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Patent Searching and Data


Title:
ELECTRODE SUPPORT FOR FUEL CELL
Document Type and Number:
WIPO Patent Application WO/2006/030590
Kind Code:
A1
Abstract:
An electrode support for fuel cell comprised of a porous body having a Ni phase of Ni or NiO and an inorganic aggregate phase, characterized in that at least one metal (M) for oxidation-reduction swelling inhibition selected from the group consisting of Fe, Co and Mn is solid dissolved in the Ni phase or is unevenly distributed in a grain boundary between the Ni phase and the inorganic aggregate phase. This electrode support minimizes a volume swelling/shrinkage change even in an environment of alternate exposure to a reducing atmosphere and an oxidizing atmosphere. The fuel cell comprising this electrode support and, superimposed thereon, afuel electrode, a solid electrolyte layer and an oxygen electrode realizes effective prevention of cracking, detachment, etc. by, for example, swelling encountered when a reduction/oxidation cycle is repeated by power generation and halting of power generation, thereby strikingly excelling in long-term reliability.

Inventors:
FUJIMOTO TETSURO (JP)
YAMASHITA SHOJI (JP)
Application Number:
PCT/JP2005/014493
Publication Date:
March 23, 2006
Filing Date:
August 02, 2005
Export Citation:
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Assignee:
KYOCERA CORP (JP)
FUJIMOTO TETSURO (JP)
YAMASHITA SHOJI (JP)
International Classes:
H01M8/02; H01M4/86; H01M8/12; H01M8/24
Foreign References:
JP2004179071A2004-06-24
JP2002352809A2002-12-06
JP3323029B22002-09-09
JPH10241702A1998-09-11
JP3350313B22002-11-25
JPH0982335A1997-03-28
JP2963119B21999-10-12
JP2005190737A2005-07-14
Other References:
See also references of EP 1801905A4
Attorney, Agent or Firm:
Ono, Hisazumi (1-21 Nishi-shimbashi 1-chom, Minato-ku Tokyo 03, JP)
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Claims:
C L A I M S
1. A combined combustion and exhaust gas filter plant com¬ prising a chamber (3) for pressurized combustion of all kinds of combustible substances and a means (10, 12) for pressurized coo¬ ling and washing with water of the created exhaust gases and separating the environment endangering materials and other conta¬ minants being present in the fuel or being produced during the combustion, comprising a means for deducting the washing water and the materials being captured, solved or condensed in it, as well as a means (14, 20) for expanding the remaining exhaust gases in one or several steps in such a way that a sufficiently low temperature is achieved at the output from the expansion means (14, 20) for condensing at least the main parts of the remanining contaminants in solid or in liquid form and collecting these in a separating means (16, 22), characterized in that a means (3, 8) is connected to the combustion means (5) for the supply of up to 100 percent oxygen enriched combustion air and that a vaccum pump (27) or similar is connected to the separating means (22) for by pumping deducting the small amounts of not con¬ densed gases being accumulated in the separating means (22) after the last expansion step (20).
2. A plant according to claim 1, characterized in that the means for supplying the oxygen enriched combustion air comprises a pressurized bottle (8) for liquid oxygen.
3. A plant according to claim 1, characterized in that the means for supplying the oxygen enriched combustion air comprises an oxygen separating membrane or any other oxygen separating means (3), its oxygen side being in connection with the comfcus tion chamber ( 5) .
4. A plant according to any one of the preceding claims, characterized in that a vaccum pump (27) or similar is connected to the separating means (22) for maintaining a vacuum in it.
5. A plant according to any one of the preceding claims, characterized in that the condensate existing in the separating means (22) is completely or partly adapted to be recycled to the means (10, 12) for cooling and washing the exhaust gases for eva¬ poration and thereafter for a following expansion of vapourized condensate together with the remaining gas mixture.
Description:
Combined Combustion and _Exhaust Gas Cleansing Plant

The present invention relates to a combined combustion and exhaust gas filter plant of a kind in accordance with the descri¬ bing part of claim 1.

Such plants are already known and have as a fact performed well. The filtering degree can be made extremely high and plants of this kind need little space, which is important during the conversion of existing plants. All steps for achieving this have been concentrate on the filter process itself. However, it has been shown to possibly achieve further improvements by a better matching of the combustion means and the expansion gas filter plant.

Therefore, it is the purpose of the invention to achieve further improvements of the filtering effect and the space requi¬ rements for a combined combustion and exhaust gas filter plant.

According to the present invention this is achieved by con¬ necting the combustion chamber in a combined combustion and ex¬ haust gas filter plant of the kind mentioned in the beginning to a means for the supply of combustion air enriched up to 100 % with oxygen gas and by connecting the separating means to a vacu¬ um pump or similar for the disposal by pumping of the small amounts of not condensed gases being accumulated in the separa¬ ting means after the last expansion step.

As a fact,, the combustion air is containing four parts of nitrogen on one part of oxygen as well as some minor quantities of other substances. The combustion is relying on the presence of sufficient quantities of oxygen, whereas the nitrogen only has a negative influence. On one hand, the nitrogen is creating a num¬ ber of dangerous substances during the combustion and on the other hand the gas mass is heavily increased. Already an increase of the oxygen of up to two parts oxygen for three parts nitrogen is decreasing the required combustion air to a half. Pure oxygen would result in a compressor effect being 80 percent less. The heavily decreased volume of combustion air makes it possible to essentially limit the size of the combustion chamber. The tempe¬ rature in the combustion chamber will rise as the same amount of energy is set free during the combustion. The temperature rise

can be balanced by means of larger heat accumulating areas and increased heat radiation.

However, the most important progress is found on the exhaust gas filter side by that an extremely pure exhaust gas can be ac¬ hieved, the content of nitrogen being possibly reduced in the combustion chamber. Otherwise, different kinds of nitrogen oxides are created in the presence of nitrogen during the combustion and these are very difficult to separate. During a combustion with pure oxygen no nitrogen oxides will be created, indepedent of if high combustion temperatures are obtained or not. In an oxygen enriched atmosphere water soluble oxides N„ and l^O- are created in the first place and these are comparatively easy to separate.

The exhaust gases will consist of N„, C0„, H_0 and small amounts of nitrogen oxides as well as contaminants coming from the fuel. Part of the water vapour is condensed in the washing means together with the water and NO., and N_0-- are solved therein as well as a major part of the existing contaminants of the SO^ and Cl type and others. After the washing means there will only occur N„, C0„ and small amounts of substances not being water soluble eller being condensed at a temperature prevailing direct¬ ly after the washing means. The more enriched with oxygen the combustion air is, so much smaller amounts of nitrogen will exist in the flue gases directly before the expansion device. Of course, the amount of nitrogen oxides and other contaminants can be reduced as a complement by adding different chemicals to the washing water.

In the expansion means the temperature is lowered to a level being determined by the incoming gas temperature and the pressure drop. If the final temperature is lying below -50 C the contami¬ nants in the exhaust gases will be condensed together with the water vapour in the gas. When the temperature is falling below -120 C even all carbon dioxide has been condensed. If the pressu¬ re drop in the expansion means occurs in one step the frozen snow and the carbon dioxide snow will contain the contaminants. There¬ fore, it might be convenient to perform the expansion in two steps, one for condensating the snow and the contaminants and the other for condensing the pure carbon dioxide.

By this means water, carbon dioxide and all contaminants in the exhaust gases possibly have been eliminated. There remain only possibly existing nitrogen and inert gases. If only oxygen had been used almost all gases would have been converted to con¬ densate and by continually feeding out the condensate and moreo¬ ver keeping the separating chamber closed to the atmosphere out¬ side, the final pressure can be kept close to 0 bar. This low pressure is increasing the pressure drop in the expansion means or the last one of these and ameliorates its efficiency very con¬ siderably. The efficiency is also increasing with oxygen contents below 100 percent, but not to such an extent. To maintain this low pressure a vaccum pump is used which continually is sucking away remaining gases from the separation means.

With lower temperature before the first expansion unit the temperature after the expansion means will drop lower. By recyc¬ ling carbon dioxide snow to the washing means a better cooling is obtained before the expansion on one part and on the other part a considerably larger gas flow is achieved through the expansion means. In straight thermodynamical terms a gas turbine system ac¬ cording to the original concept is requiring the supply of mecha¬ nical energy, the outlet temperature being lower than the inlet temperature. However, the process might be changed by recycling condensed carbon dioxide in the way mentioned above and by this means to reach a balance in the system, i.e. the expansion can produce so much energy as the compression requires. By recycling more carbon dioxide the expansion means will produce more mecha¬ nical energy than is required by the compressor. In such a way heat energy can be transformed to mechanical energy. The maximal transformation is obtained by recycling so much condensed carbon dioxide that its vaporisation heat corresponds to the energy ot¬ herwise supplied during combustion or to the system. In a practi¬ cal embodiment it should also be observed that the expansion means temperature is lying above 0 C. Also it is possible to ex¬ ternally supply thermal energy, for example, to the expansion means in form of water with a temperature lying above 0°C. Then this energi is also converted to mechanical energy.

In certain cases the pressure can be augmented between the

expansion steps by a compressor or by heating the gas by means of a heat exchanger. By limiting the amount of nitrogen in the ex¬ haust gases, the amount of gas to be compressed can be limited.

By cooling the gas between the expansion steps, conveniently by means of the cold gas, originated after the expansion, a lower final temperature is achieved or, alternatively, a given final temperature with a lower original pressure and, thus, a minor compression effect.

The simplest way to limit the amount of nitrogen in the in¬ coming combustion air is to supply the necessary oxygen from an oxygen gas bottle. In larger plants a better economy implies the use of e.g. a gas separating membrane. Then, the oxygen produced is used in the combustion plant whereas the pressurized nitrogen can drive a generator or be stored pressurized for further use. The membrane technology and other separating methods are showing a fast development and therefore the methods to obtain more or less pure oxygen can be of interest, e.g. for the production of oxygen from water.

The exhaust gases from the plant of the kind mentioned above can during the start-up period be recycled to the combustion chamber by means of a compressor. The exhaust gases are clear from all the environment effecting substances and are probably cleaner than the incoming combustion air.

The electric energy required to produce oxygen and the requ¬ ired compressors and pumps, respectively, can be obtained in plants being provided with an equipment as above. The low tempe¬ rature the plant is driven at can be used for other processes requiring low temperatures.

The plant according to the invention can be modified in dif¬ ferent ways to be used in combination with thermal or electric power plants and combustion engines can possibly be developed in this way with high efficiency rendering completely pure exhaust gases being cleared of even carbon dioxide.

The invention is illustrated in detail in the following in reference to the attached drawing showing schematically as an ex¬ ample a combined combustion and exhaust gas filter plant accor¬ ding to the invention.

The drawing shows a compressor 2 driven by a motor 1 and being connected to a oxygen/nitrogen separating membrane 3, the oxygen side of which is via eventually a further compressor 4 connected to a combustion chamber 5. into the chamber is leading a fuel supply line 6 with a burner 7 for e.g. oil. Moreover, material containing the environment endangering substances can be supplied into the combustion chamber 5 in a suitable, here not shown way for combustion purposes in the chamber 5. Possibly, also a bottle 8 containing oxygen can be connected to the chamber 5 for, if necessary, increasing the oxygen content.

The exhaust gases are leaving the chamber 5 via a line 9 being connected to a boiler/cooler 10 reducing the exhaust gas temperature somewhat before being supplied into a scrubber 12 for a washing and a further pressurized cooling. Some part of the water vapour in the exhaust gases is here condensed. The conden¬ sate is used together with the washing water in the scrubber to take care of certain contaminants in particle form as well in water soluble form being thereafter in a known manner conducted out of the pressurized scrubber. The exhaust gases containing the remaining contaminants are led from the scrubber via a line 13 to a first expansion machine 14, for example of the rotary screw type, being adapted to drive an electric generator 15. A fast pressure reduction is achieved via the expander as well as a tem¬ perature drop to about -50 C of the exhaust gases passing the ex¬ pander and thereafter being fed into a first separating chamber 16 in form of e.g. frozen condensate containing a number of con¬ taminants which can be deducted through an output means 17. The remaining exhaust gases are fed through a line 18 to a second ex¬ pander 20 driving an electric generator 19, where the exhaust gases are exposed for a further, fast pressure reduction and ac¬ companying temperature drop to ca. -120 C in such a way as to condense the remaining exhaust gases mainly consisting of carbon dioxide, the condensate then possibly been output from an second separating chamber 22 with an output line 23 connected with the expander 20 via a line 21. A further output line 24 containing a pump 25 is adapted to recycle the carbon dioxide condensate to the scrubber 12 for evaporating the carbon dioxide and for its

renewed expansion. The possibly remaining exhaust gases being filtered to a high degree are leaving the separating chamber 22 by an output line 26 being equipped with a vaccum pump 27 main¬ taining a certain vacuum in the chamber 22.

Possibly, the low temperature of the carbon dioxide in the line 24 can be used even for a further cooling at the input to the second or the further expanders of the rotary strew type, being possibly arranged. Likewise, a compressor can possibly be set in to increase the input pressure of the second expander and of further expanders being possibly arranged.

Finally the chilliness can be used to cool the compression in the compressors 2 and 4 for in this way reducing the required compression effect.

The process can for a number of points also be modified ac¬ cording to known solution principles, e.g. by heating, cooling or compressing the gas between the various expansion steps, to ac¬ hieve a lower final temperature, a larger power output and other purposes.

The carbon dioxide and especially a clean one will in future with an adaption of the invention probably become an important raw material within the chemical industry.