EP2337623A1 - Agent d'absorption, procédé de production d'un agent d'absorption et son utilisation - Google Patents

Agent d'absorption, procédé de production d'un agent d'absorption et son utilisation

Info

Publication number
EP2337623A1
EP2337623A1 EP09782962A EP09782962A EP2337623A1 EP 2337623 A1 EP2337623 A1 EP 2337623A1 EP 09782962 A EP09782962 A EP 09782962A EP 09782962 A EP09782962 A EP 09782962A EP 2337623 A1 EP2337623 A1 EP 2337623A1
Authority
EP
European Patent Office
Prior art keywords
amino acid
absorbent
carbon dioxide
acid salt
mixture
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.)
Withdrawn
Application number
EP09782962A
Other languages
German (de)
English (en)
Inventor
Ralph Joh
Rüdiger Schneider
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
Priority to EP09782962A priority Critical patent/EP2337623A1/fr
Publication of EP2337623A1 publication Critical patent/EP2337623A1/fr
Withdrawn legal-status Critical Current

Links

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
    • B01D53/14—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 absorption
    • B01D53/1456—Removing acid components
    • B01D53/1475—Removing carbon dioxide
    • 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
    • B01D53/14—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 absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20494—Amino acids, their salts or derivatives
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • 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 an absorbent, in particular for the selective absorption of carbon dioxide from the flue gas of a combustion plant.
  • the invention further relates to a method for producing an absorbent and a use.
  • Combustion products such as e.g. the gases nitrogen, sulfur dioxide, nitrogen oxide and water vapor as well as solid particles, dusts and soot.
  • the exhaust gas is released into the atmosphere after extensive separation of the solid constituents, the carbon dioxide accumulating in the atmosphere hinders the heat radiation of our earth and favors an increase in the surface temperature of the earth through the so-called greenhouse effect.
  • carbon dioxide can be separated from the exhaust gas.
  • the described separation of carbon dioxide is carried out by the absorption-desorption process with a detergent.
  • the exhaust gas is brought in an absorption column with a selective solvent as a detergent in contact, while the uptake of carbon dioxide by a chemical or physical process.
  • the loaded with carbon dioxide solvent is passed to separate the carbon dioxide and regeneration of the solvent in a desorption column, the separation in the Desporptionskolonne can be carried out thermally.
  • a gas-vapor mixture of gaseous carbon dioxide and vaporized solvent is expelled from the loaded solvent.
  • the evaporated solvent is then separated from the gaseous carbon dioxide.
  • the carbon dioxide can now be compressed, cooled and liquefied in several stages. In liquid or frozen state, the carbon dioxide can then be sent for storage or recycling.
  • the regenerated solvent is returned to the absorber column, where it can again absorb carbon dioxide from the exhaust gas containing carbon dioxide.
  • An object of the invention is therefore to provide an absorbent which has a significantly improved energy balance compared to the previously known absorbents. Another object of the invention is to provide a manufacturing method for producing the absorbent. Another task is to specify a usage.
  • an absorbent in particular for the selective absorption of carbon dioxide from the flue gas of an incinerator, comprising a mixture of a coexisting amino acid salt and a free amino acid.
  • the invention is based on the recognition that a particularly promising class of amino compounds for the absorption of carbon dioxide are those amino acids which are converted with an equimolar amount of inorganic base (usually potassium hydroxide KOH) into the corresponding amino acid salt.
  • Amino acids more specifically aminocarboxylic acids, are a class of small organic compounds with at least one carboxyl group (-COOH) and at least one amino group (-NH2).
  • the amino group in organic chemistry is the functional group (-NH 2 ) of the primary amines and amino acids.
  • the amino group is a basic functional group, since the lone pair on the
  • Nitrogen atom - analogous to that in the ammonia molecule can take a proton of an acid.
  • amino acids exist as so-called zwitterions, i. the amino group is protonated and the carboxyl group is deprotonated.
  • the amino group acts as a base since it takes up a proton (proton acceptor).
  • the carboxyl group acts as an acid as it releases a proton, proton donor). This particular property of the amino acids also benefits from the present invention.
  • the amino acid can function as both acid and base and is variable in pkB.
  • the present invention makes use of the fact that the amino acid pkB value is temperature-dependent. If, in addition to the previously used (pure amino acid salt, free amino acid also exists in the absorption medium, the temperature difference between absorber and desorber results in a variation of the pkB value of the absorption medium, whereby a high pkB value is achieved in the cold absorber, which promotes absorption and results in a low pkB value in the hot desorber, which requires less energy for the desorption. the effect that the solubility decreases with increasing temperature in exothermic dissolution processes, is specifically used.
  • this contains a non-equimolar mixture of the amino acid salt and the free amino acid. Preference is given here to an excess of free amino acid in the mixture given to the concentration of the amino acid salt. More preferably, the mixture is in aqueous solution.
  • this has a decreasing with increasing temperature base strength (pkB value).
  • the amino acid salt has a substituent, wherein the substituent is a compound selected from the group consisting of hydrogen, alkyl, hydroxyalkyl or aminoalkyl.
  • the amino acid salt has a further substituent, wherein the further substituent is taken from the group of hydrogen, alkyl, hydroxyalkyl or haloalkyl.
  • the absorbent is in a further preferred embodiment characterized in that the amino acid salt is a salt of a metal, in particular a salt of an alkali metal with an element from the group potassium or sodium, wherein in the amino acid salt in the carboxyl group, the hydrogen is replaced by the metal.
  • the amino acid salt is a salt of a metal, in particular a salt of an alkali metal with an element from the group potassium or sodium, wherein in the amino acid salt in the carboxyl group, the hydrogen is replaced by the metal.
  • the amino acid has further substituents, wherein the further substituent is taken from the group of hydrogen, alkyl, hydroxyalkyl or haloalkyl.
  • the amino acids which can be used according to the invention can thus be described in a generally valid form.
  • the abovementioned substituents of the amino acid salt and the amino acid are not necessarily identical with the addition of an additional amino acid in the amino acid salt and the free amino acid, ie, in a specific absorbent, the amino acid salt and the amino acid in excess, each with different substituents.
  • a particularly favorable energetic balance of the overall cleaning process in the absorption and desorption is given.
  • the object directed to a method for producing an absorbent is achieved according to the invention by equimolar addition of a lye to an amino acid, the amino acid is completely converted into an amino acid salt, and prepared by a further addition of an amino acid, a mixture of amino acid salt and free amino acid so that amino acid salt and free amino acid coexist.
  • the process is carried out in aqueous solution, so that an aqueous solution of amino acid salt and free amino acid is coexistent in excess.
  • a mixture of amino acid salt and free amino acid can also be prepared by a smaller addition of alkali.
  • Another possibility is the addition of an additional amino acid in an already existing equimolar mixture.
  • the coexistence of amino acid salt and free amino acid provides a variable pkB value which promotes low temperature absorption of carbon dioxide and improves desorption at high temperature.
  • the one-shot object of the invention is achieved by using an absorbent containing a mixture of a coexisting amino acid salt and a free amino acid to absorb carbon dioxide from the flue gas of an incinerator.
  • the absorbent is preferably contacted with carbon dioxide-containing offgas such that carbon dioxide is dissolved in the absorbent to form a laden absorbent, and thereafter carbon dioxide is thermally desorbed from loaded absorbent.
  • this is carried out in the absorption of carbon dioxide from the flue gas with the absorbent at a lower temperature than the desorption.
  • this is used in an absorption of carbon dioxide from the flue gas of a fossil-fired steam power plant, from the exhaust gas of a gas turbine plant or from the exhaust gas of a combined gas and steam turbine or an IGCC plant.
  • FIG. 3 shows a schematic representation of a separation device for carbon dioxide from the flue gas of a combustion plant.
  • FIG. 1 shows an amino acid salt which has substituents R, R 1 and R 2.
  • the substituent R is a compound selected from the group of hydrogen, alkyl, hydroxyalkyl or aminoalkyl.
  • the further substituents R 1, R 2 are taken from the group of hydrogen, alkyl, hydroxyalkyl or haloalkyl.
  • the amino acid salt is a salt of a metal M, in particular a salt of an alkali metal with an element selected from the group potassium, sodium, wherein in the amino acid salt in the carboxyl group the hydrogen H is replaced by the metal M.
  • a free amino acid is shown in chemical Nomentatur, as used as the second component of the mixture for the absorbent.
  • the amino acid has a carboxyl group -COOH and at least one amino group -NH2.
  • the free amino acid has a substituent R, wherein the substituent R is a compound selected from the group of hydrogen, alkyl, hydroxyalkyl or aminoalkyl.
  • the free amino acid has further substituents Rl, R2, wherein the further substituent Rl, R2 is taken from the group of hydrogen, alkyl, hydroxyalkyl or haloalkyl.
  • a preparation of the absorbent can take place in that first amino acid is converted by equimolar addition of an alkali, such as potassium hydroxide, completely into an amino acid salt.
  • a further addition of an amino acid produces a mixture of amino acid salt and free amino acid, so that the amino acid salt and the free amino acid are coexistent.
  • a smaller addition of caustic may also be made of a mixture of amino acid salt and free amino acid.
  • Another possibility is the addition of an additional amino acid.
  • This non-equimolar mixture of amino acid salt and free amino acid gives a variable pkB value, the temperature distribution of which the absorption of CO 2 favors at low temperature and the desorption at high temperature energetically significantly improved.
  • FIG. 3 a system diagram of a separation device 1 is shown in a schematic representation.
  • the separation device 1 has an absorption device 3 and a desorption device 5 associated with the absorption device.
  • the desorption device 5 is associated with a reboiler 25, to which a process steam D can be delivered in the event of operation in order to provide heat.
  • the desorption device 5 has a head region 17 of the desorber, to which a gas line 19 for CO 2 -rich gas is connected. In the gas line 19, a heat exchanger 21 and exchanger 80 is provided by the sealing unit 23 for compressing the carbon dioxide or the carbon dioxide-rich gas.
  • the absorption device 3 is connected via a line 13 to the desorption device 5.
  • the desorption device 5 is connected via a line 15 via the reboiler 25 to the absorption device 3.
  • flue gas RG from a fossil-fired incineration plant which is not shown in detail in FIG. 3, is first cooled in a flue gas cooler 7 and then delivered to the absorption device 3 via the delivery device 9.
  • a regenerated absorption medium A is conducted in the absorption device 3 in the opposite direction to the flue gas flow RG.
  • the regenerated absorbent A is guided here via the line 15, which connects the reboiler 25 with the absorption device 3 fluidically. In this way, regenerated absorbent A can be supplied to the absorption device 3 in the reboiler 25.
  • the absorbent comprises, in an aqueous solution, a mixture of an amino acid salt and a free one
  • the absorption agent A prepared from a mixture of amino acid salt and free amino acid according to the invention is specially formulated and suitable for this absorption desorption process, so that high efficiency is achieved when integrating the separation device 1 into a power plant.
  • the deposition efficiency is significantly improved compared to conventional absorbents.
  • the largely liberated from carbon dioxide exhaust 11 leaves the Abvorber worn by a fireplace, not shown.
  • the absorbent A is loaded with carbon dioxide CO2, so that a loaded absorbent A 'is formed.
  • the loaded absorbent A ' is guided via the line 13 from the absorption device 3 to the desorption device 5.
  • the carbon dioxide-laden absorbent A ' is again freed from carbon dioxide. This desorption is usually carried out by thermally expelling the carbon dioxide from the absorbent A '.
  • carbon dioxide-rich gas is first discharged from the desorption device 5 via the gas line 19 and passed through a heat exchanger 21 and a compressor 23 connected to the heat exchanger 21.
  • the carbon dioxide thus separated is compressed in the compressor 23 and used for further purposes, eg injection into an aquifer or another CO2 storage.
  • the desorption process in the desorption device 5 takes place at a desorption temperature T D which is higher than the absorption temperature T A.
  • T D desorption temperature
  • T A absorption temperature
  • the absorbent A according to the invention a variable pkB value is achieved, which varies with the temperature of the process, so that the pkB value in the region of the absorption is higher than in the region of the desorption. In this way the absorption is favored and in the hotter desorber a lower pkB-value results, whereby less desorption energy has to be applied for the desorption.
  • the thermal expulsion of the carbon dioxide from loaded absorbent A 'can therefore be carried out under significantly lower energy input.
  • the separation device 1 shown with the absorbent A according to the invention is suitable for use in a power plant, eg a steam power plant, a gas turbine plant, a combined gas and steam turbine plant, or in a gas and steam turbine plant with integrated coal gasification.
  • a power plant eg a steam power plant, a gas turbine plant, a combined gas and steam turbine plant, or in a gas and steam turbine plant with integrated coal gasification.
  • the invention here by the choice of the absorbent on a way on how the absorption-desorption process can be integrated into an existing power plant process in an efficient manner. This is also particularly advantageous in terms of power plant modernization and upgrades, in which a conventional power plant is afflicted with CO 2 emissions, equipped by the additional installation of a separator for carbon dioxide particularly climate-friendly or can be retrofitted.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treating Waste Gases (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

L'invention concerne un agent d'absorption destiné, en particulier, à séparer du dioxyde de carbone des gaz de combustion provenant d'une installation de combustion à combustibles fossiles. L'agent d'absorption comprend un mélange de deux composants, contenant un acide aminé libre et un sel d'acide aminé, qui rapporté à la concentration molaire l'acide aminé libre est en excédent par rapport au sel d'acide aminé. La variabilité de la valeur de pkb est ainsi atteinte, et cela par des températures différentes du processus d'aborption et de désorption. L'invention concerne également l'utilisation de l'agent, en particulier dans la séparation du dioxyde de carbone dans des centrales électriques.
EP09782962A 2008-10-13 2009-09-14 Agent d'absorption, procédé de production d'un agent d'absorption et son utilisation Withdrawn EP2337623A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09782962A EP2337623A1 (fr) 2008-10-13 2009-09-14 Agent d'absorption, procédé de production d'un agent d'absorption et son utilisation

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP08017913A EP2174700A1 (fr) 2008-10-13 2008-10-13 Absorbant, procédé de fabrication d'un absorbant et utilisation d'un moyen d'absorbant
PCT/EP2009/061860 WO2010043459A1 (fr) 2008-10-13 2009-09-14 Agent d'absorption, procédé de production d'un agent d'absorption et son utilisation
EP09782962A EP2337623A1 (fr) 2008-10-13 2009-09-14 Agent d'absorption, procédé de production d'un agent d'absorption et son utilisation

Publications (1)

Publication Number Publication Date
EP2337623A1 true EP2337623A1 (fr) 2011-06-29

Family

ID=40020212

Family Applications (2)

Application Number Title Priority Date Filing Date
EP08017913A Withdrawn EP2174700A1 (fr) 2008-10-13 2008-10-13 Absorbant, procédé de fabrication d'un absorbant et utilisation d'un moyen d'absorbant
EP09782962A Withdrawn EP2337623A1 (fr) 2008-10-13 2009-09-14 Agent d'absorption, procédé de production d'un agent d'absorption et son utilisation

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP08017913A Withdrawn EP2174700A1 (fr) 2008-10-13 2008-10-13 Absorbant, procédé de fabrication d'un absorbant et utilisation d'un moyen d'absorbant

Country Status (5)

Country Link
US (1) US9067170B2 (fr)
EP (2) EP2174700A1 (fr)
CN (1) CN102245278B (fr)
RU (1) RU2488429C2 (fr)
WO (1) WO2010043459A1 (fr)

Families Citing this family (21)

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WO2012003299A2 (fr) 2010-06-30 2012-01-05 Codexis, Inc. Anhydrases carboniques de classe bêta très stables et utiles dans des systèmes de capture du carbone
WO2012003277A2 (fr) 2010-06-30 2012-01-05 Codexis, Inc. Anhydrases carboniques de classe bêta hautement stables utiles dans des systèmes de capture du carbone
WO2012003336A2 (fr) 2010-06-30 2012-01-05 Codexis, Inc. Anhydrases carboniques chimiquement modifiées, utiles dans les systèmes de capture du carbone
EP2481468A1 (fr) * 2011-01-31 2012-08-01 Siemens Aktiengesellschaft Solvant, procédé de préparation d'un liquide d'absorption et utilisation du solvant
MX2014005746A (es) 2011-11-14 2014-07-09 Evonik Degussa Gmbh Metodo y dispositivo para la separacion de gases acidos de una mezcla de gases.
DE102012200907A1 (de) * 2012-01-23 2013-07-25 Evonik Industries Ag Verfahren und Absorptionsmedium zur Absorption von CO2 aus einer Gasmischung
DE102012207509A1 (de) 2012-05-07 2013-11-07 Evonik Degussa Gmbh Verfahren zur Absorption von CO2 aus einer Gasmischung
KR20150036067A (ko) * 2012-07-17 2015-04-07 지멘스 악티엔게젤샤프트 니트로사민의 형성이 감소되는 이산화탄소 흡수용 세척 용액
AU2014253837B2 (en) * 2013-04-15 2016-12-08 Siemens Aktiengesellschaft Absorbent, process for producing an absorbent, and process and device for separating off hydrogen sulphide from an acidic gas
CN106310874A (zh) * 2015-06-17 2017-01-11 中国石油化工股份有限公司 用于捕集二氧化碳的吸收剂
DE102015212749A1 (de) 2015-07-08 2017-01-12 Evonik Degussa Gmbh Verfahren zur Entfeuchtung von feuchten Gasgemischen
DE102016204931A1 (de) 2016-03-24 2017-09-28 Evonik Degussa Gmbh Verfahren, Absorptionsmedien zur Absorption von CO2 aus Gasmischungen
EP3257843A1 (fr) 2016-06-14 2017-12-20 Evonik Degussa GmbH Procédé pour préparer un sel tres pur d'imidazolium
DE102016210478A1 (de) 2016-06-14 2017-12-14 Evonik Degussa Gmbh Verfahren zur Entfeuchtung von feuchten Gasgemischen
DE102016210484A1 (de) 2016-06-14 2017-12-14 Evonik Degussa Gmbh Verfahren zur Entfeuchtung von feuchten Gasgemischen
DE102016210483A1 (de) 2016-06-14 2017-12-14 Evonik Degussa Gmbh Verfahren und Absorptionsmittel zur Entfeuchtung von feuchten Gasgemischen
DE102016210481B3 (de) 2016-06-14 2017-06-08 Evonik Degussa Gmbh Verfahren zum Reinigen einer ionischen Flüssigkeit
EP3257568B1 (fr) 2016-06-14 2019-09-18 Evonik Degussa GmbH Procede de deshumidification de melanges gazeux humides par des liquides ioniques
TWI646050B (zh) * 2016-12-02 2019-01-01 國立成功大學 二氧化碳收集方法
CN116407928B (zh) * 2023-03-21 2024-08-20 中国华电科工集团有限公司 一种二氧化碳吸收剂及其制备方法
CN116773514A (zh) * 2023-08-15 2023-09-19 之江实验室 一种二氧化碳检测装置及防护口罩

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Also Published As

Publication number Publication date
CN102245278B (zh) 2015-02-18
WO2010043459A1 (fr) 2010-04-22
RU2488429C2 (ru) 2013-07-27
CN102245278A (zh) 2011-11-16
US9067170B2 (en) 2015-06-30
EP2174700A1 (fr) 2010-04-14
US20110309295A1 (en) 2011-12-22
RU2011119092A (ru) 2012-11-20

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