Bimetallic composite pipe for high-pressure hydrogen storage and transmission and preparation method therefor

Abstract

Provided in the present application are a bimetallic composite pipe for high-pressure hydrogen storage and transmission and a preparation method therefor. The bimetallic composite pipe for high-pressure hydrogen storage and transmission is obtained by performing submerged arc welding on a bimetallic composite pipe blank. The bimetallic composite pipe blank comprises an alloy steel layer and an austenitic stainless steel deposition layer that are stacked. The austenitic stainless steel deposition layer is obtained by means of performing metal-cored welding wire deposition. An outer wall of the bimetallic composite pipe is obtained by means of performing submerged arc welding using a welding wire on the alloy steel, and an inner wall of the bimetallic composite pipe is obtained by means of performing submerged arc welding using a welding wire on the austenitic stainless steel. The bimetallic composite pipe for high-pressure hydrogen storage and transmission has excellent hydrogen embrittlement resistance and good fracture toughness and impact toughness, thus ensuring safe and efficient storage and transmission of high-pressure hydrogen.

Description

A bimetallic composite pipe for high-pressure hydrogen storage and transportation and its preparation method

[0001] This application claims priority to Chinese Patent Application No. 2024114623105, filed on October 18, 2024, entitled "A Metal-Type Flux-Cored Welding Wire, a Bimetallic Composite Pipe for High-Pressure Hydrogen Storage and Transportation and its Preparation Method," the entire contents of which are incorporated herein by reference. Technical Field

[0002] This application relates to the field of pipe manufacturing technology, and in particular to a bimetallic composite pipe for high-pressure hydrogen storage and transportation and its manufacturing method. Background Technology

[0003] With the expanding market demand for clean energy and the further processing of low-quality crude oil, hydrogenation routes are becoming increasingly common, especially for high-sulfur crude oil. This makes high-pressure hydrogenation reactors, with their large hydrogen storage capacity, increasingly important. Currently, the inlet and outlet temperatures of high-pressure hydrogenation reactors are typically around 400℃. After passing through the high-pressure reactor, the reaction products (hydrogen in a high-pressure state) enter the high-temperature / low-temperature separator inlet and outlet pipes via the high-pressure heat exchanger cooling pipes. The design temperature of these pipes is generally around 250℃, and austenitic stainless steel is commonly used. However, during long-term use, the diffusion of high-pressure hydrogen within the austenitic stainless steel pipes leads to a decrease in the pipe's plasticity and toughness, a phenomenon known as hydrogen embrittlement, ultimately causing pipe failure and material waste. Summary of the Invention

[0004] This application provides a bimetallic composite pipe for high-pressure hydrogen storage and transportation, which includes an austenitic stainless steel cladding layer formed by the deposition of a metal-cored welding wire. The gaps between the flux powder particles in the aforementioned metal-cored welding wire result in a low thermal conductivity. During welding, the outer sheath of the metal-cored welding wire melts first, forming molten droplets that encapsulate the inner flux core. This reduces the evaporation of components such as CeN, NbN, and Re2O7 in the flux core to a certain extent, fully utilizing their functions. Specifically, CeN, NbN, and Re2O7, as high-melting-point compounds, act as non-uniform nucleation sites in the molten pool, increasing external nucleation sources; they segregate at grain boundaries, hindering grain growth and refining grains; and they act as hydrogen traps, reducing the hydrogen embrittlement sensitivity of the austenitic stainless steel weld layer, forming an austenitic stainless steel weld layer with excellent resistance to hydrogen embrittlement. Consequently, the bimetallic composite pipe for high-pressure hydrogen storage and transportation exhibits excellent resistance to hydrogen embrittlement, good fracture toughness, and impact toughness.

[0005] This application also provides a method for preparing the above-mentioned high-pressure hydrogen storage and transportation bimetallic composite pipe, which can obtain a high-pressure hydrogen storage and transportation bimetallic composite pipe with excellent resistance to hydrogen embrittlement, fracture toughness and impact toughness.

[0006] This application provides a bimetallic composite pipe for high-pressure hydrogen storage and transportation in a first aspect, wherein the bimetallic composite pipe for high-pressure hydrogen storage and transportation is obtained by submerged arc welding of a bimetallic composite pipe blank.

[0007] The bimetallic composite tube blank includes a stacked alloy steel layer and an austenitic stainless steel cladding layer.

[0008] The austenitic stainless steel cladding layer is obtained by metal-type flux-cored welding wire, the outer wall of the bimetallic composite pipe is obtained by alloy steel submerged arc welding wire, and the inner wall of the bimetallic composite pipe is obtained by austenitic stainless steel submerged arc welding wire.

[0009] The flux core of the metal-type flux-cored welding wire comprises, by mass percentage: Cr powder 26%-34%, Fe50Ni50 powder 12%-20%, Fe20Mn80 powder 4.5%-9.5%, Fe30Si70 powder 1.0%-2.0%, CeN powder 0.20%-0.30%, NbN powder 0.40%-0.50%, Re2O7 powder ≤0.1%, and the remainder is Fe powder. The sum of the mass percentages of the above components is 100%.

[0010] The outer sheath of the metal-type flux-cored welding wire is made of 314 austenitic stainless steel strip. The alloy composition of the outer sheath, by mass percentage, includes: Cr 24%-26%, Ni 19%-21%, Mn 1%-2%, Si 2%-3%, C 0.08%-0.10%, S≤0.0012%, P≤0.010%, with the remainder being Fe. The sum of the mass percentages of the above components is 100%.

[0011] As described above, the filling rate of the core in the high-pressure hydrogen storage and transportation bimetallic composite tube is 25%-30%.

[0012] The high-pressure bimetallic composite pipe for hydrogen storage and transportation described above comprises, by mass percentage: C 0.06%-0.10%, Cr 0.15%-0.20%, Mo 0.15%-0.20%, Al 0.10%-0.12%, V 0.15%-0.20%, Nb 0.04%-0.06%, Ni 0.10%-0.15%, Mn 0.60%-0.65%, Si 0.18%-0.20%, S≤0.0012%, P≤0.010%, with the remainder being Fe. The sum of the mass percentages of the above components is 100%.

[0013] The high-pressure hydrogen storage and transportation bimetallic composite pipe described above comprises, by mass percentage, the austenitic stainless steel submerged arc welding wire as follows: Cr 26%-28%, Ni 14.5%-17.5%, Mn 2.5%-3.8%, Si 1.8%-2.5%, C 0.10%-0.12%, B≤0.005%, S≤0.0012%, P≤0.010%, with the remainder being Fe, and the sum of the mass percentages of the above components is 100%.

[0014] The high-pressure hydrogen storage and transportation bimetallic composite pipe described above comprises, by mass percentage, the alloy steel submerged arc welding wire as follows: Cr 0.20%-0.26%, Ni 0.10%-0.16%, Mn 0.82%-1.25%, Si 0.25%-0.32%, Mo 0.25%-0.33%, Al 0.20%-0.24%, V 0.28%-0.38%, Nb 0.075%-0.1%, S≤0.0012%, P≤0.010%, with the remainder being Fe, and the sum of the mass percentages of the above components is 100%.

[0015] In the high-pressure hydrogen storage and transportation bimetallic composite pipe described above, the thickness of the austenitic stainless steel cladding layer is 3-5 mm; and / or,

[0016] The thickness of the alloy steel layer is 12mm-22mm; and / or,

[0017] The diameter of the high-pressure hydrogen storage and transportation bimetallic composite pipe is 406mm-610mm.

[0018] This application provides a method for preparing the bimetallic composite tube according to the second aspect, comprising:

[0019] 1) A metal-cored welding wire is deposited onto the surface of the alloy steel layer to form an original austenitic stainless steel weld layer;

[0020] 2) After milling away part of the original austenitic stainless steel cladding layer, the original austenitic stainless steel cladding layer is flattened by a flattening machine and subjected to ultrasonic impact treatment to obtain a bimetallic composite plate including the austenitic stainless steel cladding layer.

[0021] 3) The bimetallic composite plate is successively passed through a milling machine, a pre-bending machine, and a JCO forming equipment to form a near "O" shape, and then after joint pre-welding, a bimetallic composite tube blank including an alloy steel layer and an austenitic stainless steel cladding layer is formed.

[0022] 4) The austenitic stainless steel cladding layer is welded using austenitic stainless steel submerged arc welding wire, and the alloy steel layer is welded using alloy steel submerged arc welding wire, finally forming the high-pressure hydrogen storage and transportation bimetallic composite pipe.

[0023] In the preparation method described above, in step 1), the pulse current is 120A-140A, the voltage is 16V-18V, the welding speed is 0.25m / min-0.28m / min, the shielding gas is pure argon, and the outer diameter of the metal-type flux-cored welding wire is 1.18mm-1.20mm.

[0024] In the preparation method described above, in step 2), the thickness of the original austenitic stainless steel cladding layer milled away is 2-3 mm; and / or,

[0025] In ultrasonic impact treatment, the frequency is 18kHz-20kHz, the power is 1000W-1200W, and the impact speed is 6mm / s-8mm / s.

[0026] In the preparation method described above, in step 4), the austenitic stainless steel cladding layer is subjected to double-wire submerged arc welding using austenitic stainless steel submerged arc welding wire. The welding current is 520A-620A, and the welding speed is 1.5m / min-1.7m / min.

[0027] In the preparation method described above, in step 4), the alloy steel layer is subjected to three-wire submerged arc welding using alloy steel submerged arc welding wire, with a welding current of 1100A-1200A and a welding speed of 1.5m / min-1.7m / min.

[0028] The high-pressure hydrogen storage and transportation bimetallic composite pipe provided in this application includes an austenitic stainless steel cladding layer formed by the deposition of a metal-cored welding wire. This layer not only possesses excellent resistance to hydrogen embrittlement but also exhibits good fracture toughness and impact toughness. This avoids problems such as ductility and plasticity loss, accelerated fatigue crack propagation rate, and hydrogen-induced hysteresis fracture that can occur when storing and transporting high-pressure hydrogen in bimetallic composite pipes, thus ensuring the safe and efficient storage and transportation of high-pressure hydrogen. Furthermore, the gaps between the flux powder particles in the aforementioned metal-cored welding wire result in a low thermal conductivity. During welding, the outer sheath of the metal-cored welding wire melts first, forming molten droplets that encapsulate the inner flux core, which can reduce the evaporation of alloying elements to a certain extent. Furthermore, CeN powder, NbN powder, and Re2O7 powder are added to the core. These compounds can act as high-melting-point compounds and serve as non-uniform nucleation sites in the molten pool, increasing external nucleation sources, or segregating at grain boundaries, hindering grain growth and refining grains. At the same time, these compounds can act as hydrogen traps, reducing the hydrogen embrittlement sensitivity of the austenitic stainless steel weld layer, resulting in an austenitic stainless steel weld layer with excellent resistance to hydrogen embrittlement.

[0029] This application provides a method for preparing high-pressure bimetallic composite tubes for hydrogen storage and transportation. This method yields high-pressure bimetallic composite tubes with excellent resistance to hydrogen embrittlement, fracture toughness, and impact toughness. Furthermore, the high-pressure bimetallic composite tubes prepared by this method also have the advantages of aesthetically pleasing appearance, high production efficiency, and low production cost. Detailed Implementation

[0030] To make the objectives, technical solutions, and advantages of this application clearer, the application will be further described in detail below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0031] The application scenarios described in this application are for the purpose of more clearly illustrating the technical solutions of this application, and do not constitute a limitation on the technical solutions provided in this application. Those skilled in the art will understand that with the emergence of new application scenarios, the technical solutions provided in this application are also applicable to similar technical problems. In the description of this application, unless otherwise stated, "multiple" means two or more.

[0032] The first aspect of this application provides a bimetallic composite pipe, which is a high-pressure hydrogen storage and transportation bimetallic composite pipe obtained by submerged arc welding of a bimetallic composite pipe blank.

[0033] Bimetallic composite tube blanks consist of stacked alloy steel layers and austenitic stainless steel cladding layers;

[0034] The austenitic stainless steel cladding layer is obtained by metal-type flux-cored welding wire. The outer wall of the bimetallic composite pipe is obtained by welding the alloy steel layer with alloy steel submerged arc welding wire. The inner wall of the bimetallic composite pipe is obtained by welding with austenitic stainless steel submerged arc welding wire.

[0035] The flux core of a metal-type flux-cored welding wire comprises, by mass percentage: Cr powder 26%-34%, Fe50Ni50 powder 12%-20%, Fe20Mn80 powder 4.5%-9.5%, Fe30Si70 powder 1.0%-2.0%, CeN powder 0.20%-0.30%, NbN powder 0.40%-0.50%, Re2O7 powder ≤0.1%, and the remainder is Fe powder. The sum of the mass percentages of the above components is 100%.

[0036] The outer sheath of the metal-cored welding wire is made of 314 austenitic stainless steel strip. The alloy composition of the outer sheath, by mass percentage, includes: Cr 24%-26%, Ni 19%-21%, Mn 1%-2%, Si 2%-3%, C 0.08%-0.10%, S≤0.0012%, P≤0.010%, with the remainder being Fe. The sum of the mass percentages of the above components is 100%.

[0037] The bimetallic composite pipe for high-pressure hydrogen storage and transportation of this application includes an austenitic stainless steel cladding layer formed by the fusion deposition of the aforementioned metal-cored welding wire. It has excellent resistance to hydrogen embrittlement, fracture toughness, and impact toughness. It can avoid the problems of ductility and plasticity loss, accelerated fatigue crack propagation rate, and hydrogen hysteresis fracture that occur when the bimetallic composite pipe for high-pressure hydrogen storage and transportation is used to store and transport high-pressure hydrogen, thereby ensuring the safe and efficient storage and transportation of high-pressure hydrogen.

[0038] The functions and roles of the components in the core and outer sheath are as follows:

[0039] Chromium (Cr): Cr has a strong solid solution strengthening effect and can increase the hardenability of steel and improve its tensile strength.

[0040] Fe50Ni50: Ni is an austenite stabilizing element. Its main function is to stabilize austenite. Adding Ni can increase the low-temperature phase transformation structure in the weld, and make the deposited metal or weld have high toughness.

[0041] Fe20Mn80, Fe30Si70: Manganese (Mn) and silicon (Si) have good solid solution strengthening effects. In addition, Si and Mn are generally used for joint deoxidation to reduce the embrittlement of austenitic stainless steel weld layer caused by oxygenation. Furthermore, the addition of Si can partially inhibit the hydrogen content entering the interior of the austenitic stainless steel weld layer.

[0042] Cerium nitride (CeN), niobium nitride (NbN), and rhenium heptoxide (Re2O7): As high-melting-point compounds, they can act as heterogeneous nucleation sites in the molten pool, increasing the number of external nucleation sources, or segregating at grain boundaries, hindering grain growth, refining grains, reducing the anisotropy of the austenitic stainless steel cladding layer, and acting as hydrogen traps, reducing the hydrogen embrittlement sensitivity of the austenitic stainless steel cladding layer, thus enabling the austenitic stainless steel cladding layer to obtain excellent hydrogen embrittlement resistance.

[0043] The metal-cored welding wire provided in this application consists of a core and an outer sheath. The gaps between the core powder particles result in a low thermal conductivity. During welding, the outer sheath melts first, forming molten droplets that encapsulate the core. This reduces the evaporation of CeN, NbN, Re2O7, and other components in the core, allowing CeN, NbN, and Re2O7 to act as high-melting-point compounds and serve as non-uniform nucleation sites in the molten pool. This increases external nucleation sources, causing them to segregate at grain boundaries, hindering grain growth, refining the grains, and acting as hydrogen traps. Furthermore, this reduces the hydrogen embrittlement sensitivity of the austenitic stainless steel weld layer, resulting in excellent hydrogen embrittlement resistance in the austenitic stainless steel weld layer formed by this metal-cored welding wire.

[0044] In the bimetallic composite pipe of the present invention, the outer wall is formed by welding an alloy steel layer, and the inner wall is formed by welding an austenitic stainless steel cladding layer.

[0045] In one specific implementation, the flux-cored wire has a flux filling rate of 25%-30%, which not only makes the austenitic stainless steel deposited layer formed by welding aesthetically pleasing, but also reduces spatter during the welding process.

[0046] For example, the flux filling rate of the austenitic stainless steel flux-cored welding wire is a range of 25%, 28%, 30%, or any combination thereof.

[0047] In one specific embodiment, the alloy composition of the alloy steel layer, by mass percentage, includes: C 0.06%-0.10%, Cr 0.15%-0.20%, Mo 0.15%-0.20%, Al 0.10%-0.12%, V 0.15%-0.20%, Nb 0.04%-0.06%, Ni 0.10%-0.15%, Mn 0.60%-0.65%, Si 0.18%-0.20%, S≤0.0012%, P≤0.010%, with the remainder being Fe. When the sum of the mass percentages of the above components is 100%, the alloy steel layer exhibits excellent hardness, strength, and toughness.

[0048] In one specific embodiment, the alloy composition of the austenitic stainless steel submerged arc welding wire includes, by mass percentage: Cr 26%-28%, Ni 14.5%-17.5%, Mn 2.5%-3.8%, Si 1.8%-2.5%, C 0.10%-0.12%, B≤0.005%, S≤0.0012%, P≤0.010%, with the remainder being Fe. When the sum of the mass percentages of the above components is 100%, the austenitic stainless steel weld layer can have good corrosion resistance and good fracture toughness, impact toughness, and resistance to hydrogen embrittlement.

[0049] In one specific embodiment, the alloy composition of the alloy steel submerged arc welding wire includes, by mass percentage: Cr 0.20%-0.26%, Ni 0.10%-0.16%, Mn 0.82%-1.25%, Si 0.25%-0.32%, Mo 0.25%-0.33%, Al 0.20%-0.24%, V 0.28%-0.38%, Nb 0.075%-0.1%, S≤0.0012%, P≤0.010%, with the remainder being Fe. When the sum of the mass percentages of the above components is 100%, it can enhance the toughness and strength of the alloy steel layer weld.

[0050] In one specific implementation, when the thickness of the austenitic stainless steel cladding layer is 3mm-5mm, the amount of stainless steel material can be reduced to a large extent while ensuring the safe delivery of hydrogen.

[0051] For example, the thickness of the austenitic stainless steel cladding layer can be any of 3 mm, 4 mm, 5 mm, or any combination thereof.

[0052] In one specific implementation, when the thickness of the alloy steel layer is 12mm-22mm, the safe delivery of high-pressure hydrogen can be guaranteed.

[0053] For example, the thickness of the alloy steel layer can be any of 12 mm, 17 mm, 22 mm, or any combination thereof.

[0054] In one specific implementation, the diameter of the bimetallic composite pipe for high-pressure hydrogen storage and transportation is 406mm-610mm.

[0055] The diameter of the high-pressure hydrogen storage and transportation bimetallic composite pipe refers to its outer diameter. When the diameter of the high-pressure hydrogen storage and transportation bimetallic composite pipe is within the above range, it can meet the requirements for high-flow-rate and high-pressure hydrogen transportation.

[0056] For example, the diameter of the bimetallic composite pipe for high-pressure hydrogen storage and transportation can be any one of 406 mm, 410 mm, 420 mm, 430 mm, 440 mm, 450 mm, 460 mm, 470 mm, 480 mm, 490 mm, 500 mm, 510 mm, 520 mm, 530 mm, 540 mm, 550 mm, 560 mm, 570 mm, 580 mm, 590 mm, 600 mm, and 610 mm, or any combination thereof.

[0057] The second aspect of this application provides a method for preparing a bimetallic composite tube for high-pressure hydrogen storage and transportation, comprising:

[0058] 1) A metal-cored welding wire is deposited onto the surface of the alloy steel layer to form an original austenitic stainless steel weld layer;

[0059] 2) After milling away part of the original austenitic stainless steel cladding layer, the plate is flattened by a flattening machine and subjected to ultrasonic impact treatment to obtain a bimetallic composite plate including the austenitic stainless steel cladding layer.

[0060] 3) The bimetallic composite plate is successively passed through a milling machine, a pre-bending machine, and a JCO forming equipment to form a near "O" shape, and then after joint pre-welding, a bimetallic composite tube blank including an alloy steel layer and an austenitic stainless steel cladding layer is formed.

[0061] 4) The austenitic stainless steel cladding layer is welded using austenitic stainless steel submerged arc welding wire, and the alloy steel layer is welded using alloy steel submerged arc welding wire, finally forming the high-pressure hydrogen storage and transportation bimetallic composite pipe.

[0062] The high-pressure hydrogen storage and transportation bimetallic composite pipe prepared by the above preparation method has excellent resistance to hydrogen embrittlement, good fracture toughness and impact toughness.

[0063] This application is not limited to the specific operation of depositing metal-cored welding wire on the surface of the alloy steel layer, as long as an austenitic stainless steel weld layer is formed on the surface of the alloy steel layer. In one specific embodiment, arc additive manufacturing can be used to deposit metal-cored welding wire on the surface of the alloy steel layer to form an austenitic stainless steel weld layer.

[0064] In one specific embodiment, in step 1), the pulse current is 120A-140A, the voltage is 16V-18V, the welding speed is 0.25m / min-0.28m / min, the shielding gas is pure argon, and the outer diameter of the metal-cored welding wire is 1.18-1.20mm. When the pulse current, voltage, welding speed, and outer diameter of the metal-cored welding wire are within the above ranges in step 1), the austenitic stainless steel weld bead can have better weld formation, toughness, and excellent resistance to hydrogen embrittlement.

[0065] For example, the pulse current can be a range of any one of 120A, 130A, 140A, or any combination thereof.

[0066] The voltage can be any of 16V, 17V, 18V, or any combination thereof.

[0067] The welding speed can be any one of 0.25 m / min, 0.26 m / min, 0.27 m / min, 0.28 m / min, or any combination thereof.

[0068] The outer diameter of the metal-cored welding wire can be any of 1.18 mm, 1.19 mm, or 1.20 mm, or any combination thereof. Furthermore, arc additive manufacturing employs pulsed current to perform a zigzag reciprocating deposition on the surface of the alloy steel layer.

[0069] In one specific implementation, in step 2), the thickness of the original austenitic stainless steel cladding layer milled away is 2-3 mm, which can improve the surface flatness of the austenitic stainless steel cladding layer while ensuring the thickness of the austenitic stainless steel cladding layer.

[0070] For example, the thickness of the original austenitic stainless steel cladding layer milled away can be any of 2 mm, 2.5 mm, 3 mm, or any combination thereof.

[0071] Furthermore, when ultrasonic impact treatment is performed at a frequency of 18kHz-20kHz, a power of 1000W-1200W, and an impact speed of 6mm / s-8mm / s, the hydrogen embrittlement resistance of the weld layer can be improved while saving energy.

[0072] In one specific implementation, in step 4), when austenitic stainless steel submerged arc welding wire is used to perform double-wire submerged arc welding on the austenitic stainless steel cladding layer of the bimetallic composite tube blank, with a welding current of 520A-620A and a welding speed of 1.5m / min-1.7m / min, the high-pressure hydrogen storage and transportation bimetallic composite tube can have better weld formation, strength and toughness, and excellent resistance to hydrogen embrittlement.

[0073] In one specific embodiment, in step 4), when alloy steel submerged arc welding wire is used to perform three-wire submerged arc welding on the alloy steel layer of the bimetallic composite tube blank, with a welding current of 1100A-1200A and a welding speed of 1.5m / min-1.7m / min, the high-pressure hydrogen storage and transportation bimetallic composite tube can have better weld formation, toughness, and resistance to hydrogen embrittlement. For example, in three-wire submerged arc welding, the welding current can be any one of 1100A, 1150A, and 1200A, or a combination of any two thereof; the welding speed can be any one of 1.5m / min, 1.6m / min, and 1.7m / min, or a combination of any two thereof.

[0074] This application does not impose any specific limitations on the welding process of double-wire submerged arc welding or triple-wire submerged arc welding. Specifically, ultra-low hydrogen aluminum alkali type sintering flux can be used for double-wire submerged arc welding or triple-wire submerged arc welding.

[0075] Furthermore, the bimetallic composite plate can be subjected to ultrasonic testing equipment to check for defects, thereby improving the quality of bimetallic composite pipes used for high-pressure hydrogen storage and transportation and enhancing the safety of hydrogen storage and transportation.

[0076] The obtained high-pressure hydrogen storage and transportation bimetallic composite pipes can also be subjected to X-ray inspection, full-size diameter expansion, hydrostatic testing, and ultrasonic flaw detection to further ensure the quality of the obtained high-pressure hydrogen storage and transportation bimetallic composite pipes.

[0077] After ultrasonic testing, the outer surface of the high-pressure hydrogen storage and transportation bimetallic composite pipe can be derusted, degreased, and polished to make the outer surface smooth. Then, a 3PE anti-corrosion layer is coated on the outer surface of the high-pressure hydrogen storage and transportation bimetallic composite pipe to extend its service life.

[0078] Existing technologies mainly prepare bimetallic composite pipes using the following methods: first, an alloy steel layer is formed by JCO molding and submerged arc welding to prepare an alloy steel pipe; then, an austenitic stainless steel cladding layer is deposited on the inner surface of the alloy steel pipe to finally obtain the bimetallic composite pipe. However, this method cannot machine or finish the austenitic stainless steel cladding layer inside small- and medium-diameter bimetallic composite pipes, resulting in a rough inner surface that makes them unsuitable for high-pressure hydrogen transportation and storage. In contrast, the method for preparing high-pressure hydrogen storage and transportation bimetallic composite pipes of this application produces small- and medium-diameter high-pressure hydrogen storage and transportation bimetallic composite pipes with a smooth inner surface and excellent resistance to hydrogen embrittlement, making them widely applicable for high-pressure hydrogen transportation and storage.

[0079] The solution of this application will be described in detail below through specific embodiments.

[0080] Example 1

[0081] The high-pressure bimetallic composite tube for hydrogen storage and transportation in this embodiment is prepared by a method including the following steps:

[0082] Step 1: Using arc additive manufacturing technology, a metal-cored welding wire is deposited on the surface of the alloy steel layer to form an original austenitic stainless steel deposited layer;

[0083] The alloy steel layer comprises, by mass percentage: C 0.06%, Cr 0.15%, Mo 0.15%, Al 0.10%, V 0.15%, Nb 0.04%, Ni 0.10%, Mn 0.60%, Si 0.18%, S 0.0010%, P 0.006%, with the remainder being Fe. The sum of the mass percentages of the above components is 100%. In the metal-cored welding wire, the outer sheath is made of 314 austenitic stainless steel strip, and the alloy composition of the outer sheath comprises, by mass percentage: Cr 24%, Ni 19%, Mn 1%, Si 2%, C 0.08%, S 0.0010%, P 0.006%, with the remainder being Fe, and the sum of the mass percentages of the above components is 100%; In the metal-type flux-cored wire, the flux filling rate is 25%, and the composition by mass percentage includes: Cr powder 26%, Fe50Ni50 powder 12%, Fe20Mn80 powder 4.5%, Fe30Si70 powder 1.0%, CeN powder 0.20%, NbN powder 0.40%, Re2O7 powder 0.01%, with the remainder being Fe powder, and the sum of the mass percentages of the above components is 100%;

[0084] Arc additive manufacturing uses pulsed current to deposit a "Z"-shaped reciprocating deposition on the surface of an alloy steel layer. The pulsed current is 120A, the voltage is 16V, the welding speed is 0.25m / min, the shielding gas is pure argon, and the outer diameter of the metal-cored welding wire is 1.18mm.

[0085] Step 2: After milling off 2mm of the original austenitic stainless steel cladding layer, flatten it with a flattening machine, and then perform ultrasonic impact treatment on the original austenitic stainless steel cladding layer to obtain a bimetallic composite plate including a smooth and flat austenitic stainless steel cladding layer.

[0086] In ultrasonic impact treatment, the frequency is 18kHz, the power is 1000W, and the impact velocity is 6mm / s.

[0087] Step 3: Use ultrasonic flaw detection equipment to check for defects in the bimetallic composite plate. Then, the bimetallic composite plate is sequentially passed through a milling machine, a pre-bending machine, and a JCO forming machine to form a near "O" shape. After pre-welding the seam, a bimetallic composite tube blank including an alloy steel layer and an austenitic stainless steel cladding layer is formed.

[0088] Step 4: Using austenitic stainless steel submerged arc welding wire, with a welding current of 520A and a welding speed of 1.5m / min, perform double-wire submerged arc welding on the austenitic stainless steel cladding layer of the bimetallic composite tube blank; using alloy steel submerged arc welding wire, with a welding current of 1100A and a welding speed of 1.5m / min, perform triple-wire submerged arc welding on the alloy steel layer of the bimetallic composite tube blank, finally obtaining a high-pressure hydrogen storage and transportation bimetallic composite tube (specific performance is shown in Table 1).

[0089] The alloy composition of austenitic stainless steel submerged arc welding wire, by mass percentage, includes: Cr 26%, Ni 14.5%, Mn 2.5%, Si 1.8%, C 0.10%, B 0.001%, S 0.0010%, P 0.006%, with the remainder being Fe. The sum of the mass percentages of the above components is 100%.

[0090] The alloy composition of the alloy steel submerged arc welding wire, by mass percentage, includes: Cr 0.20%, Ni 0.10%, Mn 0.82%, Si 0.25%, Mo 0.25%, Al 0.20%, V 0.28%, Nb 0.075%, S 0.0010%, P 0.006%, with the remainder being Fe. The sum of the mass percentages of the above components is 100%.

[0091] Step 5: Perform X-ray inspection, full-size diameter expansion, hydrostatic test, and ultrasonic flaw detection on the high-pressure hydrogen storage and transportation bimetallic composite pipe;

[0092] Step 6: Remove rust and oil from the outer surface of the high-pressure hydrogen storage and transportation bimetallic composite pipe, and polish it to make the outer surface of the high-pressure hydrogen storage and transportation bimetallic composite pipe smooth. Then, coat the outer surface of the high-pressure hydrogen storage and transportation bimetallic composite pipe with a 3PE anti-corrosion layer.

[0093] Example 2

[0094] The high-pressure bimetallic composite tube for hydrogen storage and transportation in this embodiment is prepared by a method including the following steps:

[0095] Step 1: Using arc additive manufacturing technology, a metal-cored welding wire is deposited on the surface of the alloy steel layer to form an original austenitic stainless steel deposited layer;

[0096] The alloy composition of the alloy steel layer, by mass percentage, includes: C 0.08%, Cr 0.18%, Mo 0.18%, Al 0.11%, V 0.180%, Nb 0.05%, Ni 0.13%, Mn 0.63%, Si 0.19%, S 0.0011%, P 0.008%; the remainder is Fe, and the sum of the mass percentages of the above components is 100%.

[0097] In the metal-cored welding wire, the outer sheath is made of 314 austenitic stainless steel strip. The alloy composition of the outer sheath, by mass percentage, includes: Cr 25%, Ni 20%, Mn 1.5%, Si 2.5%, C 0.09%, S 0.0011%, P 0.008%, with the remainder being Fe. The sum of the mass percentages of the above components is 100%. In the metal-cored welding wire, the filler content of the flux core is 28%, and the composition by mass percentage includes: Cr powder 28%, Fe50Ni50 powder 14%, Fe20Mn80 powder 6.5%, Fe30Si70 powder 1.5%, CeN powder 0.25%, NbN powder 0.45%, Re2O7 powder 0.05%, with the remainder being Fe powder. The sum of the mass percentages of the above components is 100%.

[0098] Arc additive manufacturing uses pulsed current to deposit a "Z"-shaped reciprocating deposition on the surface of an alloy steel layer. The pulsed current is 130A, the voltage is 17V, the welding speed is 0.26m / min, the shielding gas is pure argon, and the outer diameter of the metal-cored welding wire is 1.19mm.

[0099] Step 2: After milling away 2.5mm of the original austenitic stainless steel cladding layer, the plate is flattened by a flattening machine and subjected to ultrasonic impact treatment to obtain a bimetallic composite plate with a smooth and flat austenitic stainless steel cladding layer.

[0100] In ultrasonic impact treatment, the frequency is 19kHz, the power is 1100W, and the impact velocity is 7mm / s.

[0101] Step 3: Use ultrasonic flaw detection equipment to check for defects in the bimetallic composite plate. Then, the bimetallic composite plate is sequentially passed through a milling machine, a pre-bending machine, and a JCO forming machine to form a near "O" shape. After pre-welding the seam, a bimetallic composite tube blank including an alloy steel layer and an austenitic stainless steel cladding layer is formed.

[0102] Step 4: Using austenitic stainless steel submerged arc welding wire, with a welding current of 560A and a welding speed of 1.6m / min, perform double-wire submerged arc welding on the austenitic stainless steel cladding layer of the bimetallic composite tube blank; using alloy steel submerged arc welding wire, with a welding current of 1150A and a welding speed of 1.6m / min, perform triple-wire submerged arc welding on the alloy steel layer of the bimetallic composite tube blank, finally obtaining a high-pressure hydrogen storage and transportation bimetallic composite tube (specific performance is shown in Table 1);

[0103] The alloy composition of austenitic stainless steel submerged arc welding wire, by mass percentage, includes: Cr 27%, Ni 16%, Mn 3.1%, Si 2.1%, C 0.11%, B 0.003%, S 0.0011%, P 0.008%, with the remainder being Fe. The sum of the mass percentages of the above components is 100%.

[0104] The alloy composition of the alloy steel submerged arc welding wire, by mass percentage, includes: Cr 0.23%, Ni 0.13%, Mn 1.0%, Si 0.29%, Mo 0.29%, Al 0.22%, V 0.32%, Nb 0.085%, S 0.0011%, P 0.008%, with the remainder being Fe. The sum of the mass percentages of the above components is 100%.

[0105] Step 5: Perform X-ray inspection, full-size diameter expansion, hydrostatic test, and ultrasonic flaw detection on the high-pressure hydrogen storage and transportation bimetallic composite pipe;

[0106] Step 6: Remove rust and oil from the outer surface of the high-pressure hydrogen storage and transportation bimetallic composite pipe, and polish it to make the outer surface of the high-pressure hydrogen storage and transportation bimetallic composite pipe smooth. Then, coat the outer surface of the high-pressure hydrogen storage and transportation bimetallic composite pipe with a 3PE anti-corrosion layer.

[0107] Example 3

[0108] The high-pressure bimetallic composite tube for hydrogen storage and transportation in this embodiment is prepared by a method including the following steps:

[0109] Step 1: Using arc additive manufacturing technology, a metal-cored welding wire is deposited on the surface of the alloy steel layer to form an original austenitic stainless steel deposited layer;

[0110] The alloy composition of the alloy steel layer, by mass percentage, includes: C 0.10%, Cr 0.20%, Mo 0.20%, Al 0.12%, V 0.20%, Nb 0.06%, Ni 0.15%, Mn 0.65%, Si 0.20%, S 0.0012%, P 0.010%; the remainder is Fe, and the sum of the mass percentages of the above components is 100%.

[0111] In the metal-cored welding wire, the outer sheath is made of 314 austenitic stainless steel strip. The alloy composition of the outer sheath, by mass percentage, includes: Cr 26%, Ni 21%, Mn 2%, Si 3%, C 0.10%, S 0.0012%, P 0.010%, with the remainder being Fe. The sum of the mass percentages of the above components is 100%. In the metal-cored welding wire, the flux filling rate is 30%, and the composition by mass percentage includes: Cr powder 34%, Fe50Ni50 powder 20%, Fe20Mn80 powder 9.5%, Fe30Si70 powder 2.0%, CeN powder 0.30%, NbN powder 0.50%, Re2O7 powder 0.1%, with the remainder being Fe powder. The sum of the mass percentages of the above components is 100%.

[0112] Arc additive manufacturing uses pulsed current to deposit a "Z"-shaped reciprocating deposition on the surface of an alloy steel layer. The pulsed current is 140A, the voltage is 18V, the welding speed is 0.28m / min, the shielding gas is pure argon, and the outer diameter of the metal-cored welding wire is 1.18mm.

[0113] Step 2: After milling off 3mm of the original austenitic stainless steel cladding layer, the plate is flattened by a flattening machine and subjected to ultrasonic impact treatment to obtain a bimetallic composite plate with a smooth and flat austenitic stainless steel cladding layer.

[0114] In ultrasonic impact treatment, the frequency is 20kHz, the power is 1200W, and the impact velocity is 8mm / s.

[0115] Step 3: Use ultrasonic flaw detection equipment to check for defects in the bimetallic composite plate. Then, the bimetallic composite plate is sequentially passed through a milling machine, a pre-bending machine, and a JCO forming machine to form a near "O" shape. After pre-welding the seam, a bimetallic composite tube blank including an alloy steel layer and an austenitic stainless steel cladding layer is formed.

[0116] Step 4: Using austenitic stainless steel submerged arc welding wire, with a welding current of 620A and a welding speed of 1.7m / min, perform double-wire submerged arc welding on the austenitic stainless steel cladding layer of the bimetallic composite tube blank; using alloy steel submerged arc welding wire, with a welding current of 1200A and a welding speed of 1.7m / min, perform triple-wire submerged arc welding on the alloy steel layer of the bimetallic composite tube blank, finally obtaining a high-pressure hydrogen storage and transportation bimetallic composite tube (specific performance is shown in Table 1);

[0117] The alloy composition of austenitic stainless steel submerged arc welding wire, by mass percentage, includes: Cr 28%, Ni 17.5%, Mn 3.8%, Si 2.5%, C 0.12%, B 0.005%, S 0.0012%, P 0.010%, with the remainder being Fe. The sum of the mass percentages of the above components is 100%.

[0118] The alloy composition of the alloy steel submerged arc welding wire, by mass percentage, includes: Cr 0.26%, Ni 0.16%, Mn 1.25%, Si 0.32%, Mo 0.33%, Al 0.24%, V 0.38%, Nb 0.10%, S 0.0012%, P 0.010%, with the remainder being Fe. The sum of the mass percentages of the above components is 100%.

[0119] Step 5: Perform X-ray inspection, full-size diameter expansion, hydrostatic test, and ultrasonic flaw detection on the high-pressure hydrogen storage and transportation bimetallic composite pipe;

[0120] Step 6: Remove rust and oil from the outer surface of the high-pressure hydrogen storage and transportation bimetallic composite pipe, and polish it to make the outer surface of the high-pressure hydrogen storage and transportation bimetallic composite pipe smooth. Then, coat the outer surface of the high-pressure hydrogen storage and transportation bimetallic composite pipe with a 3PE anti-corrosion layer.

[0121] Performance testing

[0122] The following performance tests were conducted on the high-pressure hydrogen storage and transportation bimetallic composite tubes of Examples 1-3, and the test results are shown in Table 1.

[0123] (1) Hydrogen-induced cracking susceptibility: The hydrogen-induced cracking susceptibility of bimetallic composite pipes was evaluated in accordance with GB / T 8650 "Evaluation method for hydrogen-induced cracking resistance of pipeline steel and pressure vessel steel", including hydrogen-induced cracking susceptibility rate, crack length rate and crack thickness rate.

[0124] (2) Fracture toughness: The fracture toughness of bimetallic composite pipes was evaluated according to GB / T 21143 "Unified Test Method for Quasi-Static Fracture Toughness of Metallic Materials" (mainly CTOD value).

[0125] (3) Impact toughness: The impact toughness of the bimetallic composite tube was evaluated according to GB / T 229 "Metallic Materials Charpy Pendulum Impact Test Method" (mainly the impact energy value).

[0126] Table 1 Test Results

[0127] As can be seen from Table 1, the high-pressure hydrogen storage and transportation bimetallic composite pipe obtained in the embodiments of this application has excellent fracture toughness, impact toughness and resistance to hydrogen embrittlement.

[0128] The above are merely specific embodiments of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. A bimetallic composite pipe for high-pressure hydrogen storage and transportation, wherein, The high-pressure hydrogen storage and transportation bimetallic composite pipe is obtained by submerged arc welding of the bimetallic composite pipe blank; The bimetallic composite tube blank includes a stacked alloy steel layer and an austenitic stainless steel cladding layer. The austenitic stainless steel cladding layer is obtained by metal-type flux-cored welding wire, the outer wall of the bimetallic composite pipe is obtained by alloy steel submerged arc welding wire, and the inner wall of the bimetallic composite pipe is obtained by austenitic stainless steel submerged arc welding wire. The flux core of the metal-type flux-cored welding wire comprises, by mass percentage: Cr powder 26%-34%, Fe50Ni50 powder 12%-20%, Fe20Mn80 powder 4.5%-9.5%, Fe30Si70 powder 1.0%-2.0%, CeN powder 0.20%-0.30%, NbN powder 0.40%-0.50%, Re2O7 powder ≤0.1%, and the remainder is Fe powder. The sum of the mass percentages of the above components is 100%. The outer sheath of the metal-type flux-cored welding wire is 314 austenitic stainless steel strip. The alloy composition of the outer sheath, by mass percentage, includes: Cr 24%-26%, Ni 19%-21%, Mn 1%-2%, Si 2%-3%, C 0.08%-0.10%, S≤0.0012%, P≤0.010%, with the remainder being Fe. The sum of the mass percentages of the above components is 100%.

2. The bimetallic composite tube according to claim 1, wherein, In the aforementioned metal-type flux-cored welding wire, the flux filling rate is 25%-30%.

3. The bimetallic composite tube according to claim 1 or 2, wherein, The alloy composition of the alloy steel layer, by mass percentage, includes: C 0.06%-0.10%, Cr 0.15%-0.20%, Mo 0.15%-0.20%, Al 0.10%-0.12%, V 0.15%-0.20%, Nb 0.04%-0.06%, Ni 0.10%-0.15%, Mn 0.60%-0.65%, Si 0.18%-0.20%, S≤0.0012%, P≤0.010%, with the remainder being Fe. The sum of the mass percentages of the above components is 100%.

4. The bimetallic composite tube according to any one of claims 1-3, wherein, The alloy composition of the austenitic stainless steel submerged arc welding wire, by mass percentage, includes: Cr 26%-28%, Ni 14.5%-17.5%, Mn 2.5%-3.8%, Si 1.8%-2.5%, C 0.10%-0.12%, B≤0.005%, S≤0.0012%, P≤0.010%, with the remainder being Fe. The sum of the mass percentages of the above components is 100%.

5. The bimetallic composite tube according to any one of claims 1-4, wherein, The alloy composition of the alloy steel submerged arc welding wire, by mass percentage, includes: Cr 0.20%-0.26%, Ni 0.10%-0.16%, Mn 0.82%-1.25%, Si 0.25%-0.32%, Mo 0.25%-0.33%, Al 0.20%-0.24%, V 0.28%-0.38%, Nb 0.075%-0.1%, S≤0.0012%, P≤0.010%, with the remainder being Fe. The sum of the mass percentages of the above components is 100%.

6. The bimetallic composite tube according to any one of claims 1-5, wherein, The thickness of the austenitic stainless steel cladding layer is 3mm-5mm; and / or, The thickness of the alloy steel layer is 12mm-22mm; and / or, The diameter of the bimetallic composite tube is 406mm-610mm.

7. A method for preparing a bimetallic composite tube according to any one of claims 1-6, wherein, include: 1) A metal-cored welding wire is deposited onto the surface of the alloy steel layer to form an original austenitic stainless steel weld layer; 2) After milling away part of the original austenitic stainless steel cladding layer, the original austenitic stainless steel cladding layer is flattened by a flattening machine and subjected to ultrasonic impact treatment to obtain a bimetallic composite plate including the austenitic stainless steel cladding layer. 3) The bimetallic composite plate is successively passed through a milling machine, a pre-bending machine, and a JCO forming equipment to form a near "O" shape, and then after joint pre-welding, a bimetallic composite tube blank including an alloy steel layer and an austenitic stainless steel cladding layer is formed. 4) The austenitic stainless steel cladding layer is welded using austenitic stainless steel submerged arc welding wire, and the alloy steel layer is welded using alloy steel submerged arc welding wire, thus obtaining the bimetallic composite pipe.

8. The preparation method according to claim 7, wherein, In step 1), the thickness of the alloy steel layer is 12mm-22mm, the pulse current is 120A-140A, the voltage is 16V-18V, the welding speed is 0.25m / min-0.28m / min, the shielding gas is pure argon, and the outer diameter of the metal-type flux-cored welding wire is 1.18-1.20mm.

9. The preparation method according to claim 7 or 8, wherein, In step 2), the thickness of the original austenitic stainless steel weld layer milled away is 2mm-3mm; and / or, In ultrasonic impact treatment, the frequency is 18kHz-20kHz, the power is 1000W-1200W, and the impact speed is 6mm / s-8mm / s.

10. The preparation method according to any one of claims 7-9, wherein, In step 4), the austenitic stainless steel fused layer is subjected to double-wire submerged arc welding using austenitic stainless steel submerged arc welding wire. The welding current is 520A-620A and the welding speed is 1.5m / min-1.7m / min.

11. The preparation method according to any one of claims 7-10, wherein, In step 4), the alloy steel layer is subjected to three-wire submerged arc welding using alloy steel submerged arc welding wire, with a welding current of 1100A-1200A and a welding speed of 1.5m / min-1.7m / min.

Images