Apparatus for storing or delivering hydrogen and method for manufacturing the same

Abstract

The present invention relates to a device for storing or conducting hydrogen, in particular a hydrogen tank or a hydrogen line, which is made up of a number of layers from the inside to the outside, directed towards hydrogen, in which the more inner layer has a lower diffusion coefficient (D) of hydrogen than each subsequent layer: 内側 <D2<...<D n .

Description

[Technical Field]

[0001] The present invention relates to an apparatus for storing or delivering hydrogen and a method for manufacturing the same. [Background technology]

[0002] Hydrogen is becoming increasingly important as an energy source, particularly as a substitute for fossil fuels in mobile vehicles, and is also being used in the direct reduction of iron ore and in fuel cells for power generation.

[0003] Furthermore, there are numerous technological applications where hydrogen, in any form, can be released and affect the materials used in those technologies. These applications primarily include deep drilling technology, but also encompass acid-resistant construction and the entire natural gas and oil sector.

[0004] The challenge lies not only in hydrogen storage, but also in the presence of hydrogen in technological processes.

[0005] When using hydrogen as fuel, whether for direct combustion in a properly equipped internal combustion engine or for generating electricity in a fuel cell, or even when storing hydrogen for direct reduction of iron ore, appropriate storage facilities and methods are necessary. However, among the many fuels available, hydrogen clearly poses significant risks.

[0006] When hydrogen leaks, it forms a flammable mixture with the surrounding air, and if the hydrogen content exceeds 18%, a mixture of hydrogen and oxygen is formed that can even explode.

[0007] Because hydrogen is the smallest atom of all, it can diffuse through a variety of materials, which means that many materials that are perfectly suitable for conventional fuels may not be suitable for containers. The diffusion process is further accelerated by high temperatures and high internal pressures. In particular, metal containers experience a phenomenon commonly known as hydrogen embrittlement. This means that the material becomes brittle over time, and therefore does not have sufficient stability to withstand, for example, intrusion loads. This phenomenon does not occur in plastic containers, but many plastic materials are difficult to recycle.

[0008] When using liquefied hydrogen, evaporation or gas release from the container may occur. In this case, measures are needed to address the extreme increase in volume and pressure, and significant hydrogen loss can occur, especially by using an overpressure valve.

[0009] In principle, the problem of storage in pressurized containers is now considered to be solved, but known solutions are very complex, expensive, and relatively heavy.

[0010] The same problems occur when hydrogen is guided into the corresponding pipeline.

[0011] However, these problems also arise during the processing and extraction of hydrocarbon gases such as methane and natural gas, where hydrogen exposure can also occur.

[0012] In addition to storage as a liquid or pressurized gas, there are also systems known as metal hybrid storage systems, which store hydrogen in the gaps of a metal grid. Adsorption storage is also known.

[0013] As already mentioned, metals undergo embrittlement, and hydrogen-induced cracking and hydrogen embrittlement are known to occur, particularly in steel. In this case, even small amounts of hydrogen, such as ppm, are sufficient to cause premature failure of components. Hydrogen resistance varies depending on the metal material, but this embrittlement reduces strength over time. A particular problem here is that high-strength steels exhibit hydrogen embrittlement especially. This can be addressed by manufacturing containers from lower-strength metals, especially steel. However, this means that the container walls must be thicker to ensure the required stability. This leads to increased weight, and in mobile applications, the increased weight leads to increased fuel consumption. Furthermore, the pressure at which hydrogen can be stored may be limited, and storage capacity is also reduced. CFRP tanks are beneficial in terms of storage, but they are difficult to recycle and considerably more expensive than metal tanks. Storage in metal hydrides works well in principle, but in applications such as mobile devices, the loading process is time-consuming and difficult, so it must be carefully considered.

[0014] While hydrogen barriers are a possible solution, thin barrier layers carry risks, as even minimal localized damage can lead to component failure or tank rupture. Furthermore, barrier layers must be applied later, increasing the workload. Even worse, these barrier layers don't completely prevent hydrogen from passing through; atomic hydrogen will eventually permeate any material. Chemical potential is involved in hydrogen diffusion and general diffusion. Particles diffuse to areas of lower chemical potential, thereby balancing the chemical potential and reaching a more energetically favorable state. The local chemical potential of any element in a solid is determined by several factors, including the chemical composition of the local structure and temperature. However, the most important factor is the concentration of the element itself.

[0015] According to the law of diffusion, the diffusion of hydrogen through the wall creates a concentration gradient towards the outside, corresponding to a local region of a material with a particularly low potential for hydrogen, where hydrogen accumulates to an excessive concentration. Such a local excessive concentration is particularly dangerous for metal containers due to hydrogen embrittlement.

[0016] Hydrogen molecules first attach to the surface, dissociate into atomic hydrogen, and atomic hydrogen permeates through the steel. Atomic hydrogen from the gas itself may also permeate the material, but the particles are likely to recombine beforehand.

[0017] For example, zinc plating is known as a barrier layer. As described above, zinc plating partially prevents the permeation of hydrogen, but a thin zinc coating in the first half of the two-digit micrometer range is vulnerable to damage. Usually, barriers applied to both sides of a steel sheet also prevent the leakage of hydrogen from the material. In such materials, the hydrogen content in the material increases over time. When the critical hydrogen concentration is reached, as already described, the components may be damaged due to hydrogen embrittlement.

[0018] German Patent No. 102017204240A1 discloses a steel monolithic component in which different layers are formed by selective hardening and nitriding from the inside. The aim is to generate different layers in order to enable reliable hydrogen storage. However, there is a problem because the exact transition between materials is not ensured due to the diffusion depth in nitriding. Similarly, selective cooling through the wall thickness is a process that is difficult to control. Minor variations in the analysis of the monolithic substrate lead to significant changes in the results. In this specification, it is assumed that a component with two clearly defined layers of martensite and austenite is formed, but such clearly defined layers are not formed. Instead, a wall with a continuous transition between austenite and martensite, a bainite mixed phase, and different proportions of retained austenite is generated. In addition to being quite complex, such a process cannot produce components with defined properties.

[0019] U.S. Patent No. 3,785,949B1 relates to a tank with multiple layers, where the resulting pressure is discharged from the inside to the outside via valves. This is clearly intended to prevent overpressure and material damage by diverting hydrogen. Discharge to the outer layers specifically causes the hydrogen-sensitive layers to come into contact with hydrogen and be subjected to mechanical stress. Further instability is introduced by welded connections in the outer layers. [Prior art documents] [Patent Documents]

[0020] [Patent Document 1] German Patent No. 102017204240A1 [Patent Document 2] U.S. Patent No. 3,785,949B1 [Overview of the Initiative] The problem the invention aims to solve

[0021] The objective of the present invention is to create a device for storing or delivering hydrogen that has a simple design, can be manufactured in a simple and reliable manner, and has excellent hydrogen resistance and high stability. [Means for solving the problem]

[0022] This objective is achieved by an apparatus having the features of claim 1.

[0023] Useful variations are disclosed in the dependent claims.

[0024] Another objective is to create methods for manufacturing easy-to-use, inexpensive, and reliable devices.

[0025] This objective is as stated in claim 1 4 This is achieved by a method that possesses the following characteristics.

[0026] Useful variations are disclosed in the dependent claims.

[0027] The apparatus according to the present invention for storing or delivering hydrogen may be, for example, a tank for storing hydrogen, but may also be a line for delivering hydrogen, particularly a pipeline, that delivers hydrogen to a container or from a container to a consumer. In particular, the apparatus may be a supply line to a cylinder, such as in an internal combustion engine.

[0028] In the following, when the term “container” is used, it also refers to pipelines and equipment for introducing hydrogen in any embodiment, and vice versa.

[0029] Unless otherwise specified, all weights and percentages shown below are weight percentages.

[0030] According to the present invention, a device for containing, storing, or introducing hydrogen is made of a metal, particularly steel, or more specifically, different grades of steel. In this way, a multilayer structure of metal is produced. This multilayer structure has at least two layers. According to the present invention, the inner layer, i.e., the layer facing the hydrogen being introduced or stored, is made of a material that has low vulnerability to hydrogen and a low diffusion coefficient to hydrogen, particularly steel.

[0031] The metallurgically bonded outer material has a higher diffusion coefficient for hydrogen. Preferably, the metallurgically bonded outer material also has significantly higher tensile strength than the aforementioned material.

[0032] According to the present invention, as a result, the hydrogen concentration in the inner hydrogen-insensitive material decreases rapidly. Consequently, the concentration in the outer material remains low. Because the diffusion coefficient of the outer layer is relatively high, hydrogen diffusing through the inner layer is quickly released to the outside and does not exceed the critical concentration of hydrogen in the outer material.

[0033] Therefore, according to the present invention, rather than attempting to prevent the inevitable intrusion of hydrogen, the intrusion of hydrogen is controlled and kept within an acceptable range. Of course, it is also possible to use multiple metallurgically bonded layers instead of two layers bonded to each other by a material bonding formula, in which case, according to the present invention, each additional outer steel layer needs to have an even higher diffusion coefficient for hydrogen.

[0034] Preferably, metallurgical joining between materials is achieved using press welding. A well-known press welding method is generally called roll cladding (Walzplattieren), in which two or more layers of steel sheets of different steel grades are rolled together. In contrast to prior art that attempts to achieve multilayering through chemical action, press welding achieves a layer sequence with precisely defined thickness and properties. In addition, such known press welding methods ensure a porosity-free boundary layer between materials, thus preventing the recombination of atomic hydrogen at the bonding surface.

[0035] Therefore, the present invention relates in particular to a device for storing or guiding hydrogen, in particular to a hydrogen tank or hydrogen line, the device comprising multiple layers from the inside outward toward the hydrogen, wherein the innermost layers have a lower hydrogen diffusion coefficient (D) than each subsequent layer:D 内側 <D2<...<D n .

[0036] In one variation, the thickness of the inner layer (t i ) is as follows with respect to the thickness (t2) of the adjacent layer: D i * t2 <D2 * t i It behaves like this.

[0037] In one variation, the layer is made of steel or a nickel-based alloy.

[0038] In one variation, the layers are metallurgically joined to one another, press-welded, or drawn together.

[0039] In one modification example, a plastic liner and / or a ceramic liner is provided inside the device. The purpose of such a liner is to provide chemical corrosion prevention.

[0040] In one modification example, an organic corrosion prevention layer or a metal corrosion prevention layer having a hydrogen diffusion coefficient D lower than the outermost layer's diffusion coefficient is provided outside the device.

[0041] They can be, for example, polymer solutions such as rubber coatings, synthetic resin-based paints, or acrylic paints. The compatibility of the metal layer depends greatly on its composition and the application method. For example, the diffusion coefficient of pure zinc in the austenite region is very small, but the diffusion coefficient as an alloy is significantly different. For 12% Ni, the diffusion coefficient for hydrogen is about 0.5 * 10 -12 is reached. In the measurement, the influence of the application method is also shown. The corrosion prevention layer of zinc by PVD showed very high permeability to hydrogen. Therefore, corrosion prevention measures by hot-dip galvanizing or electro-galvanizing should be avoided, and other application techniques or other alloy compositions of the corrosion prevention layer or paint coating should be prioritized.

[0042] In one modification example, the multilayer structure has a thickness of 2 - 45 mm, and the thickness of the innermost layer is at least 0.3 mm.

[0043] According to one modification example, the yield strength of the strongest layer is over 350 MPa, preferably over 500 MPa, and particularly preferably over 650 MPa. <了

[0044] In one modification example, materials such as high manganese austenitic TWIP, austenitic stainless steel, or nickel-based alloys, which have a proportionally lower diffusion coefficient for hydrogen, are used as the material that contacts hydrogen on the inside.

[0045] One example of modification is the use of a delayed-transformation quench-temper steel, a quenchable boro-manganese alloy, or a quench-temperable chromium-molybdenum alloy as the outer and / or intermediate layers.

[0046] In one variation, the following materials are arranged from the inside out, and the third outer layer is optional: Layer 1: TWIP, Layer 2: 38MnSi4, Layer 3: S355, or Layer 1: 316L, Layer 2: 34CrMo4, Layer 3: S235, or Layer 1: Alloy 625, Layer 2: 42CrMo4, Layer 3: 340LA, or 1st layer 304L 2nd layer 34MnB5 3rd layer 420LA.

[0047] A further aspect of the present invention relates to a method for manufacturing a device for storing or guiding hydrogen, particularly for manufacturing a hydrogen tank or hydrogen line, wherein the device is formed of multiple layers from the inside outward toward the hydrogen, with the innermost layers having a lower hydrogen diffusion coefficient (D) than each subsequent layer:D 内側 <D2<...<D n At least two metal layers are metallurgically joined together.

[0048] In one modification, the material for forming the apparatus is subjected to rolling cladding, explosive cladding, or is drawn together.

[0049] In one variation, a plastic or ceramic liner is applied to the inner layer facing the hydrogen to prevent hydrogen dissociation. However, compared to metal, plastic liners are more permeable to hydrogen.

[0050] In one variation, a metal corrosion-preventive layer or an organic corrosion-preventive layer made of a material with a lower diffusion coefficient than the outer layer is provided on the outside of the outer layer.

[0051] In one modification, each layer of the material is welded in the same manner so that the welded joint has a material structure equivalent to the rest of the main body, forming a sealed container or connecting a pipe section.

[0052] In one modification, each layer of the material is welded by HF welding, MIG / MAG welding, or TIG welding. These welding methods allow each layer to be welded in the same manner, provided the edges are properly pre-treated. In contrast, laser welding makes it impossible to join material layers individually.

[0053] Further embodiments relate to the use of the apparatus as a stationary hydrogen tank for storing generated hydrogen, or as a hydrogen tank for a stationary internal combustion engine for generating electricity and heat, or as a hydrogen tank for use in a building heating system, or as a hydrogen tank for storing hydrogen for use in a direct reduction system for metal ore.

[0054] Further embodiments relate to the use of the device in mobile applications, such as hydrogen tanks in automobiles, trucks, agricultural vehicles, ships, aircraft, and aerospace technology.

[0055] Further embodiments relate to the use of the device as a fuel supply line and similar line or pipeline for supplying hydrogen to a combustion chamber, or to an injector, or to a direct reduction system for metal ore.

[0056] Further embodiments relate to the use of the apparatus as a liner or lining and pipe in the construction of a chemical plant for guiding hydrogen, and in the construction of tanks and pipelines in areas where hydrogen exposure occurs, as part of a drill pipe in the field of deep drilling technology.

[0057] It should be noted that when hydrogen is mentioned above, hydrogen exposure is also included. Such exposure can occur in the aforementioned methods and uses of handling other gases such as methane and natural gas. This includes underground storage of such gases or hydrogen, or the synthesis of hydrocarbon gases.

[0058] The present invention will be explained illustratively with reference to the drawings. [Brief explanation of the drawing]

[0059] [Figure 1] This paper presents a theory regarding the mechanism of material damage caused by hydrogen. [Figure 2] This demonstrates diffusion as a function of chemical potential. [Figure 3] This shows the behavior of hydrogen in relation to the hydrogen concentration in a conventional steel container. [Figure 4] This shows the hydrogen concentration across the cross-section of a material having barrier layers on both sides. [Figure 5] This shows the hydrogen distribution in the structure according to the present invention. [Figure 6] This shows a very schematic two-layer structure according to the present invention. [Figure 7] A schematic diagram of the three-layer structure according to the present invention is shown. [Figure 8] This image, taken with an electron microscope, shows the material bonding between austenitic stainless steel and quenched and tempered steel manufactured using vacuum cladding (evakuierte Plattierpakete). [Figure 9] A very schematic diagram of the hydrogen concentration across the material thickness in a two-layer material structure is shown. [Figure 10] A very schematic diagram of the hydrogen concentration across the material thickness in a three-layer material structure is shown. [Modes for carrying out the invention]

[0060] Figure 2 shows the relationship between chemical potential and concentration.

[0061] Figure 3 illustrates the relationship in a typical single-walled steel container where hydrogen molecules and atomic hydrogen are present inside the container, with hydrogen molecules diffusing into the steel but atomic hydrogen diffusing only slightly. Hydrogen molecules first adhere to the surface of the coating, then dissociate to form atomic hydrogen, which then permeates the steel. The critical concentration that damages the steel is shown by the dotted line, and the essential hydrogen concentration is shown by the solid line, decreasing outwards. As explained above, according to the law of diffusion, when hydrogen diffuses through a wall (in this case, a single-walled steel container), a concentration gradient is created outwards, as shown by the solid line. However, in materials with particularly low hydrogen potential, there are localized points where hydrogen accumulates and its concentration increases. At such points, generally called hydrogen traps, the localized critical concentration is exceeded, and it is necessary to assume that damage will occur there.

[0062] Figure 4 shows the corresponding state of materials, particularly steel, that also have barrier layers such as a metallic zinc layer. As is clear from the fact that the initial hydrogen concentration is basically low, the concentration is basically low, but as can be seen here, the barriers on both sides prevent hydrogen leakage from the material. Therefore, in the long term, the hydrogen content in the material increases, the concentration gradient changes (upper curve), and furthermore, due to the hydrogen trapping described above, it locally exceeds the critical concentration.

[0063] Figure 5 shows the state of the structure according to the present invention. This figure shows two layers: an inner layer, i.e., the layer facing hydrogen, and an outer layer facing outwards. The inner material has relatively high resistance to hydrogen diffusion. This is evident from the curve, which is a very steep drop, so the hydrogen concentration decreases very rapidly across the thickness of the material. At the same time, this material is relatively resistant to hydrogen damage. According to the present invention, since the outer material has an even higher hydrogen diffusion coefficient than the inner layer, hydrogen that enters the outer layer from the inner layer is dissipated noncritically to the outside (Figure 5, lower curve portion). In this case, even the unavoidable high-concentration hydrogen trap will not exceed the critical concentration. The outer layer in this case is made of, for example, a thicker, and in particular, high-quality steel grade that is not suitable as an inner layer but ensures the mechanical stability of the corresponding vessel by its high tensile and yield strength. This is especially important for impact stability in mobile applications. On the other hand, it is relatively easy to construct, lightweight, and inexpensive to manufacture. Furthermore, its high stability means that, in some cases, it may at least reduce the need for extreme protective measures for hydrogen containers.

[0064] Figure 6 shows how this structure basically behaves. The hydrogen layer thickness (t) i = thickness of the inner layer, t o (thickness of the outer layer) and diffusion coefficient (D i and D o ) behaves as follows: Di×T o <Do×t i .

[0065] This is particularly beneficial when the inner layer has a low material content such that Di is significantly smaller than Do. This results in a larger concentration gradient in the inner layer material, allowing the hydrogen concentration in the outer layer material to be kept low.

[0066] As shown in Figure 7, a three-part material is also possible, where the layer thickness and diffusion coefficient behave as follows: D1×t2≦D2×t1 and D2×t3 <D3×t2。

[0067] Such a layer arrangement is beneficial, for example, when it is desired to further reduce the hydrogen concentration in the outer layer or for processing reasons (simple joining of the outer layer). If desired, this arrangement can be used to protect the high-strength but brittle layer D2 from mechanical influences by the ductile outer layer D2.

[0068] Since the relationship D1 < D2 < D3 still applies, a continuous decrease in hydrogen concentration can mainly occur in the inner layer.

[0069] The diffusion coefficient of hydrogen in steel is mainly affected by the structure and chemical composition. Diffusion is also affected by many other factors such as grain size distribution and phase composition. In the case of grain size distribution, in contrast to grain boundary diffusion, it particularly affects lattice diffusion.

[0070] Therefore, in the case of the multilayer structure according to the present invention, it is reasonable to individually measure the diffusion coefficients of the materials used in order to obtain effective data. However, since some general effects are assumed, they will be described below.

[0071] Regarding the chemical composition, that is, the alloy in the case of steel, it can be said that the alloying elements nickel, molybdenum, cobalt, silicon, sulfur, carbon, and chromium reduce the diffusion coefficient of hydrogen in steel. In other words, they are alloying elements also used particularly in stainless steel. Regarding the structure, the diffusion coefficient in austenite can be said to be 10 5 times higher than that in pure ferrite. In this case, the martensite phase and the bainite phase are between the austenite phase and the ferrite phase. However, it should be noted that the actual diffusion rate greatly depends on the retained austenite content or phase composition and grain size.

[0072] For example, the diffusion coefficient of ferrite pure iron is 7×10 -9 m 2 / s at room temperature. As the alloy content or carbon content increases, the diffusion coefficient decreases, and in X65 steel, it is about 4.5×10 -10 m 2 / s, and in HSLA100, it is only 4.5×10 -13 m2 This will be / second.

[0073] As mentioned above, stainless steel tends to have a low hydrogen diffusivity, but the phase composition is important. For example, the diffusion coefficient of ferritic stainless steel is 5 × 10⁻⁶. -13 In summary, the diffusion coefficient of martensitic stainless steel is slightly lower, while the diffusion coefficient of austenitic stainless steel is 5 × 10⁻⁶. -16 m 2 It is per second.

[0074] Therefore, for the inner material that comes into contact with hydrogen, materials with a proportionally low diffusion coefficient to hydrogen are used, such as high-manganese austenitic TWIP, austenitic stainless steel (e.g., 304L, 316L, etc.), or nickel-based alloys such as Alloy 625 or Alloy 825.

[0075] An example of a grade with a high manganese content has the following composition: Carbon (C) 0.3-1 Manganese (Mn) 13-24 Silicon (Si) 0.01-2 Aluminum (Al) 0.03-2.5 Chromium (Cr) 0.03-2.5 Titanium (Ti) 0.01-0.08 Nitrogen (N) <0.04 Phosphorus (P) <0.03 Sulfur (S) <0.02 Nickel (Ni) <1 The remainder consists of iron and smelting-related impurities.

[0076] Suitable austenitic stainless steels include steels with the following alloy compositions: Carbon (C) 0.01-0.1 Manganese (Mn) 0.2-2.0 Silicon (Si) 0.01-1 Chromium (Cr) 16-20 Titanium (Ti) 0.01-0.08 Nitrogen (N) <0.05 Phosphorus (P) <0.04 Sulfur (S) <0.015 Molybdenum (Mo) 1-2.5 Nickel (Ni) 7-15 The remainder consists of iron and smelting-related impurities.

[0077] A suitable nickel-based alloy is an alloy with the following composition: Carbon (C) 0.01-0.1 Manganese (Mn) 0.01-1 Silicon (Si) 0.02-0.5 Aluminum (Al) 0.02-0.4 Cobalt (Co) <1 Chromium (Cr) 18-24 Copper (Cu) 0.05-3 Iron (Fe) <18 Molybdenum (Mo) 2-10 Niobium 3-4.5 Titanium (Ti) <0.04 Phosphorus (P) <0.02 Sulfur (S) <0.01 The remainder consists of nickel and smelting-related impurities.

[0078] Suitable outer and intermediate layers are delayed-transformation quenched and tempered steel, quenchable boro-manganese alloys, and quenched and temperable chromium-molybdenum alloys. One possible alloy composition is as follows: Carbon (C) 0.08-0.6 Manganese (Mn) 0.5-3.0 Aluminum (Al) 0.01-0.07 Silicon (Si) 0.01-0.7 Chromium (Cr) 0.02-2 Titanium (Ti) 0.01-0.08 Nitrogen (N) <0.02 Boron (B) 0.002-0.02 Phosphorus (P) <0.01 Sulfur (S) <0.01 Molybdenum (Mo) 0.01-0.5 The remainder consists of iron and smelting-related impurities.

[0079] If an outer layer is to be added, ferritic steels such as IF steel, structural steel, and microalloy steel are mainly used. The following table shows an example of a suitable microalloy steel: Carbon (C) 0.02-0.15 Manganese (Mn) 0.2-2.0 Aluminum (Al) 0.01-0.07 Silicon (Si) <0.5 Chromium (Cr) <0.3 Titanium (Ti) + Niobium (Nb) 0.01-0.15 Nitrogen (N) <0.02 Boron (B) <0.02 Phosphorus (P) <0.01 Sulfur (S) <0.01 Molybdenum (Mo) <1 The remainder consists of iron and smelting-related impurities.

[0080] As a result, arrangements like the following become possible: 1. TWIP-38MnSi4(+S355) 2.316L-34CrMo4(+S235) 3. Alloy 625-42CrMo4 (+340LA) 4.304L-34MnB5(+420LA)

[0081] As one example, the corresponding arrangement is roll-clad, where the steel sheet stack is formed in essentially known ways, heated to rolling temperature in a pusher furnace, hot-rolled, and then cold-rolled. Tests of these clad steel sheets have shown that the material can withstand hydrogen exposure. As expected, no hydrogen recombination occurs at the bonding surfaces.

[0082] The hot rolling cladding process is beneficial when carried out using airtight, vacuum-sealed cladding packs to minimize oxide formation at the joint surface during the heating process to the rolling temperature. The metallographic cross-section in Figure 8 illustrates material bonding between various possible materials.

[0083] In some material combinations, the pure nickel layer on the cladding surface was found to improve adhesion within the cladding. The auxiliary layer was thin, and the diffusion coefficient of hydrogen in pure nickel was relatively high compared to that of austenite (10 -10 m 2 ( / second) is one reason to use the adhesion-promoting substance according to the present invention.

[0084] One possible embodiment is shown in the following examples, but this is merely illustrative and should be understood as not being limiting.

[0085] The inner layer is 2 mm thick and has the following composition by weight percentage: C=0.016, Cr=17.2 Ni = 10.2, Mn=0.9, Si = 0.46, Mo=2.03, P = 0.0025, S=0.001, N=0.035, The remainder is iron and smelting-related impurities; It has 5 × 10 -16 m 2 Type 316L steel having a hydrogen diffusion coefficient of / s, The outer layer is 10 mm thick and has the following composition by weight percentage: C=0.35, Mn=0.5, Si = 0.25, Cr=1.04, Mo=0.18, S=0.015, P=0.016 The remainder is iron and smelting-related impurities; It has 1 × 10 -13 m 2 Type 34MoCr4 steel, having a hydrogen diffusion coefficient of / s, is used together to form a rolled cladding.

[0086] The concentrations of the diffusion medium into and through the wall can be expressed almost linearly in a steady state, and the slope of each concentration gradient within the multilayer material is inversely proportional to the diffusion coefficient. Due to the selection of cladding partners, in the example above, most of the hydrogen concentration (about 97% of the total concentration gradient) has already decreased by the time it reaches the cladding level, and the hydrogen content in the outer layer is kept low. This is shown in Figure 9.

[0087] Another non-restrictive example is the example of a three-layer structure. Made from nickel-based Alloy 625, with a thickness of 0.5 mm and the following composition by weight percentage: C = 0.013, Al=0.2 Si = 0.16, Cr=21.2, Mo=8.2, Ti=1.4, Nb = 3.6, The remainder is nickel and unavoidable manufacturing-related impurities; It has approximately 2 × 10 -15 m 2 An inner layer having a hydrogen diffusion coefficient of / s, Made from 42CrMo4 steel, 10mm thick, with the following composition by weight percentage: C = 0.415, Cr=0.99, Mo = 0.22, Mn=0.6, Si = 0.19, The remainder consists of iron and unavoidable melt-related impurities; It has approximately 1.5 × 10 -13 m 2 A second intermediate layer having a hydrogen diffusion coefficient of / s, Made from 340LA steel, 3mm thick, with the following composition by weight percentage: C = 0.079, Si = 0.02, Mn = 0.33, Al = 0.042, Cr=0.02, Nb = 0.054, B = 0.0002, Mo = 0.003, The remainder consists of iron and unavoidable melt-related impurities: It has approximately 4 x 10 -11 m 2 A third outer layer, having a hydrogen diffusion coefficient of / s, is subjected to rolling cladding together. The distribution of hydrogen can also be calculated in this example.

[0088] In this example, the hydrogen concentration in the Alloy625 inner layer has already been reduced by approximately 78%. As a result, the hydrogen content in the intermediate layer has already been significantly reduced. The microalloy outer layer does not change the concentration gradient as much, but its good weldability allows for the attachment of a grip or handle.

[0089] This example is shown in Figure 10.

[0090] According to the present invention, the corresponding manufacturing apparatus can be used as a stationary hydrogen generation tank, for example, for stationary internal combustion engines that generate electricity or heat. Furthermore, if this technology is further realized, it will naturally be possible to use it as a hydrogen tank for use in building heating systems.

[0091] Furthermore, such devices can be usefully used in mobile applications. They are particularly useful in automobiles, trucks, agricultural vehicles, ships, and aircraft, as well as in the aerospace industry in general.

[0092] Since the present invention also includes the manufacture of pipes, such pipes can be installed on a small scale as fuel supply lines and similar lines for supplying hydrogen to combustion chambers, injection systems, or direct reduction systems for metal ores. Furthermore, such pipes can be used on a larger scale as pipelines.

[0093] This positive property is beneficial both as part of drill pipes in the field of deep drilling technology, and as liners or linings and pipes in the construction of chemical plants for hydrogen delivery, and in the construction of tanks and pipelines in areas where hydrogen exposure occurs. Hydrogen exposure occurs not only during the processing, extraction, or storage of hydrogen, but also during the processing, extraction, or storage of natural gas.

[0094] Therefore, the present invention makes it possible to manufacture a device for storing and / or retrieving hydrogen that can reliably store or retrieve hydrogen in a mechanically safe and durable manner.

[0095] The method according to the present invention makes it possible to manufacture such devices in a simple manner, particularly on an industrial scale.

Claims

1. A device for storing or introducing hydrogen, wherein the device is composed of multiple layers arranged from the inside outward toward the hydrogen, with the innermost layers having a lower hydrogen diffusion coefficient (D) than each subsequent layer: D 内側 <D ２ <... <D ｎ , The aforementioned layers are metallurgically joined to each other, press-welded, or drawn together. The thickness of the inner layer (t ｉ ) is the thickness of the adjacent layer (t ２ ) For the following: D ｉ ＊ t ２ <D ２ ＊ t ｉ An apparatus that behaves as such.

2. The apparatus according to claim 1, characterized in that the apparatus has at least two metal layers.

3. The apparatus according to claim 2, characterized in that the metal layer has a different alloy composition.

4. The apparatus according to claim 1 or 2, characterized in that the layer is made of steel or a nickel-based alloy.

5. The apparatus according to claim 1 or 2, characterized in that a plastic liner and / or a ceramic liner are provided inside the apparatus.

6. The apparatus according to claim 1 or 2, characterized in that an organic corrosion prevention layer or a metal corrosion prevention layer having a hydrogen diffusion coefficient D lower than the diffusion coefficient of the outermost layer is provided on the outside of the apparatus.

7. The apparatus according to claim 1 or 2, characterized in that the outer coating is formed from a polymer solution and / or from a zinc-nickel alloy, or from a zinc layer or zinc alloy layer applied by the PVD method.

8. The apparatus according to claim 7, characterized in that the polymer solution is selected from the group consisting of rubber coatings, synthetic resin-based paints, and acrylic-based paints.

9. The apparatus according to claim 1 or 2, characterized in that the multilayer structure has a thickness of 2 to 45 mm, and the thickness of the innermost layer is at least 0.3 mm.

10. The apparatus according to claim 1 or 2, characterized in that the yield strength of the strongest layer is greater than 350 MPa.

11. The apparatus according to claim 1 or 2, characterized in that a material with a relatively low diffusion coefficient for hydrogen is used as the inner material that comes into contact with hydrogen.

12. The apparatus according to claim 11, characterized in that the material with a relatively low diffusion coefficient to hydrogen is selected from the group consisting of high manganese austenitic TWIP, austenitic stainless steel, and nickel-based alloys.

13. The apparatus according to claim 1 or 2, characterized in that a delayed transformation quenching and tempering steel, a quenchable boron-manganese alloy, or a quenchable and temperable chromium-molybdenum alloy is used as the outer layer, the intermediate layer, or both layers.

14. The apparatus according to claim 1 or 2, wherein the following material arrangement exists from inside to outside, and the third outer layer is optional: Layer 1: TWIP, Layer 2: 38MnSi4, Layer 3: S355, or First layer 316L, second layer 34CrMo4, third layer S235, or Layer 1 Alloy625, Layer 2 42CrMo4, Layer 3 340LA, or First layer 304L Second layer 34MnB5 Third layer 420LA.

15. A method for manufacturing a device for storing or delivering hydrogen, The apparatus is composed of multiple layers extending from the inside, which is oriented toward the hydrogen, outwards, with the innermost layers having a lower hydrogen diffusion coefficient (D) than each subsequent layer: D 内 側 <D ２ <... <D ｎ At least two metal layers are metallurgically joined, The thickness of the inner layer (t ｉ ) is the thickness of the adjacent layer (t ２ ) For the following: D ｉ ＊ t ２ <D ２ ＊ t ｉ A method characterized by behaving as follows.

16. The method according to claim 15, characterized in that the material for forming the apparatus is subjected to rolling cladding, explosive cladding, or is drawn together with the material.

17. The method according to claim 15 or 16, characterized in that a plastic or ceramic liner is provided on the inner layer facing the hydrogen side to prevent hydrogen dissociation.

18. The method according to claim 15 or 16, characterized in that a metal corrosion prevention layer or an organic corrosion prevention layer made of a material having a lower diffusion coefficient than the outer layer is applied to the outside of the outer layer.

19. Use of the apparatus according to claim 1 or 2 as a stationary hydrogen tank for storing generated hydrogen, or as a hydrogen tank for a stationary internal combustion engine for generating electricity and heat, or as a hydrogen tank for use in a building heating system, or as a hydrogen tank for storing hydrogen for use in a direct reduction system for metal ore.

20. Use of the apparatus according to claim 1 or 2 in mobile applications, as a hydrogen tank in automobiles, trucks, agricultural vehicles, ships, aircraft, and aerospace technology.

21. Use of the apparatus according to claim 1 or 2 as a fuel supply line and similar line or pipeline for supplying hydrogen to a combustion chamber, or to an injection device, or to a direct reduction system for metal ore.

22. Use of the apparatus according to claim 1 or 2 as a liner or lining and pipe in the construction of a chemical plant for introducing hydrogen, and in the construction of tanks and pipelines in areas where hydrogen exposure occurs, as part of a drill pipe in the field of deep drilling technology.

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