liquid storage vessels; and [0152] (b) one or more cryogenic liquid transfer hoses;
wherein said storage vessel has a composite wall structure, said wall structure comprising the following layers; [0153] (i) an elastic inner layer comprising a polymer fabric impregnated with a cured resin; [0154] (ii) a structural layer comprising one or more of concrete, reinforced concrete, carbon fibre, metals and alloys; and [0155] (iii) an insulating layer disposed between the elastic inner layer and the structural layer; said insulating layer comprising one or more of perlite, vermiculite, glass fibres and ceramic fibres;
wherein, in use, the elastic inner layer is in direct contact with a cryogenic liquid; and
wherein said transfer hose comprising a wall structure, said wall structure comprising the following layers: [0156] (i) an elastic inner layer comprising a polymer fabric impregnated with a cured resin; and [0157] (ii) at least one insulating layer, wherein, in use, the elastic layer is in direct contact with a cryogenic liquid.

[0158] In another exemplary embodiment there is provided a system for storing and transferring liquid cryogen comprising: [0159] (a) one or more cryogenic liquid storage vessels; and [0160] (b) one or more cryogenic liquid transfer hoses;
wherein said storage vessel has a composite wall structure, said wall structure comprising the following layers; [0161] (i) an elastic inner layer comprising a polymer fabric impregnated with a cured resin; [0162] (ii) a structural layer comprising concrete; and [0163] (iii) an insulating layer disposed between the elastic inner layer and the structural layer; said insulating layer comprising one or more of perlite, vermiculite, glass fibres and ceramic fibres;
wherein, in use, the elastic inner layer is in direct contact with a cryogenic liquid; and
wherein said transfer hose comprising a wall structure, said wall structure comprising the following layers: [0164] (i) an elastic inner layer comprising a polymer fabric impregnated with a cured resin; and [0165] (ii) at least one insulating layer, wherein, in use, the elastic layer is in direct contact with a cryogenic liquid.

[0166] In another exemplary embodiment there is provided a system for storing and transferring liquid cryogen comprising: [0167] (a) one or more cryogenic liquid storage vessels; and [0168] (b) one or more cryogenic liquid transfer hoses;
wherein said storage vessel has a composite wall structure, said wall structure comprising the following layers; [0169] (i) an elastic inner layer comprising a polymer fabric impregnated with a cured resin; [0170] (ii) a structural layer comprising carbon fibre; and [0171] (iii) an insulating layer disposed between the elastic inner layer and the structural layer; said insulating layer comprising one or more of perlite, vermiculite, glass fibres and ceramic fibres;
wherein, in use, the elastic inner layer is in direct contact with a cryogenic liquid; and
wherein said transfer hose comprising a wall structure, said wall structure comprising the following layers: [0172] (i) an elastic inner layer comprising a polymer fabric impregnated with a cured resin; and [0173] (ii) at least one insulating layer, wherein, in use, the elastic layer is in direct contact with a cryogenic liquid.

[0174] In another exemplary embodiment there is provided a system for storing and transferring liquid cryogen comprising: [0175] (a) one or more cryogenic liquid storage vessels; and [0176] (b) one or more cryogenic liquid transfer hoses;
wherein said storage vessel has a composite wall structure, said wall structure comprising the following layers; [0177] (i) an elastic inner layer comprising a polymer fabric impregnated with a cured resin; [0178] (ii) a structural layer comprising one or more of concrete, reinforced concrete, carbon fibre, metals and alloys; and [0179] (iii) an insulating layer disposed between the elastic inner layer and the structural layer; said insulating layer comprising one or more of perlite, vermiculite, glass fibres and ceramic fibres;
wherein, in use, the elastic inner layer is in direct contact with a cryogenic liquid; and
wherein said transfer hose comprising a wall structure, said wall structure comprising the following layers: [0180] (i) an elastic inner layer comprising a polymer fabric impregnated with a cured resin; and [0181] (ii) at least one insulating layer, wherein, in use, the elastic layer is in direct contact with a cryogenic liquid;
wherein, independently in each occurrence the polymer fabric comprises spandex (elastane), Lycra, block copolymers of polyurethane and polyethylene glycol, silicone rubber, segmented urea/urethane/ether copolymers, fluorinated resins such as perfluoroalkoxy alkanes (PFA), fluorinated ethylene propylene (FEP), polytetrafluoroethylene (PTFE) or combinations thereof optionally combined with one or more synthetic or natural fibres, for example, nylon, polypropylene or polyethylene; and
wherein independently in each occurrence the cured resin comprises polyurethanes, polyureas, acrylic resins, polyester resins, silicone resins, fluorinated resins, for example polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), fluorinated silicone resins, epoxy resins or combinations thereof.

[0182] In another exemplary embodiment there is provided a system for storing and transferring liquid cryogen comprising: [0183] (a) one or more cryogenic liquid storage vessels; and [0184] (b) one or more cryogenic liquid transfer hoses;
wherein said storage vessel has a composite wall structure, said wall structure comprising the following layers; [0185] (i) an elastic inner layer comprising a polymer fabric impregnated with a cured resin; [0186] (ii) a structural layer comprising one or more of concrete, reinforced concrete, carbon fibre, metals and alloys; and [0187] (iii) an insulating layer disposed between the elastic inner layer and the structural layer; said insulating layer comprising one or more of perlite, vermiculite, glass fibres and ceramic fibres;
wherein, in use, the elastic inner layer is in direct contact with a cryogenic liquid; and
wherein said transfer hose comprising a wall structure, said wall structure comprising the following layers: [0188] (i) an elastic inner layer comprising a polymer fabric impregnated with a cured resin; [0189] (ii) at least one insulating layer; and [0190] (iii) an elastic outer layer comprising a polymer fabric impregnated with a cured resin,
wherein, in use, the elastic inner layer is in direct contact with a cryogenic liquid and the elastic outer layer protects other layers of the wall structure from moisture;
wherein, independently in each occurrence the polymer fabric comprises spandex (elastane), Lycra, block copolymers of polyurethane and polyethylene glycol, silicone rubber, segmented urea/urethane/ether copolymers, fluorinated resins such as perfluoroalkoxy alkanes (PFA), fluorinated ethylene propylene (FEP), polytetrafluoroethylene (PTFE) or combinations thereof optionally combined with one or more synthetic or natural fibres, for example, nylon, polypropylene or polyethylene; and
wherein independently in each occurrence the cured resin comprises polyurethanes, polyureas, acrylic resins, polyester resins, silicone resins, fluorinated resins, for example polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), fluorinated silicone resins, epoxy resins or combinations thereof.

[0191] In any one or more of the above disclosed exemplary embodiments the polymer fabric preferably comprises nylon and one or more of spandex, Lycra or elastane and the resin comprises a polyurethane.

[0192] In one embodiment, the elastic inner or outer layer according to the present disclosure comprises a combination of a resin and a polymer fabric comprising a plurality of elastomeric fibres. In a preferred embodiment, the elastomeric fibres are provided as copolymer fibres produced from polyurethane and polyethylene glycol and comprising rigid and flexible segments. The elastomeric fibres may be provided in the form of a membrane, such as a portion of elastomeric fabric. Non-limiting examples of elastomeric fabrics are spandex (elastane) and those variations sold under proprietary trade marks such as Lycra, Elaspan, Dorlastan and Linel. Other preferred fibres include silicone rubber, segmented urea/urethane/ether copolymers, and fluorinated resins such as perfluoroalkoxy alkanes (PFA), fluorinated ethylene propylene (FEP) or polytetrafluoroethylene (PTFE).

[0193] The elastomeric fibres may be provided in the form of a portion of woven fabric or membrane in which elastomeric fibres are present in at least a small percentage of the total composition of the fabric weave. Desirably, the fabric or membrane can be provided in any size and shape suitable for a specific application. In this manner, the polymer fabric can be applied as a single continuous component.

[0194] The portion of polymer fabric may be combined with a resin or resin matrix. The resin may be provided in a liquid form and applied to the polymer fabric. Application of the resin may be as simple as painting the liquid onto the polymer fabric.

[0195] The resin may be provided in the form of any suitable liquid resin that may provide qualities of flexibility once the resin has cured or set to a solid form. The cured resin has elastic properties. Non-limiting examples of suitable resins are polyurethanes, polyureas, acrylic resins, polyester resins, silicone resins, fluorinated resins, epoxy resins or combinations thereof.

[0196] The reactants necessary in the preparation of the polyurethane resin of the present disclosure comprise:

(i) at least one member selected from among aliphatic and aromatic isocyanates, and
(ii) at least one polymeric polyol, most preferably a member selected from between polyester polyol and polyether polyol, and optionally a chain extender.

[0197] The chain extender suitable in the present context is a C2-10 hydrocarbon compound having an isocyanate-reactive chain termination. In a preferred embodiment of the present disclosure, the chain extender is hydroxy and/or an amine terminated. In a further embodiment of the disclosure, additional polyols may be included as reactants.

[0198] The isocyanate suitable in the present disclosure is any of the organic isocyanates previously disclosed as suitable in the preparation of polyurethane resins, preferably diisocyanates, and include aliphatic, aromatic and cycloaliphatic diisocyanates, and mixtures thereof.

[0199] Illustrative isocyanates but non-limiting thereof are methylene bis(phenylisocyanate) including the 4,4-isomer, the 2,4-isomer and mixtures thereof, m- and p-phenylene diisocyanates, chlorophenylene diisocyanates, a,a-xylylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, isophorone diisocyanate and the like; cycloaliphatic diisocyanates such as methylene bis(cyclohexyl isocyanate) including the 4,4-isomer, the 2,4-isomer and mixtures thereof, and all the geometric isomers thereof including trans/trans, cis/trans, cis/cis and mixtures thereof, cyclohexylene diisocyanates (1,2-; 1,3-; or 1,4-, 1-methyl-2,5-cyclohexylene diisocyanate, 1-methyl-2,4-cyclohexylene diisocyanate, 1-methyl-2,6-cyclohexylene diisocyanate, 4,4-isopropylidenebis(cyclohexyl isocyanate), 4,4-diisocyanatodicyclohexyl, and all geometric isomers and mixtures thereof and the like. Also included are the modified forms of methylene bis(phenyl isocyanate). By the latter are meant those forms of methylene bis(phenyl isocyanate) which have been treated to render them stable liquids at ambient temperature (circa 20 C.). Such products include those which have been reacted with a minor amount (up to about 0.2 equivalents per equivalent of polyisocyanate) of an aliphatic glycol or a mixture of aliphatic glycols. Mixtures of any of the above-named isocyanates can be employed if desired.

[0200] Preferred classes of organic diisocyanates include the aromatic and cycloaliphatic diisocyanates. Preferred species within these classes are methylene bis(phenyl isocyanate) including the 4,4-isomer, the 2,4-isomer, and mixtures thereof, toluene diisocyanate and methylenebis(cyclohexyl isocyanate) inclusive of the isomers described above.

[0201] The preferred isocyanates are methylene bis(phenyl isocyanate) (methylene diphenyl isocyanate) and methylene bis(cyclohexyl isocyanate).

[0202] The polymeric diols suitable in the context of the present disclosure are those conventionally employed in the art for the preparation of polyurethane resins. The formation of soft segments in the resulting polymer is attributed to the polymeric diols. Preferably, the polymeric diols have molecular weights (number average) within the range of 500 to 10,000, preferably 1000 to 4,000. Naturally, and often times advantageously, mixtures of such diols are also possible. Examples of the suitable diols include polyether diols, polyester diols, hydroxy-terminated polycarbonates, hydroxy-terminated copolymers of dialkyl siloxane and alkylene oxides such as ethylene oxide, propylene oxide and the like, and mixtures thereof.

[0203] Examples of suitable polyether polyols include polyoxyethylene glycols, polyoxypropylene glycols which, optionally, have been capped with ethylene oxide residues, random and block copolymers of ethylene oxide and propylene oxide; polytetramethylene glycol, random and block copolymers of tetrahydrofuran and ethylene oxide and/or propylene oxide. The preferred polyether polyols are random and block copolymers of ethylene and propylene oxide of functionality approximately 2.0 and polytetramethylene glycol polymers of functionality about 2.0.

[0204] The suitable polyester polyols include the ones which are prepared by polymerizing -caprolactone using an initiator such as ethylene glycol, ethanolamine and the like, and those prepared by esterification of polycarboxylic acids such as phthalic, terephthalic, succinic, azelaic and the like acids with polyhydric alcohols such as ethylene glycol, butanediol, cyclohexane-dimethanol and the like. An example of a suitable polyester polyol is butanediol adipate.

[0205] Among the suitable amine-terminated polyethers, mention may be made of the aliphatic primary diamines structurally derived from polyoxypropylene glycols.

[0206] Examples of polycarbonates containing hydroxyl groups include those prepared by reaction of diols such as propane-1,3-diol, butane-1,4-diol, hexane-1,6-diol, 1,9-nonanediol, 2-methyloctane-1,8-diol, diethylene glycol, triethylene glycol, dipropylene glycol and the like with diaryl-carbonates such as diphenylcarbonate or with phosgene.

[0207] Examples of suitable silicon-containing polyethers include copolymers of alkylene oxides with dialkylsiloxanes such as dimethyl-siloxane and the like; other suitable silicon-containing polyethers have been disclosed in U.S. Pat. No. 4,057,595 and in U.S. Pat. No. 4,631,329.

[0208] Preferred diols are polyether diols and polyester diols as referred to above.

[0209] Suitable chain extenders which are used in the preparation of the polyurethane resin of the disclosure include any of those known in the polyurethane art disclosed above. Typically the extenders may be aliphatic straight and branched chain diols having from 2 to 10 carbon atoms, inclusive, in the chain. Examples of suitable diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, and the like; 1,4-cyclohexanedimethanol; hydroquinone-bis-(hydroxyethyl)ether; cyclohexylenediols (1,4-, 1,3-, and 1,2-isomers), isopropylidenebis(cyclohexanols); diethylene glycol, dipropylene glycol, ethanolamine, N-methyldiethanolamine, and the like; and mixtures of any of the above. Minor proportions (less than about 20 equivalent percent) of the difunctional extender may be replaced by trifunctional extenders and/or monofunctional extenders, without adversely effecting the resulting polyurethane resin; illustrative of such extenders are glycerol, trimethylolpropane, and 1-octadecanol and the like.

[0210] While any of the dial extenders described and exemplified above can be employed alone, or in admixture, it is preferred to use 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, ethylene glycol, and diethylene glycol, either alone or in admixture with each other or with one or more of the aliphatic diols which were named previously. Particularly preferred dials are 1,4-butanediol, 1,6-hexanediol and 1,4-cyclohexanedimethanol. The equivalent proportions of polymeric dial to said extender may vary considerably depending on the desired hardness for the polyurethane resin. In general, the proportions fall within the range of from about 1:1 to about 1:20, preferably from about 1:2 to about 1:10. At the same time, the overall ratio of isocyanate equivalents to equivalents of active hydrogen containing materials is within the range of 0.90:1 to 1.10:1, and preferably, 0.95:1 to 1.05:1.

[0211] The preparation of the polyurethane resin of the present disclosure follows procedures and methods which are conventional and which are well known to those skilled in the art. If desired, the polyurethanes can have incorporated in them, at any appropriate stage of preparation, additives such as pigments, fillers, lubricants, stabilizers, antioxidants, coloring agents, fire retardants, and the like, which are commonly used in conjunction with polyurethane resins.

[0212] The cure time of the resin may be varied widely by appropriate selection of the resin composition. Preferred cure times are in the range of 30 minutes to 24 hours.

[0213] Furthermore, the workability (pot life) of the resin may be varied through selection of the resin composition. Desirable workability is dependent on the particular application in question and preferably will fail within the range of 10 minutes to 1 hour.

[0214] Application of the resin to the polymer fabric and subsequent curing of the resin forms a membrane or liner, that is the elastic inner or outer layer. The layer advantageously possesses both qualities of flexibility and elasticity. Furthermore, the combination of the components may impart significant tear resistance in the final layer. It has been found that the elastic inner or outer layer of the present disclosure exhibits tear resistance that is unmatched by traditional elastorneric materials, such as thermoset elastomers. It is apparent that the combination of woven polymer fabric having elastomeric fibres within the resin provides reinforcement to the layer, which advantageously provides a product which has greater tear resistance than materials having no such reinforcement.

[0215] Depending on the resin selected, the elastic layer may also have adhesive qualities, assisting in the fixation of the elastic layer directly onto surfaces.

[0216] These properties of the elastic inner or outer layer make it suitable for numerous industrial applications, particularly in situations where it is desired to provide sealing, but there are movement issues in respect of the sealing surfaces. The elastic layer, once adhered to the surface, cannot only flex in response to normal thermal expansions and contractions, but also stretches and retracts at the same time. As a result, the elastic layer can appropriately and adequately provide a sealing membrane on a surface or within a hose or pipe while causing no stressing to or upon the surfaces themselves. That is, the elastic layer is able to move in conjunction with normal expansion and contraction of a surface or within the hose or pipe surfaces themselves, resulting in adequate sealing with no stressing or cracking of the surfaces to which the elastic layer has been applied.

[0217] Further, the elastic inner or outer layer may advantageously be provided and applied as a single continuous unit, having no joins or breaks to compromise the structural integrity of the overall seal. The preferred method of application of the elastic layer comprises providing a single continuous portion of polymer fabric having elastomeric fibres woven therein. The portion of fabric may be comparable in shape and configuration to the area to which the elastic layer is to be applied. That is, the shape and configuration may accord to the entire area of application of the final seal.

[0218] The single continuous polymer fabric portion is placed upon the surface or surfaces requiring sealing. The suitable resin is then applied directly onto the fabric portion. Since the resin may be selected to have required adhesive qualities to enable adhesion to the desired surface, application of the resin to the polymer fabric enables adhesion of the resulting elastic layer to the surface or surfaces.

[0219] This method of application advantageously permits direct application at the desired site. Further, the resin may be selected such that it requires no special curing process or application of primers in order to set the final elastic layer as a seal upon surfaces. That is, the resin, once applied to the portion of woven fabric, sets or cures without any special curing methods or application of further products. This is in contrast to traditionally used elastomers such as rubber, which is sticky and can easily deform when warm and is brittle when cold. In this state, in cannot be used to make articles with a good level of elasticity and in any event, if left in a natural state, will eventually disintegrate. Rubber requires treatment by vulcanisation or other curing methods in order to attain good properties of elasticity and flexibility. Such treatment methods are completely unnecessary in application of the present disclosure. Further, elastomers such as rubber have limited or no adhesive qualities and are often unsuitable for attaching directly upon a surface.

[0220] While direct application as described above is a preferred method of application of the elastic inner or outer layer, it is also within the scope of the present disclosure to manufacture the elastic layer as a factory prepared unit prior to transportation and installation at the desired location. The woven fabric portion is, as described above, cut out or otherwise provided in a shape and size that may be comparable to the shape and size of the desired final seal. The fabric portion can be arranged upon a mould or other suitable structure that replicates the dimensions and configuration of the structure or structures to which the completed seal is intended to be applied. The resin is applied to the fabric portion as described above, thereby creating a final unit of elastic layer as a single, continuous element having no seams or joins. Advantageously, the pre-formed unit is packed, for example in foil, so as to preserve the resin in an uncured state.

[0221] This single pre-formed unit of elastic layer can then be transported and applied to a surface or surfaces as required, such as by adhering the elastic layer in place with the same or similar materials used in its construction. As an example, the resin used in construction of the elastic layer can be applied to the surface or surfaces and the prefabricated polymer fabric unit placed thereupon. The nature of the resin applied to the surface and of the prefabricated unit is such that there is bonding there between, creating the same continuous sealing construction as when the woven fabric and resin are applied directly on site as described above.

[0222] To make the elastic inner or outer layer, the binder may be melt coated or extrusion coated onto the polymer fabric. At this stage (before curing), the elastic layer can be introduced inside a hose or pipe. The flexible elastic layer can be inserted by either a drag-in or inversion method, both of which are well known in the art. Inversion is the process where the elastic layer is turned inside-out during the installation using a column of water or pressurized air; the elastic layer walks itself through the host pipe. Inversion results with the exterior coating becoming the new interior pipe wall surface with the elastic layer pressed against the host pipe wall. The inversion process can be performed using air pressure (a shooter or air inverter) or a water column (inversion water column). Once inside the cavity, heat may be applied, if required, by injecting steam and/or hot water to force the elastic layer against the inside of the pipe and to cure in place the resin. The elastic layer can also be inserted into the cavity by use of hot water under pressure. Once the resin is cured, it sets and the elastic layer forms a hose within a hose.

[0223] The elastic inner or outer layer can be made to the desired length required to line the hose, and preferably is a continuous tubular liner. The liner should have a length sufficient to line the pipe or hose with one continuous length that is not required to be spliced together from shorter pieces. The liner (elastic layer) will typically be at least 1 meter in length and can be as long as 5000 meters in length. More typically the liners are lengths of from 2 to 1000 meters in length.

[0224] The diameter of the liner, once formed into a closed tube will vary depending on the diameter of the cryogenic hose. Typical diameters are from about 5 cm to about 250 cm, but more commonly the diameters are 10 cm to about 50 cm.

[0225] The liner can conform to the shape of the inside of the pipe. The shape of the pipe does not need to be perfectly circular, but rather can be non-circular such as egg-shaped or elliptical shaped. The liner can also negotiate bends in the pipe or hose.

[0226] After the polymer fabric is impregnated with the resin and the liner (elastic layer) is made, it may be stored at low temperature, either in an ice bath or a refrigerated truck. This cold storage is sometimes necessary to prevent premature curing of the resin, before it is installed. The liner can be brought to the job site in the refrigerated truck to prevent premature curing of the resin. In some instances, the polymer fabric layer may be impregnated with the resin at the job site.

[0227] After the liner is inserted into the cryogenic hose, the resin may cure at ambient temperature, or, if required, an elevated temperature. Cure times may vary from 1 to 24 hours. Steam or hot water may be introduced to enhance curing. Steam curing requires less time, usually 3-5 hours as compared to hot water which usually takes 8-12 hours.

[0228] It is therefore apparent that the elastic inner or outer layer provides a convenient product that advantageously exhibits features of elasticity, flexibility and tear resistance that has to date not been achieved in any other product, particularly products used in the lining of cryogenic hoses. Further, the present disclosure also provides a convenient method of manufacture and application of the elastic layer to readily and efficiently create a protective barrier in cryogenic hoses.

EXAMPLES

[0229] The following Examples describe the composition of elastic layers according to exemplary embodiments of the present disclosure and are intended to illustrate the disclosure. The Examples are not to be construed as limiting in any way the scope of the present disclosure.

TABLE-US-00001 Example No. Polymer Fabric Resin 1 91% Tactel nylon/9% Polyurethane derived from Lycra fabric weave MDI (methylene diphenyl (225 g/m.sup.2) diisocyanate) 2 90% nylon/10% elastane Polyurethane derived from fabric weave (250 g/m.sup.2) MDI (methylene diphenyl diisocyanate) 3 91% Tactel nylon/9% Polyurethane derived from TDI Lycra fabric weave (toluene diisocyanate). (225 g/m.sup.2) 4 90% nylon/10% elastane Polyurethane derived from TDI fabric weave (250 g/m.sup.2) (toluene diisocyanate).

[0230] FIG. 3 illustrates a cryogenic liquid vessel (1) according to an embodiment of the present disclosure containing cryogen (2). The vessel has a composite wall structure comprising an inner elastic layer (3) an insulating layer (4) and a structural layer (5).

[0231] FIG. 4 illustrates a cryogenic liquid transfer hose (1) according to an embodiment of the present disclosure comprising an inner elastic layer according to the present disclosure (2), a metal or metal composite layer (2) and an outer protective or insulating layer (4).

[0232] FIG. 5 illustrates a cryogenic liquid transfer hose (1) according to an embodiment of the present disclosure comprising a metal or metal composite layer (2) an insulating layer (3) and an outer elastic layer according to the present disclosure (4).

[0233] It is to be understood that while the present disclosure has been described in conjunction with the specific embodiments thereof, the foregoing description is intended to illustrate and not limit the scope of the disclosure. Other aspects, advantages and modifications will be apparent to those skilled in the art to which the disclosure pertains. Therefore, the above examples are put forth so as to provide those skilled in the art with a complete disclosure and description of how to make and use the disclosed devices, and are not intended to limit the scope of the disclosure.

[0234] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.

[0235] All documents cited are herein fully incorporated by reference for all jurisdictions in which such incorporation is permitted and to the extent such disclosure is consistent with the description of the present disclosure.