CN102537653B - 包含流质密封材料的气体储存罐 - Google Patents

包含流质密封材料的气体储存罐 Download PDF

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Publication number
CN102537653B
CN102537653B CN201110461943.0A CN201110461943A CN102537653B CN 102537653 B CN102537653 B CN 102537653B CN 201110461943 A CN201110461943 A CN 201110461943A CN 102537653 B CN102537653 B CN 102537653B
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Prior art keywords
boss
gas storage
flange portion
sealing material
storage tank
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CN201110461943.0A
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CN102537653A (zh
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M·林纳
D·A·波多拉施
A·荣格
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GM Global Technology Operations LLC
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GM Global Technology Operations LLC
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17CVESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C1/00Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
    • F17C1/16Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge constructed of plastics materials
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17CVESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C1/00Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
    • F17C1/02Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge involving reinforcing arrangements
    • F17C1/04Protecting sheathings
    • F17C1/06Protecting sheathings built-up from wound-on bands or filamentary material, e.g. wires
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17CVESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2201/00Vessel construction, in particular geometry, arrangement or size
    • F17C2201/01Shape
    • F17C2201/0104Shape cylindrical
    • F17C2201/0109Shape cylindrical with exteriorly curved end-piece
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17CVESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2201/00Vessel construction, in particular geometry, arrangement or size
    • F17C2201/01Shape
    • F17C2201/0128Shape spherical or elliptical
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F17CVESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2201/00Vessel construction, in particular geometry, arrangement or size
    • F17C2201/05Size
    • F17C2201/056Small (<1 m3)
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F17CVESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00Vessel construction, in particular walls or details thereof
    • F17C2203/06Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0602Wall structures; Special features thereof
    • F17C2203/0604Liners
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    • F17CVESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
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    • F17C2203/06Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0602Wall structures; Special features thereof
    • F17C2203/0612Wall structures
    • F17C2203/0614Single wall
    • F17C2203/0619Single wall with two layers
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    • F17CVESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
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    • F17C2203/06Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0602Wall structures; Special features thereof
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    • F17C2203/0614Single wall
    • F17C2203/0621Single wall with three layers
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    • F17CVESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
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    • F17C2203/0648Alloys or compositions of metals
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    • F17C2203/0663Synthetics in form of fibers or filaments
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    • F17CVESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00Vessel construction, in particular walls or details thereof
    • F17C2203/06Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0634Materials for walls or layers thereof
    • F17C2203/0658Synthetics
    • F17C2203/0675Synthetics with details of composition
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    • F17CVESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00Vessel construction, in particular walls or details thereof
    • F17C2203/06Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/068Special properties of materials for vessel walls
    • F17C2203/0682Special properties of materials for vessel walls with liquid or gas layer
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    • F17C2205/00Vessel construction, in particular mounting arrangements, attachments or identifications means
    • F17C2205/01Mounting arrangements
    • F17C2205/0153Details of mounting arrangements
    • F17C2205/0196Details of mounting arrangements with shock absorbing means
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    • F17C2205/03Fluid connections, filters, valves, closure means or other attachments
    • F17C2205/0302Fittings, valves, filters, or components in connection with the gas storage device
    • F17C2205/0305Bosses, e.g. boss collars
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    • F17C2205/03Fluid connections, filters, valves, closure means or other attachments
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    • F17C2209/00Vessel construction, in particular methods of manufacturing
    • F17C2209/23Manufacturing of particular parts or at special locations
    • F17C2209/234Manufacturing of particular parts or at special locations of closing end pieces, e.g. caps
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    • F17C2223/00Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
    • F17C2223/01Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the phase
    • F17C2223/0107Single phase
    • F17C2223/0123Single phase gaseous, e.g. CNG, GNC
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    • F17C2223/036Very high pressure (>80 bar)
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    • F17C2260/00Purposes of gas storage and gas handling
    • F17C2260/01Improving mechanical properties or manufacturing
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    • F17C2260/00Purposes of gas storage and gas handling
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    • F17C2270/00Applications
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    • F17C2270/0165Applications for fluid transport or storage on the road
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17CVESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2270/00Applications
    • F17C2270/01Applications for fluid transport or storage
    • F17C2270/0165Applications for fluid transport or storage on the road
    • F17C2270/0184Fuel cells
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/32Hydrogen storage
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00Metal working
    • Y10T29/49Method of mechanical manufacture
    • Y10T29/49826Assembling or joining

Abstract

一个示例性实施方式包括气体储存罐,其包括外部结构层、内部衬套层、环形凸台和置于衬套层的重叠部分和凸台之间以提供气密性密封的流质密封材料。

Description

包含流质密封材料的气体储存罐
技术领域
本发明的技术领域一般涉及包括流质密封材料的气体储存罐。
背景技术
各种燃料气体,诸如天然气、氢气、乙炔和甲烷,可储存在增压气体储存罐中。为了增加储存密度和减少整个系统的重量,需要工作气体压力高和重量轻的罐设计。对于增压氢气的储存,需要特别注意罐设计和材料选择,因为氢气对大部分材料具有高渗透性,并且众所周知许多普通的金属都具有氢脆性。另外,氢气的点火电势(ignition potential)大大高于甲烷。理论上来讲,氢气比甲烷的渗透性高大约34倍。渗透和泄露被认为是主要问题。用于车辆燃料电池的压缩氢气燃料罐的压力可高达700bar(~70兆帕)。罐连接元件,例如凸台-衬套接口连接件和O型环,必须仔细设计和装配,以避免泄露。任何微小的缺陷或任何连接件装配失误都会导致重大的气体泄露。
通常,储存的氢气通过一根管从罐中流出。设置至少一个压力调节器,该调节器将罐中的氢气的压力降至适于进料到燃料电池系统的压力。当氢气从压缩罐中流出时,储存在罐中的氢气的压力将降低,且罐的温度会下降。如果氢气从罐中流出的速度足够高和/或环境温度足够低,罐中的温度可低达-80℃。另一方面,当罐被充入氢气时,由于罐内的氢气破压缩,罐中氢气的温度可上升至85℃。在反复的充/放气体的循环中,-80℃至85℃如此宽的温度波动范围给罐连接元件(包括O型环和其他密封粘合剂)施加了很大的机械应力。在这样的工作条件下,O型环和密封粘合剂会恶化,并且可能会损坏,这导致氢气泄露。因此,需要改进密封材料和罐设计,使其对于循环的应力更加有耐受力,且提供希望的自密封性能。
发明内容
一个具体实施方式包括一种气体储存罐,该储存罐包括外部结构层,内部衬套层,具有凸缘部分的环形凸台,该凸缘部分在罐内部延伸并且与衬套层的一部分重叠,和设置于衬套层和凸台凸缘部分的重叠部分之间以提供气密性密封的流质密封材料。
另一个具体实施方式包括制造气体储存罐的方法,该方法包括:提供对氢气具有低渗透性的衬套材料和具有至少一个凸缘部分的抗氢脆化的环形凸台;使用衬套材料形成与环形凸台适配的气密囊,以使凸台的凸缘部分与衬套材料重叠;在凸台的凸缘部分和衬套的重叠部分之间设置流质密封材料;和在囊的外部形成外部结构层。
本发明的其它具体实施方式将在后面的具体描述中体现。应当理解,在解释本发明的具体实施方式时,详细的说明和具体实施例仅仅是示例说明的目的,不用于对本发明范围进行限制。
具体的,本发明涉及如下内容项:
1.一钟气体储存罐,包括外部结构层、内部衬套层、具有凸缘部分的环形凸台,该凸缘部分在所述罐的内部延伸并且与所述衬套层的一部分重叠,和设置于衬套的重叠部分和所述凸台凸缘部分之间以提供气密性密封的流质密封材料。
2如项目1所述的气体储存罐,其中所述的衬套层包括聚乙烯或铝,并且所述外部结构层包含纤维增强的树脂复合材料。
3.如项目2所述的气体储存罐,其中所述的衬套包括高密度聚乙烯,并且所述的纤维包括碳的连续长丝和/或玻璃纤维,所述树脂包括环氧树脂。
4.如项目1所述的气体储存罐,其中所述的衬套具有0.2至2千兆-帕的杨氏模量,且所述凸台包括铝或铝合金。
5.如项目1所述的气体储存罐,其中所述的流质密封材料适于在罐内气体压力下流动,且封闭所述衬套和所述凸台凸缘部分之间的小空隙。
6.如项目5所述的气体储存罐,其中所述的流质密封材料包含聚合物树脂和挥发性溶剂,所述聚合物树脂能够增稠、固化且当由于气体穿过所述衬套和所述凸台凸缘部分之间的小空隙泄漏而使所述溶剂蒸发时,封闭所述小空隙。
7.如项目5所述的气体储存罐,其中所述的流质密封材料包含至少一种悬浮于粘性液体中的纤维或粒子。
8.如项目7所述的气体储存罐,其中所述的纤维或粒子具有0.01mm或更大的尺寸。
9.如项目7所述的气体储存罐,其中所述粒子为无机粒子或橡胶粒子。
10.如项目5所述的气体储存罐,其中所述流质密封材料包括100℃下测量的ASTM D1646门尼粘度为30至大约100的液态橡胶。
11.如项目10所述的气体储存罐,其中所述的流质密封材料包括二烯烃液态橡胶或饱和烃类橡胶。
12.如项目10所述的气体储存罐,其中所述的液态橡胶包含聚异戊二烯、聚丁二烯、苯乙烯/异戊二烯/丁二烯三元共聚物、氢化聚丁二烯、苯乙烯-丁二烯共聚物、聚氯丁烯(氯丁橡胶)、丙烯晴-丁二烯共聚物、乙烯-丙烯-二烯烃三元共聚物(EPDM)、乙烯-丙烯共聚物、异丁烯基弹性体、卤化丁基橡胶、溴化异丁烯-对甲基苯乙烯共聚物和它们的衍生物。
13.一种制造气体罐的方法,包括:
提供对氢气具有低渗透性的衬套材料和具有至少一个凸缘部分的抗氢脆化的环形凸台;
使用所述衬套材料形成与所述环形凸台适配的气密囊,以使所述凸台的凸缘部分与衬套材料重叠;
在凸台的凸缘部分和衬套与所述凸缘部分的重叠部分之间设置流质密封材料;和
在所述囊的外部形成外部结构层。
14.如项目13所述的方法,进一步包括在所述凸台的所述凸缘部分的外表面上设置橡胶切变层。
15.如项目13所述的方法,其中所述衬套材料包括聚乙烯或铝,且所述凸台包括铝或铝合金。
16如项目13所述的方法,其中所述外部结构层包含纤维增强的树脂复合材料。
17.如项目16所述的方法,其中所述纤维增强的树脂复合材料由长丝缠绕工艺制备,且所述纤维包括碳和/或玻璃。
18如项目13所述的方法,其中所述的流质密封材料通过喷射、刷涂、注射、挤出、浸渍、刮涂或涂覆工艺设置。
19.如项目13所述的方法,其中所述密封材料适于在罐内气体压力下流动且封闭所述衬套和所述凸台的所述凸缘部分之间的空隙。
20.如项目19所述的方法,其中所述密封材料包括至少一种液态橡胶、悬浮在粘性液体中的纤维和/或粒子和包括在挥发性溶剂中的聚合物树脂的溶液。
附图说明
本发明的具体实施方式将通过详细的说明及相应的附图得以更加充分的理解,其中:
图1是根据本发明的一个实施方式的气体储存罐的剖面图;
图2是根据本发明的一个实施方式的气体储存罐的凸台/衬套接口部分的剖面图。
具体实施方式
下面对实施方式的描述仅仅是为了解释,不能用于对本发明及其应用或用途进行限制。
在高压应用中,气体储存罐可构造为通常带有半-球形末端(圆盖)的球形或圆柱形,尽管其它的罐几何形状也是可以的。罐可包括由气密性内部衬套层形成的内部囊,其由外部结构层进行保护。可用凸台将内部衬套和外部结构层在罐壳体的增压阀口处可靠地连接,以防止衬套和壳体之间的气体泄漏。在气体储存罐中可能有多于一个的凸台。通常在凸台内有一个膛孔部分,以与充气源、气体消耗装置和压力/温度传感器形成安全可靠的气体流通。
图1是根据本发明的一个实施方式的气体储存罐的剖面图。该气体罐包括由衬套层20形成的内部囊,外部结构层10,和在圆柱形罐一端的增压阀口处连接衬套20和外部结构层10的凸台40。凸台40包括凸缘部分50,其与衬套层的一部分和外部结构层的一部分重叠。流质密封材料30设置于凸台的凸缘部分50和衬套层之间,以提供有效的防漏密封。凸台包括一个环形膛孔部分41,其穿过凸台延伸,且构造为接纳罐内阀门活塞(图中未示出)。罐内阀门活塞可包括压力调节器和温度/压力传感器。为了保护承受高应力的圆柱形罐的半球形末端部分,可在罐末端的一头或两头上放置能量吸收泡沫或橡胶垫60。
图2是根据本发明的一个实施方式的气体储存罐的凸台/衬套接口部分的剖面图。凸台40可包括锁紧槽42,该锁紧槽在凸缘部分的两个轴向相对的表面中的一个或两个上设置。可在凸缘部分朝向外部结构层的外表面上设置环形锁紧槽(图中未示出)。在凸缘部分朝向内侧的内部表面上的锁紧槽42与衬套层20保持正向互锁咬合。每个槽接收在内部衬套层相应部分上的互补部件。流质密封材料30可设置在凸台的凸缘部分和衬套层之间,以提供有效的抗剪切密封。该流质密封材料适于在罐内气体压力下流动,以填充和封闭凸台凸缘部分和衬套层之间的任何空隙。
可在外部结构层10和衬套20之间插入剪切调节薄层,以避免在罐增压过程中给外部壳体或衬套带来的剪切应力损害。该剪切调节层由任何塑料、弹性体或其它非金属材料制备,且可通过模压工艺或从已有片上剪切制得。
内部衬套层可由具有低氢气渗透率和低杨氏模量的材料制得。衬套可具有约0.2-2千兆帕的杨氏模量和大约0.1mm至大约10mm的厚度。低杨氏模量允许其在增压过程中膨胀,这使得其将所有负荷转移给罐壳体的外部结构层。衬套可由例如聚烯烃、交联聚烯烃、聚酰胺(如尼龙12)、聚酰亚胺、含氟聚合物(如Aclar和Kapton)、双环戊二烯聚合物、铝金属或铝合金制得。也可考虑涂有金属的有机聚合物薄膜。例如,可使用高密度聚乙烯形成衬套层。高密度聚乙烯可选自符合ASTM 1248 III型,Grade P34,Class C,Cat.5的产品。该高密度聚乙烯具有高水平的抗环境应力断裂抵抗力且具有高强度。内部衬套层可通过压模、吹模、注模、滚塑形成或其它任何已知的技术形成。该内部衬套提供气体渗透阻隔、结构接口(与凸台的),且用作形成外部结构层的长丝缠绕工艺中的固定轴。
内部囊的圆盖部件可通过注模工艺或滚塑工艺来制造。囊的圆柱形部分可通过管材挤出工艺来制造,以精确控制其直径和壁厚。为了生产一个完整的囊,圆盖部件被焊接在圆柱部分上。在焊接过程中,在受控的时间和压力下,在圆盖和圆柱部分之间放置一个加热的盘。在预设的升温时间结束后,将该盘移走,通过压力使表面在受控时间内熔合在一起。可在塑料衬套上添加内部薄涂层,其中内部薄涂层被选为提供抵抗氢气转移的阻隔性。
凸台40可包括金属或铝、钢、镍或钛的金属合金,但可以理解其它金属和非金属材料,例如复合材料也是可以的。应注意,选择的凸台材料应该显示出足够的抗氢脆化能力。氢脆化对于为了强度而形成“均质晶格”的材料是一个问题。人们相信,氢对结晶材料的材料性能的影响基于溶质氢(分子或原子)或氢基化学产品在分子晶格的晶粒边界的相互作用。氢和/或氢产品影响材料的晶粒边界(微观水平)的位错能。用于金属末端凸台的材料,例如,可包括6061 T6铝或在挤出、滚轧、拉伸或冷却成型时与6061 T6铝具有相似性能的其它材料。
接口元件和/或流质密封材料层设置于凸台凸缘部分上,提供连接衬套的位置。接口层可置于凸缘部分的内表面上,也可任选置于凸缘部分的外表面上。接口元件可由HDPE(高密度聚乙烯)或其它弹性体材料注模制得,固化时,其收缩为与凸台相共形(conformity),因此确保其模制或者焊接到凸台上。流质密封材料可通过喷射、刷涂、注射、挤出、浸渍、刮涂或其它涂覆工艺施加到凸台表面。衬套通过例如塑料模制,直接连接到接口元件和/或流质密封材料上。另外,可在流质密封材料连接到衬套层之前,将其放置于接口层的上面。而且,流质密封材料可以放置在凸台/衬套接口附近的任何位置,只要流质密封材料适合或可被构造为可流动到并填充进可在凸台和衬套层之间形成的任何可能的空隙。外部结构层10包含在树脂基质中的纤维加强材料。该纤维可为玻璃纤维、聚芳族酰胺、碳、石墨或任何其它的通常已知的纤维增强材料。所用的树脂基质可为环氧树脂、聚酯、乙烯基酯、热塑性或其它任何适合的能够提供需要使用储存罐的具体应用中所需的抗破碎性的树脂材料。碳纤维和玻璃纤维可包括商品级、高强度、中级模量的连续或短纤维的碳和E-玻璃纤维。纤维表面通常用环氧树脂相容上浆进行处理,以改进纤维和环氧树脂基质之间的粘接质量。
如上所述,包含与凸台适配的内部衬套层的囊可膨胀至低压,并且可用作在长丝缠绕工艺中形成外部结构层的轴。在准备长丝缠绕时,可将模制的橡胶切变层放置在凸台凸缘上。该切变层的目的是允许衬套和纤维加强的外部层之间在增压和减压过程中发生不同的增长。
复合材料层压物的长丝缠绕可用电脑控制的多轴缠绕设备完成。为了促进高速率生产,玻璃纤维和/或碳纤维在缠绕过程中用树脂进行浸渍。树脂浸渍的方法可包括浸渍-挤压、喷射、挤出或其它本领域技术人员所熟知的纤维浸渍方法。浸渍树脂的量取决于纤维数、罐尺寸或其它因素。树脂的施加重量可始终控制在±2%重量内。纤维的拉伸也使用具有相应小容限的不同的拉伸装置控制。纤维的拉伸通常是预设的,且在缠绕过程中控制在±0.25磅。层的顺序、缠绕角度以及树脂含量和纤维拉伸力,都可通过长丝缠绕电脑程序控制。在缠绕完成后,可施加另外的树脂并使纤维/树脂层固化。固化可这样完成:将纤维/树脂层加热至固化温度,直至达到足够的固化度和必要的机械性能。根据所用的树脂的化学性质也可使用辐照固化和其它固化方法。
另外,可形成一个保护性的外部玻璃纤维覆盖层来包住外部结构层,以减轻化学或环境侵蚀和操作磨损的损害。在外部结构层和保护性覆盖层之间,可在罐圆盖部分上放置泡沫插入物。在长丝缠绕工艺中,圆盖区域中厚度减小的区域在落下或冲击时更易受损。通过直接吸收部分能量(缓冲)、通过延长持续(压缩)时间以减小冲力最大值,且通过将受力分散到更大的区域,泡沫插入物对这些区域进行保护。最终的罐外表面可进一步由油漆层进行保护。油漆(如聚氨酯或丙烯酸树脂基油漆)具有抗磨损性、提供UV保护和用于美观目的的高级整饰。
流质密封材料可为在内部气体压力下适于或构造成流动到凸台/衬套层接口的空隙且密封该空隙以制止气体泄漏的任何液态组合物。按此要求,可使用不同的流质密封材料组合物和混合物。该流质密封材料可包括液态橡胶、玻璃化转变温度低于约10℃的未硫化聚合物弹性体。该密封材料中所用的液态橡胶通常具有足够的粘度和对凸台和衬套层的未硫化粘合力。液态橡胶的粘度可由门尼粘度计量。门尼粘度(Vr)是通过测量旋转嵌入橡胶或混合样品中的圆盘所需要的扭矩而得到的。该步骤在ASTM D 1646中题为“用于门尼粘度、应力松弛和预硫化性能(门尼粘度计)的标准测试方法”中进行了定义。该液态橡胶的粘度通常为100℃下测量的45至超过100。门尼粘度可表示为ML(1+4)或有时为ML(1+8),(即,用门尼大转子,一分钟停止而四或八分钟持续测试)。这样的粘度范围使得液态橡胶能够填充凸台和衬套层的空隙,且阻止气体泄漏。
该液态橡胶可包含各种橡胶组合物。该橡胶组合物可包括饱和的和不饱和烃类聚合物、硅氧烷聚合物和含氟弹性体。烃类聚合物橡胶可包括二烯橡胶和聚烯烃橡胶。烃类橡胶的例子可包括但不限于,聚异戊二烯、聚丁二烯(BR)、苯乙烯/异戊二烯/丁二烯三元共聚物、氢化聚丁二烯、苯乙烯-丁二烯共聚物(SBR)、聚氯丁烯(氯丁橡胶)、丙烯腈-丁二烯共聚物(NBR)、乙烯-丙烯-二烯烃三元共聚物(EPDM)、乙烯-丙烯共聚物、异丁烯基弹性体和它们的衍生物。异丁烯基弹性体可包括丁基橡胶、卤化丁基橡胶、这些聚合物的星形支化变体和溴化异丁烯-对甲基苯乙烯共聚物。通常,丁基橡胶包含大约1-约6重量%的衍生自异戊二烯的重复单体单元和约94-99重量%的衍生自异丁烯的重复单元。通常丁基橡胶的数均分子量例如在20,000至500,000之间,或者在大约100,000至大约400,000之间。丁基橡胶可例如在氯甲烷稀释剂中,在低于-90℃的温度下通过阳离子聚合制备。术语“星形支化”对本领域技术人员来说是一种熟知的结构。典型的星形支化的丁烯橡胶包括,例如,来自ExxonMobil公司的SB Butyl4266橡胶和SB Bromobutyl 6222橡胶。其它液态橡胶的例子,也可从ExxonMobil公司获得,包括丁基橡胶065,068,165,365,氯丁橡胶1066,1068,溴丁橡胶2211,2222,2235和Exxpro 3035,3433(Exxpro是衍生自异丁烯和对甲基苯乙烯的共聚物的一种特殊的弹性体)。饱和烃类聚合物适于包括包括数均分子量为大约500至大约500,000的衍生自至少一种碳原子数为4至6的单烯烃的聚合物。这种聚合物的例子为:由异丁烯聚合得到的聚丁烯;由异丁烯聚合得到的聚异丁烯;由一种或多种戊烯聚合得到的聚戊烯;由一种或多种己烯聚合得到的聚己烯;和由具有4至6个碳原子的单烯烃共聚得到的聚烯烃。这些聚烯烃在室温下为液态或类似液态,且为本发明的密封组合物提供粘合和密封性能。上述烃类液态橡胶通常的玻璃化转变温度低于约-10℃,具有很强的抗气体渗透性,因此可在较宽的温度范围内提供优异的密封性能。任选的,小剂量的固化剂,例如,过氧化物,胺和硫化合物可包括在液态橡胶组合物中。该液态橡胶可在施加至凸台/衬套接口之后,通过加热或其它已知的固化方法小程度固化。
该流质密封材料可包含在挥发性溶剂中的聚合物树脂。当泄露气体流穿过或接近凸台-衬套接口的流质密封材料时,部分挥发性溶剂由气流带走。结果,泄露位置处的流质密封材料的粘度增加,使得聚合物树脂固化,最终发展为具有足够的抵抗力以阻止气体泄露。可以使用任何在挥发性溶剂中的聚合物树脂,但是弹性体聚合物树脂是优选的。聚合物树脂可完全溶解在挥发性溶剂中,或分散/乳化于挥发性溶剂中。该挥发性溶剂包括水和其它挥发性有机溶剂。该挥发性溶剂可以是几种不同挥发性化合物的混合物。聚合物树脂可包括,例如,高分子量聚合物(例如上面描述的橡胶组合物、丙烯酸树脂、聚氨酯树脂和乙烯基树脂)和增粘剂(例如萜烯树脂和松香酯)的共混物。
该流质密封材料可包含悬浮在粘性液体中的纤维和/或粒子。该纤维可包括长度为约0.01mm至约10mm的短纤维,其由一种或多种纤维材料(例如纤维素、羊毛、尼龙、人造丝、毛发、硅灰石、石棉、玻璃羊毛纤维、聚酯、聚丙烯、聚乙烯、聚芳族聚酰胺、含氟聚合物和性质上类似的其它材料)制得。该粒子可包括至少一个尺寸在大约0.001mm至大约1mm的任意形状的粒子。该流质密封材料可包括具有较宽范围的形状和大小的纤维/粒子的混合物。平板状的粒子,例如云母和橡胶粒子,可包含在流质密封材料中。该纤维和/或粒子可悬浮于粘性液体例如丙二醇,聚丙二醇;增稠的含水/有机溶剂溶液中。
上面所述的流质密封材料可承受在增压气体储存罐的凸台/衬套接口处施加的重复的循环应力,而不会使机械或化学性能降低。该流质密封材料可流动并根据应力改变形状,而不会劣化或疲劳。另外,流质密封材料展示出自密封性能,这是常规的O型环或粘合剂所不具备的。流质密封材料可以流动和填充凸台/衬套接口的空隙,密封已存在或任何刚刚产生的漏洞。由于其适应性,该流质密封材料可适配于任何凸台,衬套和罐设计。因此该流质密封材料简化了罐制造工艺且降低了成本。
本发明的上述实施方式的描述仅仅是举例性的说明,因此,其变形不应认为脱离了本发明的精神和范围。

Claims (20)

1.一种气体储存罐,包括外部结构层、内部衬套层、具有凸缘部分的环形凸台,该凸缘部分在所述罐的内部延伸并且与所述衬套层的一部分重叠,和设置于衬套的重叠部分和所述凸台凸缘部分之间以提供气密性密封的流质密封材料。
2. 如权利要求1所述的气体储存罐,其中所述的衬套层包括聚乙烯或铝,并且所述外部结构层包含纤维增强的树脂复合材料。
3. 如权利要求2所述的气体储存罐,其中所述的衬套包括高密度聚乙烯,并且所述的纤维包括碳的连续长丝和/或玻璃纤维,所述树脂包括环氧树脂。
4. 如权利要求1所述的气体储存罐,其中所述的衬套具有0.2至2千兆-帕的杨氏模量,且所述凸台包括铝或铝合金。
5.   如权利要求1所述的气体储存罐,其中所述的流质密封材料适于在罐内气体压力下流动,且封闭所述衬套和所述凸台凸缘部分之间的小空隙。
6.  如权利要求5所述的气体储存罐,其中所述的流质密封材料包含聚合物树脂和挥发性溶剂,所述聚合物树脂能够增稠、固化且当由于气体穿过所述衬套和所述凸台凸缘部分之间的小空隙泄漏而使所述溶剂蒸发时,封闭所述小空隙。
7. 如权利要求5所述的气体储存罐,其中所述的流质密封材料包含至少一种悬浮于粘性液体中的纤维或粒子。
8. 如权利要求7所述的气体储存罐,其中所述的纤维或粒子具有0.01mm或更大的尺寸。
9. 如权利要求7所述的气体储存罐,其中所述粒子为无机粒子或橡胶粒子。
10. 如权利要求5所述的气体储存罐,其中所述流质密封材料包括100℃下测量的ASTM D1646门尼粘度为30至大约100的液态橡胶。
11. 如权利要求10所述的气体储存罐,其中所述的流质密封材料包括二烯烃液态橡胶或饱和烃类橡胶。
12. 如权利要求10所述的气体储存罐,其中所述的液态橡胶包含聚异戊二烯、聚丁二烯、苯乙烯/异戊二烯/丁二烯三元共聚物、氢化聚丁二烯、苯乙烯-丁二烯共聚物、聚氯丁烯、丙烯晴-丁二烯共聚物、乙烯-丙烯-二烯烃三元共聚物、乙烯-丙烯共聚物、异丁烯基弹性体、卤化丁基橡胶、溴化异丁烯-对甲基苯乙烯共聚物和它们的衍生物中的至少一种。
13. 一种制造气体罐的方法,包括:
提供对氢气具有低渗透性的衬套材料和具有至少一个凸缘部分的抗氢脆化的环形凸台;
使用所述衬套材料形成与所述环形凸台适配的气密囊,以使所述凸台的凸缘部分与衬套材料重叠;
在凸台的凸缘部分和衬套与所述凸缘部分的重叠部分之间设置流质密封材料;和
在所述囊的外部形成外部结构层。
14. 如权利要求13所述的方法 ,进一步包括在所述凸台的所述凸缘部分的外表面上设置橡胶切变层。
15. 如权利要求13所述的方法,其中所述衬套材料包括聚乙烯或铝,且所述凸台包括铝或铝合金。
16. 如权利要求13所述的方法,其中所述外部结构层包含纤维增强的树脂复合材料。
17. 如权利要求16所述的方法,其中所述纤维增强的树脂复合材料由长丝缠绕工艺制备,且所述纤维包括碳和/或玻璃。
18. 如权利要求13所述的方法,其中所述的流质密封材料通过喷射、刷涂、注射、挤出、浸渍、刮涂或涂覆工艺设置。
19. 如权利要求13所述的方法,其中所述密封材料适于在罐内气体压力下流动且封闭所述衬套和所述凸台的所述凸缘部分之间的空隙。
20. 如权利要求19所述的方法,其中所述密封材料包括至少一种液态橡胶、悬浮在粘性液体中的纤维和/或粒子和包括在挥发性溶剂中的聚合物树脂的溶液。
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US9103499B2 (en) 2015-08-11
US20120138616A1 (en) 2012-06-07
DE102011119771B4 (de) 2017-11-30

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