DE102009015035A1 - Method of operating a fossil power plant and power plant - Google Patents
Method of operating a fossil power plant and power plant Download PDFInfo
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- DE102009015035A1 DE102009015035A1 DE102009015035A DE102009015035A DE102009015035A1 DE 102009015035 A1 DE102009015035 A1 DE 102009015035A1 DE 102009015035 A DE102009015035 A DE 102009015035A DE 102009015035 A DE102009015035 A DE 102009015035A DE 102009015035 A1 DE102009015035 A1 DE 102009015035A1
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- 238000000034 method Methods 0.000 title claims abstract description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000012528 membrane Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 28
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 28
- 238000002485 combustion reaction Methods 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 7
- -1 polydimethylsiloxane Polymers 0.000 claims description 7
- 239000000446 fuel Substances 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000002803 fossil fuel Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000002309 gasification Methods 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 238000000926 separation method Methods 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000012465 retentate Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/864—Removing carbon monoxide or hydrocarbons
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- 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
- B01D53/22—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 diffusion
- B01D53/228—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 diffusion characterised by specific membranes
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- 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
- B01D53/22—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 diffusion
- B01D53/229—Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1213—Laminated layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
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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
- 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
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/152—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the reactor used
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2255/102—Platinum group metals
- B01D2255/1021—Platinum
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- B01D2255/207—Transition metals
- B01D2255/20761—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2255/40—Mixed oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/16—Hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/10—Single element gases other than halogens
- B01D2257/108—Hydrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2325/00—Details relating to properties of membranes
- B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
-
- 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
- C01B2203/0405—Purification by membrane 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
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/32—Direct CO2 mitigation
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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
- 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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
Die Erfindung betrifft eine Vorrichtung und ein Verfahren zur Verminderung des Kohlendioxidausstoßes bei fossil betriebenen Kraftwerken. Dazu wird in einer auf die eigentliche Verbrennung folgenden Reaktion das gasförmige Produkt durch eine Membran, die Kohlendioxid absorbiert, geführt.The invention relates to a device and a method for reducing carbon dioxide emissions in fossil-fueled power plants. For this purpose, in a reaction following the actual combustion, the gaseous product is passed through a membrane which absorbs carbon dioxide.
Description
Die Erfindung betrifft eine Vorrichtung und ein Verfahren zur Verminderung des Kohlendioxidausstoßes bei fossil betriebenen Kraftwerken.The The invention relates to a device and a method for reduction of carbon dioxide emissions in fossil power plants.
Die globale Kohlendioxid Konzentration in der Atmosphäre nimmt seit Jahrzehnten zu. Kohlendioxid ist ein Treibhausgas und wird unter anderem für die globale Erderwärmung verantwortlich gemacht.The global carbon dioxide concentration in the atmosphere decreases for decades too. Carbon dioxide is a greenhouse gas and will for, among other global warming responsible.
Bislang wird zwar Kohlendioxid-Abtrennung bei Kraftwerken erforscht, aber es gibt noch keine Vorrichtung und kein Verfahren mit dem der Anteil an Kohlendioxidausstoß bei fossil betriebenen Kraftwerken signifikant erniedrigt wird. Der Anteil an Kohlendioxid im Kraftwerkabgas ist jedoch signifikant und liegt bei ca. 25% des gesamten Abgases.So far Although carbon dioxide separation is explored in power plants, but There is still no device and no method with which the proportion at carbon dioxide emissions fossil-fueled power plants is significantly reduced. Of the However, the share of carbon dioxide in power plant exhaust gas is significant and is about 25% of the total exhaust gas.
Derzeit wird großtechnisch die Aminwäsche in Demonstratorkraftwerken getestet, bei der CO2 aus Rauchgasen in einem aufwändigen Verfahren absorbiert und anschließend nach Erwärmung hochrein gewonnen wird. Der Nachteil des Verfahrens liegt im hohen Energieaufwand. Der Wirkungsgrad des Kraftwerks wird durch die CO2 Abtrennung bei Integration der Aminwäsche um ca. 10–14% reduziert, wobei wertvolle Ressourcen an fossilen Brennstoffen verbraucht werden.Currently, the amine scrubbing is being tested on a large scale in demonstrator power plants, in which CO 2 from flue gases is absorbed in a complex process and then obtained highly purified after heating. The disadvantage of the method is the high energy consumption. The efficiency of the power plant is reduced by the CO 2 separation with integration of amine scrubbing by about 10-14%, whereby valuable resources are consumed on fossil fuels.
Ein Hauptproblem bei der CO2-Abtrennung aus Kraftwerken liegt darin, dass die Effizienz des Kraftwerks durch die Abtrennung möglichst wenig beeinträchtigt wird.A major problem with CO 2 separation from power plants is that the efficiency of the power plant is affected as little as possible by the separation.
Aufgabe der vorliegenden Erfindung ist daher, einen Verfahren und eine Vorrichtung zur Abtrennung von Kohlendioxid aus einem fossil betriebenen Kraftwerk zu schaffen.task The present invention is therefore a method and an apparatus for the removal of carbon dioxide from a fossil-fueled power plant to accomplish.
Lösung der Aufgabe und Gegenstand der Erfindung sind in der vorliegenden Beschreibung, der Figur und den Ansprüchen offenbart.Solution of Object and subject of the invention are in the present description, the figure and the claims disclosed.
Demnach ist es Gegenstand der Erfindung ein Verfahren zum Betreiben eines Kraftwerks, bei dem in einem auf die Vergasung des Brennstoffs folgenden Prozessschritt das Abgas aus dem Kraftwerk einer Reaktion (im Folgenden auch ”Folge-Reaktion” genannt) unterworfen wird, wobei das gasförmige Produkt dieser Reaktion in eine Membran eingeleitet wird. Außerdem ist Gegenstand der Erfindung ein Kraftwerk zur Verbrennung fossiler Brennstoffe, bei dem in der Ablassöffnung der Reaktionskammer für eine an die eigentliche Verbrennung anschließende Reaktion eine Membran vorgesehen ist.Therefore it is the subject of the invention, a method for operating a Power plant at which in one following on the gasification of the fuel Process step the exhaust gas from the power plant of a reaction (hereinafter also called "follow-up reaction") is subjected, wherein the gaseous product this reaction is introduced into a membrane. Besides that is The invention relates to a power plant for burning fossil Fuels in which in the discharge opening of the reaction chamber for one reaction following the actual combustion, a membrane is provided.
Nach einer vorteilhaften Ausführungsform der Erfindung ist die Membran eine Siloxanmembran, insbesondere bevorzugt ist es eine Polydimethylsiloxanmembran.To an advantageous embodiment of the Invention, the membrane is a siloxane membrane, particularly preferred it is a polydimethylsiloxane membrane.
Nach einer weiteren vorteilhaften Ausführungsform der Erfindung ist die Membran gekoppelt mit einem porösen katalytisch aktiven Träger, beispielsweise einer Mischoxidschicht. Diese kann selbsttragend oder auch auf einer Trägerfolie aufgebracht sein. Nach einer besonders bevorzugten Ausführungsform ist die Mischoxidschicht eine Mischung aus ausgewählt aus den folgenden Oxiden: Zinkoxid, Aluminiumoxid, Zirkonoxid, Titanoxid, sowie weiterer Nebengruppenmetalloxide und/oder der Oxide der Gruppe der seltenen Erden.To a further advantageous embodiment of the invention the membrane coupled with a porous catalytically active support, for example a mixed oxide layer. This can be self-supporting or even on one support film be upset. According to a particularly preferred embodiment the mixed oxide layer is a mixture of selected from the following oxides: zinc oxide, aluminum oxide, zirconium oxide, titanium oxide, and other minor group metal oxides and / or the oxides of the group rare earth.
Nach einer besonders bevorzugten Ausführungsform ist die Oberfläche des Mischoxid-Trägers noch mit einem Katalysator dotiert, damit das in der Membranschicht abgetrennte Kohlendioxid mit dem bei der Abtrennung ebenfalls anfallenden Wasserstoff am Mischoxidträger, bevorzugt bei den in der CO-Shift Reaktionskammer vorliegenden Temperaturen, gleich in Precursor-Chemikalien umsetzbar ist. Als Katalysator eigenen sich beispielsweise Kupfer, Platin, Palladium, und andere, bevorzugt auf der Oberfläche fein verteilte Edelmetalle.To a particularly preferred embodiment is the surface of mixed oxide carrier yet doped with a catalyst so that the separated in the membrane layer Carbon dioxide with the hydrogen also obtained during the separation on the mixed oxide carrier, preferred in the CO shift Reaction chamber present temperatures, equal in precursor chemicals is feasible. For example, copper, platinum, Palladium, and others, preferably on the surface finely dispersed precious metals.
Vorzugsweise wird eine asymmetrische Membran eingesetzt, in der die Membranschicht zur Abtrennung des Kohlendioxids auf der porösen Mischoxidschicht aufgebracht ist.Preferably an asymmetric membrane is used in which the membrane layer applied to the separation of the carbon dioxide on the porous mixed oxide layer is.
Durch die hier beschriebene Membrantechnologie mit vorzugsweise asymmetrischen Membranen wird aus dem Gasgemisch, das die Reaktionskammer der Folge-Reaktion, bevorzugt der CO-Shift-Reaktion, verlässt, Wasserstoff plus Kohlendioxid im Permeat angereichert. Die Temperatur der Folge-Reaktion liegt zwischen 200°C und 400°C, insbesondere zwischen 230°C und 380°C und besonders bevorzugt zwischen 280°C und 320°C.By the membrane technology described here with preferably asymmetric Membranes are made from the gas mixture, which is the reaction chamber of the reaction sequence, prefers the CO shift reaction, leaves, Hydrogen plus carbon dioxide enriched in permeate. The temperature of the Follow-up reaction is between 200 ° C and 400 ° C, in particular between 230 ° C and 380 ° C and more preferably between 280 ° C and 320 ° C.
Vorteilhafterweise liegt das Abgas aus der Folge-Reaktion unter einem hohen Druck vor, insbesondere von 25 bis 45 bar.advantageously, is the exhaust gas from the sequence reaction under a high pressure, in particular from 25 to 45 bar.
In der Reaktionskammer für die CO Shift Reaktion entstehen Wasserstoff, Kohlendioxid und Wasser. Der Anteil von Kohlenmonoxid liegt dort im Abgas beispielsweise nur noch 3 bis 10%. Eine Abtrennung vom Kohlendioxid an der Stelle im Kraftwerksprozess ist im Vergleich etwa zum Post Combustion Prozess wegen eines dort möglichen hohen Gasdrucks nach der CO Shift Reaktion von ca. > 25 bar, insbesondere von > 30 bar sehr günstig.In the reaction chamber for The CO shift reaction produces hydrogen, carbon dioxide and water. The proportion of carbon monoxide is there in the exhaust, for example only 3 to 10%. A separation of carbon dioxide at the site In comparison to the post-combustion process in the power plant process, for example because of a possible there high gas pressure after the CO shift reaction of about> 25 bar, in particular from> 30 bar very much Cheap.
Des Weiteren ist bevorzugt, dass das Abgas aus der Reaktionskammer der Reaktion einen relativ hohen Kohlendioxidanteil von bis zu 60%, insbesondere ca. 35 bis 50%, insbesondere von 40 bis 45% hat und daher für die Kohlendioxidabscheidung sehr günstig ist.Furthermore, it is preferred that the exhaust gas from the reaction chamber of the reaction has a relatively high carbon dioxide content of up to 60%, in particular about 35 to 50%, in particular from 40 to 45%. and therefore is very favorable for the carbon dioxide separation.
Das Abgas aus der Reaktionskammer der Folge-Reaktion wird bevorzugt mit einem für die Durchleitung durch eine Membran günstigen relativ geringen Fluss von beispielsweise ca. 5 bis 20 m3/s, insbesondere von ca. 10 m3/s, geführt werden.The exhaust gas from the reaction chamber of the reaction sequence is preferably with a favorable for the passage through a membrane relatively low flow of, for example, about 5 to 20 m 3 / s, in particular of about 10 m 3 / s, out.
Vorteilhafterweise reichen bei hohen Drücken bereits relativ geringe Selektivitäten der Membranen von CO2/H2 > 5, vorzugsweise > 10 und insbesondere > 15 aus.Advantageously, at high pressures already relatively low selectivities of the membranes of CO 2 / H 2 > 5, preferably> 10 and in particular> 15 from.
Nach einer vorteilhaften Ausführungsform wird durch die Membran, da es sich um eine Bulkmethode handelt, gleichzeitig Wasserstoff mit abgetrennt. Dies kann beispielsweise in einer Menge von bis zu 30% erfolgen. In der Membran wird dann eine Mischung aus Kohlendioxid und Wasserstoff gehalten, die sich zur Umsetzung an Katalysatoren zu Produkten wie Methanol und Wasser oder anderen industriellen Precursormaterialien direkt anbieten.To an advantageous embodiment is through the membrane, since it is a Bulk method, simultaneously Hydrogen separated with. This can for example be in a crowd up to 30%. The membrane then becomes a mixture made of carbon dioxide and hydrogen, which is used for the reaction on catalysts to products such as methanol and water or others directly offer industrial precursor materials.
Größte Triebkraft ist die bereits bestehende Druckdifferenz zwischen Feedstrom und Permeat von > 25, insbesondere > 30 bar. Dadurch verringert sich die Kohlendioxid Konzentration im Retentat. Der relativ geringe Fluss erlaubt die großtechnische Nutzung der Membrantechnologie.Greatest driving force is the existing pressure difference between feed stream and Permeate of> 25, in particular> 30 bar. This reduces the carbon dioxide concentration in the retentate. The relatively low flow allows the large-scale use of membrane technology.
Die Membran kann aus verschiedenen Kunststoffen, die thermisch stabil sind, gegen saure Gase inert und Kohlendioxid binden, sein. Insbesondere ist die Membran aus Siloxan oder einem ähnlichen synthetisch geschaffenen Kunststoff oder einem Kunststoffgemisch. Insbesondere geeignet ist unter anderen die Polydimethylsiloxanmembran, weil sie bis ca. 330°C thermisch stabil ist und gegen die sauren Umgebungsbedingungen inert. Durch Modifikationen, insbesondere auch eine chemische Modifikationen, also Bindung anderer Oberflächengruppen, kann die Selektivität der Polydimethylsiloxanmembran erhöht werden.The Membrane can be made of different plastics that are thermally stable are inert to acid gases and bind carbon dioxide, be. Especially is the membrane of siloxane or a similar synthetically created Plastic or a plastic mixture. Particularly suitable is under other the polydimethylsiloxane membrane, because they thermally to about 330 ° C. is stable and inert to the acidic environment. By Modifications, in particular also chemical modifications, So binding of other surface groups, can the selectivity the polydimethylsiloxane membrane are increased.
Die Membran selbst ist bevorzugt auf einer Trägerfolie aufgebracht, so beispielsweise auf einer Metall-, Kunststoff-Glas- oder Keramikfolie.The Membrane itself is preferably applied to a carrier film, such as for example on a metal, plastic-glass or ceramic foil.
Zwischen der Membran und der Trägerfolie ist bevorzugt ein Katalysator zur Umsetzung der durch die Membran gebundenen Gase vorgesehen. Insbesondere bevorzugt wird ein Mischoxid zwischen der Trägerfolie und der Membran angeordnet. Insbesondere bevorzugt wird das Mischoxid dabei noch mit einem Katalysator dotiert sein, so dass ein Mischoxid-Katalysator vorliegt. Nach einer besonders bevorzugten Ausführungsform ist dieser Mischoxid-Katalysator noch porös gestaltet, so dass eine hohe Oberfläche, an der die Reaktion aus der Gasphase stattfinden kann, resultiert.Between the membrane and the carrier film is preferably a catalyst for the reaction of bound by the membrane Gases provided. Particularly preferred is a mixed oxide between the support film and the membrane arranged. Especially preferred is the mixed oxide while still being doped with a catalyst, so that a mixed oxide catalyst is present. According to a particularly preferred embodiment, this mixed oxide catalyst still porous designed so that a high surface at which the reaction is off the gas phase can take place results.
Die Figur zeigt eine Prinzipskizze einer asymmetrischen Membran nach einer beispielhaften Ausführungsform der Erfindung.The Figure shows a schematic diagram of an asymmetric membrane an exemplary embodiment the invention.
Zu sehen ist eine asymmetrische Membran zur Kohlendioxid-Abtrennung und katalytischen Umwandlung von Kohlendioxid und Wasserstoff in Methanol.To see is an asymmetric membrane for carbon dioxide separation and catalytic Conversion of carbon dioxide and hydrogen into methanol.
Der
Schichtaufbau der asymmetrischen Membran zeigt von unten nach oben
folgende Abfolgt:
Die Trägerfolie
The carrier foil
Beispielsweise werden mit modifizierten Polydimethylsiloxanmembranen Selektivitäten von > 10, vorzugsweise > 20 erreicht.For example Selectivities of> 10, preferably> 20 are achieved with modified polydimethylsiloxane membranes.
Das restliche Kohlendioxid bleibt nach der Kondensation der katalytisch unterstützten Reaktionsprodukte als sauberes Gas zurück. Es kann beliebig genutzt werden, beispielsweise verflüssigt oder einer weiteren Umsetzung zugeführt werden.The residual carbon dioxide remains after the condensation of the catalytic supported Reaction products as clean gas back. It can be used as you like be liquefied, for example or be supplied to a further implementation.
Im durch die Membran geleiteten Abgas verbleiben Spurengase der Verbrennung, insbesondere Sox, NOx, oder ähnliche. Die CO2 Abtrennung über die Membran verringert den Wasserstoffdruck im Retentat für die GuD nicht.In the guided through the membrane exhaust trace gases of combustion remain, in particular So x , NO x , or the like. CO 2 separation across the membrane does not reduce the hydrogen pressure in the retentate for the gas.
Beim Einsatz von dünnen Polydimethylsiloxanmembranen können > 70% des Kohlendioxids abgetrennt werden.At the Use of thin Polydimethylsiloxane membranes can separate> 70% of the carbon dioxide become.
Der mit abgetrennte Wasserstoff ist als Brennstoff zur Methanolproduktion genutzt, eventuelle Überreste können auch später noch zur Energiegewinnung nutzbar gemacht werden. Als Methanol kann Wasserstoff beispielsweise in der Brennstoffzelle eingesetzt werden. Methanol ist so zu sagen ein ”chemischer Speicher” für Wasserstoff.Of the with separated hydrogen is used as fuel for methanol production used, any remains can even later still be harnessed for energy. As methanol can Hydrogen are used for example in the fuel cell. Methanol is a "chemical Storage tank "for hydrogen.
Die Eigenschaften des Retentats werden bei der Abtrennung über die asymmetrische Polydimethylsiloxanmembran nicht geändert: der Feed-Druck bleibt im Retentat unverändert bestehen und die nachfolgende Oxidation von Wasserstoff wird nicht beeinträchtigt. Für die Prozessführung ist es sogar vorteilhaft, wenn Wasserstoff, wie nach dem Verfahren gemäß der Erfindung möglich, noch verdünnt vorliegt.The properties of the retentate are not changed in the separation via the asymmetric polydimethylsiloxane membrane: the feed pressure remains unchanged in the retentate and the subsequent oxidation of hydrogen is not impaired. It is even for the litigation advantageous if hydrogen, as still possible according to the method according to the invention, is still present in a diluted form.
Nach vorliegenden Versuchen und Berechnungen wird der Wirkungsgrad eines fossil betriebenen Kraftwerks durch die Kohlendioxid-Abtrennung weniger als 5% belastet. Eine Optimierung des Gesamtverbrauchs durch Integration von beispielsweise Brennstoffzellen ist denkbar.To Present experiments and calculations will increase the efficiency of a fossil-fueled power plant by the carbon dioxide separation less charged as 5%. An optimization of the total consumption through integration For example, fuel cells is conceivable.
Das noch vorhandene Kohlendioxid kann beliebig weiter genutzt werden.The Any remaining carbon dioxide can be used as desired.
Die Erfindung betrifft eine Vorrichtung und ein Verfahren zur Verminderung des Kohlendioxidausstoßes bei fossil betriebenen Kraftwerken. Dazu wird in einer auf die eigentliche Verbrennung folgenden Reaktion das gasförmige Produkt durch eine Membran, die Kohlendioxid absorbiert, geführt.The The invention relates to a device and a method for reduction of carbon dioxide emissions in fossil power plants. This is done in one on the actual Combustion following reaction the gaseous product through a membrane, which absorbs carbon dioxide, led.
Claims (12)
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US20080282882A1 (en) * | 2006-11-08 | 2008-11-20 | John Charles Saukaitis | gas separation membrane comprising a substrate with a layer of coated inorganic oxide particles and an overlayer of a gas-selective material, and its manufacture and use |
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