JP5433892B2 - Startup method for stationary hydrogen generator reformer - Google Patents

Description

  The present invention provides a reforming of a stationary hydrogen production apparatus including a reformer that produces hydrogen by reforming a raw material gas containing any one of a hydrocarbon fuel, an alcohol fuel, and a synthetic fuel and steam. It is related with the starting method.

  In recent years, efforts have been made to disseminate distributed generation that generates electricity in accordance with demand in places where electricity is used. Distributed power generation enables effective use of energy, such as reducing transmission loss and improving waste heat utilization efficiency, compared to conventional centralized power generation that is generated at a large-scale power plant and transmitted to homes and factories. It becomes. In distributed power generation, fuel cells are attracting attention because they do not decrease efficiency even if they are small in size and are expected to reduce costs.

  For stationary fuel cell systems installed in homes, office buildings, factories, etc., polymer electrolyte fuel cells, phosphoric acid fuel cells, molten carbonate fuel cells, solid oxide fuel cells, etc. have been proposed. Yes. Among them, the solid oxide fuel cell is expected to have a relatively high power generation efficiency, but the operation temperature is high, and ensuring durability is a problem. The stationary fuel cell system is required to have durability. For example, a household fuel cell system is required to be able to withstand a cumulative operation time of 40,000 to 90,000 hours. Thus, conventionally, proposals for improving durability have been made (for example, see Patent Documents 1 and 2).

  In the reformer disclosed in Patent Document 1, the reaction tube through which the raw material gas mixed with hydrocarbon and steam flows is inserted into the outer tube of the straight tube arranged vertically, and the straight tube inner tube is inserted. The reforming catalyst is filled between the outer tube and the inner tube. Then, high-temperature combustion gas is circulated from the upper side to the lower side inside the inner pipe, and heat is supplied to the inner pipe. The raw material gas first flows into the inner pipe, is reformed through the reforming catalyst bed, is folded at the bottom of the reaction pipe, is led to the outer pipe, and is taken out from the outer pipe. A large number of heat transfer plates are provided between the inner tube and the outer tube to increase the heat transfer efficiency from the inner tube to the outer tube. The thermal expansion difference is reduced. Thereby, the stress acting on the reforming catalyst filled between the inner tube and the outer tube is reduced to prevent the reforming catalyst from being crushed.

Further, in the reformer start-up method disclosed in Patent Document 2, in order to prevent the reforming catalyst from being oxidized when the temperature of the reforming catalyst is raised during start-up, oxygen, gas containing combustion exhaust gas, steam, One or more kinds of circulating gas species selected from the group consisting of the raw material gas and nitrogen are circulated through the reforming catalyst while raising the temperature while changing depending on the temperature of the reforming catalyst. Specifically, oxygen-containing gas such as air or combustion exhaust gas or water vapor is circulated until the temperature of the reforming catalyst is 300 ° C., water vapor is circulated at 300 to 400 ° C., and water vapor and source gas are mixed at 400 ° C. or higher. Circulate gas.
JP-A-4-265147 JP 2002-93447 A

  In a reformer that reforms a raw material gas containing hydrocarbons and steam to produce hydrogen, a separate facility is required to circulate a circulating gas species other than steam when raising the temperature of the reforming catalyst. In the case of steam, existing equipment can be used, and the hydrogen production apparatus can be downsized. However, if water vapor is circulated at a temperature below the dew point, the water vapor is condensed on the surface or inside of the reforming catalyst, and the condensed water is vaporized by the subsequent heating. A malfunction may occur. Therefore, it is necessary to circulate water vapor after the reforming catalyst reaches a temperature higher than the dew point.

  Here, in both Patent Document 1 and Patent Document 2, the temperature of the reaction tube (catalyst) is linearly increased in one stage. When the combustion gas is circulated along the reaction tube to raise the temperature as in Patent Document 1, the temperature of the combustion gas is lowered on the downstream side of the combustion gas, and the reaction tube is in contact with the combustion gas on the downstream side. In this part, the temperature rise is delayed as compared with the part of the reaction tube in contact with the combustion gas on the upstream side.

  If water vapor is circulated at the stage where the portion of the reaction tube that contacts the combustion gas on the upstream side reaches the dew point, the portion of the reaction tube that contacts the combustion gas on the downstream side has not yet reached the dew point. There is a possibility that defects such as cracks may occur in the quality catalyst. In addition, if water vapor is circulated at the stage where the dew point has reached the part of the reaction tube that contacts the combustion gas on the downstream side, the part of the reaction tube that contacts the combustion gas on the upstream side is much hotter, The catalyst may be overheated and deteriorate.

  This invention is made | formed in view of the situation mentioned above, The objective is to provide the starting method of the stationary hydrogen production apparatus reformer which can prevent deterioration of a reforming catalyst.

The above object is achieved by the start-up method of the stationary hydrogen production apparatus reformer described in (1) to (2) below.
(1) A reformer of a stationary hydrogen production apparatus provided with a reformer that reforms a raw material gas containing any one of a hydrocarbon fuel, an alcohol fuel, and a synthetic fuel and steam to produce hydrogen The reformer has a substantially U-shaped reaction tube through which the raw material gas is circulated, and the reaction tube is filled with a first reforming catalyst on the outlet side thereof. And a vent portion between the straight portion on the outlet side and the straight portion on the inlet side, the inlet side of which is filled with a second reforming catalyst having an activity lower than that of the first reforming catalyst. An inert packing that does not function as a reforming catalyst is filled, and the reformer circulates the combustion gas along the reaction tube from the outlet side to the inlet side of the reaction tube. The reaction tube is heated to the activation temperature of the reforming catalyst,
A startup step of maintaining the outlet temperature of the reaction tube below the heat resistance temperature of the second reforming catalyst and raising the inlet temperature of the reaction tube to 350 to 380 ° C. , and after the startup step, the reaction tube And a reforming reaction preparation step of raising and maintaining the outlet temperature of the reaction tube to 700 to 750 ° C. and raising the inlet temperature of the reaction tube to 400 to 450 ° C. A start-up method for a stationary hydrogen generator reformer characterized by the above.
(2) The outlet temperature of the reaction tube is increased at 5 ° C./min in the start-up step, and the outlet temperature of the reaction tube is increased at 10 ° C./min in the reforming reaction preparation step. The start-up method of the stationary hydrogen production apparatus reformer according to (1).

  In the reformer having the above configuration, the temperature gradually increases from the inlet side to the outlet side of the reaction tube. Therefore, the reaction tube is filled with two types of reforming catalysts having different activation temperatures so that the activation temperature sequentially increases from the inlet side to the outlet side of the reaction tube. Thus, the reforming efficiency is enhanced by filling each part of the reaction tube with a suitable catalyst. According to the start-up method of the stationary hydrogen generator reformer according to the present invention, the reaction tube inlet temperature is maintained at 350 to 380 by maintaining the reaction tube outlet temperature below the heat resistance temperature of the second reforming catalyst. The temperature is raised to 0 ° C., and then the temperature of the reaction tube is further increased while water vapor is circulated through the reaction tube. The dew point in the reformer is approximately 350 ° C. at a typical pressure, although it depends on the pressure of water vapor to be circulated. The second reforming catalyst having activity at a lower temperature than the first reforming catalyst generally has a heat resistant temperature lower than that of the first reforming catalyst. By maintaining the outlet temperature of the reaction tube below the heat resistance temperature of the second reforming catalyst until the inlet temperature of the reaction tube whose temperature rise is delayed reaches 350 to 380 ° C., the second reforming near the outlet of the reaction tube It is possible to prevent the catalyst from being heated excessively. Then, after the reaction tube inlet temperature reaches 350 to 380 ° C., by raising the temperature of the reaction tube while circulating the steam, defects such as cracking of the reforming catalyst due to the volume expansion due to the condensation and vaporization of the steam Thus, the reaction tube can be further heated to the activation temperature of the reforming catalyst or in the vicinity thereof while preventing oxidation of the reforming catalyst. In this manner, the reforming catalyst can be prevented from deteriorating by raising the temperature of the reaction tube in two stages.

DESCRIPTION OF EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a schematic diagram showing a schematic configuration of a stationary hydrogen production apparatus to which a start-up method according to the present invention is applied, FIG. 2 is a longitudinal sectional view of the reformer of FIG. 1, and FIG. 3 is a diagram of the reformer of FIG. FIG. 4 is a cross-sectional view, and FIG. 4 is a flow chart of a start-up method for a stationary hydrogen production apparatus reformer according to the present invention. Note that the present invention is not limited to the embodiments described below.

(Overview of hydrogen production equipment)
As shown in FIG. 1, the hydrogen production apparatus 1 includes a raw material tank 2, a desulfurizer 3, a reformer 4, a shift reactor 5, and a PSA (Pressure Swing Adsorption) 6 as main components.

  Examples of raw materials include liquid hydrocarbon fuels such as naphtha, gasoline, kerosene, and light oil, alcohol fuels such as methanol and ethanol, or LPG (liquefied petroleum gas), DME (dimethyl ether), and GTL (gas / gas). Synthetic fuels obtained from To Liquid, etc. can be used. In the following description, the above hydrocarbon fuel is used as a raw material.

(Desulfurizer)
When hydrogen is produced using a hydrocarbon fuel, a method of steam reforming in the presence of a reforming catalyst is generally used. As the reforming catalyst, for example, at least one carrier component selected from Al ₂ O ₃ , SiO ₂ , TiO ₂ and ZrO _2, at least one selected from Ru, Rh, Pd, Pt and Ni is used. A catalyst in which the active metal is prepared by a method such as loading or coprecipitation can be used. Depending on the raw materials and reaction conditions, oxides of Li, Na, K, Rb, and Cs that are alkali metals and oxides of Be, Mg, Ca, Sr, and Ba that are alkaline earth metals may be added. Good.

  By the way, the hydrocarbon fuel generally contains a sulfur content, and the reforming catalyst is poisoned by the sulfur content in the hydrocarbon fuel. This is because the resistance of active metals such as Ni and Ru used for the reforming catalyst to sulfur is low.

  Therefore, if the hydrocarbon fuel contains a sulfur content, the hydrocarbon fuel is pre-desulfurized so that the sulfur content is 100 mass ppb or less, preferably 50 mass ppb or less. The desulfurizer 3 is a hydrocarbon-based fuel, particularly heavy hydrocarbons such as kerosene, Ni-Cu-based desulfurization under reaction conditions of a desulfurizer inlet pressure of 0.3 to 0.95 MPa and a desulfurization bed temperature of 190 to 225 ° C. And desulfurization using a Ni—Zn-based desulfurization agent. As a method for ensuring the reaction temperature, a method of heating the hydrocarbon-based fuel before entering the desulfurizer 3, a method of heating the desulfurization bed from the outside with an electric trace or the like, and a combination thereof are effective.

(Reformer)
A reformer 4, which is an embodiment of a stationary hydrogen production reformer according to the present invention, is a reactor that reforms a raw material gas in which a hydrocarbon-based fuel and steam are mixed in the presence of a reforming catalyst. is there. Mixing of the hydrocarbon fuel and water vapor is 2.0 to 6.0 mol / mol in terms of water vapor / carbon ratio (hereinafter referred to as S / C ratio). In the steam reforming reaction of hydrocarbons, an effective method for suppressing carbon deposition on the reforming catalyst is to increase the S / C ratio during the steam reforming reaction. Since the water vapor basic unit (the amount of water vapor used per unit amount of product) increases, it is preferably 2.5 to 4.0 mol / mol. Note that oxygen may be further added to the source gas.

  As shown in FIG. 2 and FIG. 3, the reformer 4 of the present embodiment houses a plurality of reaction tubes 11 that circulate a raw material gas, and these reaction tubes 11, and combustion that heats these reaction tubes 11. And a shell 12 through which gas is circulated.

  The shell 12 is formed in a cylindrical shape, and its internal space is divided into two in the axial direction by a combustion chamber 14 in which the combustion gas is circulated by the partition wall 13 and a channel portion 15 which is a source gas introduction / lead-out portion. ing. Further, the channel portion 15 is divided into two in the radial direction by the partition wall 16 into an inlet side channel portion 15a and an outlet side channel portion 15b.

  Each reaction tube 11 is formed in a substantially U shape, and both ends thereof are held by the partition wall 13 and are accommodated in the internal space of the shell 12. Each reaction tube 11 has one end opening at the inlet-side channel portion 15a and the other end opening at the outlet-side channel portion 15b, and the straight portions 11a and 11b connected to both end openings and both straight ends. A vent portion 11 c that connects the portions 11 a and 11 b is located in the combustion chamber 14. The reaction tube 11 that is U-shaped and held as described above is free from thermal expansion. Further, since only one member (partition wall 13) is required to hold the reaction tube 11, the cost is low.

  The raw material gas is introduced from the raw material gas inlet (hereinafter also referred to simply as the reformer inlet) 17 to the inlet side channel portion 15a, and flows into each reaction tube 11 in a dispersed manner. As will be described in detail later, the straight portions 11a and 11b of each reaction tube 11 are filled with a reforming catalyst, the raw material gas is reformed in each reaction tube 11, and the reformed gas is discharged from the outlet side channel portion 15b. The combined gas is led out from a reformed gas outlet 18 (hereinafter sometimes simply referred to as a reformer outlet) 18 provided in the outlet side channel portion 15b, and sent to the next step.

  Combustion gas is introduced into the combustion chamber 14 from a combustion gas inlet 19 provided on the same side as the outlet side channel portion 15 b in the vicinity of the partition wall 13, and provided on the same side as the inlet side channel portion 15 a in the vicinity of the partition wall 13. Is discharged from the combustion gas outlet 20. The combustion chamber 14 is provided with a partition plate 21 extending in the axial direction from the partition wall 13 and reaching the vicinity of the vent portion 11c of the reaction tube 11 accommodated therein, and the combustion gas is separated by the partition plate 21. Along the reaction tube 11, the combustion chamber 14 flows from the outlet side to the inlet side of the reaction tube 11.

  The combustion gas supplies heat to the reaction tube 11 and the reforming catalyst and raw material gas in the reaction tube 11 in the process of flowing through the combustion chamber 14 from the outlet side to the inlet side of the reaction tube 11, and to the inlet side of the reaction tube 11. The temperature gradually becomes lower. Typically, it is approximately 950 ° C. at the combustion gas inlet 19 and approximately 600 ° C. at the combustion gas outlet 20. On the other hand, the temperature distribution of the reaction tube 11 and the reforming catalyst and raw material gas therein gradually increases toward the outlet side of the reaction tube 11. Typically, the temperature is 400 to 500 ° C. at the inlet of the reaction tube 11 and 750 to 820 ° C. at the outlet. The reaction tube 11 is filled with a plurality of types of reforming catalysts having different activation temperatures so that the activation temperature sequentially increases from the inlet side to the outlet side of the reaction tube 11. In this way, it is possible to increase the reforming efficiency by filling each part of the reaction tube 11 with a suitable catalyst.

In the present invention, two types of reforming catalysts, ie, a high temperature active catalyst (first reforming catalyst) and a low temperature active catalyst (second reforming catalyst) having activity at a lower temperature than the high temperature active catalyst are used. The reaction tube 11 is filled with a low temperature active catalyst on the inlet side and a high temperature active catalyst on the outlet side. As the high-temperature active catalyst, for example, a reforming catalyst in which Ru is supported as an active metal on an alumina carrier and the surface area is 5 to 10 m ² / g is preferable. Such a high-temperature active catalyst is excellent in reforming activity at 650 ° C. or higher. Moreover, as a low temperature active catalyst, the reforming catalyst which carries | supports Ru as an active metal on an alumina support | carrier, for example, and a surface area is 30-90 m < ² > / g is preferable. Such a low-temperature active catalyst is excellent in reforming activity at 650 ° C. or lower. In addition, the value of said surface area shall be a value measured by BET method by nitrogen adsorption.

  The filling ratio of the high temperature active catalyst and the low temperature active catalyst is 1/1 to 3/1, preferably 1/1 to 2/1. The reforming activity of the low temperature active catalyst is higher than that of the high temperature active catalyst. However, if the filling ratio is made smaller than 1/1, the amount of low temperature active catalyst is increased, and a part of it is used in the high temperature range. to degrade. As a countermeasure, if the catalyst bed temperature is lowered as a whole so that the temperature in the range where the low-temperature active catalyst is filled is matched with the active temperature of the low-temperature active catalyst, the methane concentration in the reformed gas will be reduced due to the equilibrium reaction. Increase and decrease hydrogen production. On the other hand, when the filling ratio is higher than 3/1, the amount of low-temperature active catalyst having a higher reforming activity than that of the high-temperature active catalyst is reduced, and the reforming activity in the entire system is lowered, so that a sufficient reforming reaction can be performed. Disappear.

  In the reformer 4 of the present embodiment, the vent portion 11c of the reaction tube 11 is filled with inert (not functioning as a reforming catalyst), specifically ceramic balls, Raschig rings, metal sponges, metal wire elements. Etc. are filled. The U-shaped reaction tube 11 repeats expansion / contraction due to temperature fluctuations associated with the start / stop of the apparatus, but when the reforming catalyst is filled in the vent portion 11c that is strongly affected by the expansion / contraction, reforming is performed at that portion. This is because the catalyst may be crushed and powdered, resulting in the generation of a differential pressure and, consequently, blockage. Particularly preferable as the filler is a metal wire element in which metallic wires are connected in a loop shape. If a material harder than the reforming catalyst is filled, the reaction tube 11 may be deformed. However, this metal wire element has a high porosity, so it is highly flexible and has a low pressure loss and is easy to handle. It is.

(Shift reactor)
The shift reactor 5 reacts carbon monoxide contained in the reformed gas derived from the reformer 4 with water vapor in the presence of the shift reaction catalyst to convert it into carbon dioxide and hydrogen. The reaction temperature is 330 to 350 ° C. at the reactor inlet, 380 to 400 ° C. at the reactor outlet, the reaction pressure is about 880 kPa, and Fe and Cr oxides are generally used for the shift reaction catalyst. By this shift reaction, the carbon monoxide concentration in the reformed gas is reduced to about 2.5 mol%.

(PSA)
The PSA device 6 adsorbs and removes impurities in the reformed gas and purifies the hydrogen gas with high purity. The adsorption tower is usually filled with an adsorbent such as activated alumina, activated carbon or molecular sieve. ing. The PSA method is a known method, and for example, four towers alternately repeat adsorption (operation) / regeneration, that is, adsorption → pressure equalization → purge → blowdown → purge → equal pressure → pressure increase → adsorption continuously. The gas is separated and purified.

  Next, with reference to FIG. 1 and FIG. 4, the starting method of the hydrogen production apparatus 1 comprised as mentioned above is demonstrated. In addition, the broken line in a figure shows a heat-transfer path | route.

(Preparation for starting hydrogen production equipment)
When the hydrogen production apparatus 1 is started, the bypass pipe valve A for returning the hydrocarbon-based fuel desulfurized by the desulfurizer 3 to the raw material tank 2 is opened, and the valve B of the pipe from the desulfurizer 3 to the reformer 4 is closed. The desulfurizer 3 and the reformer 4 are separated (step S1). And the valve C of the piping from the preheater 7 for preheating the hydrocarbon fuel supplied to the desulfurizer 3 to the desulfurizer 3 is also opened, and the route of the hydrocarbon fuel is changed to the raw material tank 2 → preheater 7 → desulfurizer 3 → Set to the route of the raw material tank 2. In the system downstream of the desulfurizer 3, the valve D at the inlet of the PSA 6 is closed and the valve E of the piping toward the flare is opened, and the route of hydrogen fed for starting is changed to the reformer 4 → shift reactor 5 → Set to flare root.

(Desulfurizer start-up)
The inlet temperature of the desulfurizer 3 is increased from 200 to 250 ° C. at about 10 ° C./min by electric tracing (step S2). Until the inlet temperature of the desulfurizer 3 reaches 200 ° C., the valves A and C are closed, and the hydrocarbon-based fuel preheated by the preheater 7 is returned to the raw material tank 2 without passing through the desulfurizer 3 (step S3). ). The heat of the combustion exhaust gas from the reformer 4 is used as a heat source for the preheater 7. When the inlet temperature of the desulfurizer 3 reaches 200 to 250 ° C., the valve A and the valve C are opened, and the hydrocarbon-based fuel is supplied to the desulfurizer 3 (step S4). Until the desulfurizer 3 and the reformer 4 are connected, the hydrocarbon fuel desulfurized by the desulfurizer 3 is returned to the raw material tank 2 (step S5).

(Reformer startup)
The burner installed in the reformer 4 is ignited, and the temperature of the catalyst bed of the reaction tube 11 is raised with high-temperature combustion gas. In the present embodiment, the temperature of the catalyst bed of the reaction tube 11 is increased in two stages, that is, a start-up process and a reforming reaction preparation process.

(Start-up process)
Further, referring to FIG. 5, after the burner is ignited, the temperature of the outlet of the reaction tube 11 is increased at a rate of about 5 ° C./min until the outlet temperature of the reaction tube 11 reaches a predetermined temperature lower than the heat resistant temperature of the low temperature active catalyst After reaching the predetermined temperature, the burner is adjusted to maintain the outlet temperature at the predetermined temperature until the inlet temperature of the reaction tube 11 reaches 350 to 380 ° C. (step S6). In the reformer 4 of the present embodiment, the combustion gas is circulated from the outlet side of the reaction tube 11 toward the inlet side as described above, and the temperature of the combustion gas is reduced on the inlet side. Therefore, the temperature increase on the inlet side of the reaction tube 11 tends to be delayed compared to the temperature increase on the outlet side. In order to accelerate the temperature increase on the inlet side of the reaction tube 11, when the burner temperature is increased and heated, the heat resistance temperature of the low temperature active catalyst may be exceeded. In the present invention, the temperature control is performed at the outlet temperature in order to prevent the low temperature active catalyst near the outlet of the reaction tube 11 from being exposed to a high temperature exceeding its heat resistance temperature. The predetermined temperature at the outlet of the reaction tube 11 is 600 to 650 ° C. in consideration of the heat resistant temperature of the low temperature active catalyst (approximately 660 ° C.).

(Reforming reaction preparation process)
After the inlet temperature of the reaction tube 11 reaches 350 to 380 ° C., the supply of steam to the reformer 4 is started (step S7), and the temperature is further raised (step S8). Water vapor is produced by evaporating pure water with the evaporator 8. The heat of the combustion exhaust gas from the reformer 4 is used as a heat source for the evaporator 8. When the supply of water vapor to the reformer 4 is started, the pressure of the reformer 4 is increased to 0.4 to 0.6 MPa. At this time, it may be equal to the pressure of the desulfurizer 3. Then, the outlet temperature of the reaction tube 11 is increased at a rate of 10 ° C./min until the outlet temperature reaches 700 to 750 ° C., and the temperature of the high-temperature active catalyst on the outlet side is increased to or near its activation temperature. After the outlet temperature of the reaction tube 11 reaches 700 to 750 ° C., the outlet temperature is maintained at 700 to 750 ° C., and the temperature of the low-temperature active catalyst on the inlet side is increased to or near its activation temperature. The inlet temperature is raised to 400 to 450 ° C. In the state where the hydrocarbon fuel is not supplied to the reformer 4, there is no endothermic reaction due to the reforming reaction. Therefore, when the inlet temperature is set to 450 ° C. or higher, the low temperature active catalyst is exposed to a high temperature exceeding the heat resistance temperature. Problems such as sintering may occur.

(Connection between desulfurizer and reformer)
When the inlet temperature of the reaction tube 11 reaches 400 to 450 ° C. and the outlet temperature reaches 700 to 750 ° C., the desulfurizer 3 and the reformer 4 are connected (step S10). At this time, the inlet pressure of the reformer 4 is set 0.01 to 0.05 MPa higher than the outlet pressure of the desulfurizer 3 (step S9). It should be noted that if the pressure exceeds 0.05 MPa, it is not preferable because it takes a relatively long time to depressurize the reformer 4. By setting the pressure of the reformer 4 higher than that of the desulfurizer 3 in this way, it is possible to reliably prevent an excessive amount of hydrocarbon fuel from flowing into the reformer 4 and prevent coking of the reforming catalyst. It becomes possible to do.

(Start of raw material supply to reformer)
The opening degree of the valve E is adjusted, the pressure of the reformer 4 is gradually decreased, and the pressure is adjusted so that hydrocarbon fuel flows from the desulfurizer 3 to the reformer 4 (step S11). The raw material gas is supplied to (step S12). When the desulfurized hydrocarbon fuel is supplied to the reformer 4, the temperature of the catalyst bed is lowered due to the endothermic reaction, so the combustion amount of the burner is adjusted to maintain the reaction temperature.

(Reformer operation adjustment)
While the operation is stable, the temperature is raised so that the inlet temperature of the reaction tube 11 is 500 ° C. and the outlet temperature is 750 ° C. Thereafter, the valve E is closed and the valve D toward the PSA 6 is opened to supply the reformed gas to the PSA 6.

  As described above, according to the start-up method of the stationary hydrogen production apparatus reformer of the present embodiment, the outlet temperature of the reaction tube 11 is increased until the inlet temperature of the reaction tube 11 whose temperature rise is delayed reaches 350 to 380 ° C. Is kept below the heat resistance temperature of the low-temperature active catalyst, and the low-temperature active catalyst near the outlet can be prevented from being excessively heated. Then, after the inlet temperature of the reaction tube 11 reaches 350 to 380 ° C., the temperature of the reaction tube 11 is increased while circulating the steam, so that the reforming catalyst cracks due to the volume expansion due to the condensation and vaporization of the water vapor. Thus, it is possible to raise the temperature of the reforming catalyst to or near the activation temperature while preventing oxidation of the reforming catalyst.

  In addition, this invention is not limited to embodiment mentioned above, A deformation | transformation, improvement, etc. are possible suitably. In addition, the material, shape, dimension, numerical value, form, number, arrangement location, and the like of each component in the above-described embodiment are arbitrary and are not limited as long as the present invention can be achieved.

It is a schematic diagram which shows schematic structure of the stationary hydrogen production apparatus with which the starting method which concerns on this invention is applied. It is a longitudinal cross-sectional view of the reformer of FIG. It is a cross-sectional view of the reformer of FIG. It is a flowchart of the starting method of the stationary hydrogen production apparatus reformer which concerns on this invention. It is a graph which shows the change of the inlet temperature and outlet temperature of a reaction tube at the time of starting of the reformer of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Hydrogen production apparatus 2 Raw material tank 3 Desulfurizer 4 Reformer 5 Shift reaction apparatus 6 PSA apparatus 7 Preheater 8 Evaporator 11 Reaction tube 12 Shell 13 Partition 14 Combustion chamber 15 Channel part 15a Inlet side channel part 15b Outlet side channel part 16 Partition 17 Raw material gas inlet 18 Reformed gas outlet 19 Combustion gas inlet 20 Combustion gas outlet 21 Partition plate A valve B valve C valve D valve E valve

Claims (2)

Method for starting a reformer of a stationary hydrogen production apparatus including a reformer that reforms a raw material gas containing any one of hydrocarbon fuel, alcohol fuel, and synthetic fuel and water vapor to produce hydrogen Because
The reformer has a substantially U-shaped reaction tube through which a raw material gas is circulated . The reaction tube is filled with a first reforming catalyst on the outlet side, and the reaction tube is filled with the first reforming catalyst. The second reforming catalyst that is active at a lower temperature than the first reforming catalyst is filled, and the vent portion between the straight portion on the outlet side and the straight portion on the inlet side functions as a reforming catalyst. Is filled with an inert filling without
The reformer circulates combustion gas from the outlet side of the reaction tube toward the inlet side along the reaction tube to raise the temperature of the reaction tube to the activation temperature of the reforming catalyst,
A startup step of maintaining the outlet temperature of the reaction tube below the heat resistance temperature of the second reforming catalyst and raising the inlet temperature of the reaction tube to 350 to 380 ° C .;
After the start-up step, while allowing water vapor to flow through the reaction tube, the outlet temperature of the reaction tube is raised to 700 to 750 ° C. and maintained, and the inlet temperature of the reaction tube is raised to 400 to 450 ° C. A reforming reaction preparation step;
A start-up method for a stationary hydrogen production apparatus reformer, comprising: In the start-up process, the outlet temperature of the reaction tube is increased at 5 ° C./min,
2. The start-up method for a stationary hydrogen production apparatus reformer according to claim 1, wherein in the reforming reaction preparation step, the outlet temperature of the reaction tube is raised at 10 [deg.] C./min.

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