A high-pressure hydrogen storage container with a steel bottle and a steel wire wound outside and a manufacturing method thereof

Abstract

The present application belongs to the technical field of high-pressure hydrogen storage container in hydrogen energy storage and transportation equipment industry, and particularly relates to a high-pressure hydrogen storage container with an inner steel bottle and an outer steel wire winding self-reinforced structure and a manufacturing method thereof. The high-pressure hydrogen storage container with an inner steel bottle and an outer steel wire winding self-reinforced structure comprises an inner liner steel bottle, the two ends of the inner liner steel bottle are respectively provided with a gas inlet and a gas outlet, the outer side of the middle columnar cylinder of the inner liner steel bottle is provided with a reinforcing layer, the outer wall end ports of the inner liner steel bottle at the two ends of the reinforcing layer are respectively provided with annular anti-skid platforms at the junctions with the columnar cylinder, and the reinforcing layer is annularly wound by high-strength steel wire prepreg tapes and is solidified and formed by epoxy resin. The present application effectively improves the pressure-bearing capacity of the container by the structure of the inner liner seamless steel bottle and the winding steel wire reinforcing layer, further improves the water volume of the 103MPa or above hydrogen storage container for 70MPa hydrogenation station, simultaneously reduces the product manufacturing cost due to the fact that the price of the high-strength steel wire is far lower than that of carbon fiber, and simultaneously avoids the problem of easy aging of the non-metallic winding wire material.

Description

TECHNICAL FIELD

[0001] The application 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 bottle and an outer wound steel wire and a manufacturing method thereof. BACKGROUND

[0002] Storage is a bottleneck link for the development of hydrogen energy, and high-pressure hydrogen storage is the mainstream process at the present 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 pressure of high-pressure hydrogen storage containers for foreign 70MPa hydrogen refueling stations is generally 82MPa, 87.5MPa, 98MPa and 103MPa, and the mature types include single-layer seamless bottle container groups, multi-layer steel plate wrapping containers and steel belt winding containers. At present, domestic 70MPa hydrogen refueling station hydrogen storage containers are in the initial stage and the technology is not mature.

[0003] The single hydrogen storage capacity of the seamless bottle group is small, and the further improvement of the hydrogen storage capacity needs to rely on higher strength, larger wall thickness of hydrogen-resistant steel materials and larger water volume seamless steel bottle manufacturing technology, which requires high technical level and cognitive degree in steel smelting level, large volume seamless steel bottle high quality spinning and heat treatment process, fatigue crack propagation and hydrogen compatibility of large thickness high strength steel materials in high pressure hydrogen environment, and it is difficult to achieve under the existing theory and technology and equipment level.

[0004] The hydrogen-resistant metal liner of the multi-layer high-pressure hydrogen storage container is made of austenitic stainless steel plate with excellent hydrogen resistance, and the outer part is a multi-layer structure wrapped with steel belts and wrapped with steel plates to further improve the pressure-bearing capacity of the container. Even if the inner liner cylinder has cracks, it will not penetrate and expand the layers, has crack stopping and explosion suppression performance, and is safer. However, the steel belt winding and layer plate wrapping type high-pressure hydrogen storage container is difficult to manufacture, and multiple welding joints are generated during the production process. Welding defects and residual stress have become potential hazards affecting the safety of the container in service. For the multi-layer high-pressure hydrogen storage container, the use of high-strength fiber multi-layer winding structure can avoid the welding of the reinforcing layer steel plate / steel belt when using steel belt winding or layer plate wrapping multi-layer structure. Currently, there are related researches on high-pressure hydrogen storage containers for hydrogen stations using steel liners wrapped with glass fibers and carbon fibers. For example, CN115091732B discloses a method for manufacturing a 99MPa-level hydrogen storage container for hydrogen stations, the inner liner is a seamless steel cylinder, the winding material is glass fiber, the container volume can reach more than 500L, and the pressure-bearing capacity can reach 99MPa. There are also reports of 70MPa hydrogen station steel liner carbon fiber wrapped high-pressure hydrogen storage containers with a pressure-bearing capacity of 98MPa. However, the use of carbon fiber, glass fiber or other non-metallic fiber will face the problem of high material price or fast material aging, affecting the service life, safety and economy of the container. In summary, the existing technology cannot meet the demand for high-pressure hydrogen storage containers for 70MPa hydrogen stations with high hydrogen compatibility, large hydrogen storage capacity, high service safety and low manufacturing cost. SUMMARY

[0005] To solve the above problems, the purpose of the present application is to provide an inner steel cylinder outer steel wire type self-reinforced high-pressure hydrogen storage container and a manufacturing method thereof, to realize the manufacturing of an inner steel cylinder outer steel wire type self-reinforced high-pressure hydrogen storage container with a volume of more than 800L and a pressure-bearing capacity of more than 103MPa, and to meet the high safety and low cost hydrogen storage demand of 70MPa hydrogen stations.

[0006] The technical scheme of the present application is as follows: an inner steel cylinder outer steel wire type self-reinforced high-pressure hydrogen storage container, comprising an inner liner cylinder, the inner liner cylinder is respectively provided with a gas inlet and a gas outlet at both ends, a reinforcing layer is arranged outside the middle cylindrical body of the inner liner cylinder, and a circumferential anti-skid platform is arranged at the junction of the arc top of the outer wall port of the reinforcing layer at both ends and the cylindrical body.

[0007] The inner liner cylinder is a double-port seamless steel cylinder formed by one-piece spinning, and the chemical composition is 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 inner lining steel cylinder is 30~40mm. Based on the wall thickness of the cylindrical body, the wall thickness of both ends increases from the circumferential anti-slip platform, and the wall thickness is the largest at the arc apex, which is twice the wall thickness of the cylinder body.

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

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

[0011] The high-strength steel wire prepreg tape uses high-strength steel wire with a tensile strength Rm ≥ 2000 MPa and a wire diameter range of 0.28 mm to 0.38 mm. The surface of the high-strength steel wire is copper-plated with a copper plating layer thickness ≥ 0.20 μm. The high-strength steel wire prepreg tape is divided into two types: the first type of prepreg tape is composed of 3 layers of steel wire, and the second type of prepreg tape is composed of 4 layers of steel wire. The width of the prepreg tape of both the first type and the second type is 5 mm to 10 mm.

[0012] The yield strength of the liner cylinder R t0.5 ≥710MPa, tensile strength R m ≥820MPa, elongation A ≥20%, at -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 reduction of area 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 winding, as described above, mainly includes the following steps:

[0014] S1: Processing of steel cylinder liners and prefabrication of high-strength steel wire prepreg strips;

[0015] S2: High-strength steel wire prepreg tape is wrapped circumferentially around the inner lining of the steel cylinder;

[0016] S3: Reinforcement layer curing and shaping;

[0017] S4: container self-reinforced hydrostatic test;

[0018] S5: container inner wall drying and shot blasting treatment;

[0019] S6: valve installation and air tightness test;

[0020] S7: topcoat spraying;

[0021] S7: finished product inspection and warehousing.

[0022] The step S1: inner liner steel cylinder processing and high-strength steel wire prepreg;

[0023] The main process flow of inner liner steel cylinder processing is: material warehouse acceptance → seamless steel pipe reinspection → heating → steel cylinder two end spinning closing forming → cylinder ring winding slip prevention platform spinning forming → quenching and tempering heat treatment → mechanical property / geometry size inspection → outer surface shot blasting treatment → surface roughness inspection → both sides port inner thread processing → thread geometry size inspection → nondestructive testing → outer surface epoxy resin coating → outer coating layer curing; The main control parameters are: setting spinning heating temperature 1000℃~1200℃; Setting spinning feed ratio 2.0mm / r~3.5mm / r (8~12 passes) +0.5mm / r~1.0mm / r (1~2 passes); Spinning closing maximum wall thickness 60mm~70mm, winding slip prevention platform height 0.6mm~1.2mm; Quenching and tempering heat treatment is set to quenching temperature 900℃~950℃, medium is oil, setting tempering temperature 650℃~700℃, holding for 90min~120min; Outer surface shot blasting treatment uses coarse steel shot, after treatment, the outer surface roughness Ra25μm~Ra50μm;

[0024] The main process flow of prepreg is: high-strength steel wire preparation → epoxy resin glue heating → steel wire unwinding → epoxy resin glue dipping → excess glue removal by scraping plate and extruding roller → curing → cooling → winding; The main control parameters are: setting epoxy resin glue heating temperature 50℃~60℃; Setting unwinding tension 10N~20N, unwinding speed 20m / min~30m / min; Setting curing temperature 130℃~150℃, curing time 2h~3h; After curing, natural cooling; Prepreg width 5mm~10mm;

[0025] The step S2 is that the inner lining steel bottle is circumferentially wound with high-strength steel wire prepreg tape; main control parameters are as follows: setting the inner lining steel bottle to rotate 1 week, the wire nozzle is moved 1 prepreg tape width; setting the initial winding tension to be 20N~40N, setting the winding angle to be 86°~90°, the tension is sequentially decreased every 2~3 layers, the outermost layer winding tension is about 1 / 2 of the initial tension, the winding speed is 130m / min~160m / min; setting the first kind of prepreg tape to be wound 12 layers~15 layers, the second kind of prepreg tape to be wound 2 layers~3 layers, the tape overlap amount is 100mm~150mm; the unilateral horizontal spacing between the upper and lower prepreg tapes is 6mm~8mm, and the total thickness of the winding layer is 13mm~18mm;

[0026] The step S3 is that the reinforcing layer is cured and shaped; main control parameters are as follows: adopting sectional heating and curing, setting 90℃×1h+100℃×1h+110℃×1h+120℃×1h; naturally cooling, and the curing degree of the winding layer is controlled to be 90%~95%;

[0027] The step S4 is that the container is subjected to a self-reinforced water pressure test; main control parameters are as follows: the self-reinforced pressure is 206MPa; adopting graded pressurization, pressurizing by 30MPa every time, keeping pressure for 10min every time, keeping pressure for 15min after reaching the self-reinforced pressure; adopting graded pressure relief, relieving by 50MPa every time, keeping pressure for 10min every time until the pressure relief is completed;

[0028] The step S5 is that the inner wall of the container is dried and subjected to shot blasting treatment; main control parameters are as follows: the steel shot diameter is 0.2mm; the shot blasting speed is 800r / min, and the inner surface roughness after treatment reaches Ra1.6μm~Ra3.2μm;

[0029] The step S6 is that the valve is mounted and subjected to a gas tightness test; main control parameters are as follows: the test medium is nitrogen; the test pressure is set to be 103MPa; adopting graded pressurization, pressurizing by 30MPa every time, keeping pressure for 5min every time, keeping pressure for 5min after reaching the test pressure; adopting graded pressure relief, relieving by 30MPa every time, keeping pressure for 5min every time until the pressure relief is completed.

[0030] The technical effect of the present application is that: 1. The present application effectively improves the pressure bearing capacity of the container through the inner lining seamless steel bottle + winding steel wire reinforcing layer structure, further improves the water volume of the 103MPa or above hydrogen storage container for 70MPa hydrogen station, and simultaneously reduces the product manufacturing cost due to the fact that the price of high-strength steel wire is far lower than that of carbon fiber, and avoids the problem that the non-metallic winding material is prone to aging; 2. The present application designs the chemical composition of the inner lining steel bottle, so that the steel has good hardenability, ensures that the metallographic structure of the inner lining steel bottle after overall quenching and tempering heat treatment (quenching medium is oil) is controlled to be tempered sorbite + tempered bainite, and ensures that the yield strength of the inner lining steel bottle is 700MPa~750MPa, the tensile strength is 800MPa~850MPa, the elongation is 15%~20%, and the impact toughness is 100J~120J.R t0.5 ≥710 MPa, tensile strength R m ≥820 MPa, elongation A ≥20%, at -40°C KV 2≥60 J (lateral expansion LE ≥0.53 mm); at the same time, by reducing the contents of S and P, controlling the segregation and inclusion contents, the hydrogen compatibility of the hydrogen-containing steel material is improved, the service safety of the container is ensured, the relative tensile strength (R Rm H2 Rm Ref )≥0.90, the relative reduction of area (R Z H2 Z Ref )≥0.75, and the fracture toughness (K K IH ≥80 MPa·m 1 / 2 ​​;3. The application designs a winding slip-proof table for the inner lining steel bottle, so that the axial length of the winding layer is extended as far as possible, the stress concentration caused by the uneven wall thickness in the transition zone between the two ends of the inner lining steel bottle and the winding part is weakened, and the safety performance of the container is improved; under the condition of internal pressure of the bottle type container, the hoop stress is 2 times the axial stress, the wall thickness design of the inner lining steel bottle cylinder is thin at both ends, the hoop strength of the container cylinder is enhanced by winding, the characteristics of the high-strength steel wire are fully utilized, and the uniformity of the overall stress distribution of the container is improved, compared with the equal wall thickness design, the container weight ratio is reduced, and the steel consumption of the inner lining steel bottle is saved; 4. The application reduces the roughness of the inner surface of the inner lining steel bottle under hydrogen, improves the fatigue life of the container under high pressure hydrogen environment, improves the adhesion and corrosion resistance of the outer surface resin coating, and avoids subsequent winding sliding; the greater the surface roughness of the hydrogen material, the more serious the damage of high pressure hydrogen gas to the fatigue performance of the container, and the lower the fatigue life, which is due to the notch effect of the surface roughness, even under a lower stress level, cracks can be easily initiated on the surface of the sample, and in a high pressure hydrogen environment, hydrogen aggregation is more likely to occur, crack propagation is initiated, and fatigue failure is accelerated; 5. The application selects high-strength steel wire and pre-preg tape preforming process to ensure the strength of the pre-preg tape, reduce the bubble and pore content in the pre-preg tape, and make the surface of the tape dry and not sticky, which lays a good foundation for subsequent dry winding. The width of the pre-preg tape is reasonable, and the tape can be fully attached to the surface of the cylinder at a large angle during winding, while the production efficiency is greatly improved; 6. The application adopts dry hoop winding and curing process to ensure the hoop reinforcement of the winding layer to the container cylinder; due to the low elasticity of high-strength steel wire, appropriate winding tension can avoid pre-preg tape cracking and tensile pre-stress in the fiber winding layer caused by winding tension, ensuring the winding quality; the first layer of pre-preg tape and the second layer of pre-preg tape are connected by rapid automatic hot pressing technology, which shortens the joint length, improves the joint flatness, reduces the stress concentration, and ensures the performance of the tape; 7. The application adopts self-reinforcing process to effectively improve the pressure-bearing capacity and fatigue resistance of the container, and ensures the service safety of the container; the pressure-bearing capacity of the container reaches 103MPa, and the burst pressure exceeds 280MPa. The self-reinforcing pressure is 2 times the design pressure of the container, which can make the container form a pre-stressed state of inner layer under pressure and outer layer under tension; the compression residual stress existing in the inner cylinder can reduce the average stress, reduce the cyclic stress amplitude and improve the fatigue life of the container during operation; even if a small crack appears on the inner wall of the container, the crack is in a closed state due to the existence of compression residual stress, the crack propagation speed is slow, and the safety of the container is improved.

[0031] The application will be further described in combination with the accompanying drawings. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1This is a schematic diagram of a self-reinforced high-pressure hydrogen storage container structure with an inner steel cylinder and an outer steel wire winding, according to an embodiment of the present invention.

[0033] Attached reference numerals: 1-Inner liner of steel cylinder, 2-Circumferential anti-slip platform, 3-Reinforcing layer, 4-Air inlet, 5-Air outlet. Implementation

[0034] Example 1 Figure 1 As shown, a self-reinforced high-pressure hydrogen storage container with an inner steel cylinder and an outer steel wire winding includes an inner steel cylinder 1. The inner steel cylinder 1 has an inlet 4 and an outlet 5 at both ends. The outer side of the cylindrical body in the middle of the inner steel cylinder 1 is provided with a reinforcing layer 3. At the junction of the arc apex of the outer wall port of the inner steel cylinder 1 and the cylindrical body at both ends of the reinforcing layer 3, there are circumferential anti-slip platforms 2. The reinforcing layer 3 is made of high-strength steel wire prepreg wrapped circumferentially and cured with epoxy resin.

[0035] The inner liner cylinder 1 is a seamless double-necked steel cylinder integrally spun, and its chemical composition by mass fraction is 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%; balance is Fe.

[0036] The inner lining cylinder 1 has a cylindrical body wall thickness of 30mm~40mm. Based on the cylindrical body wall thickness, the wall thickness at both ends increases from the circumferential anti-slip platform 2, and the wall thickness is the largest at the arc apex, which is twice the thickness of the cylinder wall.

[0037] The air inlet 4 and air outlet 5 are respectively provided with threads.

[0038] The outer surface roughness of the inner liner cylinder 1 ranges from Ra25μm to Ra50μm, and the inner surface roughness ranges from Ra1.6μm to Ra3.2μm.

[0039] The high-strength steel wire prepreg tape uses high-strength steel wire with a tensile strength Rm≥2000MPa and a wire diameter range of 0.28mm~0.38mm. The surface of the high-strength steel wire is copper-plated with a copper plating layer thickness ≥0.20μm. The high-strength steel wire prepreg tape is divided into two types: the first type of prepreg tape is composed of 3 layers of steel wire, and the second type of prepreg tape is composed of 4 layers of steel wire. The tape width of both the first type of prepreg tape and the second type of prepreg tape is 5mm~10mm.

[0040] The yield strength of the inner lining steel cylinder 1 R t0.5 ≥710MPa, tensile strength R m ≥820MPa, elongation A≥ 20%, -40℃ KV 2 ≥ 60 J, side expansion LE ≥ 0.53 mm, relative tensile strength under 103 MPa high-pressure hydrogen environment Rm H2 / Rm Ref ≥ 0.90, relative cross-sectional shrinkage Z H2 / Z Ref ≥ 0.75, fracture toughness K IH ≥ 80 MPa·m 1 / 2 .

[0041] Example 2: A manufacturing method of an inner steel bottle outer winding steel wire type self-reinforced high-pressure hydrogen storage container, manufacturing an inner steel bottle outer winding steel wire type self-reinforced high-pressure hydrogen storage container as described above, sequentially mainly comprising the following steps:

[0042] S1: Inner liner steel bottle processing and high-strength steel wire prepreg;

[0043] S2: Inner liner steel bottle circumferential winding high-strength steel wire prepreg;

[0044] S3: Reinforcing layer curing and shaping;

[0045] S4: Container self-reinforced hydrostatic test;

[0046] S5: Container inner wall drying and shot blasting treatment;

[0047] S6: Valve installation and air tightness test;

[0048] S7: Topcoat spraying;

[0049] S7: Product inspection and warehousing.

[0050] The step S1: inner liner steel bottle processing and high-strength steel wire prepreg;

[0051] The main process flow of the inner lining steel cylinder processing is: material warehouse acceptance → seamless steel pipe reinspection → heating → steel cylinder two end spinning closing forming → cylinder ring winding anti-skid platform spinning forming → quenching and tempering heat treatment → mechanical property / geometric size inspection → outer surface shot blasting → surface roughness inspection → both sides port inner thread processing → thread geometric size inspection → nondestructive testing → outer surface epoxy resin coating → outer coating curing; the main control parameters are: setting the spinning heating temperature 1000℃~1200℃; setting the spinning feed ratio 2.0mm / r~3.5mm / r (8~12 passes) +0.5mm / r~1.0mm / r (1~2 passes); the maximum wall thickness of the spinning closing is 60mm~70mm, the winding anti-skid platform height is 0.6mm~1.2mm; the quenching temperature is set to 900℃~950℃, the medium is oil, the tempering temperature is set to 650℃~700℃, and the holding time is 90min~120min; the outer surface shot blasting uses coarse steel shot, and the outer surface roughness after treatment is Ra25μm~Ra50μm;

[0052] The main process flow of the prepreg tape preparation is: high-strength steel wire preparation → epoxy resin glue heating → steel wire unwinding → epoxy resin glue dipping → excess glue removal by scraping plate and extruding roller → curing → cooling → winding; the main control parameters are: setting the epoxy resin glue heating temperature 50℃~60℃; setting the unwinding tension 10N~20N, and the unwinding speed 20m / min~30m / min; setting the curing temperature 130℃~150℃, and the curing time 2h~3h; natural cooling after curing; the prepreg tape width is 5mm~10mm;

[0053] The step S2 is: winding the high-strength steel wire prepreg tape on the inner lining steel cylinder in the circumferential direction; the main control parameters are: setting the winding nozzle to move 1 prepreg tape width per 1 week of the inner lining steel cylinder; setting the initial winding tension 20N~40N, the winding angle 86°~90°, the winding speed 130m / min~160m / min, and the winding tension to decrease by turns, the outermost layer winding tension being about 1 / 2 of the initial tension; setting the first kind of prepreg tape to wind 12 layers~15 layers, the second kind of prepreg tape to wind 2 layers~3 layers, and the tape overlap amount 100mm~150mm; the unilateral horizontal distance between the upper and lower prepreg tapes is 6mm~8mm, and the total thickness of the winding layers is 13mm~18mm;

[0054] The step S3 is: reinforcement layer curing and shaping; the main control parameters are: adopting sectional heating curing, setting 90℃×1h+100℃×1h+110℃×1h+120℃×1h; natural cooling, and the winding layer curing degree being controlled in 90%~95%;

[0055] The step S4: container self-reinforced hydrostatic test; the main control parameters are: self-reinforcing pressure 206 MPa; adopting step-by-step pressurization, step-by-step pressurization by 30 MPa, pressure maintaining for 10 min at each level, and pressure maintaining for 15 min after reaching the self-reinforcing pressure; adopting step-by-step pressure relief, step-by-step pressure relief by 50 MPa, pressure maintaining for 10 min at each level until the pressure relief is completed;

[0056] The step S5: container inner wall drying and shot blasting treatment; the main control parameters are: steel shot diameter 0.2 mm; shot blasting speed 800 r / min, and the inner surface roughness after treatment reaching Ra1.6 μm-Ra3.2 μm;

[0057] The step S6: valve mounting and air tightness test; the main control parameters are: nitrogen as the test medium; setting test pressure 103 MPa; adopting step-by-step pressurization, step-by-step pressurization by 30 MPa, pressure maintaining for 5 min at each level, and pressure maintaining for 5 min after reaching the test pressure; adopting step-by-step pressure relief, step-by-step pressure relief by 30 MPa, pressure maintaining for 5 min at each level until the pressure relief is completed.

[0058] Example 3: The example adopts the manufacturing method of the self-reinforced high-pressure hydrogen storage container with an inner steel bottle and an outer steel wire as described in Example 2 to manufacture the self-reinforced high-pressure hydrogen storage container with an inner steel bottle and an outer steel wire as described in Example 1, specifically to manufacture a 103 MPa self-reinforced high-pressure hydrogen storage container with an inner steel bottle and an outer steel wire for a 70 MPa hydrogen filling station, with a specification of Φ457×33.8 mm, a total length of 9000 mm, and a water volume of 900 L.

[0059] The inner liner seamless steel bottle of the example adopts special high-strength hydrogen-resistant steel material, and the 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%; and the balance is Fe. The actual mechanical property average of the inner liner steel bottle material is (the average of 3 samples): yield strength R t0.5 785 MPa, tensile strength R m 892 MPa, elongation A 32%, relative tensile strength of the material under 103 MPa high-pressure hydrogen environment KV 2121 J (lateral expansion amount LE 0.67 mm), relative tensile strength of the material under 103 MPa high-pressure hydrogen environment Rm H2 Rm Ref Z H2 Z Ref fracture toughness​​​K IH 88 MPa·m 1 / 2 .

[0060] The high-strength steel wire used in this embodiment has a tensile strength R m The minimum value is 2860 MPa, the average wire diameter is 0.353 mm, and the average copper plating layer thickness on the surface of the steel wire is 0.22 μm.

[0061] The manufacturing process of the hydrogen storage container in this embodiment is as follows: material preparation (inner liner steel bottle processing, prepreg tape preparation) → inner liner steel bottle circumferential winding of high-strength steel wire prepreg tape → container winding layer curing and shaping → container self-reinforced hydrostatic test → container inner wall drying and shot blasting treatment → valve installation and air tightness test → topcoat spraying → finished product inspection → warehousing.

[0062] The key processes are as follows:

[0063] Inner liner steel bottle processing.

[0064] The main process flow is as follows: material warehouse acceptance → seamless steel pipe reinspection → heating → steel bottle two-end spinning closure forming → cylinder circumferential winding of anti-skid platform spinning forming → quenching and tempering heat treatment → mechanical property / geometry size inspection → outer surface shot blasting treatment → surface roughness inspection → two-side port internal thread processing → thread geometry size inspection → non-destructive testing → outer surface epoxy resin coating → outer coating curing.

[0065] The main controls are as follows: 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 of the spinning closure is 67.6mm, and the winding anti-skid platform height is 0.7mm; ④ set the quenching temperature to 900℃ and the medium to oil during quenching and tempering heat treatment, and set the tempering temperature to 700℃ and the holding time to 90min; ⑤ the outer surface shot blasting treatment uses coarse steel shot, and the outer surface roughness after treatment is Ra25μm.

[0066] Prepreg tape preparation.

[0067] The main process flow is as follows: high-strength steel wire preparation → epoxy resin glue heating → steel wire unwinding → epoxy resin glue dipping → excess glue removal by glue scraping plate and glue extruding roller → curing → cooling → winding.

[0068] The main controls are as follows: ① set the epoxy resin glue heating temperature to 55℃; ② set the unwinding tension to 10N and the unwinding speed to 25m / min; ③ set the curing temperature to 135℃ and the curing time to 2h; ④ natural cooling after curing; ⑤ the prepreg tape width is 6mm.

[0069] Inner liner steel bottle circumferential winding of high-strength steel wire prepreg tape.

[0070] Main control: ① Set the inner liner steel bottle to move 6 mm per 1 turn; ② Set the initial winding tension to be 30 N and the winding speed to be 140 m / min; ③ Set the first kind of prepreg tape to be wound for 13 layers and the second kind of prepreg tape to be wound for 2 layers, and the tape overlap to be 150 mm; ④ The single-sided lateral spacing between the upper and lower prepreg tapes is 7.1 mm. The total thickness of the winding layers reaches 16.7 mm.

[0071] Curing and shaping of the container winding layers.

[0072] Main control: ① Adopt sectional heating and curing, and set 90℃×1h+100℃×1h+110℃×1h+120℃×1h; ② Naturally air cool. The curing degree of the winding layers reaches 92%.

[0073] Self-reinforced hydraulic test of the container.

[0074] Main control: ① Self-reinforced pressure is 206 MPa; ② Adopt stepwise pressurization, and pressurize by 30 MPa step by step, and keep pressure for 10 min at each level, and keep pressure for 15 min after reaching the self-reinforced pressure; ③ Adopt stepwise depressurization, and depressurize by 50 MPa step by step, and keep pressure for 10 min at each level until the depressurization is completed. No bulging, bursting and other phenomena occur to the container during the test process.

[0075] Drying and shot blasting treatment of the inner wall of the container.

[0076] Main control: ① Steel shot diameter is 0.2 mm; ② Shot blasting speed is 800 r / min. The roughness of the inner surface after the treatment reaches Ra1.6 μm.

[0077] Valve installation and air tightness test.

[0078] Main control: ① Test medium is nitrogen; ② Set the test pressure to be 103 MPa; ③ Adopt stepwise pressurization, and pressurize by 30 MPa step by step, and keep pressure for 5 min at each level, and keep pressure for 5 min after reaching the test pressure; ④ Adopt stepwise depressurization, and depressurize by 30 MPa step by step, and keep pressure for 5 min at each level until the depressurization is completed. No leakage occurs to the container body, the valve and the connection between the container body and the valve.

[0079] The above merely describes the preferred specific embodiments of the present application, but the protection scope of the present application is not limited to this. Any changes or replacements within the technical range disclosed by the present application can be easily thought of by those skilled in the art, and should be covered within the protection scope of the present application.

Claims

1. A method for manufacturing a self-reinforced high-pressure hydrogen storage container with an inner steel cylinder and an outer steel wire winding, characterized in that: The application discloses a high-pressure hydrogen storage container with a steel wire winding type self-reinforcing outer steel bottle, which comprises an inner liner steel bottle (1), an inlet (4) and an outlet (5) arranged at two ends of the inner liner steel bottle (1) respectively, and a reinforcing layer (3) arranged outside a middle cylindrical barrel of the inner liner steel bottle (1); arc top portions of outer wall ports of the inner liner steel bottle (1) at two ends of the reinforcing layer (3) are respectively provided with annular anti-skid platforms (2) at junctions with the cylindrical barrel; the reinforcing layer (3) is annularly wound by high-strength steel wire pre-impregnated tape and is solidified and formed by epoxy resin; and a manufacturing method comprises the following steps: S1: inner liner steel bottle processing and high-strength steel wire pre-impregnated tape preparation; main process flow of the inner liner steel bottle processing is as follows: material warehouse acceptance, seamless steel pipe re-inspection, heating, steel bottle two-end spinning closing forming, barrel annular winding wire anti-skid platform spinning forming, quenching and tempering heat treatment, mechanical property and geometric size inspection, outer surface shot blasting treatment, surface roughness inspection, two-side port inner thread processing, thread geometric size inspection, nondestructive flaw detection, outer surface epoxy resin coating and outer coating layer solidification; main control parameters are as follows: setting spinning heating temperature to 1000-1200 DEG C; setting spinning feed ratio to 2.0-3.5 mm / r and carrying out 8-12 pass processing, then setting spinning feed ratio to 0.5-1.0 mm / r and carrying out 1-2 pass processing; the maximum wall thickness of the spinning closing portion is 60-70 mm, the winding wire anti-skid platform height is 0.6-1.2 mm; the quenching temperature is set to 900-950 DEG C, the medium is oil, the tempering temperature is set to 650-700 DEG C, and the holding time is 90-120 min; the outer surface shot blasting treatment adopts coarse steel shot, and the outer surface roughness after treatment is Ra25-Ra50; main process flow of the pre-impregnated tape preparation is as follows: high-strength steel wire preparation, epoxy resin glue liquid heating, steel wire unwinding, epoxy resin glue liquid immersion, excess glue liquid removal by a glue scraping plate and an extrusion roller, solidification, cooling and winding; main control parameters are as follows: setting epoxy resin glue liquid heating temperature to 50-60 DEG C; setting unwinding tension to 10-20 N and unwinding speed to 20-30 m / min; setting solidification temperature to 130-150 DEG C and solidification time to 2-3 h; and the pre-impregnated tape width is 5-10 mm. S2: The inner liner steel cylinder is circumferentially wound with high-strength steel wire prepreg tape; the high-strength steel wire prepreg tape is made of high-strength steel wire, the tensile strength Rm of the high-strength steel wire is greater than or equal to 2000 MPa, the high-strength steel wire is surface plated with copper, the thickness of the copper plating layer is greater than or equal to 0.20 μm, the high-strength steel wire prepreg tape is divided into two types, the first type of prepreg tape is made of three layers of steel wire, the second type of prepreg tape is made of four layers of steel wire, the width of the first type of prepreg tape and the second type of prepreg tape is 5 mm to 10 mm, and the main control parameters are as follows: the inner liner steel cylinder is set to rotate one turn per week, and the wire nozzle is set to move one prepreg tape width; the initial winding tension is set to 20 N to 40 N, the winding angle is set to 86° to 90°, the tension is sequentially reduced every 2 to 3 layers, the outermost layer winding tension is 1 / 2 of the initial tension, and the winding speed is 130 m / min to 160 m / min; the first type of prepreg tape is wound for 12 to 15 layers, the second type of prepreg tape is wound for 2 to 3 layers, and the tape overlap is 100 mm to 150 mm; the single-sided horizontal spacing between the upper and lower prepreg tapes is 6 mm to 8 mm, and the total thickness of the winding layers is 13 mm to 18 mm; S3: The reinforcement layer is cured and shaped; the main control parameters are as follows: segmented heating and curing is adopted, 90℃×1h+100℃×1h+110℃×1h+120℃×1h is set; natural cooling, and the curing degree of the winding layer is controlled to be 90% to 95%; S4: The container is subjected to self-reinforced hydrostatic test; the main control parameters are as follows: the self-reinforced pressure is 206 MPa; the pressure is increased in stages, and the pressure is increased by 30 MPa every time, and the pressure is kept for 10 minutes every time, and the pressure is kept for 15 minutes after reaching the self-reinforced pressure; the pressure is released in stages, and the pressure is released by 50 MPa every time, and the pressure is kept for 10 minutes every time until the pressure is completely released; S5: The inner wall of the container is dried and subjected to shot blasting treatment; the main control parameters are as follows: the diameter of the steel shot is 0.2 mm; the shot blasting speed is 800 r / min, and the inner surface roughness after treatment is Ra1.6 μm to Ra3.2 μm; S6: The valve is mounted and subjected to air tightness test; the main control parameters are as follows: the test medium is nitrogen; the test pressure is set to 103 MPa; the pressure is increased in stages, and the pressure is increased by 30 MPa every time, and the pressure is kept for 5 minutes every time, and the pressure is kept for 5 minutes after reaching the test pressure; the pressure is released in stages, and the pressure is released by 30 MPa every time, and the pressure is kept for 5 minutes every time until the pressure is completely released; S7: The topcoat is sprayed; S7: The finished product is inspected and stored.

2. The method of manufacturing a high-pressure hydrogen storage container of the type having an inner steel bottle and an outer wire of Claim 1, wherein: The inner liner steel cylinder (1) is a double-port seamless steel cylinder formed by one-body spinning, and the chemical composition is as follows: C: 0.40% to 0.50%; Si: 0.15% to 0.25%; Mn: 0.85% to 1.00%; Cr: 0.8% to 1.2%; Mo: 0.20% to 0.30%; S: less than or equal to 0.005%; P: less than or equal to 0.012%; and the balance is Fe. ​ 3. The method of manufacturing a high-pressure hydrogen storage container of the outer-wire type according to claim 1, characterized in that: The inner lining steel cylinder (1) has a cylindrical wall thickness of 30-40 mm, and the wall thickness of the two side ports increases from the anti-skid ring (2) to the maximum wall thickness of 2 times the cylindrical wall thickness at the arc top.

4. The method of manufacturing a high-pressure hydrogen storage container of the outer-wire type according to claim 1, characterized in that: The air inlet (4) and the air outlet (5) are respectively provided with threads.

5. The method of manufacturing an inner steel bottle outer winding steel wire type self- reinforcing high-pressure hydrogen storage container according to claim 1, characterized by: The outer surface roughness of the inner lining steel cylinder (1) ranges from Ra25 μm to Ra50 μm, and the inner surface roughness ranges from Ra1.6 μm to Ra3.2 μm.

6. The method of manufacturing an inner steel bottle outer winding steel wire type self-reinforced high-pressure hydrogen storage container according to claim 1, characterized by: The high-strength steel wire has a wire diameter ranging from 0.28 mm to 0.38 mm.

7. The method of producing a high-pressure hydrogen storage container of the outer-wire type according to claim 1, characterized in that: The inner liner steel bottle (1) has a yield strength R t0.5 ≥ 710 MPa, a tensile strength R m ≥ 820 MPa, an elongation A ≥ 20%, - KV2≥ 60 J, lateral expansion LE≥ 0.53 mm at -40 °C, relative tensile strength Rm in a 103 MPa high-pressure hydrogen gas environment H2 / Rm Ref ≥ 0.90, relative reduction of area Z H2 / Z Ref ≥ 0.75, fracture toughness K IH ≥ 80 MPa·m 1 / 2 .

Images