CN102740950A - 从气体混合物中分离净化的有用气体的方法以及实施该方法的装置 - Google Patents

从气体混合物中分离净化的有用气体的方法以及实施该方法的装置 Download PDF

Info

Publication number
CN102740950A
CN102740950A CN2011800076876A CN201180007687A CN102740950A CN 102740950 A CN102740950 A CN 102740950A CN 2011800076876 A CN2011800076876 A CN 2011800076876A CN 201180007687 A CN201180007687 A CN 201180007687A CN 102740950 A CN102740950 A CN 102740950A
Authority
CN
China
Prior art keywords
carbon dioxide
valuable gases
liquid carbon
harmful substance
gas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2011800076876A
Other languages
English (en)
Other versions
CN102740950B (zh
Inventor
M.巴尔道夫
C.格雷伯
M.哈尼布思
G.齐默曼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Original Assignee
Siemens AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Siemens AG filed Critical Siemens AG
Publication of CN102740950A publication Critical patent/CN102740950A/zh
Application granted granted Critical
Publication of CN102740950B publication Critical patent/CN102740950B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/506—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification at low temperatures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
    • 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
    • F25J3/0204—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 characterised by the feed stream
    • F25J3/0223—H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis gas
    • 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
    • F25J3/0228—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 characterised by the separated product stream
    • F25J3/0252—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 characterised by the separated product stream separation of hydrogen
    • 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
    • F25J3/0228—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 characterised by the separated product stream
    • F25J3/0261—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 characterised by the separated product stream separation of carbon monoxide
    • 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
    • F25J3/0228—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 characterised by the separated product stream
    • F25J3/0266—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 characterised by the separated product stream separation of carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/046—Purification by cryogenic separation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
    • 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/30—Processes or apparatus using other separation and/or other processing means using a washing, e.g. "scrubbing" or bubble column for purification purposes
    • 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/40—Processes or apparatus using other separation and/or other processing means using hybrid system, i.e. combining cryogenic and non-cryogenic separation techniques
    • 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
    • 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
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/70—Flue or combustion exhaust gas
    • 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
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/04—Recovery of liquid products
    • 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
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/80—Separating impurities from carbon dioxide, e.g. H2O or water-soluble contaminants
    • 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
    • F25J2235/00—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams
    • F25J2235/80—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams the fluid being carbon dioxide
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Analytical Chemistry (AREA)
  • Treating Waste Gases (AREA)
  • Gas Separation By Absorption (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

本发明涉及一种从气体混合物中分离净化的有用气体的方法，所述气体混合物基本上含有二氧化碳、至少一种有用气体和至少一种有害物质，其中凝聚二氧化碳，并将富集了有害物质的液态二氧化碳与有用气体分离，然后从所述液态二氧化碳中吸附性分离有害物质，并且将一部分净化的液态二氧化碳供给至有用气体以吸收仍包含在该有用气体中的有害物质。

Description

从气体混合物中分离净化的有用气体的方法以及实施该方法的装置
本发明涉及一种从气体混合物中分离净化的有用气体的方法，所述气体混合物基本上含有二氧化碳、至少一种有用气体、至少一种有害物质。
由于所谓的温室效应和与此相关的全球气候上升，向大气中排放起温室作用的气体越来越多得受到严厉的指责。相当大部分的温室作用归因于在化石燃料的燃烧中的二氧化碳(CO2)。大量的化石燃料例如在发电站和工业工厂中燃烧。
为了抵消该温室作用，将来从发电站和工业过程释放的气体中要尽可能地分离出二氧化碳。为此目的，大量的研发工作致力于设计出尽可能少或者甚至不排放二氧化碳的设备。所有设计都遵循以下目的，如果可能以尽可能小的能量消耗，从气体流中分离出尽可能全部的且高纯度的二氧化碳，从而在分离后最终可以向环境中释放出无二氧化碳的气体。
然而，除了要求分离的二氧化碳之外，在待处理的气体中还常常含有不期望的物质，即有害物质(Schadstoffe)，该物质必须根据燃烧的化石燃料(fossil Brennstoff)的类型产生并取出。就数量而言最常出现的是硫、汞和它们的化合物。也就是说，从气体中不仅要分离出二氧化碳，还要分离出有害物质。
到目前为止，废气(如在煤炭发电厂产生的废气)中的有害物质，例如所述的硫化合物和汞化合物，直接从气相中沉积出来。例如，硫化氢的分离借助气体洗涤进行。在此，将气体流传导经过吸收塔，在该吸收塔中液态媒介吸收有害物质。液态吸收塔媒介例如由醇胺水溶液，特别是甲基-二乙醇胺溶液，或者例如在低温甲醇法(Rectisol-Prozess)中使用冷甲醇。但是，此时的缺点特别是，用于气体洗涤的方法需要较高的能量。
从气体混合物中分离二氧化碳和有害物质的有效可能方案记载于稍后公开的德语专利申请DE 10 2009 035 389.5中。根据该方法，二氧化碳从气体混合物中凝结出来，也就是说，二氧化碳作为液相从气体混合物中分离出来。在气体混合物中含有的有害物质此时富集在液态二氧化碳中。接着将该液态的、携带有害物质的二氧化碳供应至吸附器装置中，在该吸附器中包含在液态二氧化碳中的有害物质被吸附，并且因此从液态二氧化碳分离出来，在吸附器装置出口处的液态二氧化碳基本上或完全不含有害物质。
因低温分离二氧化碳CO2而得到的有用气体是纯的。但是现在已经证实，在凝聚过程中不是所有的有害物质富集在CO2液相中，而是有一定剩余份额的有害物质总是包含在有用气体中。
因此，本发明的目的在于公开提供一种从气体混合物中分离净化的有用气体的方法，该有用气体中不仅基本不含CO2，而且基本不含有害物质。
为了实现该目的，在根据本发明的从基本上含有二氧化碳、至少一种有用气体以及至少一种有害物质的气体混合物中分离净化的有用气体的方法中如下设置，凝聚(Kondensation)二氧化碳，并将富集了有害物质的液态二氧化碳与有用气体分离，然后从所述液态二氧化碳中吸附性分离有害物质，并且将一部分净化的液态二氧化碳供给至有用气体以吸收仍包含在该有用气体中的有害物质。
本发明方法提供了从待净化的气体混合物中低温凝聚出二氧化碳，然后借助吸附装置从携带有害物质的液态二氧化碳取出所含的有害物质，从而在吸附过程结束时存在至少基本无有害物质的液态二氧化碳。然后将一部分这种净化的液态二氧化碳送回并再次供应至有用气体。该有用气体与液态二氧化碳的再次混合目前有利地引起了在特别由于净化而不饱和程度过高的液态二氧化碳中，在有用气体中剩余的有害物质富集在二氧化碳中。然后，将该液态二氧化碳再次供应至上述的或者另一吸附装置中，使得从液态二氧化碳成分还取出在再次“反应”中有用气体所吸收的有害物质。
也就是说，根据本发明方法的液态二氧化碳两次用作吸收器介质用于气体混合物中含有的有害物质。第一次，有害物质的吸收在液化二氧化碳的范围中进行，若使用合适的二氧化碳凝聚装置通过冷却将二氧化碳转化成液相。第二次，在将液态二氧化碳成分返回至有用气体的范围内使用总是呈液态的二氧化碳作为洗涤剂，使得从有用气体中吸收有害物质成分。也就是说，返回的液态二氧化碳类似用作“液态的气体洗涤剂”。
最后，本发明方法因此提供两个分开的净化相，即，第一相为不含二氧化碳和有害物质的有用气体，第二相为不含有害物质的液态二氧化碳。
根据本发明的一个特别有利的改进方案，将液态返回的二氧化碳注入或喷入有用气体中。通过雾化将极大程度地增加液态二氧化碳的表面，使得在气相(即有用气体)和液相(即液态CO2液滴)之间产生大的交换表面。这造成了位于有用气体中的剩余有害物质非常高的吸收率，该有害物质可以几乎完全地被吸收和取出。由此得到了非常高效的工作方式，其中携带有害物质的液态二氧化碳的分离和第二次有害物质吸附经返回的、净化的液态二氧化碳在实施相分离和有害物质吸收的同一容器中进行，所述容器例如塔(Kolonne)或闪蒸容器(Flash Behaelter)或类似物。也就是说，一方面向该塔中引入凝聚的、携带有害物质的二氧化碳以及有用气体，在该塔中实施有用气体和液态二氧化碳相的分离，另一方面同时将返回的、净化的液态二氧化碳优选喷入或注入该塔中，从而完全净化有用气体。该返回的、液态二氧化碳然后使用初始供应的、凝聚的和携带有害物质的二氧化碳取出(abgezogen)，并且接着供应进入共用的吸附装置以分离有害物质。
分离的有用气体可以为任何有用气体，其取决于燃烧的化石燃料。例氢、一氧化碳、氮、稀有气体或上述气体的混合物。
所产生的有害物质在性质上也可以不同。常见的有害物质有硫、汞以及它们的化合物或者它们的混合物。
除了该方法之外，本发明还涉及用于从气体混合物中分离出净化的有用气体的装置，所述气体混合物基本上含有二氧化碳、至少一种有用气体和至少一种有害物质。本发明的装置包括至少一个二氧化碳凝聚装置，至少一个发生相分离和吸收有害物质的容器，例如塔或闪蒸容器或者类似物，用于从携带有害物质的液态二氧化碳中分离有用气体，至少一个吸附装置用于吸收在分离的液态二氧化碳中含有的有害物质，以及返回管道用于将一部分净化的液态二氧化碳返回、优选返回至塔中以吸收在有用气体中含有的剩余有害物质。一种这种装置可以例如整合在发电站或任何工业设备中，并在此用于气体净化。向二氧化碳凝聚装置中供应产生的全部气体混合物，任选在相应地预处理之后供应。在二氧化碳凝聚装置中实施CO2凝聚。有用气体和液态二氧化碳的混合物然后供应进入适合气液分离的容器4中，在该容器中进行相分离。从塔中取出的携带有害物质的液态二氧化碳然后供应至吸附装置对有害物质进行吸附性分离。从吸附装置中取出的、净化的液态二氧化碳然后部分经返回管道回流，并再次接触已经与液态二氧化碳分离的有用气体，从而从有用气体中取出剩余有害气体。返回管道在此可以直接引入容器中，也就是说，将返回的二氧化碳再次引入容器中已经存在分离的有用气体的区域，在这里“有用气体洗涤”使用起吸收剂作用的液态二氧化碳进行。除了返回至容器中，还存在以下方案，将净化的液态二氧化碳和有用气体一起送入塔之外合适的“反应容器”中，使得在此实施有用气体洗涤。装置的操作温度范围为-70℃至-10℃，优选-60℃至-30℃。
在本发明的一个改进方案中，提供注入装置或喷入装置用于将液态二氧化碳注入或喷入容器或反应器中，在该容器或反应器(即例如在塔本身)中从有用气体中吸收有害物质。通过使用注入装置或喷入装置喷雾的程度可以调节或改变交换表面，即液态CO2相的表面，其中大的交换表面对于高效的吸收剩余有害物质是有利的。
如果注入装置或喷入装置位于容器自身中，那么有利的是所述装置位于设置在塔中的除雾器下方，有用气体流经该除雾器，通过该除雾器保留液态CO2的液滴。
吸附装置本身优选为固定床吸附器。作为吸附介质(吸附剂)例如优选使用活性炭、沸石、矾土(氧化铝)、具有大表面的聚合物以及类似物，其中优选使用可以非常容易再生的那些吸附剂。此时，设置多个吸附装置从而尤其连续地进行操作，所述多个吸附装置可以交替方式转换吸附操作和再生操作。这实现了在吸附操作中连续地操作部分吸附装置，由此连续净化CO2，并且其余部分的吸附装置得以再生。根据需要，在两个操作方式之间转换，使得在吸附操作中总有一定数量的吸附装置在操作。
本发明其他优势、特征和细节将在下文所述的实施例以及如图中给出。
附图显示了根据本发明的装置1用于从气体混合物2中分离净化的有用气体，该气体混合物形成为气体流，例如废气流(例如使用化石燃料的发电站或其他工业设备中的废气流)。该气体流2含有二氧化碳作为基本的混合物成分，还含有至少一种有用气体如氢气，以及至少一种有害物质如基于硫或汞的有害物质，如硫化氢(H2S)或羰基硫化物(COS)。废气2作为气体流首先进入二氧化碳凝聚装置3，在该装置中废气2冷却至之前在废气中以气态形式存在的二氧化碳发生凝聚的温度。其转化成液相。初始在废气2中含有的有害物质大部分，但不是全部，溶解在液态CO2相中。然后将这两个相，即，携带剩余有害物质的有用气体以及携带有害物质的液态二氧化碳引入容器4例如塔4中，在这里进行相分离。在底部的容器区域沉积着携带有害物质的液态二氧化碳5，在上部的塔区域分别在CO2水平面上方分别存在有用气体6，该有用气体6经由用于保留仍包含在气体中的液态CO2液滴的除雾器7取出(abgezogen)且作为有用气体流8。
如上所述，液态二氧化碳5积聚在下部的塔区域。根据本发明装置1关于二氧化碳凝聚装置3的运行温度，在液态二氧化碳5中也可以存在颗粒形式的固态二氧化碳。但是该运行温度应当不导致形成第三固相，从而避免了稍后要描述的吸附装置的可能的堵塞。
将富集了有害物质的液态二氧化碳5取出，且供应在至少一种、在所示实施例中为三种的吸附装置9中，在所述装置中，在液态二氧化碳5中含有的有害物质被吸附性取出。如上所述，在二氧化碳凝聚时在气态混合物中含有的有害物质自动地基本上富集在液态二氧化碳相中。这在目前实现了在吸附装置9中的简单吸附性分离。吸附装置9优选为固定床吸附器，液态二氧化碳流与有害气体一起引入其中。作为吸附介质可以例如使用活性炭、沸石、氧化铝或聚合物，根据要吸附的有害物质或有害物质混合物来决定。
在所示实施例中，三个吸附装置9彼此并行连接。这提供了如下的可能性，仅一部分、例如两个吸附装置9同时进行吸附操作，同时第三个吸附装置9进行再生操作以再生吸附介质，由此取出吸附在其上的有害物质并且再次使吸附介质去饱和。对此，以已知的但是未详细显示的方式设置相应的实现切换操作的管线和阀。
因此，从吸附装置9取出目前不再含有或几乎不再含有有害物质的净化的液态二氧化碳10。
一部分净化的液态二氧化碳然后经过返回管道11借助泵12再次输送进入塔4，并且在此借助注入装置或喷入装置13得到尽可能细的喷雾。注入或喷入装置13位于接近除雾器7底部的区域，也就是说位于存在有用气体6的塔区域。注入或喷入的净化二氧化碳10引起了在相关有用气体6中存在的有害气体与CO2细液滴之间的进一步的吸收反应，所述CO2细液滴将会吸收残余的有害物质。流经除雾器7并接着被取出的净化有用气体6因此不仅不含二氧化碳，而且不含有害物质。喷入的现在同样或再次携带有害物质的二氧化碳10然后使用原始供应的、位于塔底部的液态二氧化碳5取出，并且再次供应至吸附装置9。
将净化的二氧化碳10中未由返回管道11取出的部分供应至合适的任何类型的后处理。
如上所述，若本发明的温度最高应当为-30℃，那么为了避免二氧化碳的凝固应当防止该温度低于-60℃。该方法的压力必须基本上高于相应于温度压力图中二氧化碳的三相点。其相当于至少5巴。显然，相应的操作参数和所用的吸附介质根据所存在的气体混合物成分以及相关的有害物质而使用。

Claims (11)

1.从气体混合物中分离净化的有用气体的方法，所述气体混合物基本上含有二氧化碳、至少一种有用气体和至少一种有害物质，其中凝聚二氧化碳，并将富集了有害物质的液态二氧化碳与有用气体分离，然后从所述液态二氧化碳中吸附性分离有害物质，并且将一部分净化的液态二氧化碳供给至有用气体以吸收仍包含在该有用气体中的有害物质。
2.根据权利要求1的方法，其特征在于，将所述液态二氧化碳注入或喷入所述有用气体中。
3.根据权利要求1或2的方法，其特征在于，所述携带有害物质的液态二氧化碳与所述有用气体的分离在容器中进行，其中将所述净化的液态二氧化碳供给至该容器中。
4.前述权利要求中任一项的方法，其特征在于，作为有用气体分离的是氢气、一氧化碳、氮气、惰性气体或它们的混合物。
5.前述权利要求中任一项的方法，其特征在于，作为有害物质分离的是硫、汞、它们的化合物或它们的混合物。
6.用于从气体混合物中分离出净化的有用气体的装置，所述气体混合物基本上含有二氧化碳、至少一种有用气体和至少一种有害物质，所述装置包括：至少一个二氧化碳凝聚装置(3)，至少一个用于分离有用气体(6,8)与携带有害物质的液态二氧化碳(5)的容器(4)，至少一个用于吸收包含在分离的液态二氧化碳(5)中的有害物质的吸附装置(9)，以及用于将一部分净化的液态二氧化碳(10)送回、优选送回至所述容器(4)中用于吸收包含在所述有用气体(6)中的残余有害物质的返回管道(11)。
7.根据权利要求6的装置，其特征在于，用于注入或喷入所述液态二氧化碳(10)的注入或喷入装置(13)优选设置在所述容器(4)中。
8.根据权利要求7的装置，其特征在于，所述注入或喷入装置(13)设置在位于所述容器(4)中的除雾器(7)的下方。
9.根据权利要求6至8中任一项的装置，其特征在于，用于分离气相和液相的容器(4)为塔或闪蒸容器。
10.根据权利要求6至9中任一项的装置，其特征在于，所述吸附装置(9)为固定床吸附器。
11.根据权利要求6至10中任一项的装置，其特征在于，设置多个吸附装置(9)，该吸附装置(9)以交替方式可转换吸附操作和再生操作。
CN201180007687.6A 2010-01-28 2011-01-20 从气体混合物中分离净化的有用气体的方法以及实施该方法的装置 Expired - Fee Related CN102740950B (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102010006102.6 2010-01-28
DE102010006102A DE102010006102A1 (de) 2010-01-28 2010-01-28 Verfahren zur Abtrennung gereinigten Wertgases aus einem Gasgemisch, sowie Vorrichtung zur Durchführung dieses Verfahrens
PCT/EP2011/050756 WO2011092106A1 (de) 2010-01-28 2011-01-20 Verfahren zur abtrennung gereinigten wertgases aus einem gasgemisch, sowie vorrichtung zur durchführung dieses verfahrens

Publications (2)

Publication Number Publication Date
CN102740950A true CN102740950A (zh) 2012-10-17
CN102740950B CN102740950B (zh) 2014-11-12

Family

ID=43824224

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201180007687.6A Expired - Fee Related CN102740950B (zh) 2010-01-28 2011-01-20 从气体混合物中分离净化的有用气体的方法以及实施该方法的装置

Country Status (7)

Country Link
US (1) US20120304689A1 (zh)
EP (1) EP2528676B1 (zh)
CN (1) CN102740950B (zh)
DE (1) DE102010006102A1 (zh)
PL (1) PL2528676T3 (zh)
RU (1) RU2520544C2 (zh)
WO (1) WO2011092106A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106823443A (zh) * 2017-04-12 2017-06-13 中国石油大学(华东) 天然气中二氧化碳雪化分离器、分离系统及分离方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106241738A (zh) * 2016-08-05 2016-12-21 江苏河海新能源股份有限公司 二氧化碳和氢气分离装置

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1152547A (zh) * 1995-08-23 1997-06-25 波克股份有限公司 制备高纯度二氧化碳的方法
WO2009010690A2 (fr) * 2007-07-13 2009-01-22 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procede de purification d'un gaz contenant du co2
WO2009070785A2 (en) * 2007-11-28 2009-06-04 Brigham Young University Carbon dioxide capture from flue gas

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4263021A (en) * 1972-12-05 1981-04-21 The Babcock & Wilcox Company Gas-liquid contact system
US3962881A (en) * 1974-02-19 1976-06-15 Airco, Inc. Liquefaction of a vapor utilizing refrigeration of LNG
US5021232A (en) * 1989-09-29 1991-06-04 Cng Research Company Sulfur recovery process
DE4326279A1 (de) * 1993-08-05 1995-02-16 Veba Kraftwerke Ruhr Verfahren zum Abscheiden von Quecksilber aus Rauchgas
US5474671A (en) * 1994-04-11 1995-12-12 Phillips Petroleum Company Process for removing oil from liquefied petroleum gas
US5983663A (en) * 1998-05-08 1999-11-16 Kvaerner Process Systems, Inc. Acid gas fractionation
US5974829A (en) * 1998-06-08 1999-11-02 Praxair Technology, Inc. Method for carbon dioxide recovery from a feed stream
US6361696B1 (en) * 2000-01-19 2002-03-26 Aeronex, Inc. Self-regenerative process for contaminant removal from liquid and supercritical CO2 fluid streams
CN1331562C (zh) * 2001-10-17 2007-08-15 普莱克斯技术有限公司 中心二氧化碳纯化器
RU2202402C1 (ru) * 2002-05-17 2003-04-20 ОАО "Московский комитет по науке и технологиям" Способ очистки воздуха от токсичных компонентов выхлопных и отходящих газов
DK2121520T3 (en) * 2007-01-17 2017-01-16 Union Eng As Process for the recovery of high purity carbon dioxide
US8088196B2 (en) * 2007-01-23 2012-01-03 Air Products And Chemicals, Inc. Purification of carbon dioxide
CN105944504A (zh) * 2008-07-29 2016-09-21 由宁工程股份有限公司 一种回收高纯度二氧化碳的方法
CN102427869B (zh) * 2009-03-16 2014-12-10 可持续能源解决方案公司 从气体中分离可凝结蒸汽的方法和系统
US8042357B2 (en) * 2009-04-23 2011-10-25 Praxair Technology, Inc. Hydrogen liquefaction method and liquefier
DE102009035389A1 (de) 2009-07-30 2011-02-03 Siemens Aktiengesellschaft Verfahren zur Schadstoffentfernung aus Kohlendioxid und Vorrichtung zur dessen Durchführung

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1152547A (zh) * 1995-08-23 1997-06-25 波克股份有限公司 制备高纯度二氧化碳的方法
WO2009010690A2 (fr) * 2007-07-13 2009-01-22 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procede de purification d'un gaz contenant du co2
WO2009070785A2 (en) * 2007-11-28 2009-06-04 Brigham Young University Carbon dioxide capture from flue gas

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106823443A (zh) * 2017-04-12 2017-06-13 中国石油大学(华东) 天然气中二氧化碳雪化分离器、分离系统及分离方法
CN106823443B (zh) * 2017-04-12 2022-09-30 中国石油大学(华东) 天然气中二氧化碳雪化分离器、分离系统及分离方法

Also Published As

Publication number Publication date
RU2012136598A (ru) 2014-03-10
RU2520544C2 (ru) 2014-06-27
WO2011092106A1 (de) 2011-08-04
EP2528676B1 (de) 2014-08-13
PL2528676T3 (pl) 2015-02-27
CN102740950B (zh) 2014-11-12
EP2528676A1 (de) 2012-12-05
US20120304689A1 (en) 2012-12-06
DE102010006102A1 (de) 2011-08-18

Similar Documents

Publication Publication Date Title
Spigarelli et al. Opportunities and challenges in carbon dioxide capture
Aghel et al. A review of recent progress in biogas upgrading: With emphasis on carbon capture
Khan et al. Biogas as a renewable energy fuel–A review of biogas upgrading, utilisation and storage
US20200054983A1 (en) Methods and systems for performing chemical separations
EP3362425B1 (en) Separation methods and systems for oxidative coupling of methane
Aaron et al. Separation of CO2 from flue gas: a review
Olajire CO2 capture and separation technologies for end-of-pipe applications–A review
AU2010298708B2 (en) Maintaining low carbon monoxide levels in product carbon dioxide
CN103058188B (zh) 食品级液体二氧化碳产品生产中减少二氧化碳排放量的方法
CN102303865B (zh) 改进的食品级液体二氧化碳产品的生产方法
KR101381125B1 (ko) 합성 가스 스트림으로부터 황화수소, 철 펜타카르보닐 및 니켈 테트라카르보닐의 제거 방법
KR101443060B1 (ko) 합성 가스 스트림으로부터 금속 카르보닐의 제거 방법
KR100816649B1 (ko) 휘발성 유기화합물 제거장치
CN101978234A (zh) 高炉煤气的分离方法
US20020147109A1 (en) Sorbent composition
Wang et al. Nanoporous molecular basket sorbent for NO 2 and SO 2 capture based on a polyethylene glycol-loaded mesoporous molecular sieve
AU768603B2 (en) Thermal swing adsorption process for the removal of dinitrogen oxide, hydrocarbons and other trace impurities from air
CN102553390A (zh) 一种化工尾气净化处理工艺
CN102740950B (zh) 从气体混合物中分离净化的有用气体的方法以及实施该方法的装置
CN112755720A (zh) 气体吸附冷凝回收方法及回收系统
Xiao et al. Nanofibrous carbon microspheres with hierarchical porosity for deep eutectic solvent loading and highly efficient SO2 adsorption
CN102470287B (zh) 从液态二氧化碳中去除有害物质的方法及用于实施该方法的装置
CN102410704A (zh) 一种回收再生气的食品级液体二氧化碳产品的生产方法
Charisiou et al. Biogas Sweetening Technologies
Sahota et al. Bioresource Technology Reports

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20141112

Termination date: 20190120

CF01 Termination of patent right due to non-payment of annual fee