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CN-121992294-A - Manufacturing method of steel high-pressure hydrogen storage cylinder

CN121992294ACN 121992294 ACN121992294 ACN 121992294ACN-121992294-A

Abstract

The invention discloses a manufacturing method of a steel high-pressure hydrogen storage cylinder, wherein the cylinder is made of 4130X steel, and the 4130X steel comprises the following components in percentage by mass: 0.28% -0.33%, mn:0.40% -0.60%, ni:3.20% -3.80%, si:0.15% -0.35%, P is less than or equal to 0.035%, S is less than or equal to 0.040%, cr:0.80% -1.10%, mo:0.15% -0.25%, ti:0.01% -0.04%, nb:0.02% -0.05%, V:0.08% -0.14%, al:0.03% -0.06%, cu:0.10% -0.15%, B:0.001% -0.003%, and the balance of Fe; the invention has the characteristics of improving the comprehensive mechanical property and fatigue failure resistance of the cylinder shoulder of the gas cylinder and effectively prolonging the service life of the gas cylinder.

Inventors

  • JIN YAN
  • LI LIANGLIANG
  • SHI HONGBING
  • CHENG JIANGHUI
  • WU QIBING
  • WANG RENTAO
  • ZHANG MINGSHAN

Assignees

  • 安徽省特种设备检测院

Dates

Publication Date
20260508
Application Date
20260120

Claims (10)

  1. 1. A manufacturing approach of steel high-pressure hydrogen storage gas cylinder, the said gas cylinder is made of 4130X steel, characterized by that, the said 4130X steel each component mass percent is C：0.28%-0.33%,Mn：0.40%-0.60%,Ni：3.20%-3.80%,Si：0.15%-0.35%、P≤0.035%,S≤0.040%,Cr：0.80%-1.10%,Mo：0.15%-0.25%,Ti：0.01%-0.04%, Nb：0.02%-0.05%,V：0.08%-0.14%,Al：0.03%-0.06%,Cu：0.10%-0.15%,B：0.001%-0.003%, and the rest is iron Fe; Equivalent of Ni in 4130X steel ≥12.5: ; The manufacturing method of the bottle shoulder comprises the following steps: weighing the components of 4130X steel according to the mass percentage, putting other elements except Al, cu and B into a vacuum induction smelting furnace, controlling the vacuum induction smelting furnace to vacuumize and raise the temperature to melt the components into molten steel, adding the weighed Al into the molten steel, keeping the temperature for a period of time to melt the Al, adding the weighed Cu into the molten steel, keeping the temperature for a period of time to melt the Cu, adding the weighed B into the molten steel, and carrying out electroslag remelting; and 2, performing casting blank and forging by using molten steel to obtain a round blank, performing piercing rolling on the round blank to obtain a tubular blank, performing cold spinning on bottle shoulders with gradient temperature control on two ends of the tubular blank, and performing cold spinning on bottle openings to obtain the gas cylinder.
  2. 2. The method for manufacturing a steel high-pressure hydrogen storage cylinder according to claim 1, wherein the irreversible hydrogen trap HCF in 4130X steel is made to be equal to or larger than 1.2, 。
  3. 3. The method of manufacturing a steel high pressure hydrogen storage cylinder as claimed in claim 1, wherein said shoulder cold spinning comprises the steps of: The tubular blank is horizontally clamped by utilizing a chuck, 3 induction heating coils are arranged outside the area, corresponding to the bottle shoulder, of the right part of the tubular blank, the distance between each induction heating coil and the surface of the tubular blank is 15cm-18cm, each induction heating coil heats the tubular blank, the bottle shoulder area reaches the preset temperature, the farther the bottle shoulder area is away from the right bottle mouth, the lower the temperature of the bottle shoulder area is, and the spinning wheel of the spinning machine extends into the gap between each induction heating coil and the surface of the tubular blank to carry out bottle shoulder spinning forming; And loosening the chuck, reversing the tubular blank left and right, repeating the steps, and carrying out bottle shoulder spinning forming on the left part of the tubular blank.
  4. 4. The method for manufacturing a steel high-pressure hydrogen storage cylinder according to claim 3, wherein the temperature of the shoulder regions heated by the 3 induction heating coils is detected by using 3 infrared thermometers, the shoulder regions heated by the 3 induction heating coils are respectively called a high deformation region, a medium deformation region and a low deformation region, the high deformation region, the medium deformation region and the low deformation region are sequentially far away from the bottle mouth, and preset temperatures of the high deformation region, the medium deformation region and the low deformation region are respectively 350-400 ℃, 280-320 ℃ and 200-250 ℃.
  5. 5. The method for manufacturing a steel high-pressure hydrogen storage cylinder according to claim 4, wherein, The cold spinning parameters of the high deformation area are as follows, the temperature is 350-400 ℃, the temperature fluctuation range is less than or equal to +/-5 ℃, the rotating speed of a mandrel of the spinning machine is 80-100 r/min, the feeding amount of a spinning roller is 1.2-1.5 mm/r, the single-pass pressing amount is 3-5 mm, and the quick necking and the primary thinning of the wall thickness of the conical surface section are realized; the cold spinning parameters of the middle deformation zone are as follows, the temperature is 280-320 ℃, the temperature fluctuation range is less than or equal to +/-5 ℃, the rotating speed of a mandrel of the spinning machine is 100-120 r/min, the feeding amount of a spinning roller is 0.8-1.2 mm/r, the single-pass pressing amount is 2-3 mm, the smooth and wrinkle-free curved surface of a circular arc section is ensured, and the stress distribution is uniform; The cold spinning parameters of the low deformation area are as follows, the temperature is 200-250 ℃, the temperature fluctuation range is less than or equal to +/-5 ℃, the rotating speed of a core mold of the spinning machine is 100-120 r/min, the feeding amount of a spinning roller is 0.8-1.2 mm/r, the single-pass pressing amount is 2-3 mm, and the smooth connection between the bottle shoulder and the straight section of the bottle body is realized.
  6. 6. The method for manufacturing a steel high-pressure hydrogen storage cylinder according to claim 1, wherein the vacuum degree in the vacuum induction melting furnace in the step 1 is 5.0x10 < -3 > Pa or less, and the temperature in the furnace is monitored by an internal temperature thermocouple of the vacuum induction melting furnace to rise to 1500 ℃ to 1550 ℃; in the step 1, al is added into molten steel at a constant speed through an inert gas protection feeding device of a furnace top feeding bin, and the temperature is kept for 20-25 min; Raising the temperature in the vacuum induction melting furnace to 1600 ℃, conveying Cu into the middle area of molten steel at a constant speed through a closed feeding pipe protected by inert gas, preserving heat for 30-35 min, and starting an electromagnetic stirring device in the vacuum induction melting furnace to stir; Pouring molten steel into an electroslag remelting furnace to enable the temperature in the electroslag remelting furnace to be stabilized at 1500-1550 ℃, and starting to add B element when the rising rate of the molten steel in a crystallizer of the electroslag remelting furnace is 1.2-1.5 mm/min.
  7. 7. The method for manufacturing a steel high pressure hydrogen storage cylinder according to claim 1 or 2 or 3 or 4 or 5 or 6, wherein the casting blank and the round blank obtained after forging by using molten steel comprises the following specific steps: Pouring molten steel into a mould, pouring a casting blank, heating the casting blank to 1200-1250 ℃, preserving heat for 4-5 h, and adopting a multi-pass soft reduction forging cogging process, wherein the forging ratio is more than or equal to 5, so as to obtain a round blank of the Aza 220.
  8. 8. The method for manufacturing a steel high-pressure hydrogen storage cylinder according to claim 1, wherein the piercing-rolling of the round billet to obtain a tubular blank comprises the following specific steps: Placing the round billet into a gas heating furnace, heating the gas heating furnace to 1180-1220 ℃, preserving heat for more than or equal to 40min, perforating the round billet by utilizing a two-roller oblique rolling perforating machine at 1180-1220 ℃, wherein the inclination angle of a rolling roller of the perforating machine is controlled to be between 12 and 15 ℃ aiming at the center of the round billet, the front extension amount of a top head of the two-roller oblique rolling perforating machine is 80-100 mm, the perforation speed is 1.5m/s-2.0m/s, the perforation finishing temperature is stabilized at 1050-1100 ℃, the billet with the outer diameter of 220-280 mm, the inner diameter of 140-200 mm and the wall thickness of 40-50 mm is obtained, the rolling pass is set to be 3-5 times on a three-roller continuous tube mill, the thinning rate of 1 st rolling pass is controlled to be 25-30%, the thinning rate of 2-5 passes is 35-40%, the total thinning rate is 60-70%, the initial tubular billet with the outer diameter of 280-320 mm, the wall thickness of 12-15 and the inner diameter of 140-200 mm is obtained, and the tubular billet is obtained at the final rolling temperature of 1050-900 ℃.
  9. 9. The method for manufacturing a steel high-pressure hydrogen storage cylinder according to claim 1, further comprising the following steps after the step 2: annealing: The method comprises the steps of carrying out local annealing by using a bottle shoulder local induction annealing machine, horizontally placing a gas bottle in a V-shaped hydraulic positioning tool of the annealing machine, starting a numerical control displacement platform, moving an arc-shaped laminating induction heating coil to a bottle shoulder area of the gas bottle, enabling the arc-shaped laminating induction heating coil to cover the bottle shoulder, enabling the distance between the inner side of the arc-shaped laminating induction heating coil and the outer surface of the bottle shoulder to be 8mm-10mm, wrapping aluminum silicate heat preservation cotton with the thickness of 50mm in a bottle body and bottle mouth non-heating area, pasting 3 thermocouples arranged on the outer wall of the bottle shoulder to detect the temperature of each area of the bottle shoulder, enabling the temperature of the bottle shoulder to be 550-580 ℃, preserving heat for 30-40 min, and naturally cooling to room temperature.
  10. 10. The method for manufacturing a steel high pressure hydrogen storage cylinder according to claim 9, characterized by further comprising the steps of, after the annealing: Tempering: Heating the gas cylinder to 880-900 deg.C, maintaining the temperature for 2-3 h, cooling the gas cylinder by using a high pressure water mist quenching process, cooling the gas cylinder to room temperature, wherein the cooling speed is more than or equal to 30 deg.C/s in the range of 600-400 deg.C, heating the gas cylinder to 450 deg.C, maintaining the temperature for 1h, and then heating to 550-600 deg.C, and maintaining the temperature for 2.5-3.0 h.

Description

Manufacturing method of steel high-pressure hydrogen storage cylinder Technical Field The invention relates to the technical field of hydrogen storage containers, in particular to a manufacturing method of a steel high-pressure hydrogen storage cylinder. Background The 4130X low-alloy high-strength steel is widely used for manufacturing the steel high-pressure hydrogen storage cylinder with the pressure of less than 30MPa because of excellent hardenability, high tensile strength and good formability. However, in actual service, the 4130X steel gas cylinder needs to bear the dual functions of a high-pressure hydrogen environment and cyclic fatigue load for a long time, and is extremely easy to generate hydrogen-induced fatigue failure. In particular, the shoulder part of the gas cylinder is used as a structural transition area between the bottle mouth and the bottle body, and is subjected to severe uneven plastic deformation during spinning forming, so that the microstructure is changed, high residual tensile stress is generated, and the coupling effect of the residual tensile stress and high-pressure hydrogen enables the shoulder part to be a high-incidence area for hydrogen fatigue failure. It has been counted that about 65% of high pressure hydrogen storage cylinder failures result from shoulder fatigue cracking, which has become a core bottleneck limiting the service life of 4130X steel cylinders. In the prior art, improvement is attempted by adopting means of adding micro-alloy elements such as Ti, nb, V and the like for regulation and control, spinning process parameter adjustment and the like, but the problems that the deformation capacity of different deformation areas of the bottle shoulder is not matched, additional residual stress is generated and the fatigue failure caused by hydrogen at the bottle shoulder position cannot be fundamentally solved still exist. Disclosure of Invention The invention aims to overcome the defect of fatigue failure caused by hydrogen in the shoulder of a gas cylinder in the prior art, and provides a manufacturing method of a steel high-pressure hydrogen storage cylinder. In order to achieve the above purpose, the present invention adopts the following technical scheme: A manufacturing approach of steel high-pressure hydrogen storage cylinder, the said cylinder is made of 4130X steel, the said 4130X steel every weight percent of component is C：0.28%-0.33%,Mn：0.40%-0.60%,Ni：3.20%-3.80%,Si：0.15%-0.35%、P≤0.035%,S≤0.040%,Cr：0.80%-1.10%,Mo：0.15%-0.25%,Ti：0.01%-0.04%,Nb：0.02%-0.05%,V：0.08%-0.14%,Al：0.03%-0.06%,Cu：0.10%-0.15%,B：0.001%-0.003%, and the rest is iron Fe; Equivalent of Ni in 4130X steel ≥12.5: ; The manufacturing method of the bottle shoulder comprises the following steps: weighing the components of 4130X steel according to the mass percentage, putting other elements except Al, cu and B into a vacuum induction smelting furnace, controlling the vacuum induction smelting furnace to vacuumize and raise the temperature to melt the components into molten steel, adding the weighed Al into the molten steel, keeping the temperature for a period of time to melt the Al, adding the weighed Cu into the molten steel, keeping the temperature for a period of time to melt the Cu, adding the weighed B into the molten steel, and carrying out electroslag remelting; and 2, performing casting blank and forging by using molten steel to obtain a round blank, performing piercing rolling on the round blank to obtain a tubular blank, performing cold spinning on bottle shoulders with gradient temperature control on two ends of the tubular blank, and performing cold spinning on bottle openings to obtain the gas cylinder. According to the invention, three elements Al, cu and B are innovatively introduced to form a six-element synergistic system with original Ti, nb and V, and the four-fold synergistic effect of 'grain refinement-precipitation strengthening-grain boundary strengthening-irreversible hydrogen trap adding' is realized by precisely controlling element solid solution and distribution through three-step graded smelting. The Ni equivalent is a key index for comprehensively representing the synergistic effect of elements such as carbon (C), manganese (Mn), copper (Cu), silicon (Si), chromium (Cr), molybdenum (Mo), boron (B) and the like in steel on the hardenability. The elements can obviously improve the stability of supercooled austenite, and the Continuous Cooling Transformation (CCT) curve is shifted to the right, so that the critical cooling speed of the obtained full martensitic structure is reduced; The Ni equivalent interval set by the invention can ensure the hardenability of steel, meet the requirement of martensite transformation of the full-section uniform lath with the wall thickness of the gas cylinder of 12mm, and simultaneously consider the matching of toughness. The invention adopts the gradient temperature control of the bottle shoulder, combines the transition charac