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WO2000002643A1 - Procede regeneratif d'adsorption de co2 au moyen d'une resine echangeuse d'ions - Google Patents

Procede regeneratif d'adsorption de co2 au moyen d'une resine echangeuse d'ions Download PDF

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Publication number
WO2000002643A1
WO2000002643A1 PCT/DE1999/001792 DE9901792W WO0002643A1 WO 2000002643 A1 WO2000002643 A1 WO 2000002643A1 DE 9901792 W DE9901792 W DE 9901792W WO 0002643 A1 WO0002643 A1 WO 0002643A1
Authority
WO
WIPO (PCT)
Prior art keywords
ion exchange
exchange resin
adsorption
concentration
resin
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.)
Ceased
Application number
PCT/DE1999/001792
Other languages
German (de)
English (en)
Inventor
Lutz Schauer
Helmut Funke
Helmut Preiss
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.)
Dornier GmbH
Original Assignee
Dornier GmbH
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 Dornier GmbH filed Critical Dornier GmbH
Publication of WO2000002643A1 publication Critical patent/WO2000002643A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B01D53/02—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 adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • B01J41/07—Processes using organic exchangers in the weakly basic form
    • 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
    • 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

Definitions

  • the invention relates to a process for the adsorption of metabolically produced CO 2 in manned, closed or partially closed rooms.
  • the existing atmosphere is enriched with metabolically produced pollutants, in particular with the carbon dioxide (CO 2 ) continuously produced during metobolic breathing. Since gas exchange in the alveoli of the lungs (exchange of CO 2 for fresh oxygen) would be hindered or completely prevented at higher atmospheric CO 2 contents, it is necessary to remove this harmful gas from the closed or partially closed atmosphere.
  • CO 2 carbon dioxide
  • atmospheric CO 2 -containing air is usually passed through filters which contain substances as filter medium (e.g. alkali or alkaline earth metal hydroxides) which convert the CO 2 into a solid carbonate compound by chemical conversion with the hydroxide.
  • filters which contain substances as filter medium (e.g. alkali or alkaline earth metal hydroxides) which convert the CO 2 into a solid carbonate compound by chemical conversion with the hydroxide.
  • filter medium e.g. alkali or alkaline earth metal hydroxides
  • the CO 2 binding takes place on a macroporous ion exchange resin with vinylbenzene polymers which are crosslinked with divinylbenzene and which contain primary benzylamines as functional groups.
  • resins with primary benzylamine groups have a particularly high binding capacity for gaseous CO 2 .
  • the absorption capacity of the resin for CO 2 under normal atmospheric conditions is at least 60 g COJkg resin based on the resin dry weight when saturated.
  • the current absorption capacity of the resin depends on different parameters, for example the thermodynamic boundary conditions (e.g. temperature, humidity, CO 2 concentration in the environment) of the atmosphere to be controlled and the quality of the regeneration process.
  • the loading values mentioned could be determined experimentally and the experimental results then confirmed by the inclusion of adsorption isotherms.
  • the macroporous structure of the ion exchange resin ensures that even with the comparatively low values of the CO 2 partial pressure in manned, closed or partially closed rooms (typically less than 0.005 bar, which corresponds to a CO 2 concentration of approx. 0.5%) ) a high CO 2 binding is achieved.
  • Preferred parameters of the ion exchange resin to be used according to the invention are:
  • the ion exchange resin is exposed to the CO 2 -containing gas mixture, ie the breathing air present in closed and partially closed rooms, in that the air is passed through a bed of ion exchange resin by means of a fan.
  • the CO 2 molecules When flowing through the bed, the CO 2 molecules are bound to the functional primary benzylamine groups on the outer and inner surfaces of the macroporous resin beads (diameter typically in the range from 0.3 to 1.3 mm) and the medium flowing through is correspondingly depleted.
  • the resin can be regenerated in several ways; The choice of regeneration type depends on the current application and other technical and logistical constraints:
  • the ion exchange resin is prepared by reacting the vinylbenzene polymers crosslinked with divinylbenzene in the presence of swelling agents and subsequent saponification, the polymers being reacted with a bis (dicarbonimidoalkyl) ether in the presence of sulfur trioxide.
  • the saponification process incorporates the benzylamine groups into the matrix.
  • the sulfur trioxide can be added to the reaction mixture in undissolved form.
  • the sulfur trioxide can be added to the reaction mixture as a solution in H 2 SO 4 .
  • the bis (phthalimidomethyl) ether in particular can be used as the bis (dicarbonimidoalkyl) ether.
  • reaction components bis (dicarbonimidoalkyl) ether and sulfur trioxide, an adduct of these components can also be used for the reaction.
  • the suspension was then mixed with 120 g of liquid sulfur trioxide with stirring and external cooling at 22 to 30 ° C.
  • the sulfur trioxide ether adduct was formed and a clear solution was created.
  • 150 g of a macroporous styroiperl polymer, crosslinked by polymerization in the presence of, were crosslinked with 6% divinylbenzene (this can generally be present in different isomers, for example as o-, m and / or p-divinylbenzene) on the monomer dish, 70% of a C 12 hydrocarbon mixture had been added. After the heat had subsided, the mixture was left to react at 70 ° C. in 23 hours.
  • reaction liquid was suctioned off and the remaining ethylene chloride was driven off with steam.
  • the reaction product was heated with 25% sodium hydroxide solution at 180 to 185 ° C for 10 hours and then with Washed water neutral. This gave 1090 ml of an anion exchanger with an acid-binding capacity of 2.21 Val / I compared to / 10 HCL.
  • Measurement results that have been determined when the method according to the invention is carried out are shown in the diagram in FIG. 1.
  • the two curves in the diagram show CO 2 concentration curves over a longer period Period within a closed atmosphere with constant supply of pure CO 2 .
  • the upper curve 1 shows the CO 2 concentration in the air entering the adsorber, this concentration represents the current atmospheric concentration.
  • the lower curve 2 shows the CO 2 concentration measured in the outlet of the adsorption system.
  • the CO 2 concentration in the closed atmosphere becomes approximately constant after some time. in the case of the configuration selected in the diagram, this value is approximately 0.2 to 0.22 vol .-% CO 2 . It can thus be seen from the diagram that the adsorption process according to the invention makes it possible to effectively reduce undesirably high CO 2 concentrations in the atmosphere.
  • the adsorber (consisting of three individual adsorbent beds, two of which are in the adsorption, respectively, while the third bed is being regenerated) operates in a opposite outwardly sealed cabin Wi with about 80 m 3 internal volume of air.
  • the internal atmosphere has normal meteorological conditions (20 ° C at approx. 60% humidity).
  • a constant CO 2 inflow of 220 l / h is fed into the chamber via a regulator, which corresponds to an average CO 2 production rate that would be released by an 8 to 9-man crew working normally. Without removing these amounts of CO 2 , the CO 2 concentration in the cabin would quickly exceed critical values for humans (after just four hours, a CO 2 concentration of 1 vol.% would be exceeded).
  • the CO 2 concentration inside the cabin can easily and reliably be kept well below critical values (the limit values for the CO 2 concentration in physiological terms are between 0.2 and 1 vol.%, Depending on the exposure time).
  • the curve shape of curve 1 can be explained as follows. At the start of the experiment, the adsorber is in an undefined state, which depends on how the previous application was ended. By adding CO 2 to the closed chamber, the corresponding concentration increases. tration within the chamber continuously. Only after the first fresh bed (approx. 11:20 h) is switched into adsorption is CO 2 from the atmosphere depleted. Since at the beginning of each adsorption cycle the absorption capacity of the adsorbent resin for CO 2 is higher than the amount flowing into the chamber, more CO 2 is bound in the resin than is supplied externally. The mean CO 2 concentration in the chamber decreases accordingly, which can be clearly seen in the further course of curve 1.
  • the absorption capacity of the adsorber resin for CO 2 decreases continuously to theoretically to full saturation.
  • the average CO 2 concentration in the chamber drops as long as the remaining absorption capacity of the resin for CO 2 is higher than the amount of CO 2 flowing in from the outside at the same time.
  • the adsorber resin used had the following properties:
  • Temperature stability range: -10 to + 100 ° C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

L'invention concerne un procédé permettant l'adsorption de CO2 produit de façon métabolique dans des espaces habités fermés ou partiellement fermés, procédé selon lequel une résine échangeuse d'ions macroporeuse est exposée à l'air respiré dans l'espace fermé ou partiellement fermé, cette résine échangeuse d'ions contenant des polymères de styrène qui sont réticulés avec du divinylbenzène, ainsi que des benzylamines primaires comme groupes fonctionnels.
PCT/DE1999/001792 1998-07-08 1999-06-18 Procede regeneratif d'adsorption de co2 au moyen d'une resine echangeuse d'ions Ceased WO2000002643A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19830470A DE19830470C1 (de) 1998-07-08 1998-07-08 Regeneratives Verfahren zur CO¶2¶-Adsorption
DE19830470.6 1998-07-08

Publications (1)

Publication Number Publication Date
WO2000002643A1 true WO2000002643A1 (fr) 2000-01-20

Family

ID=7873318

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE1999/001792 Ceased WO2000002643A1 (fr) 1998-07-08 1999-06-18 Procede regeneratif d'adsorption de co2 au moyen d'une resine echangeuse d'ions

Country Status (2)

Country Link
DE (1) DE19830470C1 (fr)
WO (1) WO2000002643A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001021269A3 (fr) * 1999-09-23 2001-08-16 Edison Termoelettrica Spa Element d'absorption de dioxyde de carbone et son procede de regeneration
CN107073381A (zh) * 2014-09-12 2017-08-18 庄信万丰股份有限公司 吸附剂材料
WO2018097721A1 (fr) 2016-11-23 2018-05-31 Skytree B.V. Appareil d'adsorbtion réversible de dioxyde de carbone comprenant un empilment d'au moins deux couches contenant un matériau sorbant et procédé d'exraction de dioxyde de carbone d'un gaz au moyen de cet appareil
WO2018156020A1 (fr) 2017-02-22 2018-08-30 Skytree B.V. Procédé et appareil améliorés pour l'élimination de dioxyde de carbone métabolique d'un espace confiné
WO2018233949A1 (fr) 2017-06-19 2018-12-27 Lanxess Deutschland Gmbh Mélanges pour l'adsorption de gaz acides
EP3789100A1 (fr) 2019-09-06 2021-03-10 LANXESS Deutschland GmbH Procédé de désorption du dioxyde de carbone sur des polymères des échangeurs d'anions organiques
CN115433298A (zh) * 2021-06-02 2022-12-06 北京德润晨环保科技有限公司 一种二氧化碳吸附剂及其制备方法和应用

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DE10023970A1 (de) * 2000-05-16 2001-11-22 Bayer Ag Verfahren zur Gasadsorption mittels aminomethylierter Perlpolymerisate
US7452406B2 (en) * 2004-03-12 2008-11-18 Mmr Technologies Inc. Device and method for removing water and carbon dioxide from a gas mixture using pressure swing adsorption
CN102160957A (zh) 2005-07-28 2011-08-24 乞力马扎罗能量公司 从空气中除去二氧化碳
US9266051B2 (en) 2005-07-28 2016-02-23 Carbon Sink, Inc. Removal of carbon dioxide from air
AU2007233275B2 (en) 2006-03-08 2012-07-26 Carbon Sink, Inc. Air collector with functionalized ion exchange membrane for capturing ambient CO2
KR20090086530A (ko) 2006-10-02 2009-08-13 글로벌 리서치 테크놀로지스, 엘엘씨 공기로부터 이산화탄소를 추출하는 방법 및 장치
DE102006048716B3 (de) * 2006-10-14 2008-02-21 Howaldswerke Deutsche Werft Ag Unterseeboot mit einer CO2-Bindeeinrichtung
AU2007319211A1 (en) * 2006-11-15 2008-05-22 Global Research Technologies, Llc Removal of carbon dioxide from air
EP2139584A4 (fr) 2007-04-17 2011-05-18 Global Res Technologies Llc Captage de dioxyde de carbone (co<sb>2</sb>) dans l'air
CN101848754A (zh) 2007-11-05 2010-09-29 环球研究技术有限公司 从空气中除去二氧化碳
MX2010004447A (es) 2007-11-20 2010-05-13 Global Res Technologies Llc Colector de aire con membrana de intercambio ionico funcional para capturar co2 del ambinete.
MX339437B (es) 2008-02-19 2016-05-26 Global Res Technologies Llc Extraccion y formacion de complejos del dioxido de carbono.
DE102008015150B4 (de) * 2008-03-20 2012-03-15 Howaldtswerke-Deutsche Werft Gmbh Unterseeboot
WO2009149292A1 (fr) 2008-06-04 2009-12-10 Global Research Technologies, Llc Capteur d’air d’écoulement laminaire avec matériaux sorbants solides pour capturer le co2 ambiant
ES2488123T3 (es) 2010-06-15 2014-08-26 Astrium Gmbh Procedimiento para la regeneración de un medio de adsorción o medio de absorción
EP2438975B1 (fr) 2010-10-08 2014-04-23 Astrium GmbH Procédé de séparation du dioxyde de carbone dans des installations de biogaz
JP6653320B2 (ja) 2014-09-12 2020-02-26 ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃ Ｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ ビークルの乗客キャビンの空気の二酸化炭素除去のためのシステム及びプロセス
WO2019161114A1 (fr) 2018-02-16 2019-08-22 Carbon Sink, Inc. Extracteurs à lit fluidisé pour la capture de co2 à partir d'air ambiant
EP3670362B1 (fr) 2018-12-21 2022-06-15 Airbus Defence and Space GmbH Compartiment environnemental fermé pour accommoder les humains
EP3669968A1 (fr) 2018-12-21 2020-06-24 Airbus Defence and Space Système d'extraction et/ou de purification, en particulier système d'extraction et/ou de purification autonome

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WO1994013386A1 (fr) * 1992-12-11 1994-06-23 United Technologies Corporation Agent de sorption a base d'amine-polyol depose sur support, pouvant etre regenere
WO1998017388A1 (fr) * 1996-10-22 1998-04-30 United Technologies Corporation Sorbant amine, solide et regenerable
US5797979A (en) * 1997-01-23 1998-08-25 Air Products And Chemicals, Inc. Removal of acid gases from gas mixtures using ion exchange resins

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DE2038746A1 (de) * 1969-08-12 1971-03-04 Mine Safety Appliances Co Verfahren zur Trennung von Kohlendioxyd aus anderen Gasen
DE2519244A1 (de) * 1975-04-30 1976-11-11 Bayer Ag Verfahren zur herstellung von anionenaustauschern
EP0258747A2 (fr) * 1986-09-02 1988-03-09 Bayer do Brasil S.A. Méthode pour éliminer des gaz acides et/ou sulfureux
WO1994013386A1 (fr) * 1992-12-11 1994-06-23 United Technologies Corporation Agent de sorption a base d'amine-polyol depose sur support, pouvant etre regenere
WO1998017388A1 (fr) * 1996-10-22 1998-04-30 United Technologies Corporation Sorbant amine, solide et regenerable
US5797979A (en) * 1997-01-23 1998-08-25 Air Products And Chemicals, Inc. Removal of acid gases from gas mixtures using ion exchange resins

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001021269A3 (fr) * 1999-09-23 2001-08-16 Edison Termoelettrica Spa Element d'absorption de dioxyde de carbone et son procede de regeneration
CN107073381A (zh) * 2014-09-12 2017-08-18 庄信万丰股份有限公司 吸附剂材料
CN107073381B (zh) * 2014-09-12 2020-10-16 庄信万丰股份有限公司 吸附剂材料
WO2018097721A1 (fr) 2016-11-23 2018-05-31 Skytree B.V. Appareil d'adsorbtion réversible de dioxyde de carbone comprenant un empilment d'au moins deux couches contenant un matériau sorbant et procédé d'exraction de dioxyde de carbone d'un gaz au moyen de cet appareil
WO2018156020A1 (fr) 2017-02-22 2018-08-30 Skytree B.V. Procédé et appareil améliorés pour l'élimination de dioxyde de carbone métabolique d'un espace confiné
WO2018233949A1 (fr) 2017-06-19 2018-12-27 Lanxess Deutschland Gmbh Mélanges pour l'adsorption de gaz acides
US11207671B2 (en) 2017-06-19 2021-12-28 Lanxess Deutschland Gmbh Mixtures for the adsorption of acidic gases
EP3789100A1 (fr) 2019-09-06 2021-03-10 LANXESS Deutschland GmbH Procédé de désorption du dioxyde de carbone sur des polymères des échangeurs d'anions organiques
WO2021043767A1 (fr) 2019-09-06 2021-03-11 Lanxess Deutschland Gmbh Procédé de désorption de dioxyde de carbone à partir d'échangeurs d'anions organiques polymères
CN115433298A (zh) * 2021-06-02 2022-12-06 北京德润晨环保科技有限公司 一种二氧化碳吸附剂及其制备方法和应用

Also Published As

Publication number Publication date
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