JP4485917B2 - Hydrogen production apparatus and start / stop method of fuel cell system - Google Patents

Hydrogen production apparatus and start / stop method of fuel cell system Download PDF

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JP4485917B2
JP4485917B2 JP2004330622A JP2004330622A JP4485917B2 JP 4485917 B2 JP4485917 B2 JP 4485917B2 JP 2004330622 A JP2004330622 A JP 2004330622A JP 2004330622 A JP2004330622 A JP 2004330622A JP 4485917 B2 JP4485917 B2 JP 4485917B2
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desulfurization
hydrogen production
desulfurizing agent
temperature
desulfurizer
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JP2006137649A (en
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健 佐村
康司 佐藤
後藤  晃
猛夫 梨本
琢也 梶田
昭 藤生
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三洋電機株式会社
新日本石油株式会社
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/50Fuel cells

Description

  The present invention relates to a hydrogen production apparatus that produces a hydrogen-containing gas from a raw material for hydrogen production such as a hydrocarbon-based fuel, and also includes such a hydrogen production apparatus. The hydrogen-containing gas produced by the hydrogen production apparatus is used as a fuel for a fuel cell. The present invention relates to a fuel cell system used as a fuel cell system. In particular, the present invention relates to a hydrogen production apparatus and a fuel cell system stop method and start / stop method.

  In a fuel cell system, in particular, a polymer electrolyte fuel cell (PEFC), which has been developing remarkably in recent years, in the process of obtaining hydrogen from a raw material for hydrogen production, first, sulfur contained in the raw material for hydrogen production can be removed to a very low level. In addition, catalytic reaction processes such as subsequent reforming, water gas shift, and CO selective oxidation are desired for normal and long-term operation. For this reason, hydrogen production apparatuses included in many fuel cell systems include a desulfurization unit for removing sulfur contained in the raw material for hydrogen production by adsorption or hydrocracking.

  Hydrodesulfurization catalysts and sulfur adsorbents are used as the types of desulfurization agents and catalysts used in the desulfurization part, but in particular, the sulfur content is extremely low under mild conditions at normal pressure and relatively low temperatures close to room temperature. Zeolite-based desulfurization agents that can be removed up to 10 minutes are useful for industrial and consumer use, and households that use low-boiling hydrocarbons such as liquefied natural gas (LNG) and liquefied petroleum gas (LPG) as raw materials for hydrogen production It is being widely used for PEFC systems. Such a fuel cell system is disclosed in Patent Document 1, for example.

However, when these low-boiling hydrocarbons are desulfurized through a container filled with a zeolitic desulfurizing agent, the hydrocarbons once adsorbed at the time of shutdown are partially desorbed due to the temperature increase of the desulfurizing agent, and the inside of the desulfurizing vessel is The phenomenon of being in a pressurized state may occur. When such a phenomenon occurs, the convenience of the zeolitic desulfurizing agent that can be easily desulfurized at normal temperature and normal pressure is impaired, and the operation stability of the hydrogen production apparatus or fuel cell system using the zeolitic desulfurizing agent is impaired. Therefore, there has been a demand for a method of operating a hydrogen production apparatus or a fuel cell system that can avoid such a phenomenon.
Japanese Patent Laid-Open No. 10-237473

  An object of the present invention is to provide a hydrogen production apparatus that performs desulfurization using a zeolitic desulfurization agent and a fuel cell system including such a hydrogen production apparatus, so that the desulfurization part is pressurized due to a rise in the temperature of the desulfurization agent after stopping. Thus, there is provided a start / stop method that enables stable operation without impairing the convenience of the zeolitic desulfurization agent.

  The present inventors made various studies such as types of desulfurizing agents, combinations of a plurality of desulfurizing agents, control temperatures of desulfurizing agents, temperature control sequences, etc., and then controlled the temperature of the desulfurization unit to a certain temperature or higher when the apparatus was stopped. As a result, the apparatus stopped thereafter was cooled and the desulfurization part was also cooled, and the pressure was reduced almost without increasing, and the present invention was achieved.

  In addition, at the time of startup, hydrocarbons are adsorbed and condensed in the pores of the zeolite, and even if the raw material for hydrogen production is fed, the phenomenon that the raw material for hydrogen production does not come out of the desulfurization vessel until the adsorption is saturated. As a result, shortage of raw materials for hydrogen production and unstable flow rate may be observed. In particular, when the apparatus is stopped as described above, the inside of the reforming unit may be at a negative pressure when restarted. The inventors of the present invention have also found that a method of supplying a raw material for hydrogen production in advance at the time of start-up and performing pressure compensation is effective for suppressing such a phenomenon.

In order to produce a hydrogen-containing gas by reforming a desulfurization part containing a desulfurizing agent and a desulfurized hydrogen production raw material to reduce the concentration of sulfur contained in the gaseous hydrogen production raw material according to the present invention. In a method for starting and stopping a hydrogen production apparatus having a reforming section of
At least a part of the desulfurizing agent is a zeolitic desulfurizing agent,
When stopping, close the inlet line and outlet line of the desulfurization section in a state where the temperature of the desulfurization agent is 40 ° C or higher,
When starting up, the outlet line of the desulfurization unit is opened in a state where the pressure of the desulfurization unit is within a range of ± 10 kPa-G.
A start-stop method of the hydrogen production apparatus,
When starting up, with the outlet line of the desulfurization section closed, the inlet line of the desulfurization section is opened and the raw material for hydrogen production is introduced into the desulfurization section so that the pressure in the desulfurization section is in the range of ± 10 kPa-G.
A method for starting and stopping a hydrogen production apparatus is provided.

  The desulfurization part preferably has a layer containing a zeolite-based desulfurization agent and a layer containing a metal-based desulfurization agent containing at least one of the metal species of copper, cobalt and nickel.

  It is preferable that the layer containing the zeolite-based desulfurizing agent and the layer containing the metal-based desulfurizing agent are arranged in this order in the flow direction of the raw material for hydrogen production inside one container.

  When stopping, it is preferable that the layer containing the zeolite-based desulfurizing agent and the layer containing the metal-based desulfurizing agent have substantially the same temperature.

  The zeolitic desulfurizing agent is preferably a hydrophobic zeolite or a metal-substituted zeolite in which a metal is ion-supported on a hydrophobic zeolite.

  The raw material for hydrogen production is preferably natural gas or liquefied petroleum gas.

In order to produce a hydrogen-containing gas by reforming a desulfurization part containing a desulfurizing agent and a desulfurized hydrogen production raw material to reduce the concentration of sulfur contained in the gaseous hydrogen production raw material according to the present invention. A hydrogen production apparatus having a reforming section of a fuel cell system, and a method for starting and stopping a fuel cell system having a fuel cell using a hydrogen-containing gas obtained by the hydrogen production apparatus as fuel,
At least a part of the desulfurizing agent is a zeolitic desulfurizing agent,
When stopping, close the inlet line and outlet line of the desulfurization section in a state where the temperature of the desulfurization agent is 40 ° C or higher,
When starting up, the outlet line of the desulfurization unit is opened in a state where the pressure of the desulfurization unit is within a range of ± 10 kPa-G.
A start-stop method of the fuel cell system,
When starting up, with the outlet line of the desulfurization section closed, the inlet line of the desulfurization section is opened and the raw material for hydrogen production is introduced into the desulfurization section so that the pressure in the desulfurization section is in the range of ± 10 kPa-G.
A method for starting and stopping a fuel cell system is provided.

  According to the present invention, there are provided a hydrogen production apparatus and a method for stopping or starting and stopping a fuel cell system that can substantially avoid the inside of a desulfurization section from being pressurized with a combustible gas due to a temperature change after the apparatus is stopped. Furthermore, there are provided a hydrogen production apparatus and a method for stopping or starting and stopping the fuel cell system that can suppress malfunctions such as a shortage of raw material for hydrogen production and unstable flow rate of the raw material for hydrogen production during restart. As a result, the hydrogen production apparatus and the fuel cell system can be stably operated even in an actual environment where the temperature and the surrounding environment vary greatly.

[Raw materials for hydrogen production]
As a raw material for hydrogen production, a known substance capable of obtaining a hydrogen-containing gas by a reforming reaction can be used. For example, hydrocarbon fuels such as natural gas or city gas, LPG, naphtha, and kerosene can be used. Of these, natural gas and LPG are preferable because they can be converted into a high-purity hydrogen-rich gas relatively easily by a steam reforming reaction. When the sulfur concentration of the raw material for hydrogen production (the mass of sulfur atoms per unit mass of the fluid containing sulfur, the same applies to the sulfur concentration) is 0.1 mass ppm or less, it is subjected to the reforming reaction without desulfurization. You can also Therefore, in the present invention, a hydrogen production raw material having a sulfur concentration of 0.1 mass ppm or less can be used. Is.

  In the present invention, when a gaseous fuel that is a gas at normal temperature and normal pressure, such as natural gas, LPG, or liquefied butane gas, is used as a raw material for hydrogen production when introduced into the desulfurization section, the gaseous fuel is directly introduced into the desulfurization section. The liquid fuel such as naphtha and kerosene can be appropriately vaporized and then introduced into the desulfurization section.

[Hydrogen production equipment and fuel cell system]
The hydrogen production apparatus has a desulfurization section for removing sulfur contained in the raw material for hydrogen production, and obtains a hydrogen-containing gas (reformed gas) by a reforming reaction from the raw material for hydrogen production from which the sulfur content has been removed. It has a reforming section including a reformer. The type of the reformer is not particularly limited, and a reformer capable of performing known reforming such as steam reforming, partial oxidation reforming, and autothermal reforming can be appropriately employed. Supply means such as water vapor and air necessary for the reforming are appropriately provided in the reforming section. The hydrogen production apparatus may further include a water gas shift reactor and a CO selective oxidation reactor in order to reduce the CO concentration in the reformed gas obtained by the reformer. In addition, peripheral accessories for operating these are provided as appropriate.

  The fuel cell system includes a hydrogen production apparatus, and also includes a fuel cell such as a PEFC that uses a hydrogen-containing gas obtained by the hydrogen production apparatus as a fuel. In addition, peripheral accessories for operating these are provided as appropriate.

[Desulfurizing agent and desulfurization part]
A desulfurization part has at least one desulfurizer which filled the desulfurization agent in the container which can be sealed.

  In the present invention, at least a zeolitic desulfurizing agent is used as the desulfurizing agent. As zeolite-based desulfurization agent, single or multiple types of zeolite such as sodium substitution type, ammonia substitution type, and hydrogen substitution type may be used as they are as desulfurization agents, but ion exchange sites existing on the surface of zeolite pores are used. After the metal is ion exchange supported, it may be used as a desulfurizing agent.

  There are various types of zeolite such as X-type, Y-type, ZSM-5, and mordenite. In the present invention, the type of zeolite is not particularly limited, but from the viewpoint of adsorbing sulfur in hydrocarbons, hydrophobic zeolite It is preferable that The hydrophobicity here means that the silica ratio is 4 or more. The silica ratio of zeolite is represented by a value obtained by dividing the number of moles of silicon dioxide by the number of moles of aluminum oxide when the silicon content in the zeolite is represented by silicon dioxide and aluminum is represented by aluminum oxide.

  Zeolite has an acid point in the pore as a chemical property, and the acid point is substituted with an alkali metal such as sodium, an ammonium substituted type substituted with an ammonium salt, or a group thereof. In the present invention, the hydrogen type is not particularly limited by the substitution species. However, from the viewpoint of desulfurization performance, a copper-substituted, silver-substituted, or nickel-substituted zeolite in which those acid sites are used as ion exchange sites and a metal such as copper, silver, or nickel is supported by ion exchange is preferred. In particular, a metal-substituted zeolite in which a metal is ion-exchanged on a hydrophobic zeolite is preferable.

  Regarding the amount of zeolitic desulfurizing agent used, 1) the feed flow rate of the raw material for hydrogen production depending on the rated power generation of the fuel cell system and the hydrogen production amount of the hydrogen production system, and 2) the types of raw materials for hydrogen production and their inclusion 3) It can be determined appropriately in consideration of the desulfurization ability of the zeolite itself (the amount of sulfur that can be adsorbed per zeolite volume). For example, in the case of a fuel cell system, the amount of zeolitic desulfurization agent used is AC (from the viewpoint of preventing the desulfurization effect from being reduced due to an increase in the flow rate (space velocity) of the feed that passes through the desulfurization agent for a certain period of time. AC) The rated generated power at the power transmission end is preferably 50 mL or more, more preferably 100 mL or more, and further preferably 200 mL per kW. On the other hand, the amount of zeolitic desulfurizing agent used is AC from the viewpoint of preventing the apparatus from becoming large and preventing the desulfurizer itself from becoming a large-capacity buffer and reducing the feed flow stability due to changes in ambient temperature. The rated generated power at the power transmission end is preferably 10 L or less per kW, more preferably 6 L or less, and even more preferably 4 L or less.

  Here, the types and concentrations of sulfur compounds contained in various hydrocarbon fuels that can be used as a raw material for hydrogen production will be described. Natural gas contains almost no sulfur in its purification stage, but as an odorant for gas leak detection, lower mercaptans such as methyl mercaptan, ethyl mercaptan, isopropyl mercaptan, and t-butyl mercaptan, dimethyl sulfide In many cases, lower sulfides such as these are added, and these compounds are usually contained at 1 to 10 ppm by mass in terms of sulfur concentration. In the case of LPG, in addition to components added to natural gas, components such as carbonyl sulfide originally contained in the purification process of LPG and disulfides obtained by oxidative coupling of mercaptans are also included. In addition, the sulfur concentration is usually about 1 ppm to 10 ppm by mass. However, in the case of collecting gas from an LPG cylinder, it is known that the sulfur concentration in the gas varies depending on the residual amount of the cylinder. In some cases, it may exceed 100 ppm by mass in a short period. In addition, 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 contained in the raw material for hydrogen production is high, and the types of sulfur compounds contained are higher in molecular weight. There are many kinds. In addition to mercaptans and sulfides, sulfur compounds include thiophene / substituted thiophenes, benzothiophene, etc., and the sulfur concentration ranges from several ppm to several tens of ppm.

  By the way, the zeolitic desulfurization agent cannot adsorb and remove all the above sulfur compounds suitably, and it is not easy to remove compounds such as carbonyl sulfide having a small molecular weight or benzothiophene having a very large molecular weight. For this reason, for example, when using LPG as a raw material for hydrogen production, a desulfurizing agent layer filled with a zeolitic desulfurizing agent is disposed in the first stage, and a metallic desulfurizing agent capable of efficiently removing carbonyl sulfide is disposed in the second stage. It is preferable to arrange the filled second desulfurizing agent layer. After removing sulfur compounds other than carbonyl sulfide in the first-stage desulfurizing agent layer, carbonyl sulfide can be removed in the second-stage desulfurizing agent layer.

  As the metal-based desulfurizing agent, a desulfurizing agent containing nickel, cobalt, copper or the like can be used. For example, metal catalysts such as silica or alumina supported copper catalyst, silica or alumina supported nickel catalyst, copper / zinc coprecipitation catalyst, nickel / zinc coprecipitation catalyst are preferably used. As a silica or alumina-supported nickel catalyst, an aqueous solution containing an active metal species is sprayed or immersed on a support such as silica or alumina, dried and fired, and then subjected to a reduction treatment in a hydrogen stream before use. It is desirable to activate. The same applies to the case of using a coprecipitation catalyst such as copper / zinc or nickel / zinc, and it is often preferable to perform a reduction treatment upon use.

  Any of these metal-based desulfurization agents is preferably used by being extruded into a circular shape, a three-leaf type, a four-leaf type, or the like by a method of extrusion molding, or formed into a cylindrical pellet by tableting.

  The amount of desulfurizing agent used in the second-stage desulfurizing agent layer varies depending on the type and amount of sulfur that cannot be easily removed in the first stage, but in the case of a fuel cell system, the amount of feed that passes through the desulfurizing agent for a certain period of time. From the viewpoint of preventing the flow rate (space velocity) from being increased and the desulfurization effect from being lowered, the rated generated power at the AC power transmission end is preferably 20 mL or more, more preferably 50 mL or more, and even more preferably 100 mL or more per 1 kW. is there. On the other hand, from the viewpoint of preventing the apparatus from becoming large and preventing the desulfurizer itself from becoming a large-capacity buffer and deteriorating the feed flow stability due to changes in ambient temperature, it is preferably 5 L or less, more preferably 3 L or less. More preferably, it is 1 L or less.

  When using a zeolite-based desulfurizing agent and a metal-based desulfurizing agent as the desulfurizing agent, the zeolite-based desulfurizing agent and the metal-based desulfurizing agent may be filled in separate containers and used as two or more reactors. From the viewpoint of temperature control described later, it is preferable to provide a zeolite-based desulfurizing agent layer and a metal-based desulfurizing agent layer in one container. For this purpose, the inside of a single sealable container can be partitioned by a perforated plate or the like, filled with a zeolitic desulfurizing agent on the upstream side, and filled with a metallic desulfurizing agent on the downstream side. In addition, even when the zeolite-based desulfurizing agent and the metal-based desulfurizing agent are filled in separate containers, respectively, two zeolite-desulfurizing agents and metal-based desulfurizing agents are used, such as using two containers connected via a short pipe. A container structure that can be used at substantially the same temperature is preferred. By making the temperature of the zeolite-based desulfurizing agent layer and the metal-based desulfurizing agent layer substantially the same, even if the temperature dependence of the hydrocarbon adsorption capacity of the two is different, only the temperature of either one is controlled. The effect of the present invention is preferable because the increase in the pressure in the container after the apparatus is stopped can be easily suppressed. Although it is possible to control the temperature of the desulfurization agents in the two containers by independent means, this method makes the control system for that purpose relatively complicated. Therefore, from the viewpoint of cost and system versatility, the difference between the desulfurization agent temperatures in the two containers can be neglected practically at substantially the same temperature so that the desulfurization agents in the two containers can be managed by one index. It is preferable to use it.

  The sulfur concentration of the raw material for hydrogen production after desulfurization is limited by the influence on a catalyst such as a reforming catalyst provided downstream of the desulfurization section, and is appropriately determined depending on the catalyst type, catalyst amount, and use conditions. Coke caused by sulfur poisoning, agglomeration (sintering), or sulfur content of active metals such as nickel, ruthenium, platinum and rhodium used in reforming processes such as steam reforming and partial oxidation reforming after desulfurization The sulfur concentration of the raw material for hydrogen production after desulfurization is preferably 1 ppm by mass or less, more preferably 0.5 ppm, from the viewpoint of generating (coking) and preventing the catalyst activity from being reduced or the reactor from clogging. The mass ppm or less, more preferably 0.1 mass ppm or less.

[Start / stop procedure]
When natural gas or LPG is actually passed through the desulfurization part, the zeolite adsorbs up to the hydrocarbon component, and when there is a surplus in the adsorption capacity of the zeolite, the natural gas and the natural gas from the desulfurization part until the adsorption site is almost filled with hydrocarbons. There may be a case where LPG does not come out or a phenomenon that the desulfurizer outlet flow rate is insufficient with respect to the feed amount.

  Further, the adsorption capacity of the desulfurizing agent decreases as the temperature increases. Therefore, when the desulfurizing agent temperature rises, hydrocarbons once adsorbed on the desulfurizing agent may be released into the gas phase, thereby increasing the pressure and causing the desulfurizer to be in a pressurized state. For example, when the equipment is operated under cool conditions and the equipment is shut down with the zeolite adsorbing the hydrocarbons to the maximum, and then the temperature inside the equipment due to the rise in temperature, etc. The inside of the desulfurizer becomes pressurized due to hydrocarbons desorbed from the zeolite, and in some cases, there is a possibility that leakage may occur from the piping or electromagnetic valve, or the member may be damaged.

  In order to avoid such a phenomenon, in the present invention, the apparatus is stopped or started / stopped by the following procedure.

  First, when the hydrogen production apparatus or the fuel cell system is stopped from the operating state, the inlet line and outlet line of the desulfurization section are closed in a state where the temperature of the desulfurizing agent is equal to or higher than a predetermined temperature. That is, even if the temperature of the entire apparatus rises due to the surrounding air temperature rise or the influence of solar radiation after the apparatus is stopped, the desulfurizing agent is preliminarily raised to a temperature at which the temperature of the desulfurizing agent does not increase any more. Regarding the hydrogen production apparatus part downstream of the desulfurization part, that is, the reforming process and thereafter, the pressure behavior is not particularly limited, and when the apparatus is opened to the atmosphere after the stop by the catalyst system used, or after the stop, the apparatus part is separately provided with a valve, etc. You may close using.

  A desulfurization part may have one desulfurizer, and may have a plurality of desulfurizers connected in series and / or in parallel. The operation of closing the inlet line and outlet line of the desulfurization unit will be described. When the desulfurization section has only one desulfurizer, the stop valve 11 provided in the inlet line of the desulfurizer 1 and the stop valve 12 provided in the outlet line may be closed as shown in FIG. This figure shows a desulfurizer in which a zeolite desulfurizing agent layer 3 and a metal desulfurizing agent layer 4 are provided in one desulfurizer. A reformer is provided downstream of the desulfurization unit, but other equipment such as a heat exchanger for preheating the raw material for hydrogen production may be provided upstream of the reformer. In any case, in order to close the outlet line of the desulfurization unit, the line may be blocked by a stop valve or the like upstream of the most upstream device among these devices provided downstream of the desulfurization unit and downstream of the desulfurization unit. it can. As shown in FIG. 1 (b), when the desulfurization section has a plurality of desulfurizers 1a and 1b in parallel, a stop valve 11 on the upstream side from the branch point for supplying the hydrogen production raw material to the desulfurization section, and desulfurization The stop valve 12 downstream from the junction where the raw materials for hydrogen production discharged from the vessel are merged can be closed. FIG. 1 (c) shows a case where the desulfurization section has a desulfurizer 1 having a zeolite-based desulfurizing agent layer 3 and a desulfurizer 2 having a metal-based desulfurizing agent layer 4. When a plurality of desulfurizers are connected in series as described above, the stop valve 11 positioned upstream of the most upstream desulfurizer and the stop valve 12 positioned downstream of the most downstream desulfurizer are closed. Can do.

  For the above specified temperature, the size of the device, the conditions under which the device is installed (average temperature, daily range, whether or not it is exposed to direct sunlight, etc.), the internal configuration of the device, the installation density of the device, The heat generation and heat recovery mechanism, the arrangement of the desulfurization vessel inside the apparatus and the situation in the vicinity can be determined. For example, the highest ambient temperature assumed as the predetermined temperature can be adopted. The assumed maximum ambient temperature is the assumed maximum temperature of the atmosphere to which the desulfurizer is exposed. For example, when considering a packaged fuel cell system or hydrogen production apparatus, the assumed maximum in-machine temperature can be adopted as the maximum ambient temperature. The assumed maximum in-flight temperature is when the packaged fuel cell system or hydrogen production system stops operating, and the atmosphere inside the package reaches only due to external factors such as outside temperature and direct sunlight. It is defined as the maximum temperature. For example, the temperature inside the apparatus near the panel surface on which the western sun hits the day when the outdoor temperature at the installation site recorded the highest in summer is often the maximum internal temperature. In order to accurately measure the maximum temperature inside the machine, it is necessary to measure the ambient temperature throughout the package over time and specify the conditions for reaching the maximum temperature in terms of position and time. In many cases, the temperature deviation in the packaging machine does not matter so much, and field testing of a packaging machine equipped with elements such as thermocouples, thermistors, and thermodiodes that can measure the atmosphere that does not come into contact with metal objects (operations at multiple installation sites) In many cases, it is specified empirically from data collection.

  As described above, the maximum in-machine temperature can be considered as one guideline for the temperature to which the desulfurizer included in the fuel cell system or the hydrogen production apparatus is exposed. Such a range is usually 40 ° C. or higher, preferably 45 ° C. or higher, more preferably 50 ° C. or higher. Even if it is assumed from the statistical results of the above field test that the temperature rises in the afternoon and the atmosphere in the package reaches the maximum cabin temperature after the equipment is shut down in the cool morning hours. It can be considered as a limit value that can suppress the temperature of the desulfurizing agent from exceeding the maximum in-machine temperature and suppress an increase in the pressure in the desulfurizer. In addition, even if the temperature of the desulfurization agent exceeds 40 ° C. due to the residual heat in the apparatus after the apparatus is stopped, this is temporary, and the excess width can be reduced, and the pressure rise is increased. It can be suppressed to an allowable range. In order to reduce or eliminate this excess width, a heat insulating material can be appropriately arranged, and the arrangement of the devices can be appropriately designed.

  Note that the desulfurization agent layer may have a temperature distribution, and a single desulfurizer may be provided with a plurality of desulfurization agent layers or a desulfurization section may be provided with a plurality of desulfurizers. It is preferable to employ the temperature of the lowest temperature portion of the desulfurizing agent as the desulfurizing agent temperature, and to set the desulfurizing agent temperature to 40 ° C. or higher at the time of stoppage, because the entire desulfurizing agent can be set to 40 ° C. or higher. For this reason, it is preferable to determine theoretically or experimentally the part that becomes the lowest temperature when the desulfurization agent to be used is stopped, and to measure the temperature of the part with a thermocouple or the like.

  In order to bring the desulfurizing agent to a predetermined temperature or higher, the desulfurizing agent can be heated. For this purpose, for example, the desulfurizer can be heated by heat generated by other equipment in the hydrogen production apparatus such as a reformer. For example, other equipment such as a reformer can be adjacent to the desulfurizer, and the desulfurizer can be heated by heat transfer from the other equipment to the desulfurizer. Further, when the reformer includes a burner for obtaining heat necessary for steam reforming, a method of heating the desulfurizer using the combustion exhaust gas of the burner as a heat medium can be considered. Specifically, for example, a pipe for circulating an exhaust gas around the desulfurizing agent layer can be wound to heat the desulfurizing agent layer.

  In the case of a fuel cell system, the desulfurization agent can also be heated using the exhaust heat of the fuel cell. For example, in the case of PEFC, since the operating temperature of the cell is about 70 to 80 ° C., it is preferable to heat the desulfurizer by the cooling water of the cell or the heat recovery water line of the entire system including the cooling of the cell.

  Furthermore, the desulfurizing agent can be heated by an electric heater. For example, the desulfurizer can be heated by winding an electric heater around the desulfurizer. Although this method has a demerit of consuming electric power for the heater for heating, there is a possibility that the power consumption can be substantially reduced by combining with the heating method using the above-described heat medium, for example.

  In any method, when a combination of two or more stages of desulfurization agents is used, it is preferable that they can be managed at substantially the same temperature by a single management index.

  Now, by such a method, the temperature of the desulfurizing agent is prevented from further rising between the state where the apparatus is stopped at the desulfurizing agent temperature equal to or higher than the predetermined temperature and the next start-up, but the temperature can be decreased. The nature is high. In this case, the zeolitic desulfurizing agent having a reduced temperature increases the adsorption capacity of hydrocarbons, adsorbs hydrocarbons present in the gas phase in the desulfurizer, and the desulfurizer has a negative pressure relative to the atmospheric pressure. It is assumed that In this case, if the apparatus is started as it is, the supplied hydrogen production raw material will not come out of the desulfurization vessel until the adsorption site of the zeolite is filled up to the saturated adsorption amount at that temperature, and the apparatus start-up operation is not stable. there is a possibility. For this reason, first, the pressure in the desulfurization section is detected, and when the pressure in the desulfurization section falls below a predetermined pressure range (negative pressure), the upstream side with the line on the downstream side (reformer side) of the desulfurization section is closed Normally, after opening the valve on the supply side and introducing the raw material for hydrogen production into the desulfurization unit, the desulfurization unit is brought to a predetermined pressure range (near atmospheric pressure), and the desulfurization agent adsorbs hydrocarbons to near the saturation amount. It is preferable to shift to the starting operation. A pressure gauge can be provided to monitor the pressure in the desulfurization section. In addition, when the pressure of the desulfurization part before starting operation is in a predetermined range, you may open the inlet line and outlet line of a desulfurization part simultaneously.

  The aforementioned predetermined pressure range can be determined in consideration of the characteristics of equipment such as a pump, a flow meter or a valve used in the raw material supply system for hydrogen production. Specifically, from the viewpoint of correctly operating a device such as a pump so that a raw material for hydrogen production at a predetermined flow rate flows, a predetermined hydrogen-containing gas is manufactured, and a predetermined power generation output is obtained, In the range of ± 10 kPa-G, that is, -10 kPa-G to 10 kPa-G, preferably in the range of ± 5 kPa-G, that is, -5 kPa-G to 5 kPa-G. Note that G in the pressure unit means a gauge pressure. Since the downstream of the desulfurization unit is open to the atmosphere at the time of shutdown, if the outlet line of the desulfurization unit is opened after the pressure in the desulfurization unit is within the above range at startup, the pressure balance between the desulfurization unit and the downstream of the desulfurization unit is almost balanced. It is possible to start up the apparatus stably.

  By using the method for shutting down the hydrogen production apparatus using the zeolite-based desulfurizing agent as described above, and further using the start / stop method, the inside of the desulfurization vessel is in a pressurized state of the combustible gas due to the temperature change after the apparatus is stopped. In addition, it is possible to prevent the supply of raw materials for hydrogen production from becoming insufficient or the flow rate of raw materials for hydrogen production to become unstable at the time of restart. In addition, the hydrogen production apparatus can be operated stably. In addition, even in a fuel cell system having a hydrogen production apparatus, it is possible to operate the fuel cell system stably in the same manner by adopting the start / stop method.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[Example 1] Desulfurizer temperature rise due to atmospheric temperature in device package Fig. 2 is a schematic diagram showing an outline of the fuel cell system used here. Fuel cell including a laminated PEFC cell stack 23 with a rated load of 1.2 kW at the AC power transmission end, a hydrogen production apparatus, and a heat recovery system for recovering heat generated from these by water circulation and accumulating hot water in the hot water tank 25 A power generation system was created. In FIG. 2, a solid line connecting the devices indicates a combustible gas line, and a broken line indicates a heat recovery line.

The hydrogen production apparatus has the following 1) to 4).
1) In a stainless steel (SUS-304) container, zeolite-based desulfurization agent (manufactured by Engelhard, trade name: Selector SurfX-CNG-1) 800 mL, Ni-based desulfurization agent (manufactured by JGC Chemicals, trade name: N112) 200 mL However, the two desulfurization agents are separated by a punching metal plate (hole diameter: 1 mm), and desulfurization is performed in the order of the zeolite desulfurization agent layer 3 and the Ni desulfurization agent layer 4 in the flow direction of the raw material for hydrogen production. A laminated desulfurizer 1 in which an agent layer is laminated.
2) From a reforming reaction tube filled with 450 mL of a steam reforming catalyst in which 1.5% by mass of ruthenium and 7% by mass of lanthanum oxide are supported on an alumina carrier, and from 500 NmL / min of propane gas for heating the reforming reaction tube A reformer 21 comprising a diffusion flame type burner 21a capable of burning 2 NL / min. “N” in Nml / min means a value converted to 0 ° C. and 0.101 MPa.
3) A CO removal reactor 22 in which 2.5 L of a copper-zinc shift catalyst and 0.03% by mass of ruthenium-supported alumina-based CO selective oxidation catalyst are laminated.

  This fuel cell power generation system includes a control device, auxiliary equipment, and the like in addition to the cell stack and the hydrogen production apparatus. For example, a diaphragm type gas pump (not shown) for feeding propane gas to the reforming catalyst layer is provided downstream of the stop valve 12 and upstream of the reformer. The fuel cell power generation system was housed in a package having a height of 850 mm, a width of 1250 mm, and a depth of 475 mm, and the laminated desulfurizer was disposed adjacent to the PEFC cell stack 23 and the stack humidification tank 24.

  With the stop valves (solenoid valves) 13 and 11 open, the hydrogen production raw material supply part of the hydrogen production device, that is, the zeolite side inlet of the laminated desulfurizer, as a hydrogen production raw material for generating hydrogen required for rated power generation, A gaseous LPG of 2.6 NL / min (manufactured by Idemitsu Home Gas Co., Ltd., supplied with LPG at 280 mmAq (2.7 kPa-G) from two 20 kg cylinders through an automatic switching valve and a pressure regulator) was introduced. At this time, the composition of LPG was ethane 0.3 mol%, n-butane 0.4 mol%, i-butane 0.9 mol%, and the remainder was propane. Further, as the sulfur component to be contained, methyl mercaptan 0.2 mass ppm, ethyl mercaptan 0.8 mass ppm, propyl mercaptan (n- and i-) 1.2 mass ppm, butyl mercaptan (n-, i-, and t) -) 1.7 mass ppm, dimethyl sulfide 0.3 mass ppm, carbonyl sulfide 2.1 mass ppm, and other sulfur compounds were contained in total of 0.7 mass ppm.

  The desulfurizer temperature after opening the stop valve (solenoid valve) 12 and starting the rated power generation for 4 hours after starting the rated power generation was 55 ° C in the vicinity of the desulfurizer. The inside of the vessel (desulfurization agent) was 42 ° C. Thereafter, the apparatus was stopped, and the inlet and outlet of the desulfurizer were respectively closed by the electromagnetic valves 11 and 12 (in this case, the electromagnetic valve 13 was also closed). The downstream of the solenoid valve 12 was closed after being stopped, and the pressure temporarily increased to 24.7 kPa-G and then turned to negative pressure. After 1 hour, the temperature of the desulfurizing agent temporarily increased to 47 ° C. due to the residual heat in the apparatus, but then cooled, and after 8 hours, the temperature decreased to 26 ° C. which is substantially equal to room temperature. Further, the pressure in the desulfurizer at that time was +15.7 kPa-G at the stage of 1 h after the stop when the temperature rose, but after 8 h, the pressure turned to a negative pressure and was -43.5 kPa-G. Temporarily the temperature and pressure in the desulfurizer increased, but were slight and acceptable.

  After that, when the apparatus was started again, first, pressure adjustment was performed to bring the inside of the desulfurizer into a range of ± 10 kPa-G. That is, with the solenoid valve 12 at the outlet of the desulfurizer closed, the LPG supply side electromagnetic valve 13 and the desulfurizer inlet electromagnetic valve 11 were opened first, and the system waited in that state until the pressure in the desulfurizer became positive. The atmospheric time was about 2 minutes. Thereafter, the solenoid valve 12 was opened and hydrogen production and power generation were started in accordance with a normal startup method. However, no abnormality was observed in any of the hydrogen production apparatus, cell, and auxiliary equipment, and rated power generation was achieved.

  In accordance with the above start / stop method, the device was started in the morning on a weekday day, and the operation in the DSS (Daily Start / Stop) mode was stopped after about 8 hours of operation. Even after 10560 hours after the replacement of each desulfurizer 5 times, no abnormality was found in the hydrogen production apparatus and peripheral accessories, and the operation was continued smoothly.

[Example 2] Desulfurizer temperature rise by heat transfer from reformer In Example 1, instead of installing the desulfurizer in the vicinity of the cell stack, the desulfurizer is disposed so as to follow the reformer. It was kept warm so as to be wrapped with a heat insulating material.

  The temperature of the desulfurizer when the apparatus was stopped was 68 ° C., and then the temperature decreased monotonically, and the temperature after 8 hours was 32 ° C. The pressure at that time was -53 kPa-G.

  About 3.5 minutes after opening the solenoid valves 13 and 11 on the supply side and the desulfurizer inlet at the start-up, the desulfurizer internal pressure became positive.

  When the start / stop cycle test in the DSS mode was carried out in the same manner as in Example 1, the smooth operation could be continued even after 7700 hours had elapsed after the replacement of the desulfurizer three times.

[Example 3] Temperature increase of desulfurizer by electric heater In Example 1, instead of installing the desulfurizer in the vicinity of the cell stack, a sheath heater (2 m) of 200 W was wound around the desulfurizer, and the container surface temperature was 65 ° C. PID control was performed to keep The lowest temperature part of the desulfurizing agent at this time was 57 ° C.

  When starting the apparatus, first, the heater was operated while the solenoid valves 13, 11, 12 were closed. About 4 minutes after the start of heating of the desulfurizer by the heater, the surface temperature of the desulfurizer became constant, and at this time, the solenoid valves 13 and 11 on the supply side and the desulfurizer inlet were opened. Within 30 seconds after opening the solenoid valves 13 and 11, the pressure in the desulfurizer was positive.

  When the start / stop cycle test in the DSS mode was carried out in the same manner as in Example 1, the smooth operation could be continued even after 6200 hours had elapsed after the replacement of the desulfurizer three times.

[Example 4] Desulfurizer temperature rise by exhaust heat recovery water circulation In Example 1, after installing the desulfurizer in the vicinity of the cell stack, a hot water line that recovers heat from the fuel cell main body package 23 and goes to the hot water storage tank 25 is provided. Then, after being wound around the desulfurizer around a height of 25 cm, the heat was kept by a heat insulating material. The temperature of the desulfurizer when the apparatus was stopped was 58 ° C., and then the temperature decreased monotonically, and the temperature after 8 hours was 33 ° C. The pressure at that time was -42 kPa-G.

  About 3 minutes after opening the solenoid valves 13 and 11 on the supply side and the desulfurizer inlet at the start-up, the desulfurizer internal pressure became positive.

  When the start / stop cycle test in the DSS mode was carried out in the same manner as in Example 1, the smooth operation could be continued even after 3800 hours had elapsed after the replacement of the desulfurizer once.

[Comparative Example 1] When not raising the temperature of the desulfurizer In Example 1, the same operation as in Example 1 was performed except that the desulfurizer was installed in the vicinity of the relatively cool lower piping in the apparatus package. The desulfurizer temperature immediately after the start of rated power generation was 23 ° C., which was close to the room temperature at that time, and the temperature during operation did not increase thereafter. The electromagnetic valves 13, 11 and 12 were closed when the apparatus was stopped. After 8 hours, the desulfurizer temperature increased to 37 ° C. due to the residual heat in the package, and the pressure in the desulfurizer increased to +135 kPa-G accordingly. Thereafter, when starting the apparatus again, the solenoid valves 13 and 11 on the LPG supply side and the desulfurizer inlet were opened, but the pressurized state in the desulfurizer was not eliminated, and the desulfurizer internal pressure was still 100 kPa-G or more. The pressure inside the desulfurizer could not be adjusted to a range of ± 10 kPa-G. When the apparatus was started from this state, as soon as the valve 12 on the outlet side of the desulfurizer was opened, the flow rate could not be controlled because a high pressure was applied to the diaphragm gas pump for supplying propane gas, and a large amount of LPG was transferred to the reformer at once. As a result, the pressure in the desulfurizer was suddenly released.

  When a DSS endurance test similar to that in Example 1 was performed, the pressure in the hydrogen production apparatus after the desulfurizer increased after the operation for 352 h, and it became more difficult to introduce LPG, and the operation could not be continued. . When the hydrogen production device was disassembled and the reforming catalyst layer was extracted and analyzed, remarkable carbon deposition of about 14% by mass was seen on the ruthenium catalyst, and coking was also seen in the reforming vessel and the surrounding gas flow path. It was. It is considered that carbon deposition and coking occurred because a large amount of LPG was temporarily supplied to the reformer.

[Comparative Example 2] When no zeolitic desulfurizing agent is used The same operation as in Example 1 is performed except that no zeolitic desulfurizing agent is used. As a result of the sulfur analysis of the sampling gas after leaving the desulfurizer, carbonyl sulfide is obtained. Was less than 0.05 ppm by mass which is the lower limit of detection of the analytical instrument, but among ethyl mercaptan, propyl mercaptan (n- and i-), butyl mercaptan (n-, i-, and t-), dimethyl sulfide The amount of sulfur in dimethyl sulfide was detected at 0.9 ppm by mass. In this state, when the DSS operation similar to that in Example 1 was continued, after 580 hours, the internal pressure of the reformer exceeded 20 kPa-G, gas could not be fed, and the CO concentration at the CO selective oxidation outlet exceeded 100 mass ppm. The concentration became high, the cell voltage decreased successively, and the operation could not be continued. When the reformer was disassembled and each catalyst was extracted and analyzed, the reformed catalyst was caulked vigorously as in Comparative Example 1, and 5.3% by mass of carbon deposition was observed. In addition to carbon, a sulfur content of 0.1% by mass was also detected. Furthermore, sulfur content was also detected from the extraction part from the upper stage of the copper-zinc shift catalyst, and the upper stage part of the shift catalyst hardly generated heat immediately before the device could not be operated, and it did not function as a shift catalyst. I understood it.

[Comparative Example 3] Heating only zeolitic desulfurizing agent among zeolitic desulfurizing agent + Ni-based desulfurizing agent In Example 3, instead of laminating the zeolitic desulfurizing agent and the Ni-based desulfurizing agent in the same container, separate 2 Each container was filled, and only the zeolite desulfurizing agent desulfurizer was temperature controlled by the sheath heater by the method of Example 3, and the Ni-based desulfurizing agent desulfurizer was not temperature-controlled as in Comparative Example 1. It was. Except this, the same operation as in Example 3 was performed.

  The temperature of the desulfurizer for the Ni-based desulfurizing agent at the time of stopping was approximately 23 ° C. The pressure inside the desulfurizer after the stop rises to a maximum value of 72 kPa-G due to the desorption LPG partial pressure from the Ni-based desulfurization agent that was not subjected to temperature control, and the pressure of 60 kPa-G or more is also maintained after the restart. It remained. When a DSS durability test similar to that in Example 1 was performed in this state, the pressure in the reformer increased after the operation for 1122 h, and it became difficult to introduce LPG any more, and the operation could not be continued. When the reformer was disassembled and the reforming catalyst layer was extracted and analyzed, carbon deposition of about 6.5% by mass was observed on the ruthenium catalyst as in Comparative Example 1, and the reforming vessel and the surrounding gas flow Caulking was also seen on the road.

[Comparative Example 4] Of the zeolitic desulfurizing agent + Ni-based desulfurizing agent, only the Ni-based desulfurizing agent is heated. In Example 3, instead of laminating the zeolitic desulfurizing agent and the Ni-based desulfurizing agent in the same container, a comparative example is used. In the same manner as in No. 3, each of the two separate containers is filled, and only the Ni-based desulfurizing agent desulfurizing vessel is temperature-controlled by the sheath heater according to the method of Example 3, and the zeolite-based desulfurizing agent desulfurizing vessel is Comparative Example 1. As in the case of temperature control was not performed. Except this, the same operation as in Example 3 was performed.

  The desulfurizer of the zeolitic desulfurizing agent at the time of stopping was approximately 23 ° C. The pressure in the desulfurizer after the stop increased to 105 kPa-G at the maximum value, and a pressure of 80 kPa-G or more remained even after the restart. When the DSS endurance test similar to that in Example 1 was performed in this state, the pressure in the reformer increased after the operation for 392 h, and it became difficult to introduce LPG any more, and the operation could not be continued. When the reformer was disassembled and the reforming catalyst layer was extracted and analyzed, remarkable carbon deposition of about 11.5% by mass was observed on the ruthenium catalyst in the same manner as in Comparative Example 1, and the reforming vessel and surrounding gas were observed. Caulking was also seen in the channel.

  The hydrogen production apparatus of the present invention can be used for producing a hydrogen-containing gas to be used for a fuel cell system and to be supplied to the fuel cell, and to be used for producing a hydrogen-containing gas stored or produced in a hydrogen station. Can do.

  The fuel cell system of the present invention can be used for a power generation system or a cogeneration system for a moving object such as an automobile, industrial use, or consumer use.

It is a schematic diagram for demonstrating the structure of the desulfurization part in this invention. 1 is a schematic diagram of a fuel cell system used in Example 1. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Desulfurizer 2 Desulfurizer 3 Zeolite type desulfurization agent layer 4 Metal type desulfurization agent layer 11 Desulfurization part inlet stop valve 12 Desulfurization part outlet stop valve 12 LPG supply system stop valve 21 Reformer 21a Burner 22 CO removal reactor 23 PEFC
24 Stack humidification tank 25 Hot water storage tank

Claims (7)

  1. A desulfurization unit containing a desulfurizing agent for reducing the concentration of sulfur contained in the gaseous hydrogen production raw material, and a reforming unit for producing a hydrogen-containing gas by reforming the desulfurized hydrogen production raw material In a method for starting and stopping a hydrogen production apparatus having
    At least a part of the desulfurizing agent is a zeolitic desulfurizing agent,
    When stopping, close the inlet line and outlet line of the desulfurization section in a state where the temperature of the desulfurization agent is 40 ° C or higher,
    When starting up, the outlet line of the desulfurization unit is opened in a state where the pressure of the desulfurization unit is within a range of ± 10 kPa-G.
    A start-stop method of the hydrogen production apparatus,
    When starting up, with the outlet line of the desulfurization section closed, the inlet line of the desulfurization section is opened and the raw material for hydrogen production is introduced into the desulfurization section so that the pressure in the desulfurization section is in the range of ± 10 kPa-G.
    A method for starting and stopping a hydrogen production apparatus .
  2. The desulfurization unit comprises a layer containing a zeolite-based desulfurizing agent, at least copper, the method according to claim 1, further comprising a layer containing a metal-based desulfurizing agent containing any of the metal species of the cobalt and nickel.
  3. Wherein a layer and a layer containing a metal-based desulfurizing agent containing zeolite based desulfurizing agent is inside one of the containers, the method according to claim 2, wherein arranged in this order relative to the direction of flow of the hydrogen-producing feedstock.
  4. During stop, according to claim 2 or 3 method according to a layer and a layer containing a metal-based desulfurizing agent containing the zeolite-based desulfurizing agent to the same temperature.
  5. The method according to any one of claims 1 to 4 , wherein the zeolitic desulfurizing agent is a hydrophobic zeolite or a metal-substituted zeolite in which a metal is ion-supported on a hydrophobic zeolite.
  6. The method according to any one of claims 1 to 5 , wherein the raw material for hydrogen production is natural gas or liquefied petroleum gas.
  7. A desulfurization unit containing a desulfurizing agent for reducing the concentration of sulfur contained in the gaseous hydrogen production raw material, and a reforming unit for producing a hydrogen-containing gas by reforming the desulfurized hydrogen production raw material And a method for starting and stopping a fuel cell system having a fuel cell using the hydrogen-containing gas obtained by the hydrogen production device as fuel,
    At least a part of the desulfurizing agent is a zeolitic desulfurizing agent,
    When stopping, close the inlet line and outlet line of the desulfurization section in a state where the temperature of the desulfurization agent is 40 ° C or higher,
    When starting up, the outlet line of the desulfurization unit is opened in a state where the pressure of the desulfurization unit is within a range of ± 10 kPa-G.
    A start-stop method of the fuel cell system,
    When starting up, with the outlet line of the desulfurization section closed, the inlet line of the desulfurization section is opened and the raw material for hydrogen production is introduced into the desulfurization section so that the pressure in the desulfurization section is in the range of ± 10 kPa-G.
    A method for starting and stopping a fuel cell system .
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