CN106999834B - 用于可逆吸附二氧化碳的方法和装置 - Google Patents
用于可逆吸附二氧化碳的方法和装置 Download PDFInfo
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- CN106999834B CN106999834B CN201480081844.1A CN201480081844A CN106999834B CN 106999834 B CN106999834 B CN 106999834B CN 201480081844 A CN201480081844 A CN 201480081844A CN 106999834 B CN106999834 B CN 106999834B
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- carbon dioxide
- adsorbent
- released
- cartridge
- gas mixture
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Classifications
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Abstract
本发明涉及用于从气体混合物中可逆吸附二氧化碳的装置,所述装置包括至少一个吸附剂容器,所述至少一个吸附剂容器包括惰性且尺寸上稳定的材料的一个或多个透气的盒容器,并且每个盒包含具有伯氨基官能度的合适的聚合的特定吸附剂;涉及包括该装置的设备,并且涉及用于使二氧化碳吸附和脱附的方法。
Description
发明领域
本发明涉及用于从气体混合物中可逆吸附二氧化碳的方法和装置。
本发明涉及再生***,所述再生***包含吸附剂,所述吸附剂用于从气流(gasstream)(包括周围空气)可逆地捕获二氧化碳。
用于使二氧化碳吸附和脱附的当前应用的工艺集中于具有较高浓度二氧化碳的气流,例如来自工业和能量产生工艺比如例如整体煤气化联合循环(integratedgasification combined cycle)(IGCC)工艺的烟道气体。这里,通常使用流体组分,所述流体组分与气体混合物接触,并且是能量密集的,和/或通过相当高的二氧化碳浓度来驱动。通常,这些工艺还从烟道气体中除去其他气态组分,例如氮气和硫的氧化物(sulphuricoxide)。如此获得的二氧化碳可以被分离出并且通常然后被加压用于储存和使用;然而其通常包含难以分离出的杂质。
在具有官能化表面的固体吸附剂材料被用于二氧化碳吸附的情况下,其通常被包含在封闭的***例如烟道堆(flue stack)中。在用于受限空间(confined space)例如办公室、潜水艇和航天器的空气再循环***的情况下,材料被保持呈填充床形式并且用加压气体来供给。
可选择地,瓶装二氧化碳(bottled carbon dioxide)可购自通常使用大规模低温恒温空气液化工艺(large scale cryostatic air liquefaction process),通过分离空气生产瓶装气体的公司。再次,产品通常包括通常具有高质量的、浓缩的固体和瓶装液体二氧化碳。然而,液化工艺消耗大量的能量,附加的是到合适的使用者的运输成本和用于储存和运输的能量使用。
相反地,二氧化碳的主要用途是在温室中产生植物,并且渐增地,还用于在光生物反应器(photo-bioreactor)中产生微藻,用于燃料和衍生自其的产品。
然而,上文描述的二氧化碳生产工艺通常位于远离可能的应用的区域的工业区域,这增加用于运输瓶装二氧化碳的成本,或要求为昂贵的且难以维护的管道的安装。
同时,已知温室所有者常常燃烧天然气或甚至煤并且使用烟道气体混合物以增加植物在温室中的生长,因为用于此的成本低于用于瓶装二氧化碳的成本,尽管有负面环境影响。此外,烟道气体混合物的组分可能非常大地负面地影响植物生长。
因此,对于可以效率高地且在低能耗下产生包含比周围空气更高浓度的二氧化碳的气体混合物,优选地还不包含有害组分的工艺仍然存在需求。
最近,使用固体胺吸附以捕获大气二氧化碳的工艺已经被报告。例如,WO-A-2010/091831公开了包括纤维丝(fibre filament)的结构,其中纤维材料是碳和/或聚丙烯腈,并且该结构包含具有能够可逆吸附和脱附循环用于从气体混合物中捕获CO2的、具有氨基的吸附剂。
WO-A-2007/016271和WO-A-2008/131132公开了用于从气流中除去二氧化碳的方法,所述方法包括将气流设置成与置于辊列室(roll-geometry chamber)或串联地连接的多个辊列室中的叔胺或季铵官能化的树脂接触,用水润湿树脂,收集来自树脂的水蒸气和二氧化碳,以及使二氧化碳与水蒸气分离。
US20110296872公开了用于从气流中除去二氧化碳的工艺,所述工艺包括使气流与包含作为吸附剂的固定化的铵官能化的无机材料的固体无机吸附剂基质接触,以及随后释放二氧化碳。所公开的工艺具有通过吸附剂基质实现合适的吸附和流速、同时还必须移动基质以释放二氧化碳的问题。
WO00/02643公开了用于从封闭的或半封闭的航天器或潜水艇舱除去二氧化碳的工艺,所述工艺使用用于从封闭的或半封闭的空间、航天器或潜水艇舱除去二氧化碳的、具有苄胺基团的离子交换树脂的珠的一个或更多个平行的床;借此再生可以仅仅在进入外部空气之后发生,而没有释放的二氧化碳的毒性的问题。
本申请人现在已经发现提供具有增大的二氧化碳水平的气体混合物的工艺和用于执行该工艺的装置,所述工艺允许在较高的二氧化碳收率下并且在明显地较低的能量使用下操作。
主题工艺和装置允许在比其他已知的空气捕获工艺低的财务支出下,产生具有增大的二氧化碳水平的气体混合物,而不需要使用高度加压的设备和/或低温恒温装置。其还具有较低的体积要求、较高的稳定性;不产生可察觉的气味,例如通常当季铵将被使用时的情况,并且提供相对于重量的至少相等的或较高的CO2捕获性能,并且比使用固体或液体吸附剂的当前工艺更实用。
发明概述
因此,在第一方面中,本发明涉及用于从气体混合物中可逆吸附二氧化碳的装置,所述装置包括至少一个吸附剂容器,其包括惰性且尺寸上稳定的材料的一个或多个透气的盒容器(gas permeable cartridge vessel),每个盒包含具有以至少2.0当量/l的总容量的伯氨基官能度、在从25m2/g至75m2/g的范围内的表面积(BET)和0.01mm至0.25mm的平均孔径的合适的聚合的特定吸附剂,并且所述装置还包括通过压力、湿度和/或温度吸附改变使吸附的二氧化碳脱附的工具,和用于引导来自吸附剂盒的脱附的气体混合物的工具。
在第二方面中,本主题发明涉及一种用于增强植物生长的设备,所述设备包括上述装置,并且还包括用于分布脱附的二氧化碳的工具,例如气体导管(gas duct)和/或分布器(sparger)。
本文,术语“分布器”可以是用于分布气体的任何合适的工具,包括用于水产用途的陶瓷扩散器或金属扩散器。
在又一另外的方面中,本发明涉及用于通过压力、温度和/或湿度改变吸附-脱附过程(swing adsorption-desorption process)从气体混合物中分离二氧化碳的工艺,所述工艺包括以下步骤:(a)在包括惰性且尺寸上稳定的材料的多个透气的盒容器的吸附剂容器中,并且在压力P1、湿度H1和温度T1下,使气体混合物与至少一种具有以至少2.0当量/l的总容量的伯氨基官能度、在从25m2/g至75m2/g的范围内的表面积(BET)和0.01mm至0.25mm的平均孔径的聚合的特定吸附剂接触,直到期望的量的二氧化碳被吸附到吸附剂上,以及
(b)在总压力P2和/或温度T2下、和/或在湿度水平H2下,使在步骤(a)中吸附的二氧化碳的至少一部分脱附,以产生富含二氧化碳的流,在所述温度和/或压力下,二氧化碳具有相对于吸附剂的较低的吸附常数,并且因此至少部分地脱附。
附图简述
这些特征和另外的特征可以从说明书和附图获得,并且单个的特征可以单独地且以子组合的形式在本发明的实施方案和其他领域中被认识到,并且可以代表有利的、独立地可保护的构造,该构造据此被要求保护。本发明的实施方案关于附图在下文中更详细地被描述,在附图中:
图1公开了上文描述的工艺的示意图,其包括三个主要部件:盒、安置盒的可密封外壳体积以及工艺有关的能量和流体流动。
图2公开了吸附剂堆(adsorbent stack)的表示,包括关于周围大气CO2捕获而优化的优选的盒厚度和盒间距。
图3示出优选的设备的示意图。
图4示出CO2随时间的脱附。
图5示出在1cm和5cm厚的盒中、在周围条件(22℃,380ppm CO2,45%湿度)下,以吸附剂的%wt.计的质量增加。
图6和图7示意地示出用于水族箱的优选的设备,其具有用于再生的单个盒和电加热。
图8示出与水族箱一起使用的管线(line up)。
附图标记在表1中被整理:
表1附图标记
发明详述
本发明涉及从气体混合物优选地周围空气中的二氧化碳捕获,其可以为当前和未来的二氧化碳的使用者提供具有可持续的、现场的二氧化碳的源,这提供较强的供应可靠性和地域灵活性(location flexibility)。该技术可以有利地被用于增强在例如用于食品或能量植物(energy plant)、或装饰性目的例如花的温室中的植物生长;用于通过微藻的生物燃料或保健品生产(neutraceutical production),以及用于其它应用例如用于饮料工业中,用于在二氧化碳下的储存,用于医疗应用等等。
主题工艺和装置特别地适于通过温室环境的二氧化碳富集的施肥(fertilization),其中该工艺可以增加作物收率并且因此增加收入多达40%。
根据本发明的二氧化碳工艺当用于温室和其他应用时相对于传统的二氧化碳源的另外的优点包括CO2供应的较强的可靠性;由于不必考虑固定的CO2源的较大的温室地域灵活性;没有对植物生长不利的污染物的CO2混合物;给予温室经营者的对于CO2的更多的控制;以及使用可持续的空气捕获的CO2作为市场工具以提高温室作物的销售的可能性。
本发明的特别有用的应用涉及用于将二氧化碳供应至生态箱(vivarium)例如生物育养箱(terrarium)和水族箱的方法和装备(apparatus)。更特别地,其涉及增大水族箱中二氧化碳浓度以促进光合作用和植物生长的二氧化碳产生和递送装备以及有关方法。
熟知的是,在光合作用期间,植物从周围介质吸收二氧化碳并且利用太阳能将其转化成简单的碳水化合物,同时释放氧气。
此过程对于植物的存活和生长是必不可少的。光合作用的速率除了其他因素还受二氧化碳在周围介质中的可用性影响。较高的二氧化碳浓度将导致增大的光合作用速率,而低二氧化碳浓度将严重地减慢光合作用速率。
水生植物需要在周围水中溶解的二氧化碳以使它们能够生长。二氧化碳在水中的浓度部分地受与二氧化碳供应部(carbon dioxide supply)(例如大气)接触的水的表面积和二氧化碳可以溶解在其中的水的体积所限制。相同的逻辑适用于需要特定环境条件的其他类型的封闭的生态箱,例如被封闭以保持生态***为活的容器。本文术语“生态箱”涉及基本上填充有水用于保持活的鱼和其他水生需氧动物的罐、池或另外的容器,包括储存罐;并且涉及生物育养箱,即,用于保持并且饲养活的动物和植物并且在天然条件下观察它们的围隔(enclosure)。实例包括用于例如热带植物例如兰科植物(orchids)或蕨类植物(ferns)的封闭的微型花园,借此这些通常是在封闭的太阳光可透过的环境中,允许水蒸气气流的渗透,从而产生自我维持的生态***(self-sustained ecosystem)。
海洋、河流或湖泊对于很少光合作用的生物体具有相对大的表面积和体积,水族箱通常仅提供相对小的表面积,另外通常包含高比例的植物物质。这使在水中的相对高浓度二氧化碳成为必需以使植物能够茁壮成长。此外,水生生物体的维护常常需要特定的环境条件,包括重要的参数例如水温、pH、盐的存在以及溶解的气体的量,该溶解的气体包括氧气和一氧化碳和二氧化碳。
对于某些水生生命形式的生长和增殖的可能性还可能要求除了合适的营养物的存在之外,对于自然栖息地特定的植物群和动物群的存在。因此,还由于光合作用的氧气产生,存在促进水族箱中的某些植物物种生长的一般趋势,因此产生对于水生需氧生物体以及对于审美原因的更好的环境。通常,水族箱水的二氧化碳浓度被保持在高水平,以便促进植物生长,并且从而还帮助保持溶解氧气浓度。当前使用的***趋向利用来自压缩气罐的压缩的二氧化碳。此解决方案要求高压减压阀(high-pressure reducing valve)和高压管(high-pressure tubing),这对于普通水族箱所有者是不现实的,由于高资本支出和高维护成本,以及空的气瓶的定期更换。对于此类***的可选方案使用由从例如糖通过酵母菌的发酵以产生CO2而释放的二氧化碳,然后产生的CO2被引入到水族箱中。
本发明涉及用于提供大气二氧化碳至生态箱并且特别地水族箱的装置,所述装置不需要使用压缩气体或受限的二氧化碳产生物质。
因此,本发明的目的还是提供能够产生二氧化碳并且使二氧化碳安全地溶解到水族箱中,同时避免当前使用的***的问题的***。
此外,本发明的目的是提供能够将二氧化碳可控地选择性地引入到水族箱水中的***。
因此,本发明涉及包含用于从包括周围空气的气流可逆地捕获二氧化碳的吸附剂的、用于水族箱的再生性二氧化碳产生和递送装备,该装备包括能够产生富含二氧化碳的气流的吸附/脱附装置、能够将二氧化碳或空气引入到水族箱中的分布工具,二氧化碳通过该分布工具被递送到水族箱中。
因此,本发明涉及用于使来自气流的二氧化碳吸附在适于二氧化碳的再生性吸附的吸附剂上的装置,所述装置还包括用于使二氧化碳脱附并且将脱附的二氧化碳随后供应至水族箱的工具,包括用于将富含二氧化碳的气流供应至水族箱以形成至少部分地溶解的二氧化碳的工具。
优选地,使吸附剂再生可以通过加热、更优选地通过电加热饱和的吸附剂来进行。
本发明利用可逆的吸附和脱附过程,其中吸附剂组合物可以被再生,即吸附的二氧化碳可以通过例如温度、湿度和/或压力改变再次被释放。
根据所需的环境可以使用不同的吸附剂。对于将二氧化碳供应至例如水族箱,吸附剂可以是允许在如使用的温和的条件下再生性吸附和脱附的任何合适的吸附剂。典型的吸附剂是固体,通常具有胺官能度,例如具有充分地高的每体积的表面积的无机的或有机的聚合组分,例如沸石、氧化铝、二氧化硅、硅铝(silica alumina),和有机聚合物例如轻质且多孔的珠或膜。
实例包括沸石,其也被称为分子筛;基于陶瓷的材料例如氧化铝、氧化铝-二氧化硅;二氧化钛;活性炭,其全部可以被合适的胺例如二乙醇胺(DEA)或聚乙烯亚胺(PEI)改性;或基于二乙烯基苯的材料或乙二胺改性的硅胶。
虽然无机材料通常在高物理强度上见长,但是改性和再生条件需要高温和高压,由于例如高热容,这使得它们对于家庭使用或在温和条件下的应用常常是不合意的。
可以使用活性炭,例如DEA嵌入的活性炭(DEA embedded activated carbon);然而,发现的是,该化合物对于长期使用不是充分地稳定的,因为其在室内条件下在两个月后示出降解。
本发明工艺优选地利用具有伯氨基官能度例如苄胺的特定的吸附剂,因为发现这是最有效的,且高度稳定的。此类材料具有作为呈珠形式的离子交换树脂的广泛的用途。典型的用途是在废物处理和水纯化中。树脂可以以珠或膜的形式被产生,后者包括具有特定粒度分布的珠,取决于制造工艺。
聚合珠可以被官能化以充当用于某些分子的离子交换剂或吸收剂/吸附剂。通常,它们被保持在封闭的***中的填充床(pack bed)配置中,并且被用作过滤介质。在完成其纯化/捕获任务之后,它们常常通过用溶液洗涤或通过应用加热来再生。
本申请人发现,用于本发明工艺和装置的特别地合适的吸附剂是具有以至少2.0当量/l的总容量的伯氨基官能度、在从25m2/g至75m2/g的范围内的表面积(BET)和1nm至200nm、更优选地从5nm至150nm的平均孔径的聚合的特定吸附剂。
表面积可以优选地根据Brunauer-Emmett-Teller(BET)表面积确定-测试法-BS4359-1:1996(ISO 9277:1)来确定。总容量和其他性质可以优选地根据测试法ASTM D2187-94来确定。
特别地优选的吸附剂是被伯胺苄胺官能化的并且负载在与二乙烯基苯交联的多孔聚酯结构上的游离碱胺珠(free base amine bead)。吸附剂优选地是呈球形珠的形式,其被苄胺基团官能化。因此,聚合基质包含交联的聚苯乙烯。其优选地具有以总容量表示的至少2当量/l、更优选地至少2.1当量/l并且还更优选地至少2.2当量/l的活性。其优选地具有至多1.9、更优选地至多1.8的均匀系数。
对于存在的颗粒的至少85%,珠优选地具有在从0.25mm至1.5mm、更优选地0.3mm至1.3mm的范围内的尺寸。吸附剂优选地具有600g/l至720g/l的体积密度(bulk density),变化为+/-5%。
水保留率(water retention rate)优选地在从60wt.%至75wt.%的范围内、更优选地在从65wt.%至70wt.%的范围内。
吸附剂表面积(BET)优选地在从30m2/g至65m2/g、更优选地40m2/g至60m2/g并且最优选地45m2/g至55m2/g的范围内。
孔体积优选地在从0.2cm3/gm至0.4cm3/gm的范围内。吸附剂优选地具有25nm的平均孔径。
吸附剂被置于一个或更多个包含介质的部件中,该部件在本文还被称为盒(cartridge)。吸附剂优选地呈松散配置,即不呈填充床配置,以允许气体混合物通过吸附剂循环,而不需要使供给的气体混合物明显地加压。
盒还包括具有在从0.01mm至0.25mm的范围内的平均孔径的透气膜或分隔物(division),以允许气体混合物充分进入吸附剂颗粒,同时保持吸附剂颗粒在合适的位置。盒还可以包括保持吸附剂在合适的位置的另外的工具,例如它们可以是呈阶梯式包(stepped bag)的形状,或保持波浪形结构,条件是它们不负面地影响气体混合物通过吸附剂颗粒或珠的扩散。
吸附剂还可以以不同的方式被使用,例如其可以以珠的形式出现,而且还有其他形状例如圆柱体、片、固体块(solid block)可以是有用的,条件是它们提供如所需的表面积和活性。块可以例如通过包括注射成型的工艺来制备。
优选地,独立于所选择的实际形状,盒在气体混合物的流动的方向上具有在从5mm至50mm的范围内的厚度,并且以足以允许使在其之间的大气二氧化碳充分扩散的距离间隔开。
本申请人发现,盒的厚度与吸附速度有关,并且在很大程度上独立于各种低气体流动速度。更高的厚度不再允许具有对于工业过程有用的吸附/脱附循环,如果在周围条件下工作,所述吸附/脱附循环优选地在从2小时至24小时的范围内。
实际气体流速优选地在从0.1m/s至15m/s的范围内、更优选地在从0.5m/s至5m/s的范围内。盒的实际形状和厚度可以根据期望的吸附-脱附再生循环来调整,所述吸附-脱附再生循环优选地在从2小时至24小时的范围内。
优选地,盒相对于气体混合物的方向被相继地放置。
根据本发明的装置优选地还包括用于将气体混合物应用至盒的工具。该装置有利地允许使用低级热源、更优选地可再生的或可持续的热源(sustainable heat source),例如地热能、太阳能或工业废热,用于脱附。
热可以经由热交换器或甚至通过在合适情况下的直接或间接的太阳辐照被应用至装置。在再生期间,即,脱附过程期间,合适的构造如可逆阀或密封装置与周围空气流动的其他工具可以被应用以便捕获释放的二氧化碳。
脱附过程优选地通过流体例如气流例如使吸附剂清洁的空气、水蒸气或水,优选地在大气压或减压下来进行。此流体流还可以被用于在进入结构之前和之后,加热用于脱附过程的***。
本发明装置和工艺特别地适于产生更确切地说是(rather)包含1%至99.99%的二氧化碳的富含二氧化碳的气流,例如空气,1%至99.99%的二氧化碳例如在以较高二氧化碳浓度对其植物施肥的温室经营者所要求的范围内。
优选地,根据本发明的装置还包括用于通过压力、湿度和/或温度吸附改变使吸附的二氧化碳脱附的工具,以及用于引导来自吸附剂盒的脱附的气体混合物的工具。
装置和工艺优选地在从0.05-1.5巴、更优选地从0.1-1.3巴的范围内的压力下操作。
装置和工艺优选地在从-20℃至150℃、优选地在从0℃至120℃的范围内、还更优选地从10℃至100℃的温度下操作。
优选地,根据本发明的装置还包括用于使热和/或流体、和脱附的气体混合物恢复的工具。优选地,根据本发明的装置还包括用于测量二氧化碳吸附水平和/或气体流速的工具。
优选地,根据本发明的装置包括用于使吸附剂与温热流体接触用于诱导二氧化碳的脱附的工具。
优选地,根据本发明的装置还包括使盒经历减压、并且随后使盒与具有在从60℃至100℃的范围内的温度的水接触的设备,以及用于从释放的二氧化碳中分离水或水蒸气用于再循环至设备的工具。
优选地,在根据本发明的装置中,一个或更多个盒被相继地布置和/或是平行的,使得一个或更多个盒能够在不必须使吸附过程停止的情况下被移除用于替换和/或维修任一个盒。
本发明还涉及设备,所述设备还包括用于高等植物的温室,或用于微藻生长的光生物反应器(photo bioreactor)。
该设备优选地包括低级能量供应工具,优选地可再生热源,如上文所陈述的。
在根据本发明的工艺中,步骤(b)包括使盒与流体在从60℃至100℃的范围内的温度下和任选地在减压下接触。优选地,流体是水或空气。
可选择地,步骤(b)包括在盒中直接加热吸附剂材料。这可以有利地通过具有在盒中存在的加热工具,例如通过电阻或感应是可电加热的金属线或箔来进行。优选地,这些由对于吸附剂材料和形成的二氧化碳是惰性的合适的材料制成。此类材料的实例包括钯线、铂线、镍线、钴线、铬线、和/或铁线或其合金例如Ni/Chr。
合适的释放所需的温度取决于待被使用的材料,但通常应当不达到吸附剂借此开始释放胺或开始逆聚合(retropolymerisation)的温度。相比于加热到高于150℃的温度,应用的较低的温度,例如将吸附剂加热到从60℃至80℃的温度,将允许更多的循环,而没有吸附剂失活或分解。
该工艺优选地包括使步骤(a)和(b)以在2分钟和2天之间、更优选地在30分钟和24小时之间的模式交替。优选地,对于步骤(b),气体混合物的流动被逆转,温度升高。在期望恒定流动的情况下,这可以有利地通过使用缓冲器来实现,借此释放到最终应用中的二氧化碳量可以被保持恒定,或通过使用多于一个并联的盒、然而不同的循环阶段来实现。
对于水生应用例如水族箱,本发明具有以下的益处:释放的并且因此在水族箱中存在的二氧化碳的量可以通过在再生条件之后例如在加热之后从吸附剂中除去的空气的量来容易地调节。这允许许多高度有关的条件在水族箱的体积中通过简单的流动和温度控制来实现,并且因此使得主题工艺和装备对于此应用是特别有价值的。
因此,本发明还涉及所述装备和工艺用于控制给定的水相环境的pH的用途。通过以预定的流速和量简单添加二氧化碳来控制pH允许例如控制鱼塘和鱼类设施(fishinstallation)例如比如养鱼场和锦鲤池塘的水质量,借此保障鱼、虾或锦鲤的质量。锦鲤(鲤鱼属(Cyprinus carpio))趋向由于太高或太低pH而受污染,这对于其价值是不利的,而对于鱼幼体或鱼发育的后期,养鱼场需要不同的、然而受控制的条件。
另外的用途是提供二氧化碳用于在咸水池塘中形成碳酸钙,例如用于菌落形成(colony forming)水生生命形式,例如珊瑚,或用于形成硅藻微藻的外骨骼。
控制水的pH还可以被用于控制在封闭体系中的水质量,所述封闭体系例如在大型海洋船舶例如游轮或***上的饮用水或使用水管道。当前,这些通常使用需要以定期被交换的高压二氧化碳罐,用于控制船舶管道中的水。
该工艺优选地包括步骤(c),将包含脱附的二氧化碳的释放的气态流引导至期望的应用,所述期望的应用包括温室、(微)藻光温育器((micro)algae photo incubator)、饮料厂和/或储存设施。
该***可以有利地还包括储存缓冲器。优选地,储存缓冲器包括储存如用于特定应用的从0.1日CO2至2日CO2用量所要求的、富含二氧化碳的气体混合物的量。缓冲器可以以压缩形式、或通过利用固体储存结构例如活性炭或金属有机框架(metal organicframework)来保持CO2气体。
本发明还涉及主题装置、设备和工艺用于空气调节/通风应用的用途,借此二氧化碳可以从受限空间例如建筑物、办公室、宾馆客房、学校、飞机、潜水艇、高速列车以及类似物中被除去,无论具有或不具有加压舱。
此外,本发明涉及用于其中当前使用压缩气体的实验室/科学仪器和/或医疗设施的二氧化碳供应部。
实验部分
以下非限制性实施例例证本发明的有用性。
实施例1:吸附测试
使圆盒(round cartridge)松散地填充有吸附剂材料,将该吸附剂材料以1cm的厚度保持在两层筛网之间的容器中。吸附剂材料是伯氨基官能的离子交换树脂(具有以至少2.0当量/l的总容量的伯氨基官能度、在从25m2/g至75m2/g的范围内的表面积(BET)和5nm至150nm的平均孔径的基于二乙烯基苯的聚合的特定吸附剂)并且被保持在放置于不透气的可密封的容器中的两层适当有孔的金属筛网之间。将容器连接到真空泵和测量出来气流的二氧化碳传感器。在整个测试中,温度和湿度以及二氧化碳浓度通过合适的传感器来测量。
通过打开容器使吸附剂暴露,这允许CO2自然扩散到材料中。然后,将其加热到60℃至100℃。
在此工艺期间,吸附的CO2被释放并且在容器内的产生的富含CO2的气体被泵送通过流量计和CO2传感器。来自这些组分的组合测量结果使能够直接测量在暴露时间段内被材料吸附的CO2的量(见图4,示出在1.0l/min的连续流速下随时间的脱附)。
表2公开了二氧化碳的吸附,其中吸附水平作为[吸附的CO2质量]/[吸附剂材料干质量]的百分数被给出。
表2:CO2吸附
暴露时间段[小时] | 捕获的CO<sub>2</sub>[吸附的CO<sub>2</sub>质量]/[吸附剂材料干质量] |
5 | 0.46 |
5 | 0.41 |
5 | 0.44 |
>24 | 3.35 |
然后封闭容器,并且将吸附的气体经由应用真空来除去,同时测量二氧化碳浓度。
结果概述
如所描述的,材料盒可以以确定的厚度被暴露于周围空气,这在捕获工艺中取消了使用加压气体的需要。该测试证明通过使用使材料以10mm的厚度暴露的专用的设置,CO2在此配置中的充分的吸附。
实施例2:周围吸附测试
两个矩形盒具有10cm×20cm的长度×宽度的尺寸,并且吸附剂床厚度对于盒1为1cm,且对于盒2为5cm(长度×宽度×高度)。使包括不锈钢筛网的盒松散地填充有伯氨基官能的离子交换树脂,即基于二乙烯基苯的聚合的特定吸附剂,该基于二乙烯基苯的聚合的特定吸附剂具有以至少2.0当量/l的总容量的伯氨基官能度、在从25m2/g至75m2/g的范围内的表面积(BET)和从5nm至150nm的平均孔径。将测试盒放置于真空烘箱中,用氮气清洁(MSL)以除去所有吸附的二氧化碳。然后,将盒从真空烘箱中取出,并且放在天平上,从而暴露于周围空气。测量随时间的重量增加,并且校正湿度。通过Mettler Toledo质量天平/4kg范围(MSL),Sartorius BP310S质量天平/310g范围(MSL)测量二氧化碳吸附。
结果指示,在给定的风速下,盒1示出允许用于工业工艺的足够迅速的吸附/脱附速率的足够高的吸附速率,而在盒2中的另外的吸附剂未允许增大在此循环中可以被吸附和脱附的二氧化碳的量,如在图5中所图示的。
实施例3:电加热的再生设备
在负载有吸附剂材料之前的、具有100cm3的体积的、根据实施例2的盒中,将40cm长度的如通常在作为加热工具的吹风机中使用的镍铬线(Nichrome wire)以允许通过直接传热到与线直接接触的吸附剂来加热盒的内容物的整体的方式嵌入(见图6)。然后,使盒负载有吸附剂。将小于15W的电力应用至线允许在小于20分钟内将整个盒加热到超过80℃。
线可以以不同的方式被配置成,基于盒的形状,即在圆柱形体积的情况下螺旋形地,使加热效率最小化。
实施例4:包括计时器、流量控制和互联网连接的水族箱CO2空气捕获设备(图6和图7):
准备包括实施例3的盒的装置。允许盒在大气条件下与周围空气接触。为了使释放的二氧化碳循环,使用小型泵。
装置通过间歇地加热已经暴露于其中放置水族箱的室内空气的吸附剂盒,全部依赖于二氧化碳的自然扩散而操作。对于较大的应用,这还可以包括用于空气流动的工具,例如风扇,以通过增加在相同时间段内吸附剂暴露于的二氧化碳的总量来加速吸附过程。
在吸附时间段之后,然后使用包括起动器的密封机构使盒外壳密封,然后加热直到80℃,同时使用微泵将释放的二氧化碳通过陶瓷分布器/扩散器抽出到水族箱中。选择泵以供应通过分布器确保均匀气体分布所需的略微超压(overpressure),即,用于气体通过的在0.5巴和2.5巴之间的超压。
泵在缓慢的连续的速率下或在定期的间歇下的较快速率下工作,以便避免在水中的CO2浓度的明显的波动,以避免水族箱的活的居住者即鱼/虾/蜗牛等等的压力。
可选择地,可以使用用于CO2的储存缓冲器,CO2逐渐地从该缓冲器中释放。
该***的优点是,另外的功能性可以容易地被应用于CO2供应装置。例如,其将易于精确地调节CO2的流速,因为这可以被直接连接至泵,即不需要用压力调节器连续调节以获得正确的气泡计数。此外,计时器可以容易地集成,而不需要购买附接到调节器的另外的螺线管阀。这是重要的,因为仅当白炽光对于植物进行光合作用可用时需要CO2。该***还可以有利地远程连接,例如通过互联网,以允许远程监测和控制CO2供应、pH和其他值,而不需要替换气罐。
最后,该***完全避免否则可能伤害/杀死水族箱居住者的‘端浮箱(end-of-tank)’CO2倾卸的危险。
Claims (44)
1.一种用于从气体混合物中可逆吸附二氧化碳的装置,所述装置包括:
至少一个吸附剂容器,所述至少一个吸附剂容器包括惰性且尺寸上稳定的材料的一个或多个透气的盒容器,并且每个盒松散地填充有具有以至少2.0当量/L的总容量的伯氨基官能度、在从25m2/g至75m2/g的范围内的表面积(BET)和1nm至200nm的平均孔径的合适的聚合的特定吸附剂;每个盒中的所述吸附剂呈松散配置且不呈填充床配置,以允许所述气体混合物通过所述吸附剂循环,而不需要使所述气体混合物明显地加压;并且
所述装置还包括:
通过压力、湿度使吸附的二氧化碳脱附的工具,或用于变温吸附的工具,或上述两种工具;
用于引导来自所述吸附剂盒的脱附的气体混合物的工具;
用于将所述气体混合物供应至所述盒的工具,用于使热和/或流体、和脱附的气体混合物恢复的工具,用于测量二氧化碳吸附水平和/或气体流速的工具,和/或用于使所述吸附剂与温热流体接触用于诱导所述二氧化碳的脱附的工具;以及
使所述盒经历减压、并且随后使所述盒与具有在从60℃至100℃的范围内的温度的水接触的设备,以及用于从释放的二氧化碳中分离水或水蒸气用于再循环至设备的工具。
2.根据权利要求1所述的装置,其中所述盒容器包括具有在从0.01-0.25mm的范围内的平均孔径的透气膜。
3.根据前述权利要求中任一项所述的装置,其中所述盒的形状和厚度通过允许在2小时和24小时之间的吸附-脱附再生循环来确定。
4.根据权利要求1或2所述的装置,其中一个或多个盒被相继地布置和/或是平行的,使得一个或多个盒能够在不必须使所述吸附过程停止或不迫使拆卸捕获单元的情况下被移除用于替换和/或维修任一个盒。
5.根据权利要求3所述的装置,其中一个或多个盒被相继地布置和/或是平行的,使得一个或多个盒能够在不必须使所述吸附过程停止或不迫使拆卸捕获单元的情况下被移除用于替换和/或维修任一个盒。
6.根据权利要求1、2和5中任一项所述的装置,还包含储存缓冲器。
7.根据权利要求3所述的装置,还包含储存缓冲器。
8.根据权利要求4所述的装置,还包含储存缓冲器。
9.根据权利要求6所述的装置,其中所述储存缓冲器具有等于按照用于特定应用的从0.1日至2日CO2用量所要求的富含二氧化碳的气体混合物的量的储存体积。
10.根据权利要求7或8所述的装置,其中所述储存缓冲器具有等于按照用于特定应用的从0.1日至2日CO2用量所要求的富含二氧化碳的气体混合物的量的储存体积。
11.根据权利要求1所述的装置,其用于将富含二氧化碳的气流提供至水族箱,所述装置还包括用于使吸附的二氧化碳随后脱附以形成富含二氧化碳气流的工具和用于将所述富含二氧化碳的气流供应至水族箱以形成至少部分地溶解的二氧化碳的工具。
12.根据权利要求1、2、5、7-9和11中任一项所述的装置,包括用于电加热饱和的吸附剂的工具。
13.根据权利要求3所述的装置,包括用于电加热饱和的吸附剂的工具。
14.根据权利要求4所述的装置,包括用于电加热饱和的吸附剂的工具。
15.根据权利要求6所述的装置,包括用于电加热饱和的吸附剂的工具。
16.根据权利要求10所述的装置,包括用于电加热饱和的吸附剂的工具。
17.根据权利要求6所述的装置,其中所述储存缓冲器使所述二氧化碳保持呈压缩形式,或保持在包括活性炭和/或金属有机框架的固体储存结构中。
18.根据权利要求7-9和15-16中任一项所述的装置,其中所述储存缓冲器使所述二氧化碳保持呈压缩形式,或保持在包括活性炭和/或金属有机框架的固体储存结构中。
19.根据权利要求10所述的装置,其中所述储存缓冲器使所述二氧化碳保持呈压缩形式,或保持在包括活性炭和/或金属有机框架的固体储存结构中。
20.一种用于增强植物生长、饮料碳酸化、pH控制和/或易腐商品的储存的设备,所述设备包括根据前述权利要求中任一项的装置,并且还包括用于分布脱附的二氧化碳的工具。
21.根据权利要求20所述的设备,其中所述用于分布脱附的二氧化碳的工具包括气体导管、泵和/或分布器。
22.根据权利要求20或21所述的设备,还包括用于提高植物生长的温室、生态箱、水族箱或用于微藻生长的光生物反应器。
23.根据权利要求22所述的设备,其中低级能量供应工具通过电加热来提供,用于加热在盒中的所述吸附剂,通过与加热工具直接接触将所述吸附剂加热到从60℃至150℃的温度。
24.一种用于增强水族箱中植物生长的设备,所述设备包括根据权利要求1至19中任一项的装置或根据权利要求20至23中任一项的设备,并且还包括用于分布脱附的二氧化碳的工具。
25.一种用于通过温度和/或湿度改变吸附-脱附过程从气体混合物分离二氧化碳的工艺,所述工艺包括以下步骤:
(a)在根据权利要求1的吸附剂容器中,并且在压力P1、湿度H1和温度T1下,使所述气体混合物与所述吸附剂接触,直到期望的量的二氧化碳被吸附到所述吸附剂上,以及
(b)在总压力P2和/或温度T2下,使在步骤(a)中被吸附的所述二氧化碳的至少一部分脱附,以产生富含二氧化碳的流,在所述温度下,所述二氧化碳具有相对于所述吸附剂的较低的吸附常数,并且因此至少部分地脱附。
26.根据权利要求25所述的工艺,其中步骤(b)包括使所述一个或多个盒与流体在从60℃至150℃的范围内的温度下接触;和/或通过与加热工具直接接触将在盒中的所述吸附剂加热到从60℃至150℃的温度。
27.根据权利要求26所述的工艺,其中所述接触和/或加热在减压下进行。
28.根据权利要求25-27中任一项所述的工艺,包括使步骤(a)和步骤(b)以在0.1分钟和48小时之间的模式交替。
29.根据权利要求25-27中任一项所述的工艺,包括使用于步骤(b)的所述气体混合物的流动逆转并且升高所述温度。
30.根据权利要求25-27中任一项所述的工艺,还包括:(c)将包含所述脱附的二氧化碳的释放的气态流引导至期望的应用,所述期望的应用包括温室、微藻光温育器、饮料厂、生态箱、水族箱和/或储存设施。
31.根据权利要求28所述的工艺,还包括:(c)将包含所述脱附的二氧化碳的释放的气态流引导至期望的应用,所述期望的应用包括温室、微藻光温育器、饮料厂、生态箱、水族箱和/或储存设施。
32.根据权利要求29所述的工艺,还包括:(c)将包含所述脱附的二氧化碳的释放的气态流引导至期望的应用,所述期望的应用包括温室、微藻光温育器、饮料厂、生态箱、水族箱和/或储存设施。
33.根据权利要求30所述的工艺,其中释放的气态二氧化碳至少部分地被引导向二氧化碳储存缓冲器。
34.根据权利要求31或32所述的工艺,其中释放的气态二氧化碳至少部分地被引导向二氧化碳储存缓冲器。
35.根据权利要求30所述的工艺,其中所述释放的气态二氧化碳至少部分地通过水介质被分布。
36.根据权利要求31-33中任一项所述的工艺,其中所述释放的气态二氧化碳至少部分地通过水介质被分布。
37.根据权利要求34所述的工艺,其中所述释放的气态二氧化碳至少部分地通过水介质被分布。
38.根据权利要求25-27、31-33、35和37中任一项所述的工艺,其中所述二氧化碳以连续的或相继的方式被释放。
39.根据权利要求28所述的工艺,其中所述二氧化碳以连续的或相继的方式被释放。
40.根据权利要求29所述的工艺,其中所述二氧化碳以连续的或相继的方式被释放。
41.根据权利要求30所述的工艺,其中所述二氧化碳以连续的或相继的方式被释放。
42.根据权利要求34所述的工艺,其中所述二氧化碳以连续的或相继的方式被释放。
43.根据权利要求36所述的工艺,其中所述二氧化碳以连续的或相继的方式被释放。
44.根据权利要求1至19中任一项的装置或根据权利要求20至24中任一项的设备用于将二氧化碳提供至水族箱,或用于提供二氧化碳以控制水介质的pH的用途。
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