DE4042002A1 - Carbon di:oxide removal from waste gas - by chemical reaction with porous solid basic nitrite-sodalite - Google Patents
Carbon di:oxide removal from waste gas - by chemical reaction with porous solid basic nitrite-sodaliteInfo
- Publication number
- DE4042002A1 DE4042002A1 DE4042002A DE4042002A DE4042002A1 DE 4042002 A1 DE4042002 A1 DE 4042002A1 DE 4042002 A DE4042002 A DE 4042002A DE 4042002 A DE4042002 A DE 4042002A DE 4042002 A1 DE4042002 A1 DE 4042002A1
- Authority
- DE
- Germany
- Prior art keywords
- sodalite
- solid
- guest molecule
- temp
- chemical reaction
- 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
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Classifications
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3408—Regenerating or reactivating of aluminosilicate molecular sieves
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
- C01B33/28—Base exchange silicates, e.g. zeolites
- C01B33/2807—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures
- C01B33/2892—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures containing an element or a compound occluded in the pores of the network, e.g. an oxide already present in the starting reaction mixture
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- 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
Abstract
Description
Die Erfindung betrifft ein Verfahren zur CO2 Aufnahme aus Gasen. Kohlendioxid wird dabei durch eine chemische Reaktion in einer Festphase mit Sodalith-Struktur (poröses Gerüst) als carbonat gebunden. Im allgemeinen enthalten Sodalithe in den Käfigen ihres Strukturgerüstes z. B. NaCl als Gastmoleküle und besitzen keine signifikanten Sorptionseigenschaften. Der hier erforderliche Sodalith hingegen muß zur Erzielung seiner spezifischen Eigenschaften nun 50% reaktive Gastmoleküle (NaOH · H2O) und 50% temperaturstabilisierende Gastmoleküle (NaNO2 oder NaHO3) enthalten.The invention relates to a method for CO 2 uptake from gases. Carbon dioxide is bound by a chemical reaction in a solid phase with sodalite structure (porous framework) as a carbonate. In general, sodalites contained in the cages of their structural skeleton z. For example, NaCl as guest molecules and have no significant sorption. The sodalite required here, however, must now contain 50% reactive guest molecules (NaOH · H 2 O) and 50% temperature-stabilizing guest molecules (NaNO 2 or NaHO 3 ) to achieve its specific properties.
Die Schaffung geeigneter Methoden zur Reduzierung der hohen Mengen an CO2 in den Verbrennungsabgasen fossiler Brennstoffe stellt heute ein dominierendes Problem zur Umweltreinhaltung dar.Creating suitable methods for reducing the high levels of CO 2 in the combustion fumes of fossil fuels is now a dominant environmental concern.
Für die Reduzierung des Schadstoffes Kohlendioxid in Gasen gibt es bis heute kein befriedigendes Verfahren. Die Molsiebe (Zeolithe) nehmen zwar durch Adsorptionsprozesse CO2 in ihr Poorensystem auf. vermögen dieses aber nicht durch chemische Reaktionen fest zu binden und erleiden bei Temperaturerhöhung beträchtliche Verluste ihrer Adsorptionskapazität, bei Zeolith A z. B. rund 70% bei einen Temperaturanstieg von 195K auf 298K (D. W. Breck, Zeolite Molecular Sieves. Verlag John Wiley & Sons. New York. London. Sydney, Toronto. 1974. S. 610).There is still no satisfactory method for reducing the pollutant carbon dioxide in gases. Although the molecular sieves (zeolites) absorb CO 2 in their Poorensystem by adsorption. but are unable to bind this by chemical reactions firmly and suffer from temperature increase considerable losses of their adsorption capacity, for zeolite A z. For example, about 70% increase in temperature from 195K to 298K (DW Breck, Zeolite Molecular Sieves, John Wiley & Sons, New York, London, Sydney, 1974, p 610).
Sodalithe, die ein wesentlich engmaschigeres Gerüst als die Zeolithe A, X bzw. Y aufweisen, können in ihrer bekannten Form als "Hydrosodalithe" lediglich Wassermoleküle einlagern: eine Aufnahme von CO2 gelang bisher nicht (D. W. Breck: Zeolite Molecular Sieves. Verlag John Wiley & Sons, New York, London, Sydney, Toronto, 1974. S. 155).Sodalithe, which have a much closer-meshed scaffold than the zeolites A, X and Y, can store in their known form as "hydrosodalites" only water molecules: a recording of CO 2 has not been successful (DW Breck: Zeolite Molecular Sieves, John Wiley & Sons, New York, London, Sydney, Toronto, 1974, p. 155).
Bei der vorliegenden Methode werden nun erstmals Sodalithe benutzt, die zwei unterschiedliche Arten von Gastmolekülen in Ihren Käfigen enthalten, eine reaktive sowie eine das Gerüst thermisch stabilisierende Komponente. Dem liegt der Gedanke zugrunde, bei hohen Temperaturen (700°C) innerhalb des Sodalithgerüstes die reaktiven Gastmoleküle mit CO2 unter Bindung desselben reagieren zu lassen, wobei das Strukturgerüst durch die Wechselwirkung der thermisch stabileren Gastkomponente erhalten bleibt.The present method is the first to use sodalites containing two different types of guest molecules in their cages, a reactive component and a thermally stabilizing component. This is based on the idea at high temperatures (700 ° C) within the Sodalithgerüstes the reactive guest molecules react with CO 2 under binding thereof, wherein the structural framework is maintained by the interaction of the thermally stable guest component.
Zur Realisierung wurde eine Sodalithverbindung der Zusammensetzung Na5(AlSiO4) 6(NO2)(OH · H2O) hergestellt. Die reinen Verbindungen sind aus der Literatur bekannt, Basischer Sodalith Na5(AlSiO4)6(OH · H2O)2 (R. N. Barrer u. E. A. D. White: J. Chem. Soc. 286 (1952) 1561-1571) und Nitrit-Sodalith Na8(AlSiO4)6(NO2)2 (F. Hund: Z. Anorg. Allg. Chem. 511 (1984) 255). Reaktives Gastmolekül (statistisch in jedem zweiten Sodalith-Käfig angeordnet) ist hydratisiertes Natriumhydroxid NaOH · H2O. NaNO2 stabilisiert die Sodalithstruktur. Wird die Verbindung Na8(AlSiO4)6(NO2)(OH-H2O) nun in einer CO2- Athmosphäre erhitzt, reagiert im Temperaturbereich von 700°C-750°C lediglich NaOH · H2O mit CO2 entsprechend der Gleichung:For the realization, a sodalite compound of composition Na 5 (AlSiO 4 ) 6 (NO 2 ) (OH.H 2 O) was prepared. The pure compounds are known from the literature, basic sodalite Na 5 (AlSiO 4 ) 6 (OH.H 2 O) 2 (RN Barrer and EAD White: J. Chem. Soc., 286 (1952) 1561-1571) and nitrite -Sodalith Na 8 (AlSiO 4 ) 6 (NO 2 ) 2 (F. Dog: Z. Anorg. Allg. Chem. 511 (1984) 255). Reactive guest molecule (statistically arranged in each second sodalite cage) is hydrated sodium hydroxide NaOH · H 2 O. NaNO 2 stabilizes the sodalite structure. If the compound Na 8 (AlSiO 4 ) 6 (NO 2 ) (OH-H 2 O) is now heated in a CO 2 atmosphere, only NaOH · H 2 O reacts with CO 2 in the temperature range from 700 ° C.-750 ° C. according to the equation:
Die in den Abb. 1a und 1b dargestellten IR-Spektren der Ausgangsverbindung und des Reaktionsproduktes zeigen das Verschwinden der OH⁻ Bande (3640 cm -1) sowie das Auftreten der CO3 2--Bande (1450 cm+1) nach erfolgter Reaktion.The IR spectra of the starting compound and of the reaction product shown in FIGS. 1a and 1b show the disappearance of the OH⁻ band (3640 cm -1 ) and the appearance of the CO 3 2- band (1450 cm +1 ) after the reaction.
Die Vorteile der Methode liegen darin, daß hierbei durch chemische Reaktion Kohlendioxid in die stabile Verbindung Na2CO3 überführt wird, wobei diese dann in einem alumosilicatischen Gerüst isoliert vorliegt. Die Reaktion verläuft bei hoher Temperatur. Günstigste Ergebnisse werden im Temperaturintervall von 700°C-750°C erreicht, während in Zeolithen die Sorptionsraten bei solchen Werten sehr niedrig werden. Ein weiterer Vorteil liegt in der Regenerierbarkeit des verwendeten Feststoffes. Der carbonathaltige Sodalith kann durch Tempern bei 850°C das aufgenommene CO2 wieder vollständig abgehen, wobei die folgenden Reaktionen ablaufen:The advantages of the method are that this carbon dioxide is converted by chemical reaction in the stable compound Na 2 CO 3 , which is then isolated in an aluminosilicate scaffold. The reaction proceeds at high temperature. Most favorable results are achieved in the temperature range of 700 ° C-750 ° C, while in zeolites the sorption rates at such values become very low. Another advantage lies in the regenerability of the solid used. The carbonated sodalite can be completely removed by annealing at 850 ° C, the absorbed CO 2 , wherein the following reactions occur:
(in den carbonathaltigen Käfigen) sowie:(in the carbonate cages) such as:
(in den NaNO₂-enthaltenden Käfigen)(in the NaNO₂-containing cages)
Insgesamt liegt dann bei 850°C die Verbindung:Overall, then at 850 ° C the connection:
Na₈[AlSiO₄]₆(O)(NO₃)Na₈ [AlSiO₄] ₆ (O) (NO₃)
vor, die dann bei 700°C-750°C wieder CO₂-aufnahmefähig ist, entsprechend der Reaktion:before, then at 700 ° C-750 ° C again CO₂-receptive is, according to the reaction:
Bei dieser Regenerierung hat somit gleichzeitig eine Modifizierung der temperaturstabilisierenden Gaskomponente stattgefunden, wobei NO₂- in NO₃- übergegangen ist.In this regeneration thus simultaneously a modification of the temperature-stabilizing gas component has taken place, wherein NO₂ - in NO₃ - has passed.
Claims (4)
Na8(AlSiO4)6(NO2)(OH×H2O) = Basischer Nitrit-Sodalith).2. the reactive solid used is an aluminosilicate having a skeleton structure of space-filling packed cages (sodalite type), characterized in that in this case the cages in mixed form statistically 50% with sodium nitrite (NaNO 2 ) as temperature-stabilizing guest molecule and 50% with sodium hydroxide monohydrate ( NaOH.H 2 O) are occupied as a reactive guest molecule (chemical composition:
Na 8 (AlSiO 4 ) 6 (NO 2 ) (OH x H 2 O) = basic nitrite sodalite).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4042002A DE4042002A1 (en) | 1990-12-22 | 1990-12-22 | Carbon di:oxide removal from waste gas - by chemical reaction with porous solid basic nitrite-sodalite |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4042002A DE4042002A1 (en) | 1990-12-22 | 1990-12-22 | Carbon di:oxide removal from waste gas - by chemical reaction with porous solid basic nitrite-sodalite |
Publications (2)
Publication Number | Publication Date |
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DE4042002A1 true DE4042002A1 (en) | 1991-05-23 |
DE4042002C2 DE4042002C2 (en) | 1993-09-09 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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DE4042002A Granted DE4042002A1 (en) | 1990-12-22 | 1990-12-22 | Carbon di:oxide removal from waste gas - by chemical reaction with porous solid basic nitrite-sodalite |
Country Status (1)
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DE (1) | DE4042002A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998038132A1 (en) * | 1997-02-28 | 1998-09-03 | Grace Gmbh | Zeolitic molecular sieve, process for its preparation and its use |
DE10229910B4 (en) * | 2002-07-04 | 2005-10-27 | Buhl, Josef-Christian, Prof. Dr. | Zeolite with boron tetrahydrid-filled β-cages and process for its preparation |
DE102013013604A1 (en) * | 2013-07-20 | 2015-01-22 | Bvp Gmbh | Method for collecting fossil and biogenic carbon C14 from the exhaust air of power plants in molecular sieves and chemical solutions. |
-
1990
- 1990-12-22 DE DE4042002A patent/DE4042002A1/en active Granted
Non-Patent Citations (1)
Title |
---|
HUND, F.: Z. anorg. allg. Chem. 511 (1984), S. 225-230 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998038132A1 (en) * | 1997-02-28 | 1998-09-03 | Grace Gmbh | Zeolitic molecular sieve, process for its preparation and its use |
DE10229910B4 (en) * | 2002-07-04 | 2005-10-27 | Buhl, Josef-Christian, Prof. Dr. | Zeolite with boron tetrahydrid-filled β-cages and process for its preparation |
DE102013013604A1 (en) * | 2013-07-20 | 2015-01-22 | Bvp Gmbh | Method for collecting fossil and biogenic carbon C14 from the exhaust air of power plants in molecular sieves and chemical solutions. |
Also Published As
Publication number | Publication date |
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DE4042002C2 (en) | 1993-09-09 |
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Legal Events
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OAV | Applicant agreed to the publication of the unexamined application as to paragraph 31 lit. 2 z1 | ||
OP8 | Request for examination as to paragraph 44 patent law | ||
8125 | Change of the main classification |
Ipc: B01D 53/34 |
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8127 | New person/name/address of the applicant |
Owner name: BUHL, JOSEF-CHRISTIAN, DR., 4405 NOTTULN, DE |
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D2 | Grant after examination | ||
8364 | No opposition during term of opposition | ||
8327 | Change in the person/name/address of the patent owner |
Owner name: BUHL, JOSEF-CHRISTIAN, DR., 29339 WATHLINGEN, DE |
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8339 | Ceased/non-payment of the annual fee |