Search

JP-2026076155-A - Multilayer structure for transporting or storing hydrogen

JP2026076155AJP 2026076155 AJP2026076155 AJP 2026076155AJP-2026076155-A

Abstract

[Problem] To provide a multilayer structure configured for transporting, distributing, or storing hydrogen. [Solution] A multilayer structure comprising a sealing layer (1) and at least one composite reinforcing layer (2) from the inside out, wherein the sealing layer comprises a layer (a) made of a composition mainly comprising a short-chain polyamide thermoplastic polymer, an impact resistance modifier of more than 15% and up to 50% by weight, or mainly a semi-crystalline long-chain polyamide thermoplastic polymer, an impact resistance modifier of up to 50% by weight relative to the total weight of the composition, and a plasticizer of up to 3% by weight relative to the total weight of the composition, a hydrogen barrier layer made of PVDF or EVOH, and a layer (b) (= layer (a)), the innermost part of the composite reinforcing layer (2) is wound around the sealing layer (1), and at least one of the composite reinforcing layers is made of a fibrous material in the form of continuous fibers impregnated with a composition mainly comprising at least one polymer P1j, where j = 1 to m, and m is the number of reinforcing layers. [Selection Diagram] None

Inventors

  • デュフォール， ニコラス
  • ダン， パトリック
  • グピル， アントワーヌ

Assignees

  • アルケマ フランス

Dates

Publication Date
20260511
Application Date
20251224
Priority Date
20200128

Claims (15)

  1. A multilayer structure configured for transporting, distributing, and storing hydrogen, particularly for storing hydrogen, comprising a sealing layer (1) and at least one composite reinforcing layer (2) from the inside out. The aforementioned sealing layer is applied from the inside outwards. A layer (a) made of a composition, the composition is Short-chain aliphatic polyamide thermoplastic polymers whose Tm is measured according to ISO 11357-3:2013 and is above 160°C, specifically above 170°C. It mainly contains impact-resistant modifiers in amounts of more than 15% and up to 50%, or Long-chain semicrystalline aliphatic polyamide thermoplastic polymers whose Tm is measured according to ISO 11357-3:2013 and is above 160°C, specifically above 170°C. Impact modifiers up to 50% by weight, particularly impact modifiers up to less than 15% by weight, and more specifically, impact modifiers up to 12% by weight, relative to the total weight of the composition. Up to 3% by weight of plasticizer relative to the total weight of the composition. Layer (a) mainly contains A binder layer can be optionally selected. In particular, a hydrogen barrier layer made of a fluoropolymer, especially PVDF or EVOH, preferably EVOH. A binder layer can be optionally selected. A layer (b) comprising a composition, the composition is Short-chain aliphatic polyamide thermoplastic polymers whose Tm is measured according to ISO 11357-3:2013 and is above 160°C, specifically above 170°C. It mainly contains impact-resistant modifiers in amounts exceeding 15% and up to 50%, or Long-chain semicrystalline aliphatic polyamide thermoplastic polymers whose Tm is measured according to ISO 11357-3:2013 and is above 160°C, specifically above 170°C. Impact modifiers up to 50% by weight, particularly impact modifiers up to less than 15% by weight, and more specifically, impact modifiers up to 12% by weight, relative to the total weight of the composition. Up to 3% by weight of plasticizer relative to the total weight of the composition. Layer (b) mainly contains Includes, The innermost composite reinforcing layer (2) is wrapped around the sealing layer (1), At least one of the composite reinforcing layers is made of a fibrous material in the form of continuous fibers impregnated with the composition, the composition mainly comprises at least one polymer P1j, where j = 1 to m, and m is the number of reinforcing layers, and more specifically comprises an epoxy resin or epoxy-based resin, in a multilayer structure.
  2. The multilayer structure according to claim 1, characterized in that layer (a) and layer (b) contain the same polyamide.
  3. The multilayer structure according to claim 1, characterized in that layer (a) and layer (b) contain different polyamides.
  4. The multilayer structure according to any one of claims 1 to 3, characterized in that the polyamide of layer (a) and/or (b) is a long-chain aliphatic polyamide, more specifically selected from PA11, PA12, PA1010, PA1012, and particularly PA11 or PA12.
  5. The multilayer structure according to any one of claims 1 to 3, characterized in that the polyamide of layer (a) and/or (b) is a short-chain aliphatic polyamide, more specifically selected from PA6, PA66, and PA6/66.
  6. A multilayer structure according to any one of claims 1 to 5, characterized in that each reinforcing layer contains the same type of polymer, more specifically, an epoxy resin or epoxy-based resin.
  7. A multilayer structure according to any one of claims 1 to 6, characterized by having a single reinforcing layer.
  8. The multilayer structure according to any one of claims 1 to 6, characterized in that the polymer P1j is, in particular, PA1010, PA1012, PA1212, PA11, and PA12.
  9. The multilayer structure according to any one of claims 1 to 8, characterized in that the polymer P1j is an epoxy resin or an epoxy-based resin.
  10. The multilayer structure according to any one of claims 1 to 9, characterized in that the multilayer structure comprises a single reinforcing layer and a sealing layer, the polyamide of layer (a) and/or (b) is a short-chain aliphatic polyamide, specifically selected from PA6, PA66, and PA6/66, or a long-chain aliphatic polyamide, specifically selected from PA1010, PA1012, PA1212, PA11, and PA12, particularly PA11 and PA12, and the polymer P1j is an epoxy resin or epoxy-based resin.
  11. The multilayer structure according to any one of claims 1 to 9, characterized in that the multilayer structure comprises a single reinforcing layer and a sealing layer, the polyamide of layer (a) and/or (b) is a short-chain aliphatic polyamide, specifically selected from PA6, PA66, and PA6/66, or a long-chain aliphatic polyamide, specifically selected from PA1010, PA1012, PA1212, PA11, and PA12, particularly PA11 and PA12, and the polymer P1j is a long-chain aliphatic polyamide, specifically selected from PA1010, PA1012, PA1212, PA11, and PA12, particularly PA11 and PA12, or a semi-aromatic polyamide, specifically selected from 11/5T, 11/6T, or 11/10T polyamides, MXDT/10T, MPMDT/10T, and BACT/10T.
  12. The multilayer structure according to any one of claims 1 to 11, characterized in that the fibrous material of the composite reinforcing layer is selected from glass fibers, carbon fibers, basalt fibers, or basalt-based fibers, or mixtures thereof, particularly carbon fibers.
  13. The multilayer structure according to any one of claims 1 to 12, wherein the structure further comprises at least one outer layer made of a fibrous material consisting of continuous glass fibers impregnated with a permeable amorphous polymer, and the layer is the outermost layer of the multilayer structure.
  14. A method for producing a multilayer structure according to any one of claims 1 to 13, characterized by comprising the step of preparing a sealing layer by extrusion blow molding, rotational molding, injection molding and/or extrusion.
  15. A method for producing the multilayer structure according to claim 14, characterized by comprising the step of filament winding the reinforcing layer according to claim 1 around the pre-prepared sealing layer according to claim 1.

Description

This patent application relates to a multilayer composite structure for transporting, distributing, or storing hydrogen, and more particularly for distributing or storing hydrogen, and to a method for producing such a structure. Hydrogen tanks are currently attracting considerable attention from numerous manufacturers, particularly in the automotive sector. One of the desired goals is to propose even lower-emission vehicles. Therefore, the aim is for electric or hybrid vehicles, including batteries, to gradually replace internal combustion engine vehicles, such as gasoline or diesel vehicles. Batteries are known to be relatively complex vehicle components. Depending on the battery's location in the vehicle, it may need to be protected from impact and from external environments that can be extremely high in temperature and variable humidity. Avoiding any risk of fire may also be necessary. Furthermore, it is crucial that their operating temperatures do not exceed 55°C to avoid damaging the battery cells and extend their lifespan. Conversely, in winter, for example, it may be necessary to raise the battery temperature to optimize battery operation. Furthermore, electric vehicles still suffer from several problems today, namely battery range, the use of rare earth metals in these batteries, the limited availability of resources, charging times that are far longer than the time it takes to refill the tank, and the challenges of generating the electricity needed to charge the batteries in various countries. Therefore, hydrogen can be converted into electricity by fuel cells, and thus supply power to electric vehicles, making it a substitute for electric batteries. Hydrogen tanks typically consist of a metal liner (or sealing layer) that must protect hydrogen from permeation. One type of tank is called Type IV, which is based on a thermoplastic liner with a composite layer wrapped around it. The fundamental principle is to separate the two essential functions of sealing and mechanical strength and manage them independently of each other. In this type of tank, the liner (or sealing sheath), made of thermoplastic resin, is combined with a reinforcing structure consisting of fibers (glass, aramid, carbon), also known as a reinforcing sheath or layer. This allows it to operate at much higher pressures while reducing weight and avoiding the risk of explosion in the event of severe external impact. The liner must possess certain fundamental characteristics: Potential conversion methods include extrusion blow molding, rotational molding, injection molding, or extrusion. Low hydrogen permeability, or in fact, the permeability of the liner, is a crucial factor in limiting hydrogen leakage from the tank. Excellent mechanical properties (fatigue) at low temperatures (-40 to -70°C) Heat resistance at 120°C In practice, it is necessary to increase the hydrogen tank filling rate, which should be roughly equivalent to that of an internal combustion engine fuel tank (approximately 3 to 5 minutes). However, this increase in rate causes the tank to overheat significantly, reaching a temperature of approximately 100°C. The performance and safety of hydrogen tanks can be evaluated at the Reference European Laboratory (GasTeF: Hydrogen Tank Test Facility), as described by Galassi et al. (World Hydrogen Energy Conference 2012, Onboard compressed hydrogen storage: fast filling experiments and simulations, Energy Procedia 29 (2012), pp. 192-200). The first-generation Type IV tanks used a high-density polyethylene (HDPE) based liner. However, HDPE has the drawbacks of having too low a melting point and too high a hydrogen permeability. This presents a problem in terms of heat resistance, requiring new requirements and preventing an increase in tank filling speed. Polyamide PA6-based liners have been under development for many years. Nevertheless, PA6 has the disadvantage of having low resistance to cold. Application US2014/008373 relates to a lightweight storage cylinder for high-pressure compressed gas, having a liner surrounded by a restraining layer, The line, First inner layer of impact-resistant modified polyamide (PA) that comes into contact with gas, This document describes a cylinder that includes a thermoplastic outer layer in contact with a restraining layer, and an adhesive bonding layer between a first impact-resistant improved PA inner layer and the outer thermoplastic layer. French patent application FR2923575 describes a tank for storing fluid under high pressure, comprising metal end pieces at each of its axial ends, wherein a liner surrounds the end pieces, and a structural layer made of thermosetting resin-impregnated fibers surrounds the liner. WO 18155491 describes a hydrogen transport component having a three-layer structure, the inner layer comprising PA11, 15 to 50% impact modifier, and 1 to 3% plasticizer, or a composition lacking plasticizer, the composition possessing hydrogen barrier properties, good flexibilit