CN101473161A - 贮气罐用膜材料及使用该膜材料的贮气罐 - Google Patents

贮气罐用膜材料及使用该膜材料的贮气罐 Download PDF

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Publication number
CN101473161A
CN101473161A CNA200780022378XA CN200780022378A CN101473161A CN 101473161 A CN101473161 A CN 101473161A CN A200780022378X A CNA200780022378X A CN A200780022378XA CN 200780022378 A CN200780022378 A CN 200780022378A CN 101473161 A CN101473161 A CN 101473161A
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membrane material
gas
layer
gas tank
base cloth
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Granted
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CN101473161B (zh
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长濑谕司
森裕之
日下幹生
本石靖夫
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Teijin Frontier Co Ltd
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Teijin Fibers Ltd
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17BGAS-HOLDERS OF VARIABLE CAPACITY
    • F17B1/00Gas-holders of variable capacity
    • F17B1/24Gas-holders of variable capacity of dry type
    • F17B1/26Gas-holders of variable capacity of dry type with flexible walls, e.g. bellows
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/12Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/40Layered products comprising a layer of synthetic resin comprising polyurethanes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024Woven fabric
    • 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
    • F17C5/00Methods or apparatus for filling containers with liquefied, solidified, or compressed gases under pressures
    • F17C5/06Methods or apparatus for filling containers with liquefied, solidified, or compressed gases under pressures for filling with compressed gases
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • 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
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    • 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
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    • 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
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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Laminated Bodies (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)

Abstract

本发明提供一种贮气罐用膜材料,其除了具有纤维基布的强度外,还具有能够作为贮气罐使用的耐磨性及耐弯曲性,并且气体阻隔性高。一种贮气罐用膜材料,应用于储存或回收气体的贮气罐,所述膜材料至少由保护层、基布层、气体阻隔层、保护层这四层构成。

Description

贮气罐用膜材料及使用该膜材料的贮气罐
技术领域
本发明特别涉及大型贮气罐用膜材料,并涉及适合构建储存城市燃气及特殊气体等的贮气罐以及由畜产、水产设施的废弃物、食物残渣等有机废弃物产生沼气或热分解气体等的生物气处理设施的膜材料。
背景技术
在铸铁厂等的废气或低压燃料气体等的储存设备等中,使用由玻璃钢、金属构成的贮气罐。另外,目前,将一般污水处理设施、家畜粪尿处理设施或食物残渣、酒糟、酱油糟等的处理设施等产生的沼气等进行回收并作为能源利用的生物气处理设施、以及将有机废弃物热分解产生的气体进行有效利用的设施引起广泛的关注。特别是近年来,随着时代的需要,在新增这些设施的同时,各设施的大型化也在不断发展。在这些领域中,期待用高强度且重量轻的膜材料更经济地构建储存及回收气体的设备。例如,有涉及膜式贮气罐的专利文献1。该文献记载了一种箱式收纳型膜式贮气罐,其具有如下结构:在由玻璃钢材料、金属材料等构成的刚性结构的箱中,容纳由具有气密性和液密性的挠性膜材料构成的袋体所形成的可充放气体的储气袋。
该文献没有特别说明贮气罐用膜材料所使用的材料,只有关于膜式贮气罐系统的记载。
另一方面,作为以往的气体阻隔性膜材料,专利文献2记载了一种气体阻隔性膜材料,其中,在高分子膜基材的至少一个面上,根据需要设置粘固涂层,并依次设置金属或金属化合物薄膜层、根据需要的保护层,由此得到具有透明性的包覆膜,利用含有无机超微粒子的气体阻隔性粘合剂将该包覆膜与热封性树脂粘合。
在此所述的膜材料中,由于阻隔性粘合剂中含有的超微分散的无机材料填埋了薄膜层中的微小的针孔部,并且在形成的作为层压体的膜材料中,通过粘合剂层能够抑制与其它基材层压时等产生的膜的伸缩,并能抑制大量气体由热冲击产生的热应力所导致的薄膜层的裂缝或破裂部透出,因此具有优良的气体阻隔性。但是,该发明的用途为包装材料,单独使用该膜材料虽然能够确保气体阻隔性,但难以得到可作为本发明的用途的贮气罐用膜材料来应用的强度。
另外,专利文献3记载了具有基布及气体阻隔层这两层的超轻膜材料,以及由树脂层、纤维基布层、气体阻隔层构成的超轻膜材料。
该发明的用途是作为飞艇内部使用的气囊或膜片(隔膜),难以充分得到可作为贮气罐用膜材料来应用的耐磨性及耐弯曲性。
专利文献1:日本特开2005-48930号公报
专利文献2:日本特开2000-006304号公报
专利文献3:日本特开2005-119232号公报
发明内容
本发明的目的在于,提供一种贮气罐用膜材料,其除了具有纤维基布的强度外,还具有能够作为贮气罐使用的耐磨性及耐弯曲性,并且气体阻隔性高。
本发明涉及一种贮气罐用膜材料,应用于储存或回收气体的贮气罐,其特征在于,至少由保护层、基布层、气体阻隔层、保护层这四层依次层压而成。
在此,优选构成膜材料的至少一个保护层由聚烯烃树脂构成。
另外,优选上述基布层为织物,且纤维的细度(dtex)与密度(根/英寸)的积为2500~5000。
并且,优选在上述基布层的单面或两面上层压膜状的聚氨酯树脂层,且该聚氨酯树脂层的厚度为5~50μm。
本发明还涉及使用上述贮气罐用膜材料的贮气罐。
发明效果
根据本发明,能够提供一种膜材料,其除了具有纤维基布的强度外,还具有能够作为贮气罐使用的耐磨性及耐弯曲性,并且气体阻隔性高;通过使用该膜材料,能够用高强度且重量轻的膜材料更经济地构建储存及回收气体的设备。
附图说明
图1是表示将本发明的膜材料用于贮气罐的一例的图。
标号说明
1…贮气罐外膜
2…贮气罐内膜
3…空气室
4…气体室
5…下部喷嘴
6…送风机
7…钢制架台
8…送风管道
9…上部喷嘴
10…超声波测距仪
11…赤道部
12…顶部(坠子)
贮气罐具体实施方式
本发明中,作为用于显现膜材料的强度的层,使用由纤维构成的基布是重要的。通过制成织物,使每条纤维具有的强度在同一方向上合并,由此能够得到更高强度的膜材料。
基布的形式可以为织物、针织物、无纺布、UD片材等,没有特别的限定,但基于上述理由优选最容易显现纤维强度的织物及UD片材。在织物的情况下,其形式优选容易显现强度的平织物,为了同时提高强度和撕裂强度,也可以采用防撕裂(rip-stop)结构。
关于所用的原材料,可以使用天然纤维、合成纤维的任意一种,为了得到更高强度的膜材料,优选使用合成纤维。具体而言,可以使用聚酯、尼龙、碳纤维、芳香族聚酰胺纤维、玻璃纤维等。从强度的方面考虑,优选使用以芳香族聚酰胺纤维为代表的所谓超级纤维,但从性价比的方面考虑,认为聚酯及尼龙综合而言是优选的。
本发明中使用的纤维基布为织物时,构成基布层的纤维的细度(dtex)与密度(根/英寸)的积需为2500~5000,优选为4000~5000,滑移量需小于10mm,优选为5mm以下。
细度(dtex)与密度(根/英寸)的积低于2500时,构成织物的纤维之间产生很大的空隙,引起滑移的可能性大。滑移量需要控制为小于10mm,如果达到10mm以上,则制品的品质下降,容易产生作为贮气罐用膜材料的重大缺陷的折皱或针孔等加工缺陷。在形成贮气罐时,由于应力集中于缺陷部分,这些缺陷往往成为破裂等的原因。另外,滑移不仅是造成这些缺陷的原因,而且还降低强度的显现率,使本发明的目的无法实现。要使滑移量小于10mm,只要将构成基布层的纤维的细度与密度的积如上所述设定为2500以上即可。
另外,通常用纺织机织成织物后,为了去除在纺丝工序中附着在纤维上的油剂及在为纺织做准备的整经工序中附着的糊剂等杂质,要经过精练工序,此时,为了抑制该滑移,使用卷染机来进行是非常有用的。
另一方面,细度(dtex)与密度(根/英寸)的积超过5000时,基布的重量增大,对于用作本发明的主要目的的贮气罐用膜材料而言,重量变得过大。
另外,通过在基布层的至少单侧即单面或两面上层压膜状的聚氨酯树脂,使其表面的平滑性得到改善,与气体阻隔层及作为保护层的聚烯烃层的粘着性提高,该多层膜材料通过一体化变得牢固,并且膜材料的耐弯曲性进一步提高。另外,基布层变得易于处理,气体阻隔层或保护层的加工性也提高。该情况下,膜状的聚氨酯树脂层的厚度通常为5~50μm,优选为10~20μm。聚氨酯树脂层的厚度小于5μm时,表面的平滑性无法充分满足,不能充分得到粘着性的提高,而且往往成为气体阻隔层及保护层加工时的折皱等缺陷的原因。另一方面,聚氨酯树脂层的厚度超过50μm时,基布层的重量增大,对于用作本发明的主要目的的贮气罐用膜材料而言,重量变得过大。
其次,本发明中,需要在膜材料的上述基布层的一个面上设置气体阻隔层。如前所述,贮气罐是用于回收由废弃物产生的沼气和热分解气体等以及储存城市燃气或特殊气体的部件,因此,在此使用的原材料需要具有气体阻隔性。气体阻隔层没有特别的限定,可以使用聚酯膜、聚萘二甲酸乙二醇酯膜、聚酰胺膜、聚偏氯乙烯膜、乙烯-乙烯醇共聚物膜等,其中乙烯-乙烯醇共重聚物膜因其气体阻隔性特别优良而优选。特别是热分解气体中,含有大量的易透过膜的氢气,为了防止其泄漏,使用乙烯-乙烯醇共聚物膜是有效的。另外,对上述各膜进行金属或金属氧化物等的蒸镀加工,在进一步提高气体阻隔性的方面也是有效的。
另一方面,为了使膜材料更具有实用水准,需要用其它树脂层保护基布层及气体阻隔层。本发明提供的膜材料由于作为贮气罐用膜材料使用,因此,为了维持其气体阻隔性,在使用中不可以损伤或破损。另外,为了形成贮气罐的形状,需要具有耐弯曲性。因此,用树脂(保护层)涂布维持强度的基布层和气体阻隔层或者用该树脂膜进行层压,对于维持膜材料的功能、容易地构建贮气罐是非常有用的。并且,构建贮气罐时,为了使膜材料之间相互接合,也优选设置这种层。
用于保护层的树脂可以使用聚乙烯树脂、聚氨酯树脂(其中,不包括预先在基布上层压的上述膜状的聚氨酯树脂)、氯乙烯树脂、丙烯酸树脂、聚酯树脂等。在此,为了得到具有耐弯曲性的膜材料,优选使用耐弯曲性高的聚氨酯树脂。并且,为了赋予膜材料耐磨性,优选在聚氨酯树脂层上设置聚乙烯等聚烯烃树脂层。另外,由废弃物产生的气体中含有硫化氢和其它繁杂的混合物,为了防止膜材料的劣化,也优选保护膜使用化学性质稳定的聚乙烯等聚烯烃。这些树脂可以用一般的方法进行加工,使用粘合剂层压膜状的树脂,或直接涂布加热的树脂。
另外,基布层的单位面积重量通常为20~100g/m2,优选为30~60g/m2
另外,气体阻隔层的厚度通常为3~30μm,优选为5~15μm。
另外,基布层侧或气体阻隔层侧使用的保护层的厚度通常均为5~180μm,优选为10~100μm。
具有上述结构的本发明的贮气罐用膜材料的总厚度通常为约150μm~约300μm,优选为约200μm~约250μm。
本发明的贮气罐用膜材料中,保护层/基布层/气体阻隔层/保护层各层之间,使用氨基甲酸酯类粘合剂等粘合剂、通过通常的干法层压、挤压涂布层压、湿法层压等粘合方法进行粘合即可。另外,在保护层如上所述由多层构成时,也可以采用同样的粘合方法。
在此,各层之间的粘合剂的涂布量以干燥重量计通常为约0.01g/m2~约10g/m2,优选为约1g/m2~约5g/m2
下面,利用图1对使用上述膜材料的贮气罐进行下述说明。
球形膜制贮气罐由外膜1和内膜2构成,在球的中央部周围(赤道部11),外膜与内膜在多个位置被固定。并且,外膜1在赤道部11处在多个位置上固定于钢制台架7。
球形膜制贮气罐由内膜2分割为空气室3和气体室4,气体由下部喷嘴5进出,空气通过送风机6、送风管道8及上部喷嘴9进出空气室3。
以下述方式进行设计:通过送风机6对空气室3施加一定程度以上的压力,使贮气罐即使在风或积雪等的外力作用下也能保持球形,承受外力的作用。
另外,在内膜2的顶部12上安装膜材料或塑料等制成的坠子,随着储存气体量的增减,坠子上下移动。通过安装在外膜顶部的超声波测距仪10等测量该坠子上下移动的距离,由此能够测量气体的储存量。
空气室3和气体室4隔着内膜2取得压力的平衡,因此,通常没有过大的张力作用于内膜2,但有时由于结露等原因,顶部(坠子)12的上部也可能形成水洼,此时,作用于内膜2和内膜与外膜的固定部11的张力大。特别是如果为大型贮气罐,则膜材料由于该原因而破损的可能性增大。
通过使用本发明的贮气罐用膜材料作为上述内膜2,能够更加经济地构建耐摩损性、弯曲性、气体阻隔性优良的储存及回收气体的贮气罐。
实施例
下面,通过实施例更具体地说明本发明。另外,实施例中的物性通过下述方法测定。
(1)透气度
通过透气度试验(JIS K7126A的方法)进行评价。测定气体使用氧气。
(2)耐磨性及耐弯曲性
在进行重复揉搓试验(JIS K6406)后,进行透气度试验(JIS K7126A法),重复揉搓的次数为5000次,透气度试验的测定气体使用氧气。
实施例1~5、比较例1~4
使用44dtex/20根单纤维的聚酯多纤维丝(帝人纤维株式会社制、P300SB),制作织物密度为经纱110.0根/英寸、纬纱92.5根/英寸的平织物(单位面积重量为90g/m2)。在该织物的一个面上层压聚氨酯膜(PU)(大仓工业株式会社制、クラミロン、厚度为10μm)来制成基布。再在该基布的层压了聚氨酯的一侧层压15μm厚的乙烯-乙烯醇共聚物膜(可乐丽株式会社制、エバ—ル膜EF-XL),得到由基布层和气体阻隔层构成的两层膜。进一步,在得到的两层膜的两面上,使用氨基甲酸酯类粘合剂(5g/m2)(武田药品工业制、タヶラツク)分别层压一层10μm厚的聚氯乙烯膜(PVC)(三菱化学MKV制、アルトロン)、聚对苯二甲酸乙二醇酯膜(PET)(东丽公司制,ルミラ—)、聚氨酯膜(PU)(大仓工业制,クラミロン)、聚乙烯膜(PE)(東赛璐制、TUX)。将由上述操作得到的四层膜作为实施例1~4。
另外,实施例5中,在上述织物的两面上层压聚氨酯膜(PU)(大仓工业株式会社制クラミロン、厚度均为10μm)来制成基布,再在该基布上层压15μm厚的乙烯-乙烯醇共聚物膜(可乐丽制、エバ—ル膜EF-XL),得到由基布层和气体阻隔层构成的两层膜。进一步,在得到的两层膜的两面上,使用氨基甲酸酯类粘合剂(5g/m2)(武田药品工业制、タケラツク)分别层压一层10μm厚的聚乙烯膜(PE)(東赛璐制、TUX)。
另一方面,如下制备比较例1~4:在实施例1~4中使用的基布单体或基布的单面上,用氨基甲酸酯类粘合剂(5g/m2)(武田药品工业制、タケラツク)层压均为15μm厚的乙烯-乙烯醇共聚物膜(可乐丽制、エバ—ル膜EF-XL)、聚氨酯膜(PU)(大仓工业株式会社制、クラミロン)、聚乙烯膜(PE)(東赛璐制、TUX)。表1显示实施例的物性,表2显示比较例的物性。
表1
 
实施例1 实施例2 实施例3 实施例4 实施例5
气体阻隔层
基布层 单面PU 单面PU 单面PU 单面PU 两面PU
保护层(两面) PVC PET PU PE PE
透气度(cc/m2·24小时·atm) 13 15 3 8 1以下
揉搓试验后的透气度(") 34 18 11 9 1以下
表2
 
比较例1 比较例2 比较例3 比较例4
气体阻隔层
基布层 单面PU 单面PU 单面PU 单面PU
保护层(两面) PU PE
透气度(cc/m2·24小时·atm) 213 24 53 71
揉搓试验后的透气度(") 260 60 159 80
产业上的利用可能性
根据本发明,能够提供一种膜材料,其除了具有纤维基布的强度外,还具有能够作为贮气罐使用的耐磨性及耐弯曲性,并且气体阻隔性高,通过使用该膜材料,能够用高强度且重量轻的膜材料更经济地构建储存及回收气体的设备,产业利用价值极高。

Claims (5)

1.一种贮气罐用膜材料,应用于储存或回收气体的贮气罐,其特征在于,所述膜材料至少由保护层、基布层、气体阻隔层、保护层这四层依次层压而成。
2.如权利要求1所述的贮气罐用膜材料,其中,构成膜材料的至少一个保护层由聚烯烃树脂构成。
3.如权利要求1或2所述的贮气罐用膜材料,其中,基布层为织物,且纤维的细度与密度的积为2500~5000,其中,细度的单位为dtex,密度的单位为根/英寸。
4.如权利要求1~3中任一项所述的贮气罐用膜材料,其中,在基布层的单面或两面上层压膜状的聚氨酯树脂层,且该聚氨酯树脂层的厚度为5~50μm。
5.一种贮气罐,其使用权利要求1~4中任一项所述的贮气罐用膜材料。
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CN109838681A (zh) * 2019-03-11 2019-06-04 中冶华天工程技术有限公司 一种柔性橡胶膜耐低温的橡胶膜柜及其改善耐低温的方法

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CN107385629A (zh) * 2016-05-17 2017-11-24 韩国卡奔株式会社 具有改善的疲劳强度的柔性次级气体隔板及其制造方法
CN107385629B (zh) * 2016-05-17 2019-05-31 韩国卡奔株式会社 具有改善的疲劳强度的柔性次级气体隔板及其制造方法
CN109838681A (zh) * 2019-03-11 2019-06-04 中冶华天工程技术有限公司 一种柔性橡胶膜耐低温的橡胶膜柜及其改善耐低温的方法

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JP2007333045A (ja) 2007-12-27
EP2031293A1 (en) 2009-03-04
WO2007145153A1 (ja) 2007-12-21
CN101473161B (zh) 2012-07-25
JP5123495B2 (ja) 2013-01-23
EP2031293A4 (en) 2012-12-26
US8147595B2 (en) 2012-04-03

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