CN117581074A - 用于提供氮产品、氧产品和氢产品的方法和设备 - Google Patents
用于提供氮产品、氧产品和氢产品的方法和设备 Download PDFInfo
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- CN117581074A CN117581074A CN202280043525.6A CN202280043525A CN117581074A CN 117581074 A CN117581074 A CN 117581074A CN 202280043525 A CN202280043525 A CN 202280043525A CN 117581074 A CN117581074 A CN 117581074A
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- stream
- oxygen
- air
- product
- rectification column
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04763—Start-up or control of the process; Details of the apparatus used
- F25J3/04769—Operation, control and regulation of the process; Instrumentation within the process
- F25J3/04854—Safety aspects of operation
- F25J3/0486—Safety aspects of operation of vaporisers for oxygen enriched liquids, e.g. purging of liquids
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04006—Providing pressurised feed air or process streams within or from the air fractionation unit
- F25J3/04048—Providing pressurised feed air or process streams within or from the air fractionation unit by compression of cold gaseous streams, e.g. intermediate or oxygen enriched (waste) streams
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04006—Providing pressurised feed air or process streams within or from the air fractionation unit
- F25J3/04078—Providing pressurised feed air or process streams within or from the air fractionation unit providing pressurized products by liquid compression and vaporisation with cold recovery, i.e. so-called internal compression
- F25J3/0409—Providing pressurised feed air or process streams within or from the air fractionation unit providing pressurized products by liquid compression and vaporisation with cold recovery, i.e. so-called internal compression of oxygen
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- F25J3/04187—Cooling of the purified feed air by recuperative heat-exchange; Heat-exchange with product streams
- F25J3/0423—Subcooling of liquid process streams
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- F25J3/04236—Integration of different exchangers in a single core, so-called integrated cores
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- F25J3/04248—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
- F25J3/04254—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using the cold stored in external cryogenic fluids
- F25J3/0426—The cryogenic component does not participate in the fractionation
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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
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- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
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- F25J3/04284—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams
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- F25J3/044—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using a single pressure main column system only
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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
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- F25J3/04472—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using the cold from cryogenic liquids produced within the air fractionation unit and stored in internal or intermediate storages
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- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
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Abstract
本发明提出一种用于提供氮产品、氧产品和氢产品的方法,其中使用被适配成用于低温分离进料空气的、具有精馏塔系统(10)的空气分离设备(100、200),该精馏塔系统包括空气进料精馏塔(11)和主换热器,其中氮产品的提供特别是包括使用空气进料精馏塔(11)对进料空气进行低温精馏以获得塔顶气并将该塔顶气的一部分用作氮产品。氧产品和氢产品的提供包括使水在电解槽(20)中进行水电解以获得含水氧流和氢流,其中至少在一个运行阶段中,对该含水氧流或其一部分进行干燥(21)并且之后在该空气分离设备中以未混合的状态进行液化以获得液氧流,并且其中将该液氧流或其一部分用于提供氧产品。本发明还涉及对应的设备。
Description
本发明涉及根据独立权利要求的前序部分的一种用于提供氮产品、氧产品和氢产品的方法以及一种对应的设备。
背景技术
通过在空气分离设备中低温分离空气来制备液态或气态空气产品是已知的并且例如在Wiley-VCH出版公司2006年由H.-W.编辑出版的“Industrial GasesProcessing”一书中,特别地在章节2.2.5“Cryogenic Rectification”中进行了描述。
空气分离设备具有精馏塔系统,这些精馏塔系统通常可例如被设计为双塔系统,特别地为典型的林德双塔系统,但也可被设计成三塔或多塔系统。除了用于提取液态和/或气态的氮和/或氧的精馏塔,即用于氮氧分离的精馏塔外,还可设置用于提取其他空气组分,特别地氪、氙和/或氩的精馏塔。经常将“精馏”和“蒸馏”以及“柱”和“塔”这些术语或者由此组成的术语作为同义词使用。
使得所述精馏塔系统的精馏塔以不同的压力水平运行。已知的双塔系统具有所谓的高压塔(也被称为压力塔、中压塔或下塔)和所谓的低压塔(也被称为上塔)。高压塔通常在4bar至7bar,特别是约5.3bar的压力水平下运行。低压塔通常在1bar至2bar,特别是约1.4bar的压力水平下运行。在某些情况下,在两个精馏塔中也可使用更高的压力水平。此处和下文说明的压力为各自给定的塔的顶部处的绝对压力。
特别是为了供应半导体工厂(所谓的晶圆厂),除了气态、高纯度的氮之外,还需要氧和氢。氮典型地应当只有大约1ppb,最多1000ppb的氧,基本上没有颗粒,并且可以明显高于大气压的压力水平供货。以ppb或ppm为单位的数字与摩尔比例有关。氧应具有相当的纯度。具体要求如下。
已知现有技术中有所谓的SPECTRA方法,用来提供压缩氮作为主要产品。以下还将对此进行详细解释。在SPECTRA方法中,为了在氮产品之外提取纯氧或高纯氧,特别是可以使用所谓的氧塔,该氧塔可以在典型低压塔的压力水平下或在高于该压力水平的压力水平下运行。在相应修改的SPECTRA方法中,该氧塔存在于用于提取氮的精馏塔旁边并且从该精馏塔进料。
虽然SPECTRA方法基本上适合于为相应的应用提供氮和氧,但氧的提供通常伴随着极高的能量消耗。通常不允许使用旋转机器来生产高纯氧,以免损害氧的纯度。然而,在传统的SPECTRA方法中,有可能无法放弃使用相应的泵。借助于此类设备也无法直接提供氢。
本发明的目的在于与现有技术相比,改进氮产品、氧产品和氢产品的提供,特别是具有所提到的纯度和针对所提到的应用。
发明内容
在此背景下,本发明提出了具有独立权利要求的特征的一种用于提供氮产品、氧产品和氢产品的方法以及一种对应的设备。优选的实施方案是各从属权利要求以及后面的说明的对象。
在解释本发明的特征和优点之前,先对本发明的一些基本原理进行进一步的解释,并对下面所用的术语进行定义。
在空气分离设备中使用的装置在引用的专业文献,例如(见上文)的书中的章节2.2.5.6“Apparatus”中进行了描述。因此,除非下文的定义与之有偏差,否则本申请的上下文中的用语明确参照所引用的专业文献。
在本发明的上下文中使用的“换热器”可采用专业上常见的方式设计。换热器用于在例如彼此逆流输运的至少两股流体流之间间接传热,例如在一股热压缩空气流和一股或多股冷流体流之间,或者在一股深冷的液态空气产物和一股或多股热或较热的流体流之间,但在适当时也可在深冷的流体流之间。换热器可由单个或多个并联和/或者串联的换热器分段构成,例如由一个或多个板式换热器模块构成。换热器例如为板式换热器(英文:Plate Fin Heat Exchanger)。此类换热器具有“通道”,这些通道被设计成具有换热面的彼此分开的流道,平行并且通过其他通道分开地合并成“通道组”。换热器的特征就是在其中在某个时刻在两个移动介质之间,即至少一个待冷却的和至少一个待加热的流体流之间交换热量。
“冷凝器蒸发器”指的是在其中使冷凝流体流与蒸发流体流间接换热的换热器。每个冷凝器蒸发器具有液化室和蒸发室。液化室和蒸发室具有液化通道以及蒸发通道。在液化室中使得冷凝流体流冷凝(液化),在蒸发室中使得蒸发流体流蒸发。通过相互间存在换热关系的通道组形成蒸发室和液化室。
特别是,本发明可以包括根据开头提到的SPECTRA方法的空气低温分离,例如在EP2 789 958 A1和其中引用的其他专利文献中所描述的。这里最简单的实施方式是单塔方法。然而,本发明还可以与用于空气低温分离的任意其他方法一起使用。SPECTRA方法的描述在此仅作为示例。
如上所述,在SPECTRA方法中,作为空气进料精馏塔的补充,可以将又从空气进料精馏塔进料并用于提取氧的精馏塔用于SPECTRA方法中。这也是本发明的实施方案中的情况,而本发明的其他实施方案没有提供这种精馏塔的使用。
虽然SPECTRA方法最初并且在本发明的相应实施方案中仅旨在提供处于空气进料精馏塔的压力水平下的气态氮,但是正如本发明相应的其他实施方案中的情况,使用所阐述类型的另一精馏塔还能够额外提取纯氧。
与其他低温分离空气的方法一样,在SPECTRA方法中也将经过压缩并且初步净化的空气冷却到适合于精馏的温度。这样就可在传统方法中将其部分液化。如开头所述,在高压塔的典型压力下精馏空气,以获得相对于大气富集氮的塔顶气和液态的相对于大气富集氧的塔底液。
用于此目的的空气进料精馏塔的回流在换热器中通过冷凝空气进料精馏塔的塔顶气,更确切地说是该塔顶气的一部分来提供。在该换热器、即冷凝蒸发器中,同样从空气进料精馏塔提取出的流体用于冷却并且在此蒸发或部分蒸发。另外的塔顶气可以作为富氮产品提供。
在SPECTRA方法中,正如其也可以在本发明的范围内使用的,通过在上述冷凝蒸发器中蒸发来自空气进料精馏塔的液体,形成两种具有不同氧含量的物质流(以下称为“第一”和“第二”物质流),其中第一物质流形成为具有较低的第一氧含量,并且第二物质流形成为具有较高的第二氧含量。
在本发明的一个实施方案中,可以使用从空气进料精馏塔提取出的具有第一氧含量的液体来形成第一流,并且可以使用已经从空气进料精馏塔提取出的具有较高的第二氧含量的液体形成第二物质流。在该实施方案中,用于形成第一物质流的液体可从空气进料精馏塔中从中间塔板或从液体截留装置中抽出。在该实施方案中,用于形成第二物质流的液体特别是可为空气进料精馏塔的液体塔底产品的至少一部分。
但是在另一实施方案中,也可以先使用相同的液体来形成第一物质流和第二物质流,例如空气进料精馏塔的塔底液或从空气进料精馏塔取出的另一种液体。该液体可被引导通过第一冷凝蒸发器,在此期间被部分蒸发,并且经受相分离,得到气体馏分和液体馏分。在该实施方案中,具有第一氧含量的第一物质流可通过使用气体馏分或该气体馏分的一部分形成。在该实施方案中,第二物质流可通过在第一冷凝蒸发器中蒸发液体馏分或液体馏分的一部分形成。
然而,在两个实施方式中,第一物质流和第二物质流各自是先前在上述冷凝蒸发器中使用的流体,用于冷却和冷凝空气进料精馏塔的对应比例的塔顶气。
通常,在SPECTRA方法中,第一物质流在其用于上述冷凝蒸发器中的冷却后,可以借助于冷压缩机至少一部分地被压缩并且再循环到空气进料精馏塔中。在本发明的上下文中,也是这种情况。在SPECTRA方法中,第二物质流在其用于上述冷凝蒸发器中的冷却之后,可以至少一部分地膨胀并且作为来自空气分离设备的所谓的残余气体混合物实施。这也可以在本发明的范围内提供。
为了压缩第一物质流(或相应的部分),可以使用一个或多个压缩机,所述一个或多个压缩机与一个或多个膨胀机耦合,在所述一个或多个膨胀机中进行第二物质流(或相应的部分)的膨胀。应理解的是,也可在对应耦合的单元中仅仅使得第一或第二物质流的一部分压缩或膨胀。如果存在没有与对应的压缩机耦合的膨胀机,特别地可对其进行机械制动和/或者再生制动。与压缩机耦合的膨胀机,也能进行制动。在不脱离本发明的范围的情况下,可以提供膨胀和再压缩的任意变体。
在根据本发明的变体使用的、在从空气进料精馏塔进料的另一精馏塔中提取氧的SPECTRA方法中,在第二精馏塔的下部区域中通常存在用于使另一精馏塔的塔底液沸腾的另一冷凝蒸发器。冷凝蒸发器向来使用(至少)在主空气压缩机中压缩并且在主换热器中冷却的空气(进料空气)来运行,所述空气被供应至第一精馏塔。特别地,所述空气在这种情况下也可以是最初以气态形式存在的空气,其在被进料至空气进料精馏塔中之前在另一冷凝蒸发器中液化。它是供应至第一精馏塔的进料空气总量的一部分。可以将另外的(气态)进料空气进料至空气进料精馏塔中,而无需相应的液化。在不脱离本发明的范围的情况下,关于空气进料精馏塔的进料和另一冷凝蒸发器的运行也能够使用变体。
本发明的优点
本发明提出,允许通过低温空气分离在与氮生产相同的地点进行氢的生产,以便供应相应的消费者。其中,在氢的生产过程中产生的氧与水和可能的其他成分(例如氢)分离,接着,如下文仍将详细解释的,在存在于同一地点的空气分离设备中液化,并且如有需要,在存在于空气分离设备中的逆流式过冷器中过冷。以这种方式获得的液氧可以以液体形式储存。也可以借助于增压蒸发、低温泵等来增压,以及可以在空气分离设备的主换热器中提供后续蒸发(特别是以已知的内部压缩的方式)。在此,电解产生的氧流在液化之前并且通常也在液化之后不与空气分离工艺流混合。“空气分离工艺流”是源自进料空气的流,例如氮产品或不纯氧产品。电解产生的氧流在此并不代表空气分离工艺流。在根据本发明液化电解氧的范围内,不干预空气分离的低温分离过程,相反,优选不存在电解产生的氧流与任何空气分离工艺流的混合。空气分离设备仅提供液化冷却,但并不有助于净化电解产生的氧。
本发明利用这样的事实:当通过水电解生产氢气时,可以获得高纯氧,该高纯氧主要仅被水污染并且特别是不会因与不纯氧产品混合而受到污染。
通过能够在本发明的范围内提供的产品范围,可以以特别有利的方式提供所提到的晶圆厂所需份额的氮、氧和氢。通常,在此类晶圆厂中,需要大约含0.75%的氮气量的高纯氧和1.50%的氢,即氧和水的需求量大约为1比2。这与水电解中获得的比例完全一致。在本发明的范围内,可能的额外提供的高纯氧例如可以在市场上出售。
总体而言,本发明能够降低用于生产所述类型的氮产品、氧产品和氢产品的总能量需求和资本支出。特别是,空气分离设备在此还可以负载灵活地运行。例如,在不液化氧气而仅从罐中将其取出的情况下也可以生产液氮,或者可以将液氮供给到设备中以液化气态氧。
总体而言,本发明以专利权利要求的语言提出了一种用于提供氮产品、氧产品和氢产品的方法,其中,使用设置用于低温分离空气的、具有精馏塔系统的设备,该精馏塔系统包括空气进料精馏塔、主换热器以及必要时的逆流式过冷器。主换热器和逆流式过冷器可以组合在一个装置中作为组合的主换热器-过冷器。如前所述,该设备特别是可以被适配成用于执行SPECTRA方法,但这不是强制性要求。
术语“主换热器”在此指的是将进料空气冷却至大约露点的装置。主换热器可以由并联和/或串联连接的多个区块组成。
氮产品的提供包括使用精馏塔系统对进料空气进行低温精馏以及从精馏塔系统提取出氮产品或前体产品。
术语“前体产品”在此应特别是指物质的混合物或纯物质,使用其形成实际产品,其中这种形成可以包括例如进一步纯化、加压、加热、冷却、精馏、馏分或分量的混合或分离。
如果在本发明的范围内使用SPECTRA方法(这是可选的),则使用空气进料精馏塔对进料空气进行低温精馏以获得塔顶气,并且将该塔顶气的一部分用作氮产品或氮产品的前体产品。
另一方面,根据本发明,氧产品和氢产品的提供包括使水在电解槽中进行水电解以获得含水氧流和氢流,其中至少在一个运行阶段中,对含水氧流或其一部分进行干燥并且随后在主换热器中液化以获得液氧流,并且其中该液氧流或其一部分用于提供氧产品。下面阐述细节和根据本发明的实施方案。根据本发明提出的措施的优点已在上文中进行了阐述。
在本发明的范围内,以下氧气液化配置是可能的:
配置1(仅主换热器)
-在主换热器的温部分中进行冷却
-在主换热器的冷部分中完全液化
配置2(仅逆流式过冷器)
-在逆流式过冷器中冷却并完全液化
配置3(主换热器和逆流式过冷器)
-3a:在主换热器中冷却并完全液化-接着在逆流式过冷器中过冷
-3b:在主换热器中冷却并部分液化-接着在逆流式过冷器中进一步液化,然后过冷
-3c:在主换热器中仅冷却-接着在逆流式过冷器中液化,然后过冷
在配置1至3c中,主换热器和逆流式过冷器可以实现为分离的装置,或者替代地实现为组合的主换热器-过冷器。
流过逆流式过冷器的例如除了电解产生的氧流之外,还包括从蒸馏系统中提取出、在逆流式过冷器中冷却并重新引入蒸馏系统的液体以及从精馏塔系统中提取出并在逆流式过冷器中加温的气体。
配置4(仅单独的换热器)
-在单独的换热器的温部分中进行冷却
-在主换热器的冷部分中完全液化
配置5(单独的换热器和逆流式过冷器)
-3a:在单独的换热器中冷却并完全液化-接着在逆流式过冷器中过冷
-3b:在单独的换热器中冷却并部分液化-接着在逆流式过冷器中进一步液化,然后过冷
-3c:在单独的换热器中仅冷却-接着在逆流式过冷器中液化,然后过冷
优选使用一种或多种空气分离工艺流(例如空气、氮气或氧气)作为单独的换热器中的冷却剂。这些工艺流通过间接热交换去除电解产生的氧流中的热量。单独的换热器例如可以并联连接至空气侧的主换热器。
在单独的换热器中,电解产生的氧气优选在与氮含量大于30mol%的液态冷流的间接热交换中液化,其中该冷流被蒸发。优选地,没有第三工艺流流过单独的换热器。
本发明可以包括通过在逆流式过冷器中过冷形成过冷液氧流,该液氧流用于供应氧产品。在这种情况下,电解产生的氧流在主换热器中冷却并完全或部分液化;在部分液化的情况下,首先在逆流式过冷器中进行完全液化,然后液体被过冷。替代地,也可以仅通过使液氧流穿过主换热器来进行相应的冷却或过冷,特别是当该液氧流处于超大气压水平时。
在本发明的范围内,可以使用低压电解来提供含水氧流。替代地,也可以使用高压电解来提供。在本发明的范围内,水电解可以例如以碱性电解(AEL)的形式或以在质子交换膜(PEM)或阴离子交换膜(AEM)上电解的形式进行。这两种工艺均为低温电解,通常可在低于60℃的工作温度下使用。高温电解方法,例如使用固体氧化物电解槽(英语:solid oxideelectrolysis cell;SOEC)的高温电解方法,也用于电解例如水和/或二氧化碳,并且可以与本发明结合使用。全部的方法请参阅相关专业文献。
根据主换热器中发生液化应有的压力水平和水电解的压力水平,可以在干燥之后和在主换热器中液化之前对含水氧流或其一部分进行压缩。
氧产品的提供可以特别是包括(进一步)纯化、特别是用于贫化氩的精馏,特别是可以对蒸发的液氧进行该精馏。
如上所述,本发明特别是能够实现负载灵活的运行。换句话说,在本发明的一个实施方案中,液氧流可以只在第一运行阶段中形成,其中液氧流可以在第一运行阶段中被暂时储存以用于后续提供氧产品,并且其中在第二运行阶段中,使用暂时储存的液氧流或其一部分并通过在主换热器中进行加热,氧产品可以作为气态加压的氧产品而获得。特别是,在第二运行阶段中,可以在主换热器中对气态氮流进行液化以获得液氮流,并且该液氮流或其一部分可以用作所述氮产品或另一氮产品、或者被暂时储存以供以后提供所述氮产品或另一氮产品。也可以在没有或有暂时储存的情况下对液氮流进行已知类型的内部压缩。这可以在第一和第二运行模式下完成。针对其中一种运行模式提及的任何措施也可以在其他运行模式中执行。
本发明也可以特别是包括使用另外的冷却介质,使得在根据本发明的一个实施方案的方法中,使用液态空气进行液化。
在本发明的使用SPECTRA方法的实施方案中,空气进料精馏塔可以使用冷凝蒸发器来运行,在该冷凝蒸发器中通过在低于空气进料精馏塔的运行压力水平的压力水平下蒸发来自空气进料精馏塔的液体来形成第一物质流和第二物质流,其中空气进料精馏塔的另外的塔顶气在冷凝蒸发器中冷凝并作为回流再循环到空气进料精馏塔。
此外,在该实施方案中可以形成具有第一氧含量的第一物质流和具有高于第一氧含量的第二氧含量的第二物质流,其中将该第一物质流或其一部分再压缩至第一压力水平并送入空气进料精馏塔中,并且对第二物质流或其一部分进行做功膨胀并将其排出设备。
如上所述,本发明可以在没有或有额外的氧塔的情况下用于SPECTRA方法中,其中在后一种情况下,该氧塔用作从空气进料精馏塔进料的另一精馏塔,并且其中该第二精馏塔的塔底液用于提供氧产品。液氧流可以被供给到该另一精馏塔中,由此使得进一步纯化成为可能。
在本发明的范围内,还可以减少来自罐的蒸发损失,其中特别是在罐中蒸发的氧气被供给到设备的主换热器和/或逆流式过冷器中。特别是在逆流式过冷器或主换热器中被加温。
本发明还涉及一种用于提供氮产品、氧产品和氢产品的设备,其中该设备被适配成用于空气的低温分离并具有精馏塔系统,该精馏塔系统包括空气进料精馏塔、主换热器和逆流式过冷器,其中,用于提供氮产品的设备被适配成用于使用空气进料精馏塔对进料空气进行低温精馏以获得塔顶气,并使用该塔顶气的一部分作为氮产品。
根据本发明,该设备包括电解槽,该电解槽被适配成用于进行水电解来获得含水氧流和氢流以提供氧产品和氢产品,其中该设备被适配成用于至少在一个运行阶段中对含水氧流或其一部分进行干燥、然后在主换热器中进行液化以获得液氧流,并使用该液氧流或其一部分提供氧产品。
关于根据本发明的空气分离设备的其他特征和优点,该空气分离设备特别是被适配用于执行如之前在不同实施方案中所解释的方法并且具有对应的以器件形式实现的装置,参考根据本发明的方法及其实施方案的上述解释。
下面参考附图更详细地解释本发明,这些附图示出了本发明的优选的实施方案。
附图说明
图1示出了根据本发明的一种实施方式的设备。
图2示出了根据本发明的另一实施方式的设备。
图3示出了根据本发明的集成有主换热器和逆流式过冷器的系统。
在附图中,在结构上和/或功能上彼此对应的元件以相同的附图标号给出,并且仅为了清楚起见在下文中不重复解释。
具体实施方式
图1以示意性设备图的形式示出了根据本发明的实施方式的设备100。
设备100被适配成用于空气的低温分离并且为此包括具有空气进料精馏塔11的精馏塔系统10,该空气进料精馏塔被适配成用于提取氮并利用冷凝蒸发器13运行。用于提取氧气的、从空气进料精馏塔11进料的另一精馏塔12并不存在,但仍然(以打叉划掉的形式)示出,以展示在本发明的范围内对根据现有技术的设备进行的修改。
借助于空气分离设备100的主空气压缩机1,经由未单独标示的过滤器从大气中吸入空气并压缩空气。在主空气压缩机1下游的同样未单独标示的后冷却器中冷却之后,以这种方式形成的进料空气流a在以水运行的直接接触冷却器2中得以进一步冷却。然后,进料空气流a在吸附器单元3中进行清洁。在这方面的进一步阐述可以参考专业文献,例如联系的图2.3A(见上文)。
在主换热器4中冷却之后,进料空气流a进料至空气进料精馏塔11中,在其中相应的进料空气被精馏。空气进料精馏塔11的塔顶气部分地以物质流d的形式作为氮产品或密封气体从空气分离设备100排出。
在此处所说明的具体实施方案中,在冷凝蒸发器13中,对第一物质流g和第二物质流h在低于空气进料精馏塔11的运行压力水平的压力水平下(为此,特别是在未单独标示的阀中进行对应的膨胀)进行蒸发。
使用从空气进料精馏塔11中提取出的具有第一氧含量的液体形成第一物质流g,并且使用从空气进料精馏塔11中提取出的具有高于第一氧含量的第二氧含量的液体(特别是塔底液)形成第二物质流h。
空气进料精馏塔11的另外的塔顶气以物质流i的形式在第一冷凝蒸发器13中冷凝,并且作为回流再循环到空气进料精馏塔11。一部分(如在此以物质流k的形式所示)也可以在逆流式过冷器5中过冷并作为液氮提供。相应的,也可以进料液氮。在此加热的物质流l如下面更详细地解释的那样处理。也可以设置吹扫流m形式的另外的排出物。可能的(另外的)液氮进料(LIN注入)以物质流x的形式示出。
第一物质流g的气体在第一冷凝蒸发器13中蒸发或部分蒸发后,在压缩机6中再压缩至第一压力水平并进料至空气进料精馏塔11。虚线示出的部分也可以再循环至压缩机6中进行压缩。物质流g的一部分也可以以物质流n的形式排放到大气中。
在此处所示的示例中,第二物质流h的气体:在第一冷凝蒸发器13中被蒸发或部分蒸发之后,在与压缩机6耦合的膨胀机7中经受膨胀;并且在主换热器4中被加热后,在吸附器单元3中用作再生气体或者排放到大气中并由此从空气分离设备100排出。
在电解槽20中,在第一运行阶段中通过水电解形成氢流(未示出)和氧流o。前者作为氢产品提供。后者由于生产类型而含有水,因此在干燥器21中去除水和其他成分。(例如,干燥器由一对常用的吸附剂容器组成,该吸附剂容器交替运行,如图3所示。)继续以o标示的干燥后的氧流被引导穿过主换热器4,在那里液化,然后在逆流式过冷器5中过冷并以液化、过冷状态进料到罐单元22中。以这种方式就形成了氧产品。
如果需要,特别是在第二运行阶段中,可以将存储在罐单元中的氧(如此处继续示出为氧流o)例如通过增压压缩加压、在主换热器4中加热并在此蒸发、并且提供为相应的(另外的)氧产品。
替代地,在图1中,逆流式过冷器5可以以本身已知的方式集成到主换热器4中。
图2以示意性设备图的形式示出了根据本发明的实施方式的设备200。
在该设备中存在上述用于提取氧的另一精馏塔12。向该另一精馏塔12供给来自空气进料精馏塔11的侧流p,该侧流首先被引导通过另一精馏塔12的底部蒸发器14并在其中液化,然后被送入另一精馏塔12的上部区域中。
空气流a的一部分(在此以物质流b的形式示出)也被引导通过底部蒸发器14,然后以液化状态供给至空气进料精馏塔11。
另一精馏塔12的塔底液以物质流q的形式被引入罐单元23中,并且可以如之前对物质流o所阐述的那样从该罐单元中使用以提供氧产品,如继续以q标示的物质流q所示的那样。先前在主换热器4中液化并随后在逆流式过冷器5中过冷的氧流o被供给到另一精馏塔12中以用于进一步纯化。
替代地,在图2中,逆流式过冷器5可以以本身已知的方式集成到主换热器4中。
图3示出了配置3的实施例,其中氧流o在单独的换热器300中冷却和液化。液化氧经由管道201和302供给到罐单元22中。图3的所有其他特征均与图2相对应。
Claims (14)
1.一种用于提供氮产品、氧产品和氢产品的方法,其中使用被适配成用于低温分离进料空气的、具有精馏塔系统(10)的空气分离设备(100、200),所述精馏塔系统包括空气进料精馏塔(11)和用于冷却所述进料空气的主换热器(4),其中所述氮产品的提供包括使用所述精馏塔系统(10)对进料空气进行低温精馏以及从所述精馏塔系统(10)提取出所述氮产品或所述氮产品的前体产品,其特征在于,所述氧产品和氢产品的提供包括使水在电解槽(20)中进行水电解以获得含水氧流和氢流,其中至少在一个运行阶段中,为获得液氧流,对所述含水氧流或其一部分进行干燥(21)和可能的进一步纯化步骤,之后将干燥后的氧流引入所述空气分离设备中而不与所述空气分离设备的工艺流混合、并在所述空气分离设备中以未混合的状态进行液化(4),并且其中将在此产生的液氧流或其一部分用于提供所述氧产品。
2.根据权利要求1所述的方法,其中,对所述干燥后的氧流的液化在所述主换热器(4)中、在所述空气分离设备的逆流式过冷器(5)中、在组合式主换热器-过冷器的过冷部分中、或者在所述空气分离设备的独立于主换热器和可能的逆流式过冷器的单独的换热器中进行。
3.根据权利要求1所述的方法,其中,使用所述空气进料精馏塔(11)对所述进料空气进行低温精馏以获得塔顶气,其中将所述塔顶气的一部分用作所述氮产品或所述氮产品的前体产品,其中通过在冷凝蒸发器(13)中蒸发来自所述空气进料精馏塔(11)的液体来形成具有不同氧含量的两种物质流,并且其中所述塔顶气的另一部分在所述冷凝蒸发器(13)中冷凝并再循环到所述空气进料精馏塔(11)。
4.根据前述权利要求中任一项所述的方法,其中,使用电解、特别是高压电解来提供所述含水氧流。
5.根据前述权利要求中任一项所述的方法,其中,在所述干燥(21)之后和在所述主换热器(4)中液化之前对所述含水氧流或其一部分进行压缩。
6.根据前述权利要求中任一项所述的方法,其中,所述氧产品的提供包括纯化、特别是用于贫化氩的精馏。
7.根据前述权利要求中任一项所述的方法,其中,所述液氧流只在第一运行阶段中形成,其中所述液氧流在所述第一运行阶段中被暂时储存以用于后续提供所述氧产品,并且其中在第二运行阶段中,使用所述暂时储存的液氧流或其一部分并通过在所述主换热器(4)中进行加热,所述氧产品作为气态加压的氧产品而获得。
8.根据权利要求7所述的方法,其中,在所述第二运行阶段中,在所述主换热器(4)中对气态氮流进行液化以获得液氮流,并且其中所述液氮流或其一部分用作所述氮产品或另一氮产品、或者被暂时储存以供以后提供所述氮产品或另一氮产品。
9.根据前述权利要求中任一项所述的方法,其中,使用液态空气进行所述液化。
10.根据前述权利要求中任一项所述的方法,其中,所述空气进料精馏塔(11)使用冷凝蒸发器(13)来运行,在所述冷凝蒸发器中通过在低于所述空气进料精馏塔(11)的运行压力水平的压力水平下蒸发来自所述空气进料精馏塔(11)的液体来形成第一物质流和第二物质流,其中所述空气进料精馏塔(11)的另外的塔顶气在所述冷凝蒸发器(13)中冷凝并作为回流再循环到所述空气进料精馏塔(11)。
11.根据权利要求10所述的方法,其中,形成具有第一氧含量的所述第一物质流和具有高于所述第一氧含量的第二氧含量的所述第二物质流,其中将所述第一物质流或其一部分再压缩至第一压力水平并送入所述空气进料精馏塔(11)中,并且对所述第二物质流或其一部分进行做功膨胀并将其排出所述设备(100、200)。
12.根据权利要求10或11所述的方法,其中,使用从所述空气进料精馏塔(11)进料的另一精馏塔(12),其中所述第二精馏塔(12)的塔底液用于提供所述氧产品。
13.根据权利要求12所述的方法,其中,所述液氧流被供给到所述另一精馏塔(12)中。
14.一种用于提供氮产品、氧产品和氢产品的设备(100、200),其中所述设备(100、200)包括用于低温分离进料空气的空气分离设备,所述空气分离设备又具有精馏塔系统(10),所述精馏塔系统包括空气进料精馏塔(11)和用于冷却所述进料空气的主换热器(4),其中,用于提供所述氮产品的所述设备被适配成用于使用所述精馏塔系统(10)对进料空气进行低温精馏以及从所述精馏塔系统(10)提取出所述氮产品或所述氮产品的前体产品,其特征在于,所述设备(100、200)包括电解槽(20),所述电解槽被适配成用于进行水电解来获得含水氧流和氢流以提供所述氧产品和氢产品,并且其中所述设备(100、200)被适配成用于至少在一个运行阶段中,为获得液氧流,在不与所述空气分离设备的工艺流混合的情况下对所述含水氧流或其一部分进行干燥(21)、之后在所述空气分离设备中以未混合的状态进行液化,并且将在此产生的液氧流或其一部分用于提供所述氧产品。
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WO2024223491A1 (en) * | 2023-04-24 | 2024-10-31 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process and apparatus for air separation by cryogenic distillation |
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US7272954B2 (en) * | 2004-07-14 | 2007-09-25 | L'air Liquide, Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Proceded Georges Claude | Low temperature air separation process for producing pressurized gaseous product |
US8136369B2 (en) * | 2006-07-14 | 2012-03-20 | L'air Liquide Societe Anonyme Pour L'etude | System and apparatus for providing low pressure and low purity oxygen |
EP2789958A1 (de) | 2013-04-10 | 2014-10-15 | Linde Aktiengesellschaft | Verfahren zur Tieftemperaturzerlegung von Luft und Luftzerlegungsanlage |
KR20210077705A (ko) * | 2018-10-23 | 2021-06-25 | 린데 게엠베하 | 저온 공기 분리를 위한 방법 및 유닛 |
EP3739714A1 (de) * | 2019-05-16 | 2020-11-18 | Linde GmbH | Verfahren zum betreiben einer industrieanlage und entsprechende industrieanlage |
CN114017993B (zh) * | 2022-01-06 | 2022-06-07 | 杭氧集团股份有限公司 | 一种利用绿电电解水制氢副产氧气的装置及方法 |
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- 2022-06-07 EP EP22731992.8A patent/EP4363782A1/de active Pending
- 2022-06-07 WO PCT/EP2022/025263 patent/WO2023274574A1/de active Application Filing
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