EP0160648A1 - Means and procedure for removal of carbon dioxide - Google Patents
Means and procedure for removal of carbon dioxideInfo
- Publication number
- EP0160648A1 EP0160648A1 EP84900134A EP84900134A EP0160648A1 EP 0160648 A1 EP0160648 A1 EP 0160648A1 EP 84900134 A EP84900134 A EP 84900134A EP 84900134 A EP84900134 A EP 84900134A EP 0160648 A1 EP0160648 A1 EP 0160648A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- air
- carbon dioxide
- carbonate
- aluminum oxide
- alkali metal
- 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- Withdrawn
Links
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 25
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 12
- 150000004645 aluminates Chemical class 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 238000010521 absorption reaction Methods 0.000 claims description 14
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims 1
- -1 alkali metal hydrogen Chemical class 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 239000000446 fuel Substances 0.000 abstract description 5
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- 238000011069 regeneration method Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002737 fuel gas Substances 0.000 description 3
- KKEBXNMGHUCPEZ-UHFFFAOYSA-N 4-phenyl-1-(2-sulfanylethyl)imidazolidin-2-one Chemical compound N1C(=O)N(CCS)CC1C1=CC=CC=C1 KKEBXNMGHUCPEZ-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009291 secondary effect Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- PTLRDCMBXHILCL-UHFFFAOYSA-M sodium arsenite Chemical compound [Na+].[O-][As]=O PTLRDCMBXHILCL-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- Air contains a little above 300 ppm carbon dioxide.
- the metal air batteries mainly the iron- and zink/air batteries, have a very high energy density but have in spite of this not yet found practical application as batteries for electric cars.
- One reason for this is that the alkaline electrolyte picks up carbon dioxide from the reaction air.
- the electrolyte has to be changed after a small number of cycles.
- One possi- bility to go around this problem is to clean the electrolyte by electro-dialysis in a continuous or discontinuous process.
- the carbon dioxide of the air is, owever, the cause of other problems in this application which cannot be sol- ved by electrolyte change or electrolyte purification. Carbonates are precipitated in channels and air cham ⁇ bers which is connected with the "creeping" property of the alkaline electrolyte. Such a “carbonate beard” can in its turn cause secondary effects with serious battery damage as a consequence.
- the present invention is an efficient and surprisingly simple solution to this problem which meets all require ⁇ ments put up, in particular the requirements on simplicity, reliability and small size.
- the invention can also be used in an analogous manner for elimination of carbon dioxide from air and fuel gas for fuel cell generators with alkaline electro ⁇ lyte. Another related application is elimination of carbon dioxide from reaction air for chlor alkali cells with air cathodes, electro-chemical so-called oxygen generators with air cathodes etc. There are also many applications outside the proper electro-chemical energy technology, e.g. removal of carbon dioxide from the atmosphere aboard submarines, space vehicles etc.
- the invention is concerned with an apparatus and a pro ⁇ cedure for removal of carbon dioxide from gas mixtures characterized in that it comprises a fixed bed absorp ⁇ tion reactor containing one body or a multitude of bodies of a supporting material, the surface of which at least consists of porous aluminum oxide or aluminate impregnated with a carbonate of an alkali metal.
- Figure 1 shows in principal a metal/air battery with an absorption reactor for air purificatio .
- the basic process for the invention is the reaction between sodium carbonate and carbon dioxide at a tem ⁇ perature below - 100 C preferably ⁇ 50 C.
- the sodium carbonate is regenerated by heat treatment at a temperature above 100°C, preferably 150-200°C.
- the carrier material consists of aluminum oxide,Al-O-, > or is a mixture of aluminum oxide or aluminate with other resistant oxides like magnesium oxide, zirconium oxide, heat stabilized silicon dioxide, silicates etc.
- the absorption reactor is designed in the same way as a catalytic reactor e.g. of the type which is used for exhaust gas cleaning in cars i.e. a pellet bed or mono ⁇ lith structure.
- the absorption reactor is dimensioned preferably for one battery cycle. The height should be 0,2 meter or somewhat above.
- Regeneration can take place by means of electrical heat or in connection with the charging procedure. Regene ⁇ ration may also take place by means of exhaust gas heat in case of hybride systems.
- Another application is a fuel cell generator of the alkaline type intended to replace-the mechanically driven alternating current generator for heavy trucks.
- the hydrogen for the fuel cell generator is produced by steam reforming of methanol.
- Absorption reactors according to the in ⁇ vention can be used as well for purification of the fuel gas as for the reaction air.
- the exhaust gas heat from the main engine is used for regeneration of the absorption reactors with a scheme with several parallell reactors in a permutated cycle of operation.
- Figure 1 shows completely schematically an iron/air battery with circulating electrolyte according to the U.S. patent 3,801,376 .
- the battery is air cooled. Cooling air and process air are coming into Suite contact with the electrolyte.
- Figure 1 shows the battery pile (1) which is enclosed in a surrounding electrolyte vessel (2) . The air comes into contact with the air electrodes in an air chamber which is not shown. The air flow in the air chamber is shown by dotted flow arrows (3) .
- the electrolyte is circula ⁇ ting through the electrolyte chamber (4) via over flow (5) to the electrolyte trough (6) in the battery vessel.
- the electrolyte flow is shown with the flow arrows (7) .
- Air is supplied by means of two fans, one is governed by the temperature (8) and the other one (9) by the air demand for the discharge current in question. There is also a heat exchanger- (10) in the air system for recovery of water. Pre-heat of the process air is taking place in the battery vessel since the process air is first supplied to the surrounding vessel whereby the air is heated up in contact with the hot electrolyte whi ⁇ le at the same time the air is taking up moisture.
- the system contains also an electrical heater (11) which is used for heating up the battery during cold whether and for regeneration of the absorption reactor (12) . Regeneration is taking place by means of the heat element (13). Air with a temperature around 150 - 200°C is* flowing up through the absorption reac ⁇ tor and is taking with it evaporated carbon dioxide. The air is taken in through the valve (14) which is opened for the regeneration procedure.
- Figure 2 shows a simple embodiment of such an absorp ⁇ tion reactor which thus consists of a vessel contai ⁇ ning a bed of porous pellets of activated aluminum oxide (15) .
- suitable commercially available carriers of this kind are BASF D10-10 or Kebo 1.1108. Impregnation is taking place with e.g. saturated sodium carbonate solution around 50 C whereafter the pellets are dried in an oven at around 150 C for two hours. Potassium carbonate can also be used but it is not more efficient than the cheaper sodium carbonate. Addition of sodium arsenite, which is a known catalyst for this reaction, does not give a further improvement of the catalytic action of the carrier.
- the vessel is furnished with an inlet and an outlet.
- the electrical element (13) is situated in the bed.
- Figure 3 shows another embodiment with a carrier in the form of a monolith ' structure (16) like those which are used for exhaust gas cleaning or final combustion of stack gases from wood stoves etc.
- the porous carrier of aluminum oxide has been impregnated with a sodium carbonate solution.
- the process is complicated with several steps.
- the reaction is not studied in the literature and it has not been possible to elucidate which step is rate determining.
- the absorption is, however, taking place rapidly and with a high efficiency i a.small reactor volume thanks to a not clarified catalytic action devel ⁇ oped by the carrier.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Gas Separation By Absorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treating Waste Gases (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Du gaz carbonique se trouvant dans l'air et/ou par exemple dans un gaz combustible pour des piles à combustible à hydrogène/air est absorbé dans des corps poreux (15) ou éléments (16) consistant entièrement ou partiellement d'oxyde d'aluminium ou d'aluminate, dont la surface a été imprégnée avec une solution de carbonate alcalin. Dans ces conditions, le gaz carbonique est absorbé rapidement avec formation de carbonate hydrogéné. Le carbonate est régénéré par des moyens thermiques. Le nouveau procédé est simple et efficace et est particulièrement approprié pour des applications légères telles que l'extraction de gaz carbonique de l'air pour des batteries au métal/air, des piles à combustible etc.Carbon dioxide present in the air and / or for example in a combustible gas for hydrogen / air fuel cells is absorbed in porous bodies (15) or elements (16) consisting entirely or partially of oxide of aluminum or aluminate, the surface of which has been impregnated with an alkaline carbonate solution. Under these conditions, carbon dioxide is absorbed quickly with the formation of hydrogenated carbonate. The carbonate is regenerated by thermal means. The new process is simple and efficient and is particularly suitable for light applications such as extracting carbon dioxide from the air for metal / air batteries, fuel cells etc.
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE8207022A SE8207022L (en) | 1982-12-08 | 1982-12-08 | SET AND DEVICE FOR CARBON Dioxide REMOVAL |
| SE8207022 | 1982-12-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0160648A1 true EP0160648A1 (en) | 1985-11-13 |
Family
ID=20348929
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84900134A Withdrawn EP0160648A1 (en) | 1982-12-08 | 1983-12-07 | Means and procedure for removal of carbon dioxide |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0160648A1 (en) |
| JP (1) | JPS60500165A (en) |
| SE (1) | SE8207022L (en) |
| WO (1) | WO1984002283A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5595949A (en) * | 1994-03-18 | 1997-01-21 | Electric Fuel (E.F.L.) Ltd., | Scrubber system for removing carbon dioxide from a metal-air or fuel cell battery |
| GB2305139A (en) * | 1995-09-12 | 1997-04-02 | Electric Fuel | Coated absorbent particles for a carbon dioxide scrubber system |
| US5899187A (en) * | 1996-07-11 | 1999-05-04 | Jenbacher Energiesysteme Aktiengesellschaft | Engine arrangement |
| CN100449841C (en) * | 2001-06-15 | 2009-01-07 | 兹特克公司 | Zero or low emission and co-production type energy supply station |
| US20070141430A1 (en) * | 2005-12-21 | 2007-06-21 | Qunjian Huang | Gas scrubber and method related thereto |
| JP2014133219A (en) * | 2013-01-11 | 2014-07-24 | Ngk Insulators Ltd | Gas removal device and gas removal method using the same |
| US10074884B2 (en) | 2015-05-19 | 2018-09-11 | Samsung Electronics Co., Ltd. | Metal air battery having air purification module and method of operating the metal air battery |
| CN113856399A (en) * | 2021-10-31 | 2021-12-31 | 中国船舶重工集团公司第七一八研究所 | Equipment for removing carbon dioxide based on cyclic regeneration mode |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE101390C (en) * | ||||
| US3232028A (en) * | 1962-07-02 | 1966-02-01 | Isomet Corp | Composition and method for absorption and regeneration of carbon dioxide |
| US3865924A (en) * | 1972-03-03 | 1975-02-11 | Inst Gas Technology | Process for regenerative sorption of CO{HD 2 |
-
1982
- 1982-12-08 SE SE8207022A patent/SE8207022L/en not_active Application Discontinuation
-
1983
- 1983-12-07 JP JP84500206A patent/JPS60500165A/en active Pending
- 1983-12-07 WO PCT/SE1983/000433 patent/WO1984002283A1/en not_active Ceased
- 1983-12-07 EP EP84900134A patent/EP0160648A1/en not_active Withdrawn
Non-Patent Citations (1)
| Title |
|---|
| See references of WO8402283A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60500165A (en) | 1985-02-07 |
| SE8207022L (en) | 1984-06-09 |
| SE8207022D0 (en) | 1982-12-08 |
| WO1984002283A1 (en) | 1984-06-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB LI LU NL SE |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
| 18D | Application deemed to be withdrawn |
Effective date: 19850813 |
|
| RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: LINDSTROEM, OLLE Inventor name: HOEGLUND, LARS, OLOF |