WO2008149587A1 - 炭化水素系燃料の脱硫システム - Google Patents
炭化水素系燃料の脱硫システム Download PDFInfo
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- WO2008149587A1 WO2008149587A1 PCT/JP2008/054239 JP2008054239W WO2008149587A1 WO 2008149587 A1 WO2008149587 A1 WO 2008149587A1 JP 2008054239 W JP2008054239 W JP 2008054239W WO 2008149587 A1 WO2008149587 A1 WO 2008149587A1
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- WO
- WIPO (PCT)
- Prior art keywords
- desulfurization
- gas
- fuel
- zeolite
- copper
- Prior art date
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- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
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- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/12—Liquefied petroleum gas
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- 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
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- 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
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
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- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
- Y10S502/515—Specific contaminant removal
- Y10S502/517—Sulfur or sulfur compound removal
Definitions
- the present invention relates to a desulfurization system for hydrocarbon fuel containing a trace amount of methanol. Furthermore, the present invention relates to a fuel cell system using a hydrocarbon fuel containing a trace amount of methanol as a raw fuel.
- Zeolite-based desulfurization agents loaded with silver or copper by ion exchange are industrially useful, and are household fuel cells that use low-boiling hydrocarbons such as natural gas and LP gas (liquefied petroleum gas) as raw fuel. Widely used in systems and the like (see, for example, Patent Documents 1 to 5 and Non-Patent Document 1).
- Patent Document 1 Japanese Patent Laid-Open No. 2001-286 753
- Patent Document 2 Japanese Patent Laid-Open No. 2001-305 1 23
- Patent Document 3 Japanese Patent Laid-Open No. 2004-168648
- Patent Document 4 Japanese Unexamined Patent Publication No. 2004-277747
- Patent Document 5 Japanese Patent Laid-Open No. 2-73887
- Non-patent literature 1 “Journal of Chemical Society of Japan”, 1 98 1 year, [Disclosure of the Invention]
- methanol may be added as needed.
- methanol may be added to prevent freezing of mixed water, especially in winter. It has been found that the performance of the zeolite desulfurization agent decreases when a hydrocarbon fuel to which methanol is added is used. In this way, when methanol coexists, the phenomenon of desulfurization performance decreasing is undesirable because it impairs the durability of the fuel cell system, and a desulfurization agent having high desulfurization performance is desired even when methanol is added. It was.
- Patent Document 1 discloses that a high-performance desulfurization performance can be obtained when water is mixed in a hydrocarbon fuel by supporting silver on a hydrophobic zeolite.
- the present inventors have found that the desulfurization agent described in Patent Document 1 shows only limited performance under the use conditions in which the hydrocarbon-based fuel contains methanol.
- the present inventors diligently studied to obtain a desulfurization system capable of maintaining the performance of the desulfurization agent for a long period in a state where a trace amount of methanol and a trace amount of water are mixed.
- a Y-type zeolite desulfurizing agent containing at least copper in the former stage and using an X-type zeolite desulfurizing agent containing at least silver in the latter stage.
- the present invention has been completed.
- the present invention is a system for desulfurizing a hydrocarbon fuel containing methanol and water, and a Y-type zeolite desulfurizing agent containing at least copper as a desulfurizing agent is disposed in the latter stage.
- the present invention relates to a hydrocarbon fuel desulfurization system characterized by arranging an X-type zeolite desulfurization agent containing silver.
- the present invention also relates to the hydrocarbon fuel desulfurization system described above, wherein the reaction temperature is 10 ° C. or less.
- the present invention also relates to the above hydrocarbon fuel desulfurization system, wherein the hydrocarbon fuel is LP gas.
- the present invention also relates to the above-described hydrocarbon fuel desulfurization system, wherein the zeolite desulfurization agent is obtained by ion-exchange-supporting copper or silver on zeolite.
- the present invention also relates to a hydrogen production apparatus for a fuel cell system using the hydrocarbon-based fuel desulfurization system described above.
- the present invention relates to a fuel cell system characterized by using the hydrocarbon-based fuel desulfurization system described above.
- the performance of the desulfurization agent can be maintained over a long period of time in a state where a trace amount of methanol and a trace amount of water are mixed in the hydrocarbon fuel.
- hydrocarbon fuel examples include natural gas, LP gas, naphtha, gasoline, and kerosene.
- a fuel that is a gas at normal temperature and pressure such as natural gas or LP gas, is preferable, and LP gas is more preferable.
- a hydrocarbon-based fuel containing a sulfur content of 0.1 m a ss p pm or more, preferably one containing a sulfur content of 0.5 ⁇ 5 m as s p pm or more is used.
- the upper limit is not particularly limited, but is preferably 200 m s s s p pm or less, more preferably 50 m s s s p p m or less.
- sulfur compounds that have been mixed since the production of hydrocarbon fuels and those that have been artificially mixed as odorants, but both can be effectively removed according to the present invention.
- Natural gas contains almost no sulfur in the purification stage, but as an odorant for gas leak detection, lower mercaptans such as ethyl mercaptan, isopropyl mercaptan, and t-butyl mercaptan, dimethyls Low-sulfides such as Rufide, Ethylmethylsulfide and Tetrahydrothiophene are added. These compounds are usually contained in a concentration of about 0.1 to 1 Oma ssp pm in terms of sulfur concentration (weight of sulfur atoms per weight of sulfur-containing hydrocarbon).
- lower mercaptans such as methyl mercaptan, ethyl mercaptan and propyl mercaptan, which are originally included in the LP gas production process
- lower sulfides such as dimethyl sulfide.
- components such as carbonyl sulfide, and disulfides that are oxidatively coupled with mercaptans.
- the sulfur concentration is usually about 0.1 to 1 Oma ssp pm. However, when collecting gas from LP gas cylinders, it is known that the sulfur concentration varies depending on the remaining amount of the cylinder. In some cases, it may exceed 10 Oma ssp pm in the short term.
- naphtha and kerosene with a high average molecular weight are liquid at room temperature, so there is no need to add an odorant, but the concentration of sulfur in the raw material is high, and the types of sulfur compounds contained are higher in molecular weight. Range of types. Sulfur compounds include thiophenes, substituted thiophenes, and benzothiophenes in addition to mercabtan and sulfides.
- the sulfur content ranges from several ma s s p pm to several tens of ma s s p pm.
- a hydrocarbon-based fuel in which methanol is mixed in addition to the above sulfur compound is used.
- the methanol content is usually more than 1 m a s s p p m, for example:! ⁇ 10, O O Oma s s s pm, preferably 10 to 5, O O Oma s s s p pm, more preferably 100 to 2, O O Oma s s s p pm.
- methanol is usually added artificially to prevent the mixed water from freezing, especially in winter, and causing inconveniences such as clogging of piping and switching regulators.
- this methanol is added to the liquid LP gas in the cylinder at 100 to 5,000 Omass sppm, preferably 300 to 2,500 mass sppm.
- the methanol concentration in the hydrocarbon fuel introduced into the fuel cell system is equal to the methanol concentration in the liquid LP gas.
- the methanol concentration in the vaporized LP gas does not necessarily match the concentration in the liquid LP gas, but usually 1 to: 1 0 , 000 massppm, preferably 10 to 5,000 ma ssp pm, more preferably about 100 to 2,000 massppm.
- LP gas with a ethanol concentration is introduced into the fuel cell system.
- a hydrocarbon-based fuel in which water is mixed in addition to the above sulfur compound and methanol is used.
- the water content is usually more than 1 m a s s p p m, for example ':! ⁇ 500 ma s s p pm, preferably 2 to 200 ma s s p pm.
- a zeolite-based desulfurization agent containing copper is used as a desulfurization agent in the previous stage.
- various zeolites such as A type and faujasite type can be used, and among them, Y type is preferably used.
- the range of the copper loading is 3 to 20 mass%, preferably 5 to 15 mass% based on the total amount of the desulfurization agent.
- the loading amount is less than 3 m s s%, the desulfurization performance is not sufficient, and when it is more than 20 m s s%, the desulfurization performance corresponding to the amount of copper added cannot be exhibited.
- an ion exchange method is preferably used.
- the zeolite used for ion exchange various types such as sodium type, ammonium type and hydrogen type can be used, but sodium type is most preferably used.
- copper is usually prepared as a cation dissolved in water. Specific examples thereof include aqueous solutions of copper sulfate, copper nitrate, copper chloride, copper acetate, and aqueous solutions of copper complex ions such as copper ammine complex ions.
- the concentration of the aqueous solution containing copper ions is usually in the range of 0.1 to 1 Oma s s s%, preferably 0.5 to 5 m s s% as the concentration of copper.
- the ion exchange method is not particularly limited, but usually the above-mentioned zeolite is added to a solution containing the above-mentioned cationic copper, and usually in a temperature range of 0 to 90 ° C, preferably 20 to 70 ° C. Ion exchange treatment is performed for about 1 to several hours, preferably with stirring. Next, the solid is separated by means such as filtration, purified with water, and then dried at a temperature of 50 to 200 ° C, preferably 80 to 150 ° C. This ion exchange process can be repeated. Next, if necessary, it may be fired at 200 to 600 ° C, preferably 300 to 500 ° C for about several hours. By such a method, the target copper ion exchange zeolite can be obtained.
- Zeolite carrying copper prepared by the above method is made by extrusion molding, tableting molding, rolling granulation using alumina, silica, clay minerals, etc. or precursors such as boehmite as appropriate binders. Spray dry and fire if necessary For example, it can be molded and used in the usual way. In addition, it is also preferable to preliminarily form zeolite and apply the above-described ion exchange method.
- a zeolite desulfurization agent containing silver is used after the desulfurization agent.
- various zeolites such as A type and faujasite type can be used, and among them, X type is preferably used.
- the range of silver loading is preferably 10 to 30 m s s%, more preferably 15 to 25 m s s%, based on the total amount of the desulfurization agent. If the loading is less than 10 m s s%, the desulfurization performance is not sufficient, and if it is more than 30 m s s%, the desulfurization performance commensurate with the amount of silver added cannot be exhibited.
- an ion exchange method is preferably used.
- the zeolite used for ion exchange various types such as sodium type, ammonium type and hydrogen type can be used, but sodium type is most preferably used.
- silver is usually prepared as a cation dissolved in water. Specific examples thereof include an aqueous solution of silver nitrate or silver perchlorate, an aqueous solution of silver ammine complex ion, and the like, and an aqueous solution of silver nitrate is most preferably used.
- the concentration of the aqueous solution containing silver ions is usually in the range of 0.5 to 1 O m s s%, preferably 1 to 5 m s s% as the concentration of silver.
- the ion exchange method is not particularly limited. Usually, the above zeolite is added to the above-described solution containing cationic silver, and the temperature is usually 0 to 90 ° C, preferably 20 to 70 ° C. Ion exchange treatment is performed for about 1 to several hours in the temperature range, preferably with stirring. Next, the solid is separated by means such as filtration, washed with water and the like, and then dried at a temperature of 50 to 20 ° C., preferably 80 to 150 ° C. This ion exchange process can be repeated. Next, if necessary, the calcination treatment may be carried out at 2200 to 600 ° C, preferably 2550 to 400 ° C for several hours. By such a method, the target silver ion exchange zeolite can be obtained.
- Zeolite carrying silver produced by the above method is made by extrusion molding, tableting molding, rolling molding using alumina, silica, clay minerals, etc., or precursors such as boehmite as appropriate binders. It can be molded and used by conventional methods such as granulation, spray-drying, and firing if necessary. In addition, it is also preferable to preliminarily form zeolite and apply the above ion exchange method.
- the copper ion exchange zeolite and the silver ion exchange zeolite thus produced as a desulfurization agent are disposed in the preceding stage and the copper ion exchange zeolite is disposed in the previous stage, and the silver ion exchange zeolite is performed in the subsequent stage for desulfurization. .
- the copper ion exchange zeolite and silver ion exchange zeolite produced in this way are hydrocarbon fuels, preferably hydrocarbon fuels that are gaseous at normal temperature and pressure, such as natural gas or LP gas, more preferably LP It can be suitably used for removing sulfur compounds contained in gas. Under desulfurization conditions, it is usually preferable that the hydrocarbon fuel is in a vaporized state.
- the desulfurization temperature is preferably 100 ° C. or less, and is selected, for example, in the range of 150 ° C. to 100 ° C., more preferably in the range of ⁇ 20 ° C. to 80 ° C. When the temperature is higher than 100 ° C, the transformation of copper and silver is accelerated under the condition containing methanol, and when the temperature is lower than 150 ° C, sufficient activity is not exhibited.
- GHSV When using a fuel that is gaseous at normal temperature and pressure, such as natural gas or LP gas, GHSV is selected between 10 and 10 ; preferably between 100,000 h- 1 and preferably between 100 and 10 000 h _ 1 Is done. If GHS V is lower than 10 h 1 , desulfurization performance will be sufficient, but since a desulfurizing agent is used more than necessary, the desulfurizer becomes excessively undesirable. On the other hand, GH SV is 1 00, 000 h one greater than 1 and sufficient desulfurization performance is not obtained. Liquid fuel can also be used. In that case, WHS V is used in the range of 0.1 to 1, 000 h- 1 .
- the working pressure is usually selected from the range of normal pressure to IMP a (gauge pressure, the same shall apply hereinafter), preferably from normal pressure to 0.5 MPa, and more preferably from normal pressure to 0.2 MPa. It can be most preferably carried out under atmospheric pressure conditions.
- the zeolite desulfurizing agent is usually used by being filled in a desulfurizer installed in a flow-type reaction pipe.
- the flow-type reaction tube may be of any known type and shape, and may be provided with, for example, a temperature control function, a pressure control function, etc., or may not be provided.
- another desulfurization agent can be disposed in the subsequent stage.
- the desulfurization agent that can be used at that time include a desulfurization agent including at least one selected from nickel, chromium, manganese, cobalt, copper, silver, zinc, and iron, but preferably includes nickel.
- the desulfurization system of the present invention can be used as a part of a hydrogen production apparatus for a fuel cell system.
- the hydrogen production apparatus is usually generated in a desulfurization section that removes sulfur from hydrocarbon fuel, a reforming section that decomposes hydrocarbon fuel in the presence of steam and oxygen if necessary, and a reforming section.
- Carbon monoxide mixed in hydrogen is converted into carbon dioxide and hydrogen by reaction with water vapor, and a small amount of carbon monoxide remaining in the shift portion is selectively converted into carbon dioxide by reaction with oxygen. It consists of a selective oxidation part to be removed.
- an apparatus for obtaining pure hydrogen can be assembled by arranging a membrane separation hydrogen purification apparatus using a palladium membrane or the like in the reforming section or the shift section.
- the configuration of the hydrogen production apparatus of the present invention may be any known one, but it is preferable that the desulfurization unit using the desulfurization system of the present invention is disposed in front of the reforming unit.
- the hydrogen production equipment can consist of a desulfurization section, a reforming section, a shift section, and a selective oxidation section.
- the desulfurization section is as described above.
- the reforming section can take any form of a steam reforming reaction or an autothermal reforming reaction.
- the reforming catalyst used in the reforming section is not particularly limited, and any one of the known catalysts conventionally known as hydrocarbon fuel reforming catalysts can be appropriately selected and used. .
- a reforming catalyst for example, a catalyst in which a noble metal such as nickel, ruthenium, rhodium or platinum is supported on a suitable carrier can be used.
- the supported metal may be one kind or a combination of two or more kinds.
- the reaction temperature is 450 ° C to 900 ° C, preferably 500 ° C to 850 ° C, more preferably 550 ° C to 800 ° C. I can.
- the amount of steam introduced into the reaction system is defined as the ratio of the number of moles of water molecules to the number of moles of carbon atoms contained in the feed hydrocarbon fuel (steam / carbon ratio), and this value is preferably 0.5 to 1. 0, more preferably 1-7, and even more preferably 2-5.
- the space velocity (WHSV) at this time can be expressed as A / B when the flow rate in the liquid state of the hydrocarbon fuel is A (kg / h) and the catalyst weight is B (kg).
- it is set in the range of 0.05 to 20 h, more preferably 0.1 to 1 0 h " ⁇ , more preferably 0.2 to 5 h 1 .
- oxygen preferably air
- oxygen is introduced into the reforming section so that the combustion reaction and the decomposition reaction are the same.
- an autothermal reforming reaction that proceeds in the reactor, which also typically represents Group VIII metals of the periodic table such as nickel, cobalt, iron, ruthenium, rhodium, iridium, platinum, etc.
- the reaction is carried out in the presence of an exemplary metal catalyst.
- the amount of steam introduced into the reaction system is preferably the steamnocarbon ratio.
- oxygen is added to the raw material in addition to steam.
- the oxygen source may be pure oxygen, but air is often used.
- oxygen is added to the extent that it can generate a heat quantity that can balance the endothermic reaction associated with the steam reforming reaction, but the amount added is appropriately determined in relation to heat loss and external heating that is installed if necessary.
- the amount is preferably 0.05 to 1, more preferably 0.1 to 0.75, and more preferably 0.1 to 0.75 as the ratio of the number of moles of oxygen molecules to the number of moles of carbon atoms contained in the raw hydrocarbon fuel (oxygen Z carbon ratio).
- it is 0.2 to 0.6.
- the reaction temperature of the autothermal reforming reaction is 450 ° C to 900 ° C, preferably 500 ° C to 850 ° C, more preferably 550 ° C to 800 ° C, as in the steam reforming reaction.
- Space velocity at this time is preferably from 0.:! ⁇ 30 h- more preferably 0. 5 to 20 h- more preferably selected in the range of. 1 to 1 0 h one 1.
- the pressure of the reforming reaction is not particularly limited, but is preferably in the range of atmospheric pressure to 2 MPa, more preferably atmospheric pressure to 0.5 MPa, and even more preferably atmospheric pressure to 0.2 MPa. Is done.
- the reformed gas generated in the reformer contains carbon monoxide, carbon dioxide, methane, water vapor and the like in addition to hydrogen. Nitrogen is also contained when air is used as the oxygen source in autothermal reforming. Shifting the process of converting carbon monoxide to water and carbon dioxide by reacting it with water to increase the hydrogen concentration and carbon monoxide can be a catalyst poison. Part. Usually, the reaction proceeds in the presence of a catalyst,
- the carbon monoxide content (mol% calculated excluding water vapor) is preferably 2 mass% or less, more preferably 1 mass% In the following, it is more preferably reduced to 0.5 mass% or less.
- the shift reaction can also be carried out in two stages. In this case, it is preferable to comprise a high temperature shift reactor and a low temperature shift reactor. For example, in the polymer electrolyte fuel cell system, it is preferable to further reduce the carbon monoxide concentration, and for this purpose, the shift reactor outlet gas is treated in the selective oxidation section.
- a catalyst containing iron, konnore, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, or gold is used, and the remaining number of moles of carbon monoxide is preferably ⁇ 5 to 10 times mole, more preferably 0.7 to 5 times mole, and still more preferably 1 to 3 times mole oxygen is added to selectively convert carbon monoxide to carbon dioxide.
- the concentration is preferably reduced to 10 m_assppm or less. In this case, the carbon monoxide concentration can be reduced by reacting with the coexisting hydrogen simultaneously with the oxidation of carbon monoxide to produce methane.
- the fuel cell system of the present invention hydrogen having a low carbon monoxide content thus obtained is introduced into the fuel cell and used for power generation.
- known cell stacks such as a solid polymer type (PEFC), a phosphoric acid type (PAFC), a solid oxide type (SOFC), and a molten carbonate type (MCFC) can be used. High molecular type is used.
- PEFC solid polymer type
- PAFC phosphoric acid type
- SOFC solid oxide type
- MCFC molten carbonate type
- High molecular type is used.
- a polymer electrolyte fuel cell is composed of an anode (fuel electrode) and a force sword (air electrode) and a solid polymer electrolyte sandwiched between these electrodes, and the anode side contains hydrogen obtained by the above reformer.
- the reformed gas is supplied after the carbon monoxide concentration is reduced through the shift reactor and the selective oxidation reactor, and oxygen-containing gas such as air is supplied to the power sword side.
- oxygen-containing gas such as air is supplied to the power sword side.
- the supplied gas is introduced after appropriate humidification treatment if necessary.
- both anode and force sword catalysts are formed into a porous catalyst layer together with polytetrafluoroethylene, low molecular weight polymer electrolyte membrane material, activated carbon, etc. as necessary.
- the fuel cell can be assembled by sandwiching the MEA with a separator that has a gas supply function consisting of metal materials, graphite, carbon composite, etc., a current collection function, and in particular a drainage function that is important for power swords.
- the electrical load is electrically connected to the anode and force sword.
- Distilled water 600 ml was added to 30 g of silver nitrate to prepare an aqueous silver nitrate solution.
- 5 g of alumina binder was mixed and extruded to 1 mm to obtain a desulfurizing agent (B).
- the supported amount of silver in the desulfurizing agent (B) was 24 mass%.
- SCD Sulf ur C chem i um es c ce nc ce te ctor
- Table 1 shows the time required to break through 2 Oma s s p p b, which is the detection limit for the sulfur concentration in the outlet gas after the start of the experiment. However, if the sulfur concentration was below the detection limit even after 200 hours, it was shown as below the detection limit.
- Desulfurization agent (A) A performance test of the desulfurization agent was performed under the same conditions as in Example 1 except that 6 ml 1 was charged into the flow reaction tube. The results are shown in Table 1.
- Desulfurization agent (B) A performance test of the desulfurization agent was performed under the same conditions as in Example 1 except that 6 ml 1 was charged into the flow reaction tube. The results are shown in Table 1.
- Figure 1 shows the present invention. It is the schematic which shows an example of a fuel cell system.
- the fuel vaporized in the LP gas cylinder 3 flows through a pressure reducing valve 4 into a desulfurizer 5 filled with a desulfurizing agent (A) in the front stage and a desulfurizing agent (B) in the rear stage.
- the GHS V of the desulfurizer is set to 500 h- 1 .
- the fuel desulfurized in the desulfurizer 5 is mixed with the water vapor produced from the water tank 1 through the water pump 2 and the vaporizer 6 and filled with 2 mass% Ru / A 1 2 0 3 as a catalyst. Is sent to the reformer 7. At this time, the steam / carbon ratio is set to 3.0.
- the space velocity of the distribution raw material is set to 0.5 h- 1 for WH SV.
- the reformer reaction tube is heated by a burner 18 using fuel from the fuel tank and the anode off gas as fuel, and adjusted to 700 ° C.
- the gas containing hydrogen and carbon monoxide produced in this way uses a high-temperature shift reactor 9 using an iron-chromium catalyst, a low-temperature shift reactor 10 using a copper-zinc catalyst, and a ruthenium catalyst. By sequentially passing through the selective oxidation reactor 11, the concentration of carbon monoxide is reduced to a level that does not affect the characteristics of the fuel cell.
- the polymer electrolyte fuel cell 1 7 is composed of an anode 1 2, a force sword 1 3, and a solid polymer electrolyte 14, and a fuel gas containing high-purity hydrogen obtained by the above method is applied to the anode side.
- a fuel gas containing high-purity hydrogen obtained by the above method is applied to the anode side.
- air sent from the air blower 8 is introduced after appropriate humidification treatment (humidifier not shown) if necessary.
- the electrical load 15 is electrically connected to the anode and the force sword.
- the anode off gas is burned in the burner 18 and used to heat the reforming tube, and then discharged. Power sword-off gas is exhausted from the exhaust port 16.
- FIG. 1 is a schematic view showing an example of the fuel cell system of the present invention. (Explanation of symbols)
- the desulfurization system of the present invention can maintain the performance of the desulfurization agent for a long time in a state where a trace amount of methanol and a trace amount of water are mixed in the hydrocarbon fuel, the industrial utility value is great.
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Abstract
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Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
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CN200880012405XA CN101663379B (zh) | 2007-03-07 | 2008-03-04 | 用于烃燃料的脱硫系统 |
EP08825881A EP2119757B1 (en) | 2007-03-07 | 2008-03-04 | Desulfurization system for hydrocarbon fuel |
CA2683630A CA2683630C (en) | 2007-03-07 | 2008-03-04 | Desulfurization system for hydrocarbon fuel |
DK08825881.9T DK2119757T3 (da) | 2007-03-07 | 2008-03-04 | Afsvovlingssystem til kulbrintebrændsel |
ES08825881T ES2387472T3 (es) | 2007-03-07 | 2008-03-04 | Sistema de desulfuración para combustible de hidrocarburo |
KR1020097020468A KR101426112B1 (ko) | 2007-03-07 | 2008-03-04 | 탄화수소계 연료의 탈황 시스템 |
US12/530,110 US8043989B2 (en) | 2007-03-07 | 2009-03-04 | Desulfurization system for hydrocarbon fuel |
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JP2007-056905 | 2007-03-07 | ||
JP2007056905A JP4907391B2 (ja) | 2007-03-07 | 2007-03-07 | 炭化水素系燃料の脱硫方法 |
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CA (1) | CA2683630C (ja) |
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WO2012090957A1 (ja) * | 2010-12-28 | 2012-07-05 | Jx日鉱日石エネルギー株式会社 | 脱硫システム、水素製造システム、燃料電池システム、燃料の脱硫方法及び水素の製造方法 |
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US8323603B2 (en) * | 2004-09-01 | 2012-12-04 | Sud-Chemie Inc. | Desulfurization system and method for desulfurizing a fuel stream |
JP5116177B2 (ja) * | 2010-06-28 | 2013-01-09 | 株式会社豊田自動織機 | リチウムシリケート系化合物の製造方法 |
JP5809413B2 (ja) * | 2010-12-28 | 2015-11-10 | Jx日鉱日石エネルギー株式会社 | 燃料電池用脱硫システム、燃料電池用水素製造システム、燃料電池システム及び炭化水素系燃料の脱硫方法 |
JP5726513B2 (ja) * | 2010-12-28 | 2015-06-03 | Jx日鉱日石エネルギー株式会社 | 燃料電池用脱硫システム、燃料電池用水素製造システム、燃料電池システム及び炭化水素系燃料の脱硫方法 |
US20130109895A1 (en) * | 2011-09-23 | 2013-05-02 | Exxonmobil Research And Engineering Company | Low temperature adsorbent for removing sulfur from fuel |
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JP2012140525A (ja) * | 2010-12-28 | 2012-07-26 | Jx Nippon Oil & Energy Corp | 脱硫システム、水素製造システム、燃料電池システム、燃料の脱硫方法及び水素の製造方法 |
JP2012140524A (ja) * | 2010-12-28 | 2012-07-26 | Jx Nippon Oil & Energy Corp | 脱硫システム、水素製造システム、燃料電池システム、燃料の脱硫方法及び水素の製造方法 |
EP2660304A4 (en) * | 2010-12-28 | 2014-07-09 | Jx Nippon Oil & Energy Corp | DESULFURING, HYDROGEN, AND FUEL CELL SYSTEMS, METHODS OF FUELS DESULFURIZATION AND HYDROGEN MANUFACTURING |
Also Published As
Publication number | Publication date |
---|---|
CN101663379A (zh) | 2010-03-03 |
EP2119757A1 (en) | 2009-11-18 |
KR20090127899A (ko) | 2009-12-14 |
ES2387472T3 (es) | 2012-09-24 |
US8043989B2 (en) | 2011-10-25 |
KR101426112B1 (ko) | 2014-08-05 |
JP2008218308A (ja) | 2008-09-18 |
CN101663379B (zh) | 2013-04-24 |
US20100160152A1 (en) | 2010-06-24 |
DK2119757T3 (da) | 2012-08-20 |
JP4907391B2 (ja) | 2012-03-28 |
EP2119757A4 (en) | 2011-05-11 |
EP2119757B1 (en) | 2012-05-23 |
CA2683630A1 (en) | 2008-12-11 |
CA2683630C (en) | 2015-02-03 |
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