Self-reinforced high-pressure hydrogen storage container with inner steel cylinder and outer winding steel wire and manufacturing method of self-reinforced high-pressure hydrogen storage container

Abstract

The invention belongs to the technical field of high-pressure hydrogen storage containers in the hydrogen energy storage and transportation equipment industry, and particularly relates to a self-reinforced high-pressure hydrogen storage container with an inner steel cylinder and an outer winding steel wire and a manufacturing method thereof. A self-enhancement high-pressure hydrogen storage container with an inner steel cylinder and an outer winding steel wire comprises a lining steel cylinder, a gas inlet and a gas outlet are formed in the two ends of the lining steel cylinder respectively, an enhancement layer is arranged on the outer side of a cylindrical cylinder in the middle of the lining steel cylinder, and annular anti-skid tables are arranged at the junctions of the arc tops of end openings of the outer walls of the lining steel cylinder at the two ends of the enhancement layer and the cylindrical cylinder respectively. And the reinforcing layer is formed by annularly winding a high-strength steel wire prepreg tape and curing the high-strength steel wire prepreg tape through epoxy resin. By means of the structure of the lining seamless steel cylinder and the winding steel wire reinforcing layer, the pressure bearing capacity of the container is effectively improved, the water volume of the hydrogen storage container of 103 MPa or above for the 70 MPa hydrogen refueling station is further increased, meanwhile, due to the fact that the price of high-strength steel wires is far lower than that of carbon fibers, the product manufacturing cost is reduced, and meanwhile the problem that non-metal wire winding materials are prone to aging is solved.

Description

Technical Field

[0001] The present invention belongs to the technical field of high-pressure hydrogen storage containers in the hydrogen energy storage and transportation equipment industry, and in particular relates to a self-reinforced high-pressure hydrogen storage container with an inner steel cylinder and an outer steel wire wrapped therearound and a manufacturing method thereof. Background Art

[0002] Storage is the bottleneck link in the development of hydrogen energy, and high-pressure hydrogen storage is the mainstream process at this stage. Improving hydrogen storage density, capacity and safety, and reducing the comprehensive cost of hydrogen storage are the main development directions of high-pressure hydrogen storage. At present, the design pressures of high-pressure hydrogen storage containers for 70MPa hydrogen refueling stations abroad are generally 82MPa, 87.5MPa, 98MPa, and 103MPa. The mature types include single-layer spun seamless bottle container groups, multi-layer steel plate wrapped and steel belt staggered containers. At present, domestic 70MPa hydrogen storage containers for hydrogen refueling stations are in their infancy and the technology is not yet mature.

[0003] The hydrogen storage capacity of a single seamless cylinder is small. Further improvement of its hydrogen storage capacity requires reliance on higher strength, thicker wall hydrogen-resistant steel and larger water volume seamless steel cylinder manufacturing technology. This requires high technical levels and levels of cognition in steel smelting, high-quality spinning and heat treatment processes for large-volume seamless steel cylinders, fatigue crack propagation of thick-walled high-strength steel under high-pressure hydrogen environments, and the laws of hydrogen compatibility. It is difficult to achieve under the existing theoretical, technical and equipment levels.

[0004] The hydrogen-proof metal liner of the multi-layer high-pressure hydrogen storage container is welded by austenitic stainless steel plates with excellent hydrogen resistance. The multi-layer structure with steel strips wrapped and steel plates wrapped on the outside further improves the pressure bearing capacity of the container. Even if cracks appear in the inner liner cylinder, they will not penetrate the layers and expand. It has crack arrest and explosion suppression performance and is safer. However, the manufacturing of steel strip-wrapped and layer-wrapped high-pressure hydrogen storage containers is difficult, and multiple welding joints will be generated during the production process. Welding defects and residual stress have become potential hidden dangers that affect the service safety of the container. For multi-layer high-pressure hydrogen storage containers, the use of high-strength fiber multi-layer winding structure can avoid the welding of the reinforcing layer steel plate / steel strip when using steel strip winding or layer-wrapped multi-layer structure. At present, there are related studies on high-pressure hydrogen storage containers for hydrogenation stations using steel linings and externally wrapped glass fibers and carbon fibers. For example, CN115091732B discloses a composite-molded method for preparing a 99MPa-level hydrogen storage container for hydrogenation stations. The inner lining uses a seamless steel cylinder, and the winding material is glass fiber. The container volume can reach more than 500L and the pressure can reach 99MPa. There are also reports that 70MPa hydrogen refueling stations use steel inner shells wrapped with carbon fiber high-pressure hydrogen storage containers, which can withstand pressures up to 98MPa. However, the use of carbon fiber, glass fiber or other non-metallic fibers will face the problem of expensive materials or rapid material aging, affecting the service life, safety and economy of the container. In summary, it can be seen that the existing technology cannot meet the requirements of high-pressure hydrogen storage containers for 70MPa hydrogen refueling stations with excellent hydrogen compatibility, large hydrogen storage capacity, high service safety and low manufacturing cost. Summary of the invention

[0005] In view of the above problems, the purpose of the present invention is to provide a self-reinforced high-pressure hydrogen storage container with an inner steel cylinder and an outer steel wire, and a manufacturing method thereof, so as to realize the manufacturing of a self-reinforced high-pressure hydrogen storage container with an inner steel cylinder and an outer steel wire, with a capacity of more than 800L and a pressure resistance of more than 103MPa, and meet the high-safety and low-cost hydrogen storage needs of 70MPa hydrogen refueling stations.

[0006] The technical solution of the present invention is: a self-reinforced high-pressure hydrogen storage container with an inner steel cylinder wrapped with steel wire, comprising an inner liner cylinder, an air inlet and an air outlet are respectively provided at both ends of the inner liner cylinder, a reinforcement layer is provided on the outside of the cylindrical barrel in the middle of the inner liner cylinder, and annular anti-slip platforms are respectively provided at the junction of the arc top of the outer wall port of the inner liner cylinder and the cylindrical barrel at both ends of the reinforcement layer, and the reinforcement layer is circumferentially wound by high-strength steel wire prepreg tape and cured by epoxy resin.

[0007] The lined steel cylinder is a double-mouth seamless steel cylinder formed by integral spinning, and its chemical composition is calculated by mass fraction as follows: C: 0.40%~0.50%; Si: 0.15%~0.25%; Mn: 0.85%~1.00%; Cr: 0.8%~1.2%; Mo: 0.20%~0.30%; S≤0.005%; P≤0.012%; and the balance is Fe.

[0008] The wall thickness of the cylindrical body of the lined steel cylinder is 30-40 mm. Based on the wall thickness of the cylindrical body, the wall thickness of the ports on both sides increases from the annular anti-slip platform, and the wall thickness is the largest at the arc top, which is twice the wall thickness of the body.

[0009] The air inlet and the air outlet are respectively provided with threads.

[0010] The outer surface roughness of the lined steel cylinder ranges from Ra25μm to Ra50μm, and the inner surface roughness ranges from Ra1.6μm to Ra3.2μm.

[0011] The high-strength steel wire prepreg tape uses high-strength steel wire, the tensile strength of the high-strength steel wire is Rm ≥ 2000MPa, the wire diameter range is 0.28mm~0.38mm, the surface of the high-strength steel wire is copper-plated, and the thickness of the copper-plated layer is ≥ 0.20μm. The high-strength steel wire prepreg tape is divided into two types, the first prepreg tape is formed by stacking 3 layers of steel wire, and the second prepreg tape is formed by stacking 4 layers of steel wire. The prepreg tape widths of the first prepreg tape and the second prepreg tape are both 5mm~10mm.

[0012] The yield strength of the lined cylinder R t0.5 ≥710MPa, tensile strength R m ≥820MPa, elongation A ≥20%, -40℃ KV 2≥60J, lateral expansion LE ≥0.53mm, relative tensile strength under 103MPa high pressure hydrogen environment Room H2 / Room Ref ≥0.90, relative section shrinkage Z H2 / Z Ref ≥0.75, fracture toughness K IH ≥80 MPa·m 1 / 2 .

[0013] A method for manufacturing a self-reinforced high-pressure hydrogen storage container with an inner steel cylinder and an outer steel wire, manufacturing the self-reinforced high-pressure hydrogen storage container with an inner steel cylinder and an outer steel wire, mainly comprising the following steps in sequence: S1: Lined steel cylinder processing and high-strength steel wire prepreg tape prefabrication; S2: High-strength steel wire prepreg tape is wound around the inner liner cylinder; S3: Curing and shaping of the reinforcement layer; S4: Self-enhanced water pressure test of the container; S5: Drying and shot blasting of the inner wall of the container; S6: Install the valve and conduct air tightness test; S7: topcoat spraying; S7: Finished product inspection and warehousing.

[0014] The step S1: processing the lined steel cylinder and prefabricating the high-strength steel wire prepreg tape; The main process flow of lining steel cylinder processing is: material warehousing acceptance → seamless steel pipe re-inspection → heating → spinning and closing the ends of the steel cylinder → spinning of the cylinder with annular wire winding and anti-skid table → quenching and tempering heat treatment → mechanical properties / geometric dimension inspection → external surface shot blasting → surface roughness inspection → internal thread processing of both sides of the port → thread geometric dimension inspection → non-destructive testing → epoxy resin coating on the external surface → curing of the external coating layer; the main control parameters are: setting the spinning heating temperature to 1000℃~1200℃; setting the spinning feed ratio to 2.0mm / r ~3.5mm / r (8~12 passes) + 0.5mm / r~1.0mm / r (1~2 passes); the maximum wall thickness at the spinning joint is 60mm~70mm, and the height of the wire winding anti-slip table is 0.6mm~1.2mm; during the quenching and tempering heat treatment, the quenching temperature is set to 900℃~950℃, the medium is oil, the tempering temperature is set to 650℃~700℃, and the insulation is 90min~120min; the outer surface shot blasting uses coarse steel shot, and the outer surface roughness after treatment is Ra25μm~Ra50μm; The main process flow of prepreg tape prefabrication is: high-strength steel wire preparation → epoxy resin glue heating → steel wire laying → impregnation with epoxy resin glue → scraper and squeeze roller to remove excess glue → curing → cooling → winding; the main control parameters are: setting the epoxy resin glue heating temperature to 50℃~60℃; setting the laying tension to 10N~20N and the laying speed to 20m / min~30m / min; setting the curing temperature to 130℃~150℃ and the curing time to 2h~3h; natural cooling after curing; prepreg tape width 5mm~10mm; The step S2: the liner cylinder is circumferentially wound with a high-strength steel wire prepreg tape; the main control parameters are: setting the liner cylinder to rotate once, the wire winding nozzle moves one prepreg tape width; setting the initial winding tension to 20N~40N, setting the winding angle to 86°~90°, and the tension decreases successively after every 2~3 layers of winding, the outermost layer winding tension is about 1 / 2 of the initial tension, and the winding speed is 130m / min~160m / min; setting the first prepreg tape to be wound with 12~15 layers, the second prepreg tape to be wound with 2~3 layers, and the tape overlap amount to 100mm~150mm; the single-side lateral spacing between the upper and lower prepreg tapes is 6mm~8mm, and the total thickness of the winding layer is 13mm~18mm; The step S3: curing and shaping of the reinforcement layer; main control parameters: adopting segmented heating curing, setting 90℃×1h+100℃×1h+110℃×1h+120℃×1h; natural cooling, the curing degree of the winding layer is controlled at 90%~95%; Step S4: self-enhanced water pressure test of the container; the main control parameters are: self-enhanced pressure 206MPa; adopting graded pressurization, pressurizing step by step at 30MPa, maintaining pressure for 10 minutes at each level, and maintaining pressure for 15 minutes after reaching the self-enhanced pressure; adopting graded pressure relief, releasing pressure step by step at 50MPa, maintaining pressure for 10 minutes at each level, until the pressure relief is completed; Step S5: drying and shot blasting the inner wall of the container; the main control parameters are: steel shot diameter 0.2mm; shot blasting speed 800r / min, and the inner surface roughness after treatment reaches Ra1.6μm~Ra3.2μm; The step S6: install the valve and conduct an air tightness test; the main control parameters are: the test medium is nitrogen; the test pressure is set to 103MPa; graded pressurization is adopted, the pressure is increased step by step by 30MPa, and the pressure is maintained for 5 minutes at each level, and after reaching the test pressure, the pressure is maintained for 5 minutes; graded pressure relief is adopted, the pressure is relieved step by step by 30MPa, and the pressure is maintained for 5 minutes at each level until the pressure relief is completed.

[0015] The technical effects of the present invention are as follows: 1. The present invention effectively improves the pressure bearing capacity of the container through the inner lining seamless steel cylinder + winding steel wire reinforcement layer structure, further increases the water volume of the hydrogen storage container above 103MPa used in the 70MPa hydrogenation station, and at the same time, since the price of high-strength steel wire is much lower than that of carbon fiber, the product manufacturing cost is reduced, and the problem of easy aging of non-metallic wire winding materials is avoided; 2. The present invention designs the chemical composition of the inner lining steel cylinder so that the steel has good hardenability, ensures that the metallographic structure of the inner lining steel cylinder after overall tempering heat treatment (quenching medium is oil) is controlled to tempered troostite + tempered bainite, and ensures the yield strength of the inner lining steel cylinder R t0.5 ≥710MPa, tensile strength R m ≥820MPa, elongation A ≥20%, -40℃ KV 2≥60J (lateral expansion LE ≥0.53mm); at the same time, by reducing the S and P contents and controlling the segregation and inclusion content, the hydrogen compatibility of hydrogen-adjacent steel is improved, the service safety of the container is guaranteed, and the relative tensile strength ( Room H2 / Room Ref )≥0.90, relative section shrinkage ( Z H2 / Z Ref )≥ 0.75, fracture toughness K IH ≥80 MPa·m 1 / 2 ; 3. The present invention uses the design of an anti-skid table for winding wires on the liner cylinder to extend the axial length of the winding layer as much as possible, weakening the stress concentration caused by uneven wall thickness in the transition zone between the two ends of the liner cylinder and the winding part, thereby improving the safety performance of the container; when the bottle-type container is subjected to internal pressure, the circumferential stress is twice the axial stress, and the liner cylinder is thin and the wall thickness at both ends is designed. The circumferential strength of the container cylinder is enhanced by winding wire, so that the high-strength steel wire has a high strength in the drawing direction. The uniformity of the overall stress distribution of the container is improved, and compared with the design of equal wall thickness, the volume-to-weight ratio is reduced, and the amount of steel used in the liner cylinder is saved; 4. The present invention reduces the roughness of the inner surface of the liner cylinder exposed to hydrogen and improves the container through surface treatment of the liner cylinder. Fatigue life in a high-pressure hydrogen environment improves the adhesion and anti-corrosion performance of the resin coating on the outer surface, and avoids subsequent wire slippage; the greater the surface roughness of the hydrogen-adherent material, the more serious the damage to the fatigue performance of the container by high-pressure hydrogen, and the lower the fatigue life. This is due to the notch effect of the surface roughness. Even at a lower stress level, it can more easily induce cracks on the surface of the sample, and it is easier to form hydrogen aggregation, induce crack propagation, and accelerate fatigue failure in a high-pressure hydrogen environment; 5. The present invention ensures the strength of the prepreg tape and reduces the content of bubbles and pores in the prepreg tape through the selection of high-strength steel wire and the prefabrication process of the prepreg tape. The appropriate degree of curing keeps the surface of the tape in a relatively dry and non-sticky state, and can be stably unwound, laying a good foundation for subsequent dry winding. The width of the prepreg tape is reasonable, and it can fully fit on the surface of the cylinder at a large angle during winding, while greatly improving production efficiency; 6. The present invention ensures the circumferential reinforcement of the container cylinder by the winding layer through a dry circumferential winding and curing process; due to the low elasticity of the high-strength steel wire, the appropriate winding tension avoids the cracking of the prepreg tape and avoids the tensile prestress generated in the fiber winding layer due to the winding tension, thereby ensuring the winding quality; the rapid automatic hot pressing technology is used at the overlap of the first layer of prepreg tape and the second layer of prepreg tape, which shortens the joint length, improves the joint flatness, reduces stress concentration, and ensures the performance of the tape; 7. The present invention effectively improves the pressure bearing capacity and fatigue resistance of the container through the self-reinforcement process, thereby ensuring the service safety of the container; the pressure bearing capacity of the container reaches 103MPa and the bursting pressure exceeds 280MPa. The self-strengthening pressure is twice the design pressure of the container, which can make the container form a prestressed state with the inner layer under pressure and the outer layer under tension; the compressive residual stress in the inner cylinder can reduce the average stress of the container during operation, reduce the cyclic stress amplitude, and increase the fatigue life; even if tiny cracks appear on the inner wall of the container, due to the existence of compressive residual stress, the cracks are in a closed state, the crack propagation speed is slowed down, and the safety of the container is improved.

[0016] The following is a further description with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is a schematic structural diagram of a self-reinforced high-pressure hydrogen storage container with an inner steel cylinder and outer steel wire wrapped around it according to an embodiment of the present invention.

[0018] Figure numerals: 1-lined steel cylinder, 2-annular anti-slip platform, 3-reinforcement layer, 4-air inlet, 5-air outlet. Implementation

[0019] Example 1 Figure 1 As shown, a self-reinforced high-pressure hydrogen storage container with an inner steel cylinder and an outer steel wire wrapped therearound comprises an inner lining steel cylinder 1, an air inlet 4 and an air outlet 5 are respectively arranged at two ends of the inner lining steel cylinder 1, a reinforcement layer 3 is arranged on the outer side of a cylindrical barrel in the middle of the inner lining steel cylinder 1, and an annular anti-slip platform 2 is respectively arranged at the junction of the arc top of the outer wall port of the inner lining steel cylinder 1 and the cylindrical barrel at both ends of the reinforcement layer 3, and the reinforcement layer 3 is circumferentially wound by a high-strength steel wire prepreg tape and is cured and formed by epoxy resin.

[0020] The lined steel cylinder 1 is a double-mouth seamless steel cylinder formed by integral spinning, and its chemical composition is calculated by mass fraction as follows: C: 0.40%~0.50%; Si: 0.15%~0.25%; Mn: 0.85%~1.00%; Cr: 0.8%~1.2%; Mo: 0.20%~0.30%; S≤0.005%; P≤0.012%; and the balance is Fe.

[0021] The cylindrical body wall thickness of the lined steel cylinder 1 is 30 mm to 40 mm. Based on the cylindrical body wall thickness, the wall thickness of the ports on both sides increases from the annular anti-slip platform 2, and the wall thickness is the largest at the arc top, which is twice the wall thickness of the body.

[0022] The air inlet 4 and the air outlet 5 are respectively provided with threads.

[0023] The outer surface roughness of the lined steel cylinder 1 is in the range of Ra25μm~Ra50μm, and the inner surface roughness is in the range of Ra1.6μm~Ra3.2μm.

[0024] The high-strength steel wire prepreg tape uses a high-strength steel wire with a tensile strength of Rm≥2000MPa, a wire diameter range of 0.28mm~0.38mm, a surface of the high-strength steel wire copper-plated, and a thickness of the copper-plated layer ≥0.20μm. The high-strength steel wire prepreg tape is divided into two types, the first prepreg tape is formed by stacking 3 layers of steel wire, and the second prepreg tape is formed by stacking 4 layers of steel wire. The tape widths of the first and second prepreg tapes are both 5mm~10mm.

[0025] The yield strength of the lined steel cylinder 1 Rt0.5 ≥710MPa, tensile strength R m ≥820MPa, elongation A ≥20%, -40℃ KV 2≥60J, lateral expansion LE ≥0.53mm, relative tensile strength under 103MPa high pressure hydrogen environment Room H2 / Room Ref ≥0.90, relative section shrinkage Z H2 / Z Ref ≥0.75, fracture toughness K IH ≥80 MPa·m 1 / 2 .

[0026] Embodiment 2 A method for manufacturing a self-reinforced high-pressure hydrogen storage container with an inner steel cylinder and an outer steel wire is described. The method mainly comprises the following steps: S1: Lined steel cylinder processing and high-strength steel wire prepreg tape prefabrication; S2: High-strength steel wire prepreg tape is wound around the inner liner cylinder; S3: Curing and shaping of the reinforcement layer; S4: Self-enhanced water pressure test of the container; S5: Drying and shot blasting of the inner wall of the container; S6: Install the valve and conduct air tightness test; S7: topcoat spraying; S7: Finished product inspection and warehousing.

[0027] The step S1: processing the lined steel cylinder and prefabricating the high-strength steel wire prepreg tape; The main process flow of lining steel cylinder processing is: material warehousing acceptance → seamless steel pipe re-inspection → heating → spinning and closing the ends of the steel cylinder → spinning of the cylinder with annular wire winding and anti-skid table → quenching and tempering heat treatment → mechanical properties / geometric dimension inspection → external surface shot blasting → surface roughness inspection → internal thread processing of both sides of the port → thread geometric dimension inspection → non-destructive testing → epoxy resin coating on the external surface → curing of the external coating layer; the main control parameters are: setting the spinning heating temperature to 1000℃~1200℃; setting the spinning feed ratio to 2.0mm / r ~3.5mm / r (8~12 passes) + 0.5mm / r~1.0mm / r (1~2 passes); the maximum wall thickness at the spinning joint is 60mm~70mm, and the height of the wire winding anti-slip table is 0.6mm~1.2mm; during the quenching and tempering heat treatment, the quenching temperature is set to 900℃~950℃, the medium is oil, the tempering temperature is set to 650℃~700℃, and the insulation is 90min~120min; the outer surface shot blasting uses coarse steel shot, and the outer surface roughness after treatment is Ra25μm~Ra50μm; The main process flow of prepreg tape prefabrication is: high-strength steel wire preparation → epoxy resin glue heating → steel wire laying → impregnation with epoxy resin glue → scraper and squeeze roller to remove excess glue → curing → cooling → winding; the main control parameters are: setting the epoxy resin glue heating temperature to 50℃~60℃; setting the laying tension to 10N~20N and the laying speed to 20m / min~30m / min; setting the curing temperature to 130℃~150℃ and the curing time to 2h~3h; natural cooling after curing; prepreg tape width 5mm~10mm; The step S2: the liner cylinder is circumferentially wound with a high-strength steel wire prepreg tape; the main control parameters are: setting the liner cylinder to rotate once, the wire winding nozzle moves one prepreg tape width; setting the initial winding tension to 20N~40N, setting the winding angle to 86°~90°, and the tension decreases successively after every 2~3 layers of winding, the outermost layer winding tension is about 1 / 2 of the initial tension, and the winding speed is 130m / min~160m / min; setting the first prepreg tape to be wound with 12~15 layers, the second prepreg tape to be wound with 2~3 layers, and the tape overlap amount to 100mm~150mm; the single-side lateral spacing between the upper and lower prepreg tapes is 6mm~8mm, and the total thickness of the winding layer is 13mm~18mm; The step S3: curing and shaping of the reinforcement layer; main control parameters: adopting segmented heating curing, setting 90℃×1h+100℃×1h+110℃×1h+120℃×1h; natural cooling, the curing degree of the winding layer is controlled at 90%~95%; Step S4: self-enhanced water pressure test of the container; the main control parameters are: self-enhanced pressure 206MPa; adopting graded pressurization, pressurizing step by step at 30MPa, maintaining pressure for 10 minutes at each level, and maintaining pressure for 15 minutes after reaching the self-enhanced pressure; adopting graded pressure relief, releasing pressure step by step at 50MPa, maintaining pressure for 10 minutes at each level, until the pressure relief is completed; Step S5: drying and shot blasting the inner wall of the container; the main control parameters are: steel shot diameter 0.2mm; shot blasting speed 800r / min, and the inner surface roughness after treatment reaches Ra1.6μm~Ra3.2μm; The step S6: install the valve and conduct an air tightness test; the main control parameters are: the test medium is nitrogen; the test pressure is set to 103MPa; graded pressurization is adopted, the pressure is increased step by step by 30MPa, and the pressure is maintained for 5 minutes at each level, and after reaching the test pressure, the pressure is maintained for 5 minutes; graded pressure relief is adopted, the pressure is relieved step by step by 30MPa, and the pressure is maintained for 5 minutes at each level until the pressure relief is completed.

[0028] Example 3 This example adopts the manufacturing method of a self-reinforced high-pressure hydrogen storage container with an inner steel cylinder and an outer steel wire as described in Example 2 to manufacture a self-reinforced high-pressure hydrogen storage container with an inner steel cylinder and an outer steel wire as described in Example 1, specifically a 103MPa self-reinforced high-pressure hydrogen storage container with an inner steel cylinder and an outer steel wire for a 70MPa hydrogen refueling station, with specifications of Φ457×33.8mm, a total length of 9000mm, and a water capacity of 900L.

[0029] The seamless steel cylinder lined in this embodiment adopts special high-strength hydrogen-resistant steel, and its chemical composition detection values ​​are: C: 0.44%; Si: 0.22%; Mn: 0.87%; Cr: 0.92%; Mo: 0.28%; S: 0.003%; P: 0.008%; the balance is Fe. The average mechanical properties of the steel cylinder lined material are (average of 3 samples): yield strength R t0.5 785MPa, tensile strength R m 892MPa, elongation A 32%, -40℃ KV 2121J (lateral expansion LE 0.67mm), relative tensile strength of materials under 103MPa high pressure hydrogen environment ( Room H2 / Room Ref ) 0.93, relative section shrinkage ( Z H2 / Z Ref ) 0.81, fracture toughness K IH88 MPa·m 1 / 2 .

[0030] The high-strength steel wire used in this embodiment has a tensile strength R m The minimum value is 2860MPa, the average wire diameter is 0.353mm, and the average thickness of the copper plating layer on the steel wire surface is 0.22μm.

[0031] The manufacturing process flow of the hydrogen storage container in this embodiment is: material preparation (lining steel cylinder processing, prepreg tape prefabrication) → circumferential winding of high-strength steel wire prepreg tape on the lining steel cylinder → curing and shaping of the container winding layer → self-reinforcement water pressure test of the container → drying and shot blasting of the inner wall of the container → valve installation and air tightness test → topcoat spraying → finished product inspection → warehousing.

[0032] The key processes are as follows: Lined steel cylinder processing.

[0033] The main process flow is: material acceptance → seamless steel pipe re-inspection → heating → spinning and closing the ends of the cylinder → spinning of the cylinder with annular wire winding and anti-skid table → tempering heat treatment → mechanical properties / geometric dimension inspection → external surface shot blasting → surface roughness inspection → internal thread processing of both sides of the port → thread geometric dimension inspection → non-destructive testing → epoxy resin coating on the external surface → curing of the external coating layer.

[0034] Main controls: ① Set the spinning heating temperature to 1200℃; ② Set the spinning feed ratio to 3.2mm / r (8 passes) + 0.5mm / r (1 pass); ③ The maximum wall thickness at the spinning joint is 67.6mm, and the height of the wire winding anti-slip table is 0.7mm; ④ During the tempering heat treatment, the quenching temperature is set to 900℃, the medium is oil, the tempering temperature is set to 700℃, and the insulation time is 90min; ⑤ The outer surface is shot blasted with coarse steel shots, and the outer surface roughness after treatment is Ra25μm.

[0035] Prepreg tape prefabrication.

[0036] The main process flow is: high-strength steel wire preparation → epoxy resin glue heating → steel wire laying → impregnation with epoxy resin glue → scraper plate and squeeze roller to remove excess glue → curing → cooling → winding.

[0037] Main controls: ① Set the heating temperature of epoxy resin glue to 55℃; ② Set the pay-off tension to 10N and the pay-off speed to 25m / min; ③ Set the curing temperature to 135℃ and the curing time to 2h; ④ Cool naturally after curing; ⑤ Prepreg tape width 6mm.

[0038] The inner liner cylinder is circumferentially wound with high-strength steel wire prepreg tape.

[0039] Main controls: ① Set the winding nozzle to move 6mm for every rotation of the liner cylinder; ② Set the initial winding tension to 30N and the winding speed to 140m / min; ③ Set the first type of prepreg tape to be wound with 13 layers, the second type of prepreg tape to be wound with 2 layers, and the tape overlap to 150mm; ④ The single-side lateral spacing between the upper and lower prepreg tapes is 7.1mm. The total thickness of the winding layer reaches 16.7mm.

[0040] Curing and shaping of container wrapping layer.

[0041] Main control: ① Use segmented heating curing, set at 90℃×1h+100℃×1h+110℃×1h+120℃×1h; ② Natural air cooling. The curing degree of the winding layer reaches 92%.

[0042] Self-intensified water pressure test of containers.

[0043] Main control: ① Self-enhancement pressure 206MPa; ② Use graded pressure increase, pressurize step by step at 30MPa, maintain pressure for 10 minutes at each level, and maintain pressure for 15 minutes after reaching the self-enhancement pressure; ③ Use graded pressure relief, release pressure step by step at 50MPa, maintain pressure for 10 minutes at each level until the pressure relief is completed. There is no bulging or bursting in the container during the test.

[0044] The inner wall of the container is dried and shot blasted.

[0045] Main control: ① Steel shot diameter 0.2mm; ② Shot blasting speed 800r / min. After treatment, the inner surface roughness reaches Ra1.6μm.

[0046] Install the valve and perform an air tightness test.

[0047] Main control: ① The test medium is nitrogen; ② Set the test pressure to 103MPa; ③ Use graded pressurization, pressurize step by step at 30MPa, maintain pressure for 5 minutes at each level, and maintain pressure for 5 minutes after reaching the test pressure; ④ Use graded pressure relief, release pressure step by step at 30MPa, maintain pressure for 5 minutes at each level until the pressure relief is completed. There is no leakage in the container body, bottle valve and the connection between the bottle body and the bottle valve.

[0048] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by any technician familiar with the technical field within the technical scope disclosed by the present invention should be covered within the protection scope of the present invention.

Claims

1. A self-reinforced high-pressure hydrogen storage container with an inner steel cylinder and an outer steel wire, characterized in that: The invention comprises a lined steel cylinder (1), wherein the two ends of the lined steel cylinder (1) are respectively provided with an air inlet (4) and an air outlet (5), a reinforcement layer (3) is provided on the outer side of a cylindrical body in the middle of the lined steel cylinder (1), and an annular anti-skid platform (2) is provided at the junction of the arc top of the outer wall port of the lined steel cylinder (1) and the cylindrical body at both ends of the reinforcement layer (3), and the reinforcement layer (3) is formed by annularly winding a high-strength steel wire prepreg tape and curing it with epoxy resin.

2. According to claim 1, a self-reinforced high-pressure hydrogen storage container with an inner steel cylinder and an outer steel wire, characterized in that: The liner steel cylinder (1) is a double-mouth seamless steel cylinder formed by integral spinning, and its chemical composition by mass fraction is: C: 0.40%~0.50%; Si: 0.15%~0.25%; Mn: 0.85%~1.00%; Cr: 0.8%~1.2%; Mo: 0.20%~0.30%; S≤0.005%; P≤0.012%; the balance is Fe.

3. According to claim 1, a self-reinforced high-pressure hydrogen storage container with an inner steel cylinder and an outer steel wire, characterized in that: The cylindrical body wall thickness of the liner cylinder (1) is 30 mm to 40 mm. Based on the cylindrical body wall thickness, the wall thickness of the two side ports increases from the annular anti-slip platform (2), and the wall thickness is the largest at the arc top, which is twice the wall thickness of the body.

4. According to claim 1, a self-reinforced high-pressure hydrogen storage container with an inner steel cylinder and an outer steel wire, characterized in that: The air inlet (4) and the air outlet (5) are respectively provided with threads.

5. According to claim 1, a self-reinforced high-pressure hydrogen storage container with an inner steel cylinder and an outer steel wire, characterized in that: The outer surface roughness of the lined steel cylinder (1) is in the range of Ra25 μm to Ra50 μm, and the inner surface roughness is in the range of Ra1.6 μm to Ra3.2 μm.

6. According to claim 1, a self-reinforced high-pressure hydrogen storage container with an inner steel cylinder and an outer steel wire, characterized in that: The high-strength steel wire prepreg tape uses high-strength steel wire, the tensile strength of the high-strength steel wire is Rm ≥ 2000MPa, the wire diameter range is 0.28mm~0.38mm, the surface of the high-strength steel wire is copper-plated, and the thickness of the copper-plated layer is ≥ 0.20μm. The high-strength steel wire prepreg tape is divided into two types, the first prepreg tape is formed by stacking 3 layers of steel wire, and the second prepreg tape is formed by stacking 4 layers of steel wire. The prepreg tape widths of the first prepreg tape and the second prepreg tape are both 5mm~10mm.

7. According to claim 1, a self-reinforced high-pressure hydrogen storage container with an inner steel cylinder and an outer steel wire, characterized in that: The yield strength of the lined steel cylinder (1) R t0.5 ≥710MPa, tensile strength R m ≥820MPa, elongation A ≥20%, -40℃ KV 2≥60J, lateral expansion LE ≥0.53mm, relative tensile strength under 103MPa high pressure hydrogen environment Rm H2 / Rm Ref ≥ 0.90, relative section shrinkage Z H2 / Z Ref ≥0.75, fracture toughness K IH ≥80 MPa·m 1 / 2 .

8. A method for manufacturing a self-reinforced high-pressure hydrogen storage container with an inner steel cylinder and an outer steel wire, manufacturing a self-reinforced high-pressure hydrogen storage container with an inner steel cylinder and an outer steel wire as claimed in claims 1 to 7, characterized in that: The main steps are as follows: S1: Lined steel cylinder processing and high-strength steel wire prepreg tape prefabrication; S2: High-strength steel wire prepreg tape is wound around the inner liner cylinder; S3: Curing and shaping of the reinforcement layer; S4: Self-enhanced water pressure test of the container; S5: Drying and shot blasting of the inner wall of the container; S6: Install the valve and conduct air tightness test; S7: topcoat spraying; S7: Finished product inspection and warehousing.

9. The method for manufacturing a self-reinforced high-pressure hydrogen storage container with an inner steel cylinder and outer steel wire as claimed in claim 8, characterized in that: The step S1: processing the lined steel cylinder and prefabricating the high-strength steel wire prepreg tape; The main process flow of lining steel cylinder processing is: material warehousing acceptance → seamless steel pipe re-inspection → heating → spinning and closing the ends of the steel cylinder → spinning of the cylinder with annular wire winding and anti-skid table → quenching and tempering heat treatment → mechanical properties / geometric dimension inspection → external surface shot blasting → surface roughness inspection → internal thread processing of both sides of the port → thread geometric dimension inspection → non-destructive testing → epoxy resin coating on the external surface → curing of the external coating layer; the main control parameters are: setting the spinning heating temperature to 1000℃~1200℃; setting the spinning feed ratio to 2.0mm / r ~3.5mm / r (8~12 passes) + 0.5mm / r~1.0mm / r (1~2 passes); the maximum wall thickness at the spinning joint is 60mm~70mm, and the height of the wire winding anti-slip table is 0.6mm~1.2mm; during the quenching and tempering heat treatment, the quenching temperature is set to 900℃~950℃, the medium is oil, the tempering temperature is set to 650℃~700℃, and the insulation is 90min~120min; the outer surface shot blasting uses coarse steel shot, and the outer surface roughness after treatment is Ra25μm~Ra50μm; The main process flow of prepreg tape prefabrication is: high-strength steel wire preparation → epoxy resin glue heating → steel wire laying → impregnation with epoxy resin glue → scraper and squeeze roller to remove excess glue → curing → cooling → winding; the main control parameters are: setting the epoxy resin glue heating temperature to 50℃~60℃; setting the laying tension to 10N~20N and the laying speed to 20m / min~30m / min; setting the curing temperature to 130℃~150℃ and the curing time to 2h~3h; natural cooling after curing; prepreg tape width 5mm~10mm; The step S2: the liner cylinder is circumferentially wound with a high-strength steel wire prepreg tape; the main control parameters are: setting the liner cylinder to rotate once, the wire winding nozzle moves one prepreg tape width; setting the initial winding tension to 20N~40N, setting the winding angle to 86°~90°, and the tension decreases successively after every 2~3 layers of winding, the outermost layer winding tension is about 1 / 2 of the initial tension, and the winding speed is 130m / min~160m / min; setting the first prepreg tape to be wound with 12~15 layers, the second prepreg tape to be wound with 2~3 layers, and the tape overlap amount to 100mm~150mm; the single-side lateral spacing between the upper and lower prepreg tapes is 6mm~8mm, and the total thickness of the winding layer is 13mm~18mm; The step S3: curing and shaping of the reinforcement layer; main control parameters: adopting segmented heating curing, setting 90℃×1h+100℃×1h+110℃×1h+120℃×1h; natural cooling, the curing degree of the winding layer is controlled at 90%~95%; Step S4: self-enhanced water pressure test of the container; the main control parameters are: self-enhanced pressure 206MPa; adopting graded pressurization, pressurizing step by step at 30MPa, maintaining pressure for 10 minutes at each level, and maintaining pressure for 15 minutes after reaching the self-enhanced pressure; adopting graded pressure relief, releasing pressure step by step at 50MPa, maintaining pressure for 10 minutes at each level, until the pressure relief is completed; Step S5: drying and shot blasting the inner wall of the container; the main control parameters are: steel shot diameter 0.2mm; shot blasting speed 800r / min, and the inner surface roughness after treatment reaches Ra1.6μm~Ra3.2μm; The step S6: install the valve and conduct an air tightness test; the main control parameters are: the test medium is nitrogen; the test pressure is set to 103MPa; graded pressurization is adopted, the pressure is increased step by step by 30MPa, and the pressure is maintained for 5 minutes at each level, and after reaching the test pressure, the pressure is maintained for 5 minutes; graded pressure relief is adopted, the pressure is relieved step by step by 30MPa, and the pressure is maintained for 5 minutes at each level until the pressure relief is completed.

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