CN103261775A - 用于填充气体储存容器的方法 - Google Patents
用于填充气体储存容器的方法 Download PDFInfo
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- CN103261775A CN103261775A CN2011800603906A CN201180060390A CN103261775A CN 103261775 A CN103261775 A CN 103261775A CN 2011800603906 A CN2011800603906 A CN 2011800603906A CN 201180060390 A CN201180060390 A CN 201180060390A CN 103261775 A CN103261775 A CN 103261775A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
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- A62D1/0092—Gaseous extinguishing substances, e.g. liquefied gases, carbon dioxide snow
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- B67—OPENING, CLOSING OR CLEANING BOTTLES, JARS OR SIMILAR CONTAINERS; LIQUID HANDLING
- B67D—DISPENSING, DELIVERING OR TRANSFERRING LIQUIDS, NOT OTHERWISE PROVIDED FOR
- B67D1/00—Apparatus or devices for dispensing beverages on draught
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Abstract
气体储存容器(例如储气瓶)填充有在压力下的包含第一气体和第二气体的气体混合物,做法是通过向气体储存容器中进料包含液化的第一气体和固化的第二气体的液体/固体混合物;将气体储存容器对气体进入或离开容器的通道关闭;和允许所述液化的第一气体和所述固化的第二气体在所述关闭的气体储存容器内变为气态。与直接压缩过程相比,这样的过程更容易并且更加能量有效,并且与直接液体注入过程相比,更加安全并且导致较少的损耗。
Description
本发明涉及一种使用两种或更多种气体的混合物填充气体储存容器的方法。所述气体储存容器通常为用于储存和/或分配在压力(通常为高压,例如,至少100巴)下的气体混合物的储气瓶。
气体的混合物可通过将单独的气体以适当的比例混合而现场形成。然而,可能更方便的是使用在高压下在容器中储存的预先混合的气体混合物。
日常使用的气体混合物的实例包括焊接气体,例如氩/二氧化碳/氧混合物;“啤酒”气体,即,用于酒馆和酒吧以帮助从加压的金属小桶分配啤酒的气体,例如氮/二氧化碳混合物;麻醉气体,例如氧/氧化亚氮混合物;和灭火气体,例如氮/二氧化碳混合物。
装有在高压(例如,100巴以上)下的气体混合物的储气瓶可通过使用气体压缩机向气瓶中简单地泵送气体混合物而制备。这样的填充过程倾向于在填充较少数量的气瓶的场所使用。
使用气体压缩机填充的储气瓶的实例包括用于潜水的压缩空气气瓶,其使用潜水空气压缩机来压缩空气随后进料至气瓶而制备。
US
5,826,632 (1998年10月公布)公开了一种使用气体混合物填充气体储存器皿的方法。所述方法包括在压力下提供均匀共混的气体混合物的流,监测混合物的流速和组成,和适当地调节流速和/或组成以保持在气体混合物中气体的所需比例。随后将气体混合物进料至一个或多个储气瓶。US 5,826,632举例说明制备装有在182巴下的90%氩/10%二氧化碳的储气瓶。
装有在高压下的气体混合物的储气瓶还可通过向气瓶中序贯进料气体混合物的各组分而制备。该方法包括在加入各组分期间测量气瓶中分压的增加(测压法)或气瓶质量的增加(重量法)。
测压法可能不准确,特别是对于非理想气体,并且通常涉及使用用于低压和高压的不同类型的压力计。更换压力计劳动密集并且延长填充气瓶所耗的时间。此外,这样的压力计通常昂贵。
比起测压法,重量法通常更准确。然而,重量法仍涉及使用昂贵的设备并且可能相当复杂。
US
5,427,160 (在1995年6月公布)公开了一种使用气体的可燃混合物填充气体储存容器的方法。该方法优选包括引导在压力下的易燃气体从其第一中间容器至气体储存器皿,和随后引导在压力下的氧化剂气体从其第二中间容器至气体储存器皿。通过合适的阀和压力变换器控制气体至储存器皿的流动。US
5,427,160举例说明制备旨在用于车辆气囊系统的气体储存容器,其装有在2,500 psi (约172巴)压力下的空气(其中空气中的氧用作氧化剂气体)和氢气的混合物作为易燃气体。
包括序贯加入气体混合物的组分的方法的一个缺点在于,气瓶中的气体可能分层直至气体混合物达到平衡。通过借助混合管向气瓶的底部引入较轻的组分或通过滚动已填充的气瓶,可克服这种分层。另一种选择是以密度增加的顺序向气瓶中装载期望量的各气体。US
5,353,848 (在1994年10月公布)公开了这样的一种方法。
直接压缩方法的显著缺点在于,各气瓶必须缓慢填充,例如,小于1巴/s,以控制气瓶通过绝热压缩气体的加热和/或使该加热最小化。使用气体混合物填充气瓶可能耗时1-2小时,因此在制备高压储气瓶中是限速步骤之一。此外,需要显著量的能量来压缩气体至填充气瓶的足够的压力。此外,高压压缩机的资金和操作成本通常高。
直接压缩方法的又一缺点在于,压缩的热量可能对于监测进入气瓶的气体流量的计量精度具有显著不利的影响。明显地,由于气体混合物的组成通常是关键的,该影响是不期望的。
US
2008/0202629 (在2008年8月公布)公开了一种制备装有在高压下的气体混合物的气体容器的两步法,其包括在将气体容器冷却的同时向气体容器中供应液化的或固化的第一气体,随后向气体容器中引入第二气体,之后关闭气体容器。关闭后,可将容器温热至环境温度,此时液化的或固化的第一气体变为气态,从而提高容器内部的压力。在15℃下容器中的压力可为250巴-1300巴。该方法特别适用于制备用于气囊系统的高压气体容器,涉及气体例如氩、氧、氮、氢气、氦、一氧化二氮(N2O)作为纯气体或混合物,并且公开了有利的是第一气体可为氩,并且第二气体可为氦。US 2008/02026289公开了该方法允许更严密地计量控制气体混合物的组分。
包含固体CO2和低温液体的某些低温浆料为本领域已知的。例如,US3,393,152
(在1968年7月公布)公开了一种制冷剂组合物,其包含在沸腾温度低于约-300°F (~184℃)的低温液体中悬浮的固体二氧化碳颗粒。优选的低温液体为液氮,但是公开了可使用液体空气或液体氩。在组合物中固体二氧化碳的比例可为5重量%-95重量%,但是当需要较高的制冷能力时,优选超过40重量%的比例。US3,393,152举例说明如下任一形成组合物:通过在压力槽中使压缩的二氧化碳气体通过液氮;或者通过使液体二氧化碳膨胀以产生干冰,干冰随后直接落在液氮上,在液氮内悬浮。公开了该组合物可用作制冷剂和作为惰性气体来源。该组合物还可用作冷却介质并且同样可用于多种领域,例如焊接和吹塑。
US
5,368,105 (在1994年11月公布)公开了一种用作灭火剂的低温浆料。该浆料包含以1:1重量比率在液氮中悬浮的固体二氧化碳颗粒的混合物。
WO
00/36351 (在2000年6月公布)公开了一种含有在液氮(或液体空气;例如,50-90重量%)和乙醇(例如,20-60重量%)的混合物中悬浮的固体二氧化碳颗粒(例如,10-50重量%)的低温浆料。公开了该组合物可具有凡士林样或奶油样稠度,并且可用于处理疣、冷冻密封管线和冷却实验室样品。WO
00/36351还推测该混合物可用于在许多领域中代替干冰,并且提出混合物的良好的重量/冷却性质意味着其可用于输送/储存冷冻的/冷却的产品,例如食品。
本发明的优选的实施方案的一个目的是提供一种用在压力下的气体混合物填充气体储存容器的新的方法,优选不具有现有技术的一个或多个缺点。
根据本发明的第一方面,提供了一种用在压力下的至少第一气体和第二气体的气态混合物填充气体储存容器的方法,所述方法包括:
用包含液化的第一气体和固化的第二气体的液体/固体混合物装载气体储存容器;
将所述气体储存容器对气体进入或离开容器的通道关闭;和
允许所述液化的第一气体和所述固化的第二气体在所述关闭的气体储存容器内变为气态。
本发明人观察到,当进料至储气瓶时,液体氩/固体二氧化碳浆料不像液体氩本身那样容易沸腾。在填充期间抑制沸腾意味着可实现更高压力填充,或者相对于纯低温液体,当使用浆料注入气瓶时,需要更低的压力。此外,在填充期间低温流体的损失降低。
不希望束缚于任何具体的理论,本发明人相信是由于固体二氧化碳的比热容提供另外的制冷能力,而产生该观察结果。本发明人充分预期,使用涉及液化的气体和固化的气体的不同混合物(例如,液氮/二氧化碳)的其它低温浆料,应观察到类似的沸腾抑制效果。
本发明人还观察到,当固体二氧化碳存在于液体/固体混合物中时,固体二氧化碳看起来抑制液化的第一气体的立即沸腾,并且由于混合物具有比单独的液化的第一气体高的粘度,在填充期间存在较少的液化的第一气体的“飞溅”。
术语“在压力下”旨在是指气体混合物在超过大气压的压力下,例如,至少40巴。容器通常适于储存和/或分配至高达约500巴压力的气体。通常,容器适于储存和/或分配在至少100巴,例如,至少200巴或至少300巴的压力下的气体。
在环境压力(例如,约1-约2巴)下,液体/固体混合物通常稳定至少10分钟,优选至少30分钟,更优选高达1小时。在本上下文中,术语“稳定”意味着混合物可在环境压力下处理,而不显著损失一种或多种组分。
液体/固体混合物通常为使混合物能被倾倒、沿着导管泵送/管道输送和装阀门的流体。取决于液化的气体和固化的气体的相对比例,混合物的稠度和外观可在稠厚的奶油状物质(并非不像搅奶油或白矿脂)到稀薄的乳状物质范围内。混合物的粘度范围通常为约1 cPs
(对于稀薄的乳状混合物)至约10,000
cPs (对于稠厚的奶油状混合物)。粘度可为约1,000-约10,000 cPs。优选,混合物由在液相中悬浮的细碎的固体颗粒组成。液体/固体混合物可描述为低温浆料或雪泥。
本发明人观察到,当让液体氩/固体二氧化碳混合物温热至环境温度时,液体氩首先蒸发,留下实质量的固体二氧化碳,其随后逐步升华。通过在容器内扩散气体,形成均匀共混的氩/二氧化碳混合物。本发明人预期含有固体二氧化碳的其它液体/固体混合物的行为表现为类似的方式。
在混合物中液体和固体组分的相对比例由期望的气体混合物和对混合物具有流体特性的期望来规定。在优选的实施方案中,存在约40重量%-约99重量%液体组分和约1重量%-约60重量%固体组分。
第一和第二气体的身份由填充容器的气体混合物规定。以本发明方式使用的合适的气体混合物的实例包括焊接气体;“啤酒”气体;麻醉气体;和灭火气体。
合适的焊接气体包括氮/二氧化碳混合物(例如,约80重量%-约95重量%氮和约5重量%-约20重量%二氧化碳)和氩/二氧化碳混合物(例如,约80重量%-约95重量%氩和约5重量%-约20重量%二氧化碳)。在这样的焊接气体混合物中,氧可代替一些氮或氩气体。因此,焊接气体可含有0重量%-约5重量%氧。
特别合适的焊接气体含有约80重量%-约90重量%氩、0重量%-约5重量%氧和约5重量%-约20重量%二氧化碳。合适的焊接气体的一个实例含有约2.5重量%氧、约7重量%-约20重量%二氧化碳、余量(约77.5重量%-约90.5重量%)为氩。
合适的“啤酒”气体包括氮/二氧化碳混合物(例如,约40重量%-约70重量%氮和约30重量%-约60重量%二氧化碳)。
合适的麻醉气体包括氧/氧化亚氮混合物(例如,约65重量%-约75重量%氧和约25重量%-约35重量%氧化亚氮)。
合适的灭火气体包括氮/二氧化碳混合物(例如,以1:1的重量比)。
因此第一气体可选自氮;氩;和氧。其它合适的气体包括氦;氖;氙;氪;和甲烷。
在环境压力下第二气体通常固体形式为稳定的。在本上下文中术语“稳定”意味着第二气体的固体形式不会在环境压力下过快地变为气态(通过升华,或通过熔融和蒸发),使得在这些条件下固体形式可容易处理。第二气体通常选自二氧化碳和氧化亚氮。
液体/固体混合物可为液化的气体和固化的气体的二元混合物。然而,液体/固体混合物可为多于一种液化的气体和一种固化的气体的混合物,或者一种液化的气体和多于一种固化的气体的混合物。在一些优选的实施方案中,液体/固体混合物包含液化的第三气体。液化的第三气体可与液化的第一气体不可混溶,但是,在优选的实施方案中,液化的第一和第三气体彼此可混溶。
在气体储存容器填充焊接气体的优选的实施方案中,液化的第一气体为液体氩,并且固化的第二气体为固体二氧化碳。在这样的实施方案中,液体/固体混合物还可包含与液体氩可混溶的液体氧。因此,液体/固体混合物可包含约80-约90重量%液体氩;0-约5重量%液体氧;和约5-约20重量%固体二氧化碳。
本发明可应用于储存和/或分配在压力下的气体的任何类型的容器,例如气体槽或其它气体储存器皿。气体储存容器通常包含外部器皿,其限定用于容纳在压力下的气体混合物的内部空间,所述外部器皿包含开口用于接受流体流动控制单元;和安装在所述开口内用于控制流体流入和流出外部器皿的流体流动控制单元。
本发明特别适用于储气瓶,例如,由例如钢或铝制成的高压储气瓶。在一些优选的实施方案中,容器为单个储气瓶。在其它优选的实施方案中,容器为在多气瓶组(multi-cylinder
pack)中与多个“次要”气瓶平行气体流动连通的中心“主要”气瓶。在这样的实施方案中,中心气瓶的外部器皿通常由铝制成,而各次要气瓶的外部器皿通常由钢制成。
气体储存容器可为具有内衬绝热材料的内表面的气瓶。这样的气瓶的合适的实例描述于GB 2,277,370,其公开内容通过引用结合到本文中。然而,气体储存容器优选不内衬。
气体储存容器还可包含至少一个在所述内部空间内提供的内部器皿,所述内部器皿限定一部分所述内部空间用于容纳液体/固体混合物,与所述外部器皿为间隔关系,并且与所述内部空间的其余部分流体流动连通。这样的配置防止外部器皿脆裂。
在这些实施方案中,将低温流体进料至在容器内的内部器皿。随后将容器密封,并且随后让低温流体变为气态,从而用在压力下的气体填充容器和与之关联的任何次要容器。内部器皿不仅将低温流体与容器的外壁隔离(从而防止容器脆裂),而且由于它们往往薄壁,也降低沸腾的速率并且提供更均匀的汽化。
该或各内部器皿优选“松配合”,即,不是固定安装在容器内。
由于内部器皿仅暴露于等静压力,该或各内部器皿优选为“薄壁”。该或各内部器皿通常具有足够厚的基底和封闭壁,使得当装有低温流体时,内部器皿能够支撑自身。基底和封闭壁的厚度取决于制备内部器皿的材料,但是通常内部器皿的基底和壁的厚度为约0.1
mm-约10 mm,优选约0.25
mm-约5 mm。例如,当内部器皿由金属(例如,钢、铝或镍)制成时,基底和壁的厚度通常不大于约2 mm,例如,约1 mm-约2 mm。此外,当内部器皿由聚合材料(例如,硅酮或聚酯膜)制成时,基底和壁的厚度通常稍多,例如,小于约5 mm,例如,约1.5
mm-约4 mm。
该或各内部器皿优选为“顶部敞开”或“端部敞开”罐形式,即,具有基底和封闭壁的器皿,壁通常(但是不必然)为环形,基本上垂直于基底提供。这样的内部器皿的口为敞开端。在一些实施方案中,所述罐的敞开端为倒转的圆锥体形式。
气体储存容器优选包含至少一个支撑物用于以相对于所述外部器皿为所述间隔关系地支撑内部器皿。可使用任何合适的支撑物,例如用于内部器皿的间隔臂和/或支柱,或者在其上放置内部器皿的支撑基。支撑物可(但是不必然)固定于内部器皿。该或各支撑物通常由耐低温材料制成,并且通常具有低传热系数。合适的材料包括塑料和聚合物,但是也可使用填充材料。
容器可包含多个内部器皿。例如,各内部器皿可为具有关闭底端和形成口的敞开顶端的长的薄壁管。管的直径可大于外部器皿的开口的直径(在这种情况下,应在封闭之前,将管引入外部器皿中)或小于外部器皿中开口的直径(在这种情况下,各管可经由该开口插入外部器皿中)。
在优选的实施方案中,容器包含单个内部器皿。在这样的实施方案中,内部器皿的口优选直径大于所述开口。内部器皿的口的直径可比开口的直径大至少100 %,优选大至少200 %,例如,大至少400 %。内部器皿的口的直径可为外部器皿的内径的至多约99 %。
该或各内部器皿通常自身-支撑,即使当装载低温流体时也如此。内部器皿可为刚性的,即,自身-支撑,并且可能抗变形。或者,该或至少一个内部器皿可变形。在这样的实施方案中,该或各内部器皿可例如通过滚动、折叠或压缩(crushing)而变形,随后通过外部器皿中的开口插入容器中。使用气体压力或液压压力,该或各内部器皿可随后在容器内展开。或者,在该或各内部器皿有弹性的实施方案中,在容器的内部,内部器皿恢复其独立的初始形状。就此而论,内部器皿由弹性材料制成,或者内部器皿包含固有的弹性或“弹簧加载的”框架,该框架支撑形成器皿的基底和壁的可变形片材。
由于待装载低温流体,该或各内部器皿通常由在其将暴露的低温温度下耐脆裂的材料制成。合适的材料包括特定的金属,例如,铝;镍;和钢,例如,不锈钢;和聚合材料,例如,硅酮例如催化固化硅酮和聚二甲基硅氧烷;聚酯,例如聚对苯二甲酸乙二酯(PET或Mylar™);聚乙烯例如聚四氟乙烯(PTFE);和全氟化弹性体(PFE)。
除了口以外,内部器皿可包含至少一个孔,用于在由内部器皿限定的内部空间的部分和由外部器皿限定的内部空间的其余部分之间提供另外的气体流动连通。这样的孔通常提供在内部器皿的壁中,在待装载至该器皿的低温流体的最大水平之上。然而,在优选的实施方案中,在该或各内部器皿中,口优选为唯一的开口。
术语“间隔关系”旨在是指间隔开或在之间具有间隙。因此,在本发明中,外部器皿与内部器皿间隔开,使得装载至内部器皿的低温流体与外部器皿通过它们之间提供的间隙而隔离。间隙通常大于1 mm,优选大于5 mm。
术语“敞开”旨在是指至少不完全关闭。因此,在本发明中,口至少不完全关闭,并且优选对内部空间的其余部分完全敞开。在优选的实施方案中,口不与容器的任何部分(特别是流体流动控制单元)直接连接。
该或各内部器皿的口优选关于流体流动控制单元为间隔关系。
内部空间通常具有上半部和下半部。内部器皿延伸进入内部空间的下半部或上半部的程度取决于待装载至内部器皿的低温流体的量。该或各内部器皿可从内部空间的下半部延伸至上半部中。例如,在其中容器为在多气瓶组中的中心主要气瓶的实施方案中,内部器皿可基本上从接近内部空间的底部延伸至顶部,或直至达内部空间长度的90%。然而,在其中容器为单个储气瓶的实施方案中,优选内部器皿完全提供在下半部内,或甚至内部空间的下三分之一。
用于储存和/或分配在压力下的气体的某些优选的容器公开于共同待审的欧洲专利申请号(待通知)并且标识为APCI卷号07492 EPC,其通过引用结合到本文中。
本发明人已发现,顶部敞开罐形式的内部器皿优越于口部密封袋形式的内部器皿,这是由于袋抑制形成均匀共混的气态混合物所需的第二气体的扩散。此外,本发明人观察到,在容器的基底中使用内部罐避免了如果将混合物进料至与流体流动控制单元连接的内部袋会遇到的剧烈对流。此外,本发明人观察到,内部罐比内部袋更稳健。
本文提供的气体储存容器或内部器皿可使用插入通过流体流动控制单元的通道中的喷嘴来装载液体/固体混合物。喷嘴通常包含第一导管配置和第二导管配置,通过第一导管进料低温流体,通过第二导管在向容器装载流体时将置换的空气和/或气态低温流体从容器排出。第一导管配置可处于第二导管配置内,并优选与第二导管配置共轴。在内部器皿与流体流动控制单元间隔开的实施方案中,喷嘴通常延伸通过流体流动控制单元,到内部器皿的口水平之下。采用这种方式,来自喷嘴末端的喷雾被内部器皿的壁捕捉。
可使用压力帽或类似物手动打开和关闭通道,但是在优选的实施方案中,通道具有位于容器内部通道末端的阀,其通过弹簧偏置于关闭位置。
该过程可包括通过除去压力帽打开通道,随后将喷嘴插入敞开的通道和向容器中进料低温流体。或者,该过程可包括通过插入喷嘴打开通道,其中喷嘴的末端逆着弹簧推开阀。
合适的喷嘴配置公开于2010年12月16日提交的共同待审的欧洲专利申请号10
195 461.8,其公开内容通过引用结合到本文中。
液体/固体混合物可通过使第二气体与液化的第一气体接触而产生。第二气体可为气态形式,但是通常为液化的或固化的颗粒形式。
液体/固体混合物可通过在绝热槽中使在压力下的第二气体通过液化的第一气体而形成。液化的第一气体冷却并且固化第二气体为细碎的固体颗粒形式,其随后在液化的第一气体内分散。这样的过程的合适的实例描述于US3,393,152,其公开内容通过引用结合到本文中。
液体/固体混合物还可通过使气态或液体形式的经加压第二气体流快速膨胀并且将经膨胀流与液化的第一气体的喷雾混合而形成。这样的过程的合适的实例描述于US
5,368,105和WO 00/36351,其公开内容通过引用结合到本文中。本发明人注意到,液体二氧化碳的喷嘴可加热,以避免被固体二氧化碳阻塞。
通过从装有加压的二氧化碳的气瓶排放二氧化碳到液体氩上,本发明人产生了液体氩/固体二氧化碳混合物。当排放时,二氧化碳液化/固化以形成细液滴/颗粒,其随后落在表面上并且与液体氩混合。本发明人观察到,如果它们要足够稳定以能够装载至储气瓶,采用这种方式制备的混合物应为“乳状”的。
液体/固体混合物可在槽中间歇生产,或者在连续的在线过程中生产。混合物可按照重量计量,或者使用流量计例如科里奥利(coriolis)流量计。
计算进料或装载至气体储存容器的液体/固体混合物的量,以便一旦混合物变为气态,则在容器中提供期望压力的气体混合物。
当要用在压力下的气体填充气体储存容器时,可使用理想气体方程式计算待装载至内部器皿的低温液体的量,即:
PV=nRT
其中P为在容器中气体期望的压力;V为容器的体积;n为气体的摩尔数;R为气体常数;和T为绝对温度。
一旦选择具体的容器,V和最大P是已知的,R和环境温度同样已知。则因此可计算n的值:
n=PV/RT
通过乘以分子量A,随后将气体的摩尔数n转化为气体的质量M,以克(g)计:
M=nA
对于在超过比如50巴的压力下的真实气体,该基本公式要加入校正,其取决于分子之间的吸引力和排斥力以及分子的有限和不同尺寸。通过在方程式中包括因数Z——气体的“压缩能力”,可计入这些校正:
PV=nRTZ
在宽范围的压力和温度内,对于许多气体存在表列结果(tabulation),并且对于一些气体存在复杂的近似公式。
适当时可修改计算,以确定用在压力下的气体混合物填充气体储存容器所需的包含液化的第一气体和固化的第二气体的液体/固体混合物的量。
在间歇过程中,可按量配给(例如,按照重量或按照体积)预定量,随后使用例如漏斗或虹吸管装载至容器。或者,在使用填充管线的连续过程中,可计量(例如,使用流量计,或者通过重量或体积法)到第一容器的液体/固体混合物的流量,一旦已向第一容器装载预定的量,可中断流动,使得将第一容器关闭并且从管线除去,并且将第二容器移动至准备好装载液体/固体混合物的位置。
向单个容器的内部器皿装载低温液体/固体混合物通常耗时不大于1分钟,并且可能耗时低至10-20秒。
气体储存容器通常允许在环境温度下保持至少允许混合物变为气态和使气体扩散以提供均匀共混的气体混合物的足够时间。就此而论,气体储存容器可允许保持约12小时至高达1周,以确保完全扩散。通过水平卧放容器(例如,气瓶)或通过移动容器(例如,通过滚动),可增强或促进扩散。
根据本发明的第二方面,提供了包含液体氩、液体氧和固体二氧化碳的液体/固体混合物。液体/固体混合物优选包含约80-约90重量%液体氩;大于0重量%,例如,约0.1重量%-约5重量%液体氧;和约5-20重量%固体二氧化碳。优选的液体/固体混合物基本上由这些比例的液体氩、液体氧和固体二氧化碳组成。
通过仅为示例的方式,并且参考附图,以下描述本发明的目前优选的实施方案。关于附图:
图1为本发明的气体储存容器的一个实施方案的示意性横截面图示;和
图2为曲线图,描述(i) 对于具有装载由液体氩和固体二氧化碳形成的低温浆料的内部袋的储气瓶,随着时间的加速压力,和(ii) 在气瓶上在不同的点处,随着时间的温度变化。
关于图1,储气瓶2具有限定用于容纳在压力下的气体的内部空间6的外部器皿4。外部器皿4由钢制成,并且具有开口8用于接受流体流动控制单元10,后者用于控制流体流入和流出气瓶2。流体流动控制单元10具有带压力帽14的填充入口12和具有控制阀18的消费者出口16,填充入口12适于向气瓶中填充液化的第一气体和固化的第二气体的液体/固体混合物。流体流动控制单元10还具有减压阀20。
由铝制成的内部器皿22完全提供在内部空间6的下半部内。内部器皿22限定内部空间的一部分24,用于容纳低温流体26,关于外部器皿为间隔关系。支撑物28在内部器皿22和外部器皿4之间提供该间隔关系。内部器皿22具有口30,用于经由由铝制成的导管32或浸渍管从流体流动控制单元10接受液体/固体混合物。导管32的末端34延伸到内部器皿22的口30之下,从而确保来自导管32的喷雾被内部器皿22捕捉。导管32的末端34通常不延伸到内部器皿22的口30之下、致使在内部器皿22已装载混合物之后,该末端将在液体/固体混合物26的表面之下的程度。
口30对内部空间6的其余部分敞开,从而在内部器皿22和内部空间6的其余部分之间提供流体流动连通。
通过除去压力帽14和沿着导管32向下进料液体/固体混合物到内部器皿22中来填充气瓶2。在消费者出口16上的控制阀18可敞开,以允许置换的气体从气瓶2泄出。
基于气瓶中气体的目标压力(和因此,气瓶的体积、液化的第一气体和固化的第二气体和气体混合物的密度),预先确定待进料至气瓶2的液体/固体混合物的量(例如,体积或质量),并且计量进入气瓶的进料以确保加入正确量的低温流体。一旦所需量的液体/固体混合物已加入到气瓶2中,使用压力帽14将入口12封闭,并且将消费者出口16中的控制阀18关闭。随后通过蒸发和适当时通过升华,使得混合物变为气态,从而使用气体填充气瓶2至期望的压力。
实施例
具有大(40 mm)颈的23.5 L钢储气瓶配备具有低温流体填充孔和管的流体流动控制单元、消费者阀和安全泄压阀。Mylar™袋与液体填充管连接,并且提供在气瓶内。所得到的气瓶和内部构件与在US3,645,291中描述的类型类似。
通过将液体二氧化碳从喷嘴喷在液体氩的通气槽(vented tank)的表面上,制备97重量%液体氩/7重量%固体二氧化碳的浆料。在已加入足够的二氧化碳之后,检查所得到的浆料的自由流动特性和颜色。获得不透明的白色水样液体。
在填充前,系统使用LIN预先冷却。在预先冷却后,将约4.2升(总计6升,其中由于回吹和喷溅等,损失1.8升)的混合物通过在共轴喷嘴中的中心管倒入填充管和袋。当倾倒混合物时,消费者阀打开,并且随后在已倒入混合物后,将消费者阀和液体填充孔二者关闭。随后将气瓶的压力和温度随着时间求对数。在若干天内,每隔几小时测量二氧化碳含量,直至其返回至7%的平衡值。
图2中的曲线图描述当LAr/CO2浆料变为气态时,气瓶内观察到的压力如何随着时间而提高。在第一个30秒期间,主要由于LAr从浆料蒸发,气瓶内的压力快速提高。约30秒后,基本上所有的LAr已蒸发。在液体氩已蒸发后,由于剩下的固体CO2从浆料升华,压力继续提高(虽然以较低速率)。
图2中的曲线图还说明,在填充过程期间的任何点,在气瓶的最冷点(中间)处温度不下降低于-20℃。这些结果说明气瓶的外部器皿可由往往不太耐低温温度的材料(例如钢)制成。
本发明人预期,如果将混合物装载至在气瓶的基底中的内部罐,回吹和喷溅等导致的混合物的损失将显著降低。
本发明的优选的实施方案的优点包括:
• 当与直接压缩过程相比时,用气体混合物更容易和更快速填充气体储存容器;
• 当与直接压缩过程相比时,更加能量有效地填充气体储存容器;
• 当与直接液体注射过程相比时,更加可靠和更加安全地填充气体储存器皿;和
• 在气体储存容器填充期间,液化的气体较少损耗。
应认识到,本发明不应局限于以上参考优选的实施方案描述的细节,而是在不偏离如所附权利要求限定的本发明的精神或范围的情况下,可以进行众多修改和变化。
Claims (12)
1. 用在压力下的至少第一气体和第二气体的气态混合物填充气体储存容器的方法,所述方法包括:
用包含液化的第一气体和固化的第二气体的液体/固体混合物装载气体储存容器;
将所述气体储存容器对气体进入或离开容器的通道关闭;和
允许所述液化的第一气体和所述固化的第二气体在所述关闭的气体储存容器内变为气态。
2. 权利要求1的方法,其中所述第一气体选自:氮(N2);氩(Ar);氧(O2);氦;氖;氪;甲烷;和它们的混合物。
3. 权利要求1或权利要求2的方法,其中所述第二气体选自二氧化碳(CO2)和氧化亚氮(N2O)。
4. 前述权利要求中任一项的方法,其中所述混合物包含约40重量%-约99重量%液体组分和约1重量%-约60重量%固体组分。
5. 前述权利要求中任一项的方法,其中所述液体/固体混合物包含液化的第三气体。
6. 权利要求5的方法,其中所述液化的第三气体与所述液化的第一气体可混溶。
7. 前述权利要求中任一项的方法,其中所述气态混合物为焊接气体。
8. 前述权利要求中任一项的方法,其中所述液化的第一气体为液体氩,所述固化的第二气体为固体二氧化碳。
9. 权利要求8的方法,其中所述液体/固体混合物包含液体氧。
10. 权利要求8或权利要求9的方法,其中所述液体/固体混合物包含:
约80-约90重量%液体氩;
0-约5重量%液体氧;和
约5-约20重量%固体二氧化碳。
11. 一种液体/固体混合物,所述液体/固体混合物包含液体氩、液体氧和固体二氧化碳。
12. 权利要求11的液体/固体混合物,所述液体/固体混合物包含:
约80-约90重量%液体氩;
至多约5重量%液体氧;和
约5-20重量%固体二氧化碳。
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KR20130094348A (ko) | 2013-08-23 |
WO2012080172A3 (en) | 2012-08-09 |
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Application publication date: 20130821 |