AU2023327946A1 - Method for manufacturing compositely molded 99-mpa-grade hydrogen storage container for hydrogen refueling station - Google Patents
Method for manufacturing compositely molded 99-mpa-grade hydrogen storage container for hydrogen refueling station Download PDFInfo
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C53/00—Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
- B29C53/56—Winding and joining, e.g. winding spirally
- B29C53/58—Winding and joining, e.g. winding spirally helically
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D51/00—Making hollow objects
- B21D51/16—Making hollow objects characterised by the use of the objects
- B21D51/24—Making hollow objects characterised by the use of the objects high-pressure containers, e.g. boilers, bottles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C53/00—Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
- B29C53/80—Component parts, details or accessories; Auxiliary operations
- B29C53/8008—Component parts, details or accessories; Auxiliary operations specially adapted for winding and joining
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Filling Or Discharging Of Gas Storage Vessels (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
Disclosed in the present invention is a method for manufacturing a compositely molded 99-MPa-grade hydrogen storage container for a hydrogen refueling station. The method is a process of obtaining a steel lining which meets design requirements by means of spinning necking, a heat treatment and thread machining, and enveloping and curing a fiber material on the surfaces of a cylinder body section and a circular arc transition section of a bottle shoulder via a thermosetting resin to form a composite layer. The method comprises the steps of: subjecting a steel lining to a surface treatment; formulating a thermosetting resin system and keeping same in a state; pre-winding a polyester surfacing mat and a first glass fiber layer which serves as an isolating inner layer; prefabricating fiber composite unidirectional cloth, and manufacturing a reinforced fiber layer on the isolating inner layer in a layered manner; winding a second glass fiber layer which serves as a protective layer; and subjecting same to re-curing and a shaping treatment. The steel lining is stable in terms of heat treatment performance, and hoop winding is beneficial for multiplying the strength action rate of fibers, such that the winding efficiency is improved while the consumption of the fibers is reduced, and a finished container is allowed to have a volume of 500 L or more and bear a pressure up to 100 MPa.
Description
METHOD FOR MANUFACTURING COMPOSITELY MOLDED 99-MPA-GRADE HYDROGEN STORAGE CONTAINER FOR HYDROGEN REFUELING STATION
[1] The present disclosure relates to the field of manufacturing of high-capacity and high pressure gas storage devices, and in particular to a method for manufacturing circumferential winding of a composite shell for a 99 MPa-grade hydrogen storage container with a volume of 500 L or more for a hydrogen refueling station.
[2] The implementation of the global dual carbon plan of "Carbon Neutrality" and "Carbon Peak" has promoted the development of new energy technologies. The development of hydrogen energy has become a global consensus. In particular, in the direction of technological breakthroughs for hydrogen energy, hydrogen storage containers are developing in the direction of large volumes and high capacities.
[3] High-pressure hydrogen storage is the main hydrogen storage manner for hydrogen refueling stations, and hydrogen refueling stations are divided into 35 MPa-grade hydrogen refueling stations and 70 MPa-grade hydrogen refueling stations according to hydrogen refueling pressures. Most of hydrogen refueling stations in use and under construction in China are 35 MPa grade hydrogen refueling stations, and corresponding hydrogen storage containers generally have a design pressure of 50 MPa and are made of single-layer spinning-molded seamless steel pipes.
[4] Design pressures of 99 MPa-grade hydrogen storage containers for hydrogen refueling stations are generally 87.5 MPa, 98 MPa, and 103 MPa. Stainless steel multilayer wrapped containers are usually adopted, such as steel belt staggering-wrapped containers and laminate wrapped containers, and there is also exploration of the use of single-layer spinning-molded seamless steel pipe structures and steel lining carbon fiber full spiral winding structures.
151 The current stainless steel multilayer wrapping weld-molding method has problems such as a low mechanical automation degree, poor product quality consistency, a large dead load, a long production cycle, and a low batch production efficiency. However, if a 100 MPa-grade hydrogen storage container is manufactured by spinning with a single-layer spinning-molded seamless steel pipe, it is necessary to increase a volume and a bearing capacity of the container, and the container is designed to have a very large wall thickness, which brings a series of technical problems. The primary technical bottleneck encountered is the homogenization problem during a rolling process of a large-volume seamless steel pipe, and a thermal treatment device and process cannot fully ensure the full quenching of a steel cylinder in a thickness direction, which makes the crack propagation in a hydrogen environment too rapid and is easy to cause the hydrogen embrittlement phenomenon. In addition, the difficulty of a hot spinning process of a spinning device increases. Therefore, this structure poses a great challenge to a processing capacity of a large-scale device.
[6] If the steel lining fiber spiral full winding method is used for manufacturing, although the problems in steel lining materials and processes are solved, a device required for fully winding a large-volume hydrogen storage container needs to meet high requirements, and it takes more than 6 h to wind a 500 L to 1,000 L container, resulting in a very low efficiency. Due to the long winding time, a resin system used is very prone to abnormal curing during a winding process, which affects a manufacturing quality of a product.
[71 In view of the above-mentioned demands of the prior art, an objective of the present disclosure is to provide a method for manufacturing a compositely molded 99 MPa-grade hydrogen storage container for a hydrogen refueling station, so as to improve a volume, a volume-to-weight ratio, and a pressure capacity of a gas cylinder product. In particular, a hydrogen storage container with a volume of 500 L or more and a design pressure of nearly 100 MPa is manufactured.
[8] The following technical solutions are adopted to allow the objective of the present disclosure: A method for manufacturing a compositely molded 99 MPa-grade hydrogen storage container for a hydrogen refueling station is provided, implemented on a basis of spinning-molding a steel lining, and forming a composite layer on a surface of the steel lining through fiber enveloping and thermosetting resin curing for increasing a structural strength, and the method specifically including the following steps:
191 Si, preparing a steel lining meeting design requirements through spinning and necking, a heat treatment, and thread processing, where a cylinder body segment of the steel lining has a uniform wall thickness, and after the spinning and necking, a wall thickness gradually increases from edges of two ends of a cylinder body to cylinder mouths;
[10] S2, preparing a thermosetting resin glue solution of an epoxy resin/anhydride curing agent system, thoroughly stirring and thereby mixing the thermosetting resin glue solution, and keeping the thermosetting resin glue solution at a temperature of 20°C to 60°C in a water bath;
[11] S3, applying the thermosetting resin glue solution on an outer surface of the steel lining, spirally and circumferentially winding a polyester surface felt, and evenly applying the thermosetting resin glue solution on a surface of the polyester surface felt until the polyester surface felt is impregnated, so as to bottom-wrap the cylinder body segment and cylinder shoulder arc shaped transition segments of the steel lining, where an overlapping width for spiral lapping of the polyester surface felt is 10 mm to 20 mm;
[12] S4, preparing a first glass fiber layer on the polyester surface felt: setting winding parameters according to a length of the cylinder body segment, and spirally and circumferentially winding a glue-impregnated glass fiber strip along an axial direction of the steel lining in a reciprocating manner to form an isolating inner layer with a coverage range between the cylinder shoulders at two sides;
[13] S5, prefabricating a fiber composite unidirectional cloth, and preparing a reinforcing fiber layer on the isolating inner layer in a layered manner:
[14] S51, adjusting winding parameters in a layer-by-layer size-decreasing manner according to the coverage range of the first glass fiber layer, and circumferentially winding a glue-impregnated fiber composite in a reciprocating manner in a range smaller than the coverage range of the first glass fiber layer to form a plurality of circumferential fiber layers;
[15] S52, using a fiber composite unidirectional cloth with a matching width, making the fiber composite unidirectional cloth tightly attached to a surface of the circumferential fiber layers and fully cover a periphery of the cylinder body segment, and applying the thermosetting resin glue solution to impregnate the fiber composite unidirectional cloth, where a length of the fiber composite unidirectional cloth is smaller than an enveloping range of the wrapped circumferential fiber layers; and
[16] S53, repeating the S51 and the S52 according to a preset number of arranged layers and a preset arrangement spacing, and keeping a circumferential fiber layer as an outermost layer until a thickness requirement of the reinforcing fiber layer is met;
[17] S6, preparing a second glass fiber layer on an outermost circumferential fiber layer: adjusting winding parameters once again according to the length of the cylinder body segment, and spirally and circumferentially winding the glue-impregnated glass fiber strip along the axial direction of the steel lining in a reciprocating manner to form a protective layer having a consistent coverage range with the first glass fiber layer; and
[18] S7, placing the steel lining wrapped with the composite layer in a curing furnace to allow oven-drying and curing, and shaping.
[19] Further, in the Si, a heat loss of a heating segment of a steel pipe is delayed and slowed down by adding a thermal insulation gun, and during the spinning and necking, a counter spinning pass is added to allow a smooth transition and make a thickness gradually increase from the edges of the two ends of the cylinder body to the cylinder mouths; and the heat treatment is conducted by a full-immersion double-sided quenching process.
[20] Further, before the S3, the method further includes: shot-peening inner and outer surfaces of the steel lining.
[21] Further, winding ranges of the isolating inner layer prepared in the S4 and the protective layer prepared in the S6 both exceed a winding range of the reinforcing fiber layer prepared in the S5bymore than5 mm.
[22] Further, in the S51, the fiber composite is a fiber yarn with a strength of 3,000 MPa or more, and is wound in a form of a multi-strand mixed yarn.
[23] Further, the S51 further includes: subjecting the arc-shaped transition segments from the cylinder body to the cylinder shoulders to a stepped reinforcement treatment, where an enveloping length of the fiber composite exceeds the cylinder body segment and is less than the coverage range of the first glass fiber layer, and adding a plurality of sub-reciprocating motions with different length close to the arc-shaped transition segments at two sides corresponding to the reciprocating circumferential winding.
[24] Further, in the S7, the composite layer is cured in the curing furnace according to the following stepped temperature control manner: 80°C for 3 h, 90°C for 1 h, 100°C for 1 h, 110°C for 1 h, 120°C for 1 h, 130°C for 1 h, and 140°C for 3 h, with a heating rate of 1.5°C/min.
[25] Further, after the S7, the method further includes: evenly applying a light-curable resin with ultraviolet (UV) corrosion resistance to a surface of the composite layer.
[26] The application of the technical solutions of the method for manufacturing a compositely molded hydrogen storage container in the present disclosure brings the following technical effects:
[27] 1) Compared with single-layer steel hydrogen refueling containers or hydrogen storage containers, the hydrogen storage container produced by circumferentially winding a steel lining with a fiber composite can allow a wall thickness reduction of 40%, improve the consistency and stability of heat treatment performance of the steel lining and a hydrogen storage capacity under the same external size, and is more conducive to greatly reducing a crack propagation rate of the steel lining in a hydrogen environment.
[28] 2) The circumferential winding of a fiber composite around a steel lining is conducive to multiplying an exertion rate of a strength of the traditionally and fully wound fibers, thereby improving the quality and stability of a finished hydrogen storage container product.
[29] 3) The method for manufacturing a hydrogen storage container by circumferentially winding a steel lining with a fiber is mature and suitable for a plurality of specifications, batch design, and continuous automatic production. Compared with a hydrogen storage container manufactured by a full winding manner, under the same external size, a winding efficiency of a reinforcing fiber layer in the hydrogen storage container of the present disclosure can increase by % or more, which expands a selectable range of resin systems used for winding and is conducive to the significant reduction of a manufacturing cost.
[30] FIG. 1 is a schematic diagram of a cross-section structure along a central axis of the hydrogen storage container for a hydrogen refueling station in the present disclosure;
[31] FIG. 2 is a schematic diagram of a detailed structure produced through local enlargement of an upper right comer of the hydrogen storage container shown in FIG. 1; and
[32] FIG. 3 is a process flow chart of the method for manufacturing a compositely molded 99 MPa-grade hydrogen storage container for a hydrogen refueling station in the present disclosure.
[33] Reference numerals: 1-steel lining, 11-cylinder body segment, 12-cylinder shoulder, 12a cylinder shoulder arc-shaped transition segment, 13-cylinder mouth, 2-composite layer, 21 polyester surface felt, 22-first glass fiber layer, 23-reinforcing fiber layer, 231-circumferential fiber layer, 231a-reinforcing segment, 232-longitudinal reinforcing layer, 24-second glass fiber layer, and -light-curable resin.
[34] The specific implementation structures of the present disclosure are further described in detail below in conjunction with the accompanying drawings to make the technical solutions of the present disclosure easy to understand and grasp, such that the protection scope of the present disclosure is clearly defined.
[35] In the present disclosure, a composite structure is optimized to improve a volume, a volume-to-weight ratio, and a pressure capacity of a gas cylinder product, so as to obtain a steel lined hydrogen storage container with a volume of 500 L or more and a design pressure of close to 100 MPa. The steel-lined hydrogen storage container can be used for a 99 MPa-grade hydrogen refueling station to allow high-pressure and steady-state hydrogen storage.
[36] FIG. 1 and FIG. 2 show a cross-section structure along a central axis and a detailed structure produced through local enlargement of a preferred embodiment of a finished hydrogen storage cylinder product manufactured by the method of the present disclosure, respectively. The compositely molded 99 MPa-grade hydrogen storage container for a hydrogen refueling station includes a steel lining 1 and a composite layer 2 formed on a surface of the steel ling through fiber enveloping and thermosetting resin curing for increasing a structural strength. Key technological innovations are as follows: a cylinder body segment 11 of the steel lining 1 has a uniform wall thickness, and a wall thickness gradually increases from edges of two ends of a cylinder body to a cylinder shoulder 12 and cylinder mouths 13. The composite layer 2 is only formed on surfaces of the cylinder body segment 11 and cylinder shoulder arc-shaped transition segments 12a of the steel lining, and in the composite layer 2, a polyester surface felt 21, a first glass fiber layer 22, a reinforcing fiber layer 23 with alternate circumferential winding and longitudinal reinforcing, and a second glass fiber layer 24 are arranged sequentially from inside and outside.
[37] With reference to the figures, the structural optimization is understood from two aspects. In a first aspect, a material of the steel lining is a chromium-molybdenum steel that has excellent compatibility with hydrogen, such as a chromium-molybdenum steel 4130X with a high strength, prominent toughness, and excellent hydrogen embrittlement resistance. Size data of the spinning molded steel lining are as follows: a diameter: 485 mm, a length: 4,000 mm, and a volume: 500 L. It can be seen from FIG. 1 that the steel lining is formed through an improved process as follows: the cylinder body segment 11 has a uniform wall thickness di, a wall thickness gradually increases from the edges of the two ends of the cylinder body to the cylinder shoulder arc-shaped transition segments, the cylinder shoulder has an average wall thickness d 2, and d 2> di. Principles that can be confirmed for the above design and improvement are as follows: Firstly,because a hydrogen storage container for a hydrogen refueling station needs to be long, lengths of cylinder mouths and a cylinder shoulder of the hydrogen storage container are much smaller than a length of a cylinder body segment. Therefore, the reduction of the wall thickness of the cylinder body segment is inevitably more practical than the reduction of the wall thicknesses of the cylinder shoulder and the cylinder mouths, and leads to a large weight-reduction ratio. Secondly,in order to ensure a pressure capacity of a hydrogen storage container, a wall thickness is directly proportional to a pressure resistance level. In terms of the cylinder body segment of the hydrogen storage container, a wall thickness of the lining needs to be uniform to avoid the concentration of a pressure, thereby meeting the design requirements for a strength of the hydrogen storage container.
[38] In a second aspect, a cured composite layer is enveloped based on a steel lining. Different from the composite shell structure in which cylinder mouths, a cylinder shoulder, and a cylinder body are fully wound with fibers (referred to as full winding hereinafter) in the prior art, the composite layer of the present disclosure mainly covers a cylinder body segment and slightly covers cylinder shoulder arc-shaped transition segments. Instead, each sub-layer basically adopts a spiral and circumferential winding structure (referred to as circumferential winding hereinafter). Principles that can be confirmed for the above design and improvement are as follows: Firstly,a surface region on a cylinder body that is wound with fibers is reduced, and thus at the same molding thickness, an amount of a fiber material can be significantly reduced. Secondly,the existing disclosed full winding refers to a longitudinal fiber layer formed through reciprocating longitudinal winding, and in order to conform to the requirements of slip resistance of arc coating of cylinder shoulder transition segments, such longitudinal winding requires a specified inclination angle usually of 48 to 65°. The above inclination angle will inevitably cause a compromise of the exertion of a fiber strength, and a strength can only be compensated by increasing a number of wound layers. Finally,because a hydrogen storage container for a large-volume hydrogen refueling station is long, in order to reduce an excessive bending moment of a composite caused by an excessive deflection, a plurality of fiber composite unidirectional cloth layers are arranged in the composite layer within a straight segment of the entire cylinder body to enhance the longitudinal stiffness of the composite layer and prevent the cracking of the composite layer during long-term use.
[39] In order to obtain the hydrogen storage container with an improved structure and improved performance, the present disclosure proposes a number of optimization adjustments for corresponding links on the basis of the traditional manufacturing process for similar products, so as to allow a technical solution of low-cost, high-molding-efficiency, high-performance-consistency, and large-scale manufacturing of the hydrogen storage container. The method of the present disclosure includes: a composite layer is formed on a surface of a spinning-molded steel lining through fiber enveloping and thermosetting resin curing for increasing a structural strength , and specifically includes the following steps:
[40] S1, A steel lining meeting design requirements is prepared through spinning and necking, a heat treatment, and thread processing, where a cylinder body segment of the steel lining has a uniform wall thickness, and after the spinning and necking, a wall thickness gradually increases from edges of two ends of a cylinder body to cylinder mouths.
[41] S2, A thermosetting resin glue solution of an epoxy resin/anhydride curing agent system is prepared and thoroughly stirred and thereby mixed, and the thermosetting resin glue solution is kept at a temperature of 20°C to 60°C in a water bath.
[42] S3, The thermosetting resin glue solution is applied on an outer surface of the steel lining, a polyester surface felt is spirally and circumferentially wound, and the thermosetting resin glue solution is evenly applied on a surface of the polyester surface felt until the polyester surface felt is impregnated, so as to bottom-wrap the cylinder body segment and cylinder shoulder arc-shaped transition segments of the steel lining, where an overlapping width for spiral lapping of the polyester surface felt is 10 mm to 20 mm. Specifically, the thermosetting resin glue solution is applied on an outer surface of the cylinder body segment of the steel lining, the polyester surface felt is arranged on the cylinder body segment, and then the thermosetting resin glue solution is evenly applied on a surface of the polyester surface felt until the polyester surface felt is impregnated.
[43] S4, A first glass fiber layer is prepared on the polyester surface felt: winding parameters are set according to a length of the cylinder body segment, and a glue-impregnated glass fiber strip is spirally and circumferentially wound along an axial direction of the steel lining in a reciprocating manner to form an isolating inner layer with a coverage range between the cylinder shoulders at two sides.
[44] S5, A fiber composite unidirectional cloth is prefabricated, and a reinforcing fiber layer is prepared on the isolating inner layer in a layered manner:
[45] S51, Winding parameters are adjusted in a layer-by-layer size-decreasing manner according to the coverage range of the first glass fiber layer, and a glue-impregnated fiber composite is circumferentially wound in a reciprocating manner in a range smaller than the coverage range of the first glass fiber layer to form a plurality of circumferential fiber layers.
[46] S52, A fiber composite unidirectional cloth with a matching width is used, the fiber composite unidirectional cloth is tightly attached to a surface of the circumferential fiber layers and is allowed to fully cover a periphery of the cylinder body segment, and the thermosetting resin glue solution is applied to impregnate the fiber composite unidirectional cloth, where a length of the fiber composite unidirectional cloth is smaller than an enveloping range of the wrapped circumferential fiber layers.
[47] S53, The S51 and the S52 are repeated according to a preset number of arranged layers and a preset arrangement spacing, and a circumferential fiber layer is kept as an outermost layer until a thickness requirement of the reinforcing fiber layer is met.
[48] S6, A second glass fiber layer is prepared on an outermost circumferential fiber layer: winding parameters are adjusted once again according to the length of the cylinder body segment, and the glue-impregnated glass fiber strip is spirally and circumferentially wound along the axial direction of the steel lining in a reciprocating manner to form a protective layer having a consistent coverage range with the first glass fiber layer.
[49] S7, The steel lining wrapped with the composite layer is placed in a curing furnace to allow oven-drying and curing, and then shaped.
[50] In order to understand the practicability of the method for manufacturing a hydrogen storage container, each step and process details thereof not mentioned above are introduced in detail below with reference to FIG. 3 (however, the conventional low-importance links in the process flow are omitted).
[51] Design link before manufacturing: With reference to the relevant standards, safety design factors such as a heat treatment strength guarantee value and a burst strength are input to design a wall thickness, a shape, and a size of a steel lining. A fiber arrangement design is conducted based on composite design criteria, fiber composite performance, and design safety factors. Stress and strain states of each material layer under each working conditions are calculated by a finite element analysis method. The design is confirmed with reference to a fatigue analysis model and material performance.
[52] Manufacturing of the steel lining: A steel pipe with a wall thickness and a material that meet the design requirements is selected to ensure that the roughness of an inner surface meets a specified requirement. According to specified process requirements, a lining meeting design requirements is produced through procedures such as spinning and necking, a heat treatment, and threadprocessing. During the spinning and necking, a number of thermal insulation and heating guns and a flame intensity are increased to delay and slow down a heat loss of a heating segment of a steel pipe during a hot spinning process and ensure the thermoplasticity of thick-wall spinning. In addition, a spinning and necking procedure for a thick-wall steel pipe is designed. That is, a counter spinning pass is added to allow a smooth transition and gradual thickening from the cylinder body to a sealing head, which offsets the thinning of a transition between the cylinder body and the sealing head caused by the conventional forward spinning process, and ensures that a wall thickness gradually increases from the cylinder body segment to the cylinder mouths and the whole spinning and necking procedure has no pressure bearing weak link.
[53] For the heat treatment, based on the original quenching mechanism, two inner and outer spraying units, a spring pressing mechanism, and a frequency-conversion rotation mechanism are added to allow the smooth, uniform-velocity, rapid, and all-round cooling of a product in a quenching tank in combination with a full-immersion quenching manner. The product process is changed from the original quenching of merely an outer surface to the quenching of both inner and outer surfaces, which improves a quenching efficiency. In combination with the segmented control of a process temperature, the matching of a heating time and temperature, and the selection of a cooling rate of a quenching liquid, performance indexes are allowed to meet the design requirements, such that the performance uniformity of the cylinder body can be effectively guaranteed. The threading here and hereafter is not the focus of the present disclosure, and thus the detailed description of corresponding process parameters and a corresponding specific manufacturing process is omitted. In order to well improve the steel lining to match the subsequent winding process and improve a service life of a finished product, after the heat treatment, inner and outer surfaces of the steel lining can also be shot-peened (which has the same meaning as the "shot blasting" shown in the process flow chart of FIG. 3), and an outer surface of the steel lining is subjected to an anti-rust and anti-corrosion treatment.
[54] Pre-preparation of the glue solution: The epoxy resin/anhydride curing agent system is adopted. In order to ensure the fluidity of the glue solution and a sufficient operation time, a temperature of the glue solution needs to be controlled. Before mixing, the resin is baked to ensure the fluidity, which is conducive to weighing and making a temperature of a prepared glue solution meet the process requirements. After being prepared, a glue solution is stirred at a high speed for thorough mixing, then added to a glue tank, and heated in a water bath throughout the process to ensure that a temperature of the glue solution is controlled in a range of 20°C to 60°C.
[55] A core point for the optimization of the method is a forming process of the composite layer. According to structural composition characteristics of the composite layer, it is inevitably necessary to conduct enveloping outwards from a surface of the steel lining sequentially.
[56] From the perspective of an anti-electrochemical corrosion layer, the composite layer includes a polyester surface felt and an isolating inner layer that are arranged sequentially. Specifically, the glue solution is evenly applied to a cylinder body segment and a cylinder shoulder arc-shaped transition segment of the steel lining (referred to as the lining hereinafter), a polyester surface felt with an appropriate length is cut according to a specification of the lining and a width of the polyester surface felt, one end of the polyester surface felt is attached to a surface of the lining, a winding angle is adjusted, and a winding machine is turned on to make the lining reversely rotate and make the polyester surface felt spirally arranged on the surface of the lining. In order to ensure the all-round coverage without exposing the bottom, an overlapping width for spirally lapped parts is controlled at 10 mm to 20 mm. After the all-round coverage is completed, the excess parts at two ends are removed, and then the glue solution is evenly applied on a surface of the polyester surface felt to impregnate the polyester surface felt. It should be clearly noted that an arrangement range of the polyester surface felt needs to be larger than a winding range of the subsequent reinforcing fiber layer (a carbon fiber is preferably adopted). The arrangement of the polyester surface felt is conducive to the load transfer from the lining to the composite layer, and can also play an anti electrochemical corrosion role.
[57] On the basis of the formation of the polyester surface felt, a winding program is set according to a length of a straight segment of the lining, and a glue-impregnated glass fiber strip is spirally and circumferentially wound around the polyester surface felt along an axial direction of the lining in a reciprocating manner to evenly cover the polyester surface felt. A winding range of the first glass fiber layer is exceed a winding range of the reinforcing fiber layer by more than 5mm, and an isolating inner layer with a coverage range between cylinder shoulders at two sides is formed to further play an anti-electrochemical corrosion role.
[58] From the perspective of structural strengths of the reinforcing cylinder body segment and the cylinder shoulder arc-shaped transition segment, based on the isolating inner layer, the composite layer further includes a circumferential fiber layer 231 that is wound and a longitudinal reinforcing layer 232 that is wrapped. Specifically, a carbon fiber yam with a strength of 3,000 MPa or more is used as a fiber composite for the reinforcing fiber layer, and is wound in the form of a multi-strand mixed yam. Process parameters are set with circumferential winding as a main forming manner. During a winding process, a winding start point and a winding length are controlled to ensure that the following three conditions all are met: firstly,during a carbon fiber winding process, the failed winding of edges should be avoided, and a part to be reinforced should be fully enveloped. Secondly,a winding length of carbon fibers cannot exceed a winding length of the first glass fiber layer wound internally, so as to ensure that the isolating inner layer can still be exposed at two ends by about 5 mm after the carbon fiber winding is completed. Thirdly,there should be no yarn slippage during the carbon fiber winding, and thus a specified size is reduced layer by layer to prevent the yam slippage.
[59] Generally, a transition segment between the cylinder body segment and the cylinder shoulder arc-shaped transition segment of the lining is a weak part in the structure, and thus a reinforcement design is adopted for this part. That is, a winding length is controlled during a winding process, such that a carbon fiber enveloping range exceeds the cylinder body segment by a specified distance to ensure the reinforcement for the transition segment. It should be emphasized that the first glass fiber layer exceeds the cylinder body segment by a larger distance than the carbon fiber enveloping range. In addition, a plurality of short reciprocating motions and a plurality of long reciprocating motions (which can be understood as sub-reciprocating motions with different length) are added at two ends for winding to form a reinforcing segment 231a in which a local thickness d increases towards two ends in a stepped manner. An enveloping effect for the forming is shown in FIG. 2. A thickness gradually increases from the cylinder body segment 11 to the cylinder shoulder arc-shaped transition segment 12a in the arrow shown in this figure, and the above third winding requirements are met in the range where the cylinder shoulder arc-shaped transition segment 12a is located. In this way, it makes up for the possible differences in the process enveloping, and a weak point of the container is transferred to a middle part of the cylinder body segment, such that cracks in a bursting test all appear in a middle part of the cylinder body.
[60] Because the container has a large length and a large deflection, in order to reduce the influence of a bending moment on the composite layer and avoid the longitudinal fracturing or circumferential cracking, the longitudinal reinforcing layer is added during a carbon fiber winding process. That is, according to a diameter of the cylinder body, a plurality of carbon fiber unidirectional cloths with appropriate widths are selected, horizontally straightened, and tightly attached to a straight segment of the cylinder body. A fiber direction of the carbon fiber unidirectional cloths needs to be parallel to an axis direction. When the carbon fiber unidirectional cloths are arranged, the entire cylinder body segment needs to be fully covered, and there is an overlap between cloths. After the arrangement is completed, the excess part is cut off to ensure that there is a specified distance from an end of the isolating inner layer. The glue solution is applied, and then the fiber composite is wound for covering. A number of arranged layers and an arrangement spacing are determined according to a product model and design.
[61] From the perspective of the protection of the reinforcing fiber layer, an outermost layer of the composite layer further includes a protective layer formed by arranging the second glass fiber layer. In order to prevent the performance of the reinforcing fiber layer from being destroyed due to possible bumping and scratching during handling and use processes, a plurality of glass fiber layers are wound on the reinforcing fiber layer. A winding program is set, the winding is conducted layer by layer outwards from a position closest to a surface of the lining and an edge of the isolating inner layer, and a reciprocating motion length for the winding gradually converges in accordance with a decreasing size of the circumferential fiber layer for yarn slippage resistance until wound glass fibers completely cover the reinforcing fiber layer, thereby playing a protective role.
[62] Another core point for the optimization of the method is the curing of the composite layer. Because wound layers have a large thickness, the composite layer has a low thermal conductivity coefficient. In addition, the steel lining has a large wall thickness, and there is heat absorption during a heating process, which causes the slow rise of an actual temperature inside a cured product and is easy to make a product have problems such as a low curing efficiency and an abnormal curing quality. The improvement of details of a curing process is conducive to avoiding adverse curing results such as bubbles, incomplete curing, and surface yellowing while improving an efficiency. Through the test verification and the temperature curve test during curing, it has been found that a surface temperature of a cured product lags behind a furnace temperature for a specified time at a curing and heating stage, and there is a large temperature difference. In combination with a small heat transfer coefficient of the composite layer, a multi-gradient and long term curing system is adopted. According to measured temperature curves of a furnace and a surface of a product during contrastive curing, through experimental verification, the following stepped temperature control manner is adopted: the furnace is kept at 80°C for 3 h, at each of 90°C, 100°C, 110C, 120°C, and 130°C for 1h, and at 140°C for 3 h, where a heating rate at each stage is set at 1.5°C/min to ensure the uniformity of a furnace temperature. In particular, a temperature difference between the above set values and an actual furnace temperature does not exceed ±5C. When the curing is completed, a cured product needs to be slowly cooled to 80°C or lower and then discharged, which can avoid fiber breakage caused by sharp cooling and shrinkage.
[63] Post-treatment for the integrated molding of the steel lining and the composite layer: firstly,a self-tightening treatment is conducted according to a self-tightening pressure and a pressure-holding time calculated at a design stage, such that the composite layer produces a preload for the steel lining, which is conducive to the improvement of fatigue performance. Then a hydrostatic test is conducted according to a specified hydrostatic test pressure and pressure-holding time to detect whether a finished product meets a pressure resistance index. Secondly,a helium detector is used to conduct a gas tightness test through the combination of helium leak detection and liquid coating. After an inflation pressure reaches a requirement, test results are acquired according to standard test requirements to determine whether a finished product meets the gas tightness requirements. Thirdly,a surface of the composite layer is subjected to correction operations such as polishing, and then a light-curable resin 25 with UV corrosion resistance is selected, evenly applied on the surface of the composite layer, and irradiated by a light-curing lamp to allow rapid curing, thereby avoiding degradation, destruction, and performance degradation of the composite layer caused by UV corrosion. Specifically, an epoxy UV light-curable resin is adopted, and appropriate amounts of an epoxy UV absorber and an anti-yellowing agent are added. A UV LED lamp is adopted for light curing. Fourthly,after a treatment for an inner wall of the steel lining is completed, a process plug is arranged, and then the nitrogen replacement is conducted according to a specified pressure, that is, an inner cavity of the hydrogen storage container is vacuumed and then filled with nitrogen to play a protective role for an inner wall of the container.
[64] A high-pressure hydrogen storage container produced by the method of the present disclosure is subjected to a hydraulic bursting test: with water as a pressurization medium, a pressure gradually increases until the failure of the container. During the test, a pressure measuring device is ensured to monitor an actual pressure in the container, and when a pressure rise rate exceeds 0.35 MPa/s, a pressure is maintained at a minimum design bursting pressure for 5s and then further increases until bursting. An actual bursting pressure is 5% higher than the minimum design bursting pressure. After bursting, there are no fragments, the entirety is maintained, and a main fracture starts from a cylinder body part of the container and presents as a plastic fracture, that is, there is an obvious shear lip at an edge of the fracture.
[65] The bursting test of the container is a composite layer process evaluation test. In addition to the above-mentioned test methods, in order to verify the rationality of a composite layer process and design for a container, a small-size sample can also be used to conduct fatigue and bursting tests, and a qualified and stable composite layer process evaluation procedure is established.
[66] In summary, according to the detailed embodiments of the method for manufacturing a compositely molded99 MPa-grade hydrogen storage container for a hydrogen refueling station in the present disclosure that are provided with reference to the accompanying drawings, the present disclosure has outstanding substantive characteristics and significant progresses, which are described as follows point by point:
[67] 1) Compared with single-layer steel hydrogen refueling containers, the hydrogen storage container produced by circumferentially winding a steel lining with a fiber composite can allow a wall thickness reduction of 40%, improve the consistency and stability of heat treatment performance of the steel lining and a hydrogen storage capacity under the same external size, and is conducive to greatly reducing a crack propagation rate of the steel lining in a hydrogen environment.
[68] 2) The circumferential winding of a fiber composite around a steel lining is conducive to multiplying an exertion rate of a strength of the traditionally and fully wound fibers, thereby improving the quality and stability of a finished hydrogen storage container product.
[69] 3) The method for manufacturing a hydrogen storage container by circumferentially winding a steel lining with a fiber is mature and suitable for a plurality of specifications, batch design, and continuous automatic production. Compared with a hydrogen storage container manufactured by a full winding manner, under the same external size, a winding efficiency of a reinforcing fiber layer in the hydrogen storage container of the present disclosure can increase by % or more, which expands a selectable range of resin systems used for winding and is conducive to the significant reduction of a manufacturing cost.
[70] In addition to the above-mentioned embodiments, the present disclosure may have other embodiments, and all technical solutions produced through equivalent substitutions or equivalent transformations fall within the protection scope of the present disclosure.
Claims (8)
1. A method for manufacturing a compositely molded 99 MPa-grade hydrogen storage container for a hydrogen refueling station, implemented on a basis of spinning-molding a steel lining, and forming a composite layer on a surface of the steel lining through fiber enveloping and thermosetting resin curing for increasing a structural strength, and the method specifically comprising the following steps: S1, preparing a steel lining meeting design requirements through spinning and necking, a heat treatment, and thread processing, wherein a cylinder body segment of the steel lining has a uniform wall thickness, and after the spinning and necking, a wall thickness gradually increases from edges of two ends of a cylinder body to cylinder mouths; S2, preparing a thermosetting resin glue solution of an epoxy resin/anhydride curing agent system, thoroughly stirring and thereby mixing the thermosetting resin glue solution and keeping the thermosetting resin glue solution at a temperature of 20°C to 60°C in a water bath; S3, applying the thermosetting resin glue solution on an outer surface of the steel lining, spirally and circumferentially winding a polyester surface felt, and evenly applying the thermosetting resin glue solution on a surface of the polyester surface felt until the polyester surface felt is impregnated, so as to bottom-wrap the cylinder body segment and cylinder shoulder arc shaped transition segments of the steel lining, wherein an overlapping width for spiral lapping of the polyester surface felt is 10 mm to 20 mm; S4, preparing a first glass fiber layer on the polyester surface felt: setting winding parameters according to a length of the cylinder body segment, and spirally and circumferentially winding a glue-impregnated glass fiber strip along an axial direction of the steel lining in a reciprocating manner to form an isolating inner layer with a coverage range between the cylinder shoulders at two sides; S5, prefabricating a fiber composite unidirectional cloth, and preparing a reinforcing fiber layer on the isolating inner layer in a layered manner: S51, adjusting winding parameters in a layer-by-layer size-decreasing manner according to the coverage range of the first glass fiber layer, and circumferentially winding a glue-impregnated fiber composite in a reciprocating manner in a range smaller than the coverage range of the first glass fiber layer to form a plurality of circumferential fiber layers; S52, using a fiber composite unidirectional cloth with a matching width, making the fiber composite unidirectional cloth tightly attached to a surface of the circumferential fiber layers and fully cover a periphery of the cylinder body segment, and applying the thermosetting resin glue solution to impregnate the fiber composite unidirectional cloth, wherein a length of the fiber composite unidirectional cloth is smaller than an enveloping range of the wrapped circumferential fiber layers; and S53, repeating the S51 and the S52 according to a preset number of arranged layers and a preset arrangement spacing, and keeping a circumferential fiber layer as an outermost layer until a thickness requirement of the reinforcing fiber layer is met; S6, preparing a second glass fiber layer on an outermost circumferential fiber layer: adjusting winding parameters once again according to the length of the cylinder body segment, and spirally and circumferentially winding the glue-impregnated glass fiber strip along the axial direction of the steel lining in a reciprocating manner to form a protective layer having a consistent coverage range with the first glass fiber layer; and S7, placing the steel lining wrapped with the composite layer in a curing furnace to allow oven drying and curing, and shaping.
2. The method for manufacturing a compositely molded 99 MPa-grade hydrogen storage container for a hydrogen refueling station according to claim 1, wherein in the S, a heat loss of a heating segment of a steel pipe is delayed and slowed down by adding a thermal insulation gun, and during the spinning and necking, a counter spinning pass is added to allow a smooth transition and make a thickness gradually increase from the edges of the two ends of the cylinder body to the cylinder mouths; and the heat treatment is conducted by a full-immersion double-sided quenching process.
3. The method for manufacturing a compositely molded 99 MPa-grade hydrogen storage container for a hydrogen refueling station according to claim 1, wherein before the S3, the method further comprises: shot-peening inner and outer surfaces of the steel lining.
4. The method for manufacturing a compositely molded 99 MPa-grade hydrogen storage container for a hydrogen refueling station according to claim 1, wherein winding ranges of the isolating inner layer prepared in the S4 and the protective layer prepared in the S6 both exceed a winding range of the reinforcing fiber layer prepared in the S5 by more than mm.
5. The method for manufacturing a compositely molded 99 MPa-grade hydrogen storage container for a hydrogen refueling station according to claim 1, wherein in the S51, the fiber composite is a fiber yarn with a strength of 3,000 MPa or more, and is wound in a form of a multi strand mixed yarn.
6. The method for manufacturing a compositely molded 99 MPa-grade hydrogen storage container for a hydrogen refueling station according to claim 1, wherein the S51 further comprises: subjecting the arc-shaped transition segments from the cylinder body to the cylinder shoulders to a stepped reinforcement treatment, wherein an enveloping length of the fiber composite exceeds the cylinder body segment and is less than the coverage range of the first glass fiber layer, and adding a plurality of sub-reciprocating motions with different length close to the arc-shaped transition segments at two sides corresponding to the reciprocating circumferential winding.
7. The method for manufacturing a compositely molded 99 MPa-grade hydrogen storage container for a hydrogen refueling station according to claim 1, wherein in the S7, the composite layer is cured in the curing furnace according to the following stepped temperature control manner: °C for 3 h, 90°C for 1 h, 100°C for 1 h, 110°C for 1 h, 120°C for 1 h, 130°C for 1 h, and 140°C for 3 h, with a heating rate of 1.5°C/min.
8. The method for manufacturing a compositely molded 99 MPa-grade hydrogen storage container for a hydrogen refueling station according to claim 1, wherein after the S7, the method further comprises: evenly applying a light-curable resin with ultraviolet (UV) corrosion resistance to a surface of the composite layer.
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| CN202211022647.5A CN115091732B (en) | 2022-08-25 | 2022-08-25 | Method for manufacturing composite-formed hydrogen storage container for 99 MPa-level hydrogenation station |
| CN202211022647.5 | 2022-08-25 | ||
| PCT/CN2023/107389 WO2024041262A1 (en) | 2022-08-25 | 2023-07-14 | Method for manufacturing compositely molded 99-mpa-grade hydrogen storage container for hydrogen refueling station |
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| CN115091732B (en) * | 2022-08-25 | 2023-04-11 | 中材科技（苏州）有限公司 | Method for manufacturing composite-formed hydrogen storage container for 99 MPa-level hydrogenation station |
| CN115958815A (en) * | 2022-12-27 | 2023-04-14 | 航天特种材料及工艺技术研究所 | Composite thick-wall pipe and preparation method thereof |
| CN118468371B (en) * | 2024-07-02 | 2024-09-06 | 合肥通用机械研究院有限公司 | Checking method of multilayer binding spherical shell inner shell based on warp instability |
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| JP2007198531A (en) * | 2006-01-27 | 2007-08-09 | Kyoritsu Kogyo Kk | Fiber-reinforced pressure vessel by lost-wax casting method and its manufacturing method |
| DE102010002881A1 (en) * | 2010-03-15 | 2011-09-15 | Benteler Sgl Gmbh & Co. Kg | Container for use as liquid gas tank of motor car, has outer wall region partly or completely surrounding inner wall region, where outer wall region is attached to outer side of liner and formed from carbon fiber reinforced material |
| WO2011159521A2 (en) * | 2010-06-17 | 2011-12-22 | 3M Innovative Properties Company | Composite pressure vessels |
| CN105333302B (en) * | 2015-09-25 | 2018-01-02 | 石家庄安瑞科气体机械有限公司 | A kind of preparation method of Large Copacity high-pressure hydrogen storage winding composite shell |
| CN105605415B (en) * | 2015-09-25 | 2017-11-21 | 石家庄安瑞科气体机械有限公司 | Big volume winds the processing technology of high-pressure hydrogen storage entirely |
| CN205101850U (en) * | 2015-09-25 | 2016-03-23 | 石家庄安瑞科气体机械有限公司 | Compound shell structurre of full winding of large capacity high pressure hydrogen storage vessel |
| JP6381563B2 (en) * | 2016-03-01 | 2018-08-29 | 株式会社日本製鋼所 | Combined pressure vessel and hoop wrap pressure vessel |
| CN108692181B (en) * | 2018-03-28 | 2020-08-14 | 航天材料及工艺研究所 | Preparation method of composite material gas cylinder |
| CN112189031A (en) * | 2018-05-21 | 2021-01-05 | 东丽株式会社 | Tow impregnation material, method for producing same, and method for producing pressure vessel |
| DE102018121012A1 (en) * | 2018-08-28 | 2020-03-05 | Alzchem Trostberg Gmbh | Process for manufacturing a pressurized gas container |
| CN111645343A (en) * | 2020-05-27 | 2020-09-11 | 江苏海洋大学 | Corrosion-resistant high-strength glass fiber reinforced plastic storage tank and production method thereof |
| CN113432030A (en) * | 2021-06-07 | 2021-09-24 | 浙江蓝能燃气设备有限公司 | Method for manufacturing bottle type container with stainless steel liner and carbon fiber wound completely |
| CN215722474U (en) * | 2021-06-07 | 2022-02-01 | 浙江蓝能燃气设备有限公司 | Large-capacity seamless stainless steel liner carbon fiber full-winding bottle type container |
| CN114110413B (en) * | 2021-11-10 | 2023-07-28 | 航天材料及工艺研究所 | Carbon fiber composite material thick-wall gas cylinder and preparation method thereof |
| CN114571712A (en) * | 2022-03-30 | 2022-06-03 | 中氢国储(杭州)精密制造有限公司 | Winding structure and method for plastic inner container of composite high-pressure hydrogen storage container |
| CN114919204A (en) * | 2022-05-14 | 2022-08-19 | 浙江理工大学绍兴柯桥研究院有限公司 | Winding forming method of hydrogen storage tank reinforced by chopped carbon fibers |
| CN115091732B (en) * | 2022-08-25 | 2023-04-11 | 中材科技（苏州）有限公司 | Method for manufacturing composite-formed hydrogen storage container for 99 MPa-level hydrogenation station |
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