WO2000063114A1 - Reformeur cylindrique monotube et procede pour faire fonctionner ledit reformeur - Google Patents
Reformeur cylindrique monotube et procede pour faire fonctionner ledit reformeur Download PDFInfo
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- WO2000063114A1 WO2000063114A1 PCT/JP2000/002581 JP0002581W WO0063114A1 WO 2000063114 A1 WO2000063114 A1 WO 2000063114A1 JP 0002581 W JP0002581 W JP 0002581W WO 0063114 A1 WO0063114 A1 WO 0063114A1
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- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
- H01M8/0625—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material in a modular combined reactor/fuel cell structure
- H01M8/0631—Reactor construction specially adapted for combination reactor/fuel cell
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- C01B3/583—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction the reaction being the selective oxidation of carbon monoxide
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Definitions
- the present invention relates to a single-tube cylindrical reformer for producing a hydrogen-rich reformed gas by steam reforming hydrocarbon-based raw fuels such as city gas, natural gas, LPG and the like, and alcohols.
- the present invention relates to a reformer used in combination with a fuel cell. Background technology:
- the reformer is a device that generates a reformed gas with a high hydrogen concentration (hydrogen-rich) by steam reforming raw hydrocarbons such as city gas, natural gas, and LPG, and / or alcohol. It is widely used to produce hydrogen for use in optical fiber and semiconductor manufacturing processes and fuel cells.
- the reforming reaction in the reformer is as follows, using the example of methane.
- a reformer for producing a relatively small volume of hydrogen for example, a single-tube cylindrical reformer as disclosed in Japanese Patent Application Laid-Open No. 11-191001 is known.
- a heating means such as a wrench is provided at the center of a cylindrical container having a catalyst layer built in between two cylinders. The catalyst layer is heated by the heating means, and the reforming material passed through the catalyst layer The gas is reformed by water vapor.
- FIG. 1 is a longitudinal sectional view showing a schematic configuration of a conventional single-tube cylindrical reformer.
- the illustrated single-tube cylindrical reformer has an elongated outer cylinder 1 with a circular cross section, an upright cylinder, a circular inner cylinder 3 arranged inside the outer cylinder 1, and a constant inner cylinder 3 inside the outer cylinder 1.
- a lid plate (bottom plate) 1a which is a common single plate, is attached.
- the parner 7 is arranged at the upper part of the combustion chamber 9.
- a banana (not shown) arranged at the lower part of the combustion chamber 9. a is attached as a ceiling plate to the upper ends of the outer cylinder 1 and the inner cylinder 3 as a common single disk.
- the single-tube cylindrical reformer shown in FIG. 1 operates as follows.
- High-temperature combustion gas is generated inside the combustion chamber 9 by the combustion flame 8 of the wrench 7, and the heat is transferred to the radially outer side of the inner cylinder via the radiation cylinder 4 to heat the reforming catalyst 5 and At the same time, the high-temperature combustion gas enters the inside of the inner cylinder 3 from the lower part of the radiating cylinder 4 and becomes an ascending flow to directly heat the reforming catalyst 5.
- the combustion gas is discharged from the upper end of the reformer after heating.
- the reforming raw material gas introduced from the upper part of the reformer is heated while rising down the annular flow path filled with the reforming catalyst 5 to 70 (to about TC),
- the reformed raw material gas (reformed gas) is inverted at the lower end of the reformer and turns into an upward flow generated in a passage formed between the outer cylinder 1 and the inner cylinder 3.
- the sensible heat of the reformed gas is recovered in the reforming section inside the intermediate cylinder 2 and the temperature drops, and is taken out of the upper end of the reformer as reformed gas.
- the conventional single-tube cylindrical reformer shown in FIG. 1 has the following problems.
- a common lid plate 1a is fixed to the lower end of the outer cylinder 1 and inner cylinder 3 that require fluid partitioning in a sealed manner by welding or the like. Due to the thermal stress generated in cylinder 1 and inner cylinder 3, buckling deformation of inner cylinder 3, which becomes particularly hot, may occur, and the performance of the reformer may decrease due to the following factors. . Outflow of reformed gas due to cracks in inner cylinder 3,
- the reformed gas generated by the conventional single-tube cylindrical reformer contains about 10% of CO. If it is used as fuel for polymer electrolyte fuel cells, a CO converter must be installed. After reducing the C ⁇ concentration to about 0.5%, it is necessary to further install a CO selective oxidizer to perform the C ⁇ selective oxidation reaction to reduce the C ⁇ concentration to about 10 ppm. is there.
- the steam generator, CO converter, and CO selective oxidizer are provided separately from the single-tube cylindrical reformer, it is not preferable in terms of miniaturization, high efficiency, and startability.
- the present invention has been made in view of the above problems in the prior art, and a first object of the present invention is to make the thermal displacement in the axial direction of the outer cylinder and the inner cylinder constituting the reformer free. To prevent the occurrence of buckling deformation of the inner cylinder and the reduction in the performance of the reformer due to this, and to reduce the heat loss from the combustion chamber through the cover plate. To provide a single-tube cylindrical reformer.
- a second object of the present invention is to realize a low CO content, efficient, good start-up, small size and light weight, and thermally stable and efficient.
- An object of the present invention is to provide a single-tube cylindrical reformer.
- an upright circular outer cylinder which is disposed concentrically inside the outer cylinder at a radial interval.
- a circular inner cylinder ; a circular intermediate cylinder unit disposed between the outer cylinder and the inner cylinder and concentrically spaced apart in a radial direction; and a radially inner space inside the inner cylinder.
- a radial radiating tube arranged concentrically with a radiator, a wrench fixed at one axial end of the reformer so as to be located at the radial center of the radiating tube, the inner tube and the intermediate tube
- a reforming catalyst serving as a reforming catalyst layer
- a single-tube cylindrical reformer having an annular flow path, the side opposite to the fixed position of the above-mentioned panner.
- the axial ends of the outer cylinder and the inner cylinder are double-bottomed structures sealed with individual lid plates so as to be spaced apart from each other at a predetermined interval.
- a single tube cylindrical reformer is provided.
- the burner is fixed to an upper end of a reformer, and the individual cover plates are attached to lower ends of the outer cylinder and the inner cylinder, respectively.
- the burner is fixed to a lower end of the reformer, and the individual cover plates are attached to upper ends of the outer cylinder and the inner cylinder, respectively.
- a steam generator is further provided inside or outside the reformer.
- the single-tube cylindrical reformer according to the first aspect of the present invention is used for a fuel cell.
- a circular radiation tube arranged in a shape, a parner fixed to one end in the axial direction of the reformer so as to be located at a radial center of the radiation tube, and between the inner cylinder and the innermost intermediate cylinder.
- a single-tube cylindrical reformer having a plurality of annular flow passages, each of which is formed in a radial layer shape between at least a portion thereof and at least partially filled with a reforming catalyst to be a reforming catalyst layer and communicates with each other,
- the invention has the following characteristic aspects.
- a steam generator is provided on the inner radiation tube, and the steam generator is heated via the wall surface of the radiation tube.
- a preheating layer filled with a heat transfer enhancer is provided in front of the upper part of the reforming catalyst layer filled with the reforming catalyst.
- a heat recovery layer is provided on the outer periphery of the reforming catalyst layer, which is connected to the reforming catalyst layer at the lower end, raises the reformed gas, and transfers the heat held by the reformed gas to the reforming catalyst layer. ing.
- the inside of the heat recovery layer is filled with ceramic balls of a predetermined diameter.
- the reforming catalyst layer for reforming the reforming raw material gas is connected to the outer periphery of the reforming catalyst layer at the lower end, the reforming gas rises inside, and the heat held by the reforming gas is converted to the reforming catalyst.
- a CO conversion catalyst layer (hereinafter also referred to as a shift layer) is provided on the outer periphery of the shift layer, connected to the shift layer at a lower portion, and the reformed gas rises inside and reacts with oxygen in the air.
- a CO selective oxidation catalyst layer (hereinafter also referred to as a PR ⁇ X layer) for reducing CO in the reformed gas and the NO or the shift layer at the lower part, and the reformed gas rises inside and the reformed gas is
- a second shift layer for reducing CO in the substrate and a second shift layer between the shift layer and the PROX layer and Z or the second shift layer.
- the upper part of the heat recovery layer that is, a part on the downstream side is a sub CO conversion catalyst layer (sub shift layer).
- the cooling fluid passage may include combustion air, raw material gas introduced into the reforming catalyst layer, gaseous or liquid reforming water, or a combination thereof. A fluid is introduced.
- a predetermined interval is provided between the outer wall surface of the heat recovery layer and the inner wall surface (inner cylinder) of the shift layer, and the bottom of the inner wall (inner cylinder) of the shift layer and the heat
- the collection layer has a double bottom structure in which the bottom of the outer wall is separated from the bottom.
- the PROX layer comprises a PROX layer and an air mixing layer provided before the PROX layer for mixing the oxygen and the reformed gas.
- the air mixing layer is located at the position of the air introduction hole. It is provided in.
- the reforming water flowing into the cooling fluid passage cools the shift layer and the PR ⁇ X layer and / or the second shift layer in contact with the cooling fluid passage, and is heated and vaporized by the heat of reaction. It has become.
- Insulation material is properly filled at the bottom or between the inner cylinder and the intermediate cylinder, between the intermediate cylinders, and between the intermediate cylinder and the outer cylinder.
- the axial lengths of the shift layer, the PR ⁇ ⁇ ⁇ X layer, and the no or second shift layer are shorter than those of the heat recovery layer.
- the reformed gas from the shift layer once enters the air passage formed outside the PROX layer and Z or the second shift layer. After being discharged and merged with air in the air passage, they are introduced again into the PR ⁇ X layer and the NO or second shift layer.
- the opening of the regulating valve provided at the outlet of the wet steam is adjusted according to the fluctuation of the operating state, and the temperature of the turning point of the shift layer and the temperature of the PR ⁇ X layer and / or the second shift layer are adjusted.
- the temperature is maintained at a predetermined value.
- the boiler By providing a steam generator that is heated with a part of the radiant tube as a heat transfer surface, the boiler can be integrated with a small reformer, preventing damage due to overheating, and reducing the calorific value of the combustion exhaust gas. Thermal efficiency can be improved because it can be used effectively.
- the temperature rise of the O shift catalyst layer can be suppressed.
- the CO selective oxidation catalyst layer and Z or the air for the second shift layer are introduced into the air passage formed between the container outer cylinder and the C0 selective oxidation catalyst layer and / or the second shift layer, and the CO selective oxidation catalyst layer is introduced. And / or by providing an air supply hole on the outer surface of the second shift layer ', air can be evenly supplied to the CO selective oxidation catalyst layer and Z or the second shift layer to reduce hydrogen loss, and heat insulation Heat loss can be reduced. Since the CO selective oxidation catalyst layer and / or the air mixing layer that mixes the air of the second shift layer is formed by filling the packing material, the mixing of the reformed gas and air can be performed without providing a separate mixing device. In addition, hydrogen loss can be reduced.
- the boiler Since the reforming water is vaporized in the cooling fluid passage provided between the CO shift catalyst layer and the CO selective oxidation catalyst layer and Z or the second shift layer, the boiler is used without using fuel. Can be configured. Sufficient cooling capacity can be obtained for the C ⁇ conversion catalyst layer, the CO selective oxidation catalyst layer, and the Z or second shift layer.
- the configuration of the nozzle and the like can be simplified.
- the concentration of carbon monoxide in the reformed gas can be reduced to a predetermined value or less, it can be used as a hydrogen generator of a polymer electrolyte fuel cell, and a compact and highly efficient fuel cell can be configured.
- FIG. 1 is a longitudinal sectional view showing a schematic configuration of a conventional single-tube cylindrical reformer
- FIG. 2 is a longitudinal sectional view showing a schematic configuration of a single-tube cylindrical reformer according to a first embodiment of the present invention
- FIG. 3 is a longitudinal sectional view showing a schematic configuration of a single-tube cylindrical reformer according to a second embodiment of the present invention
- FIG. 4 is a horizontal sectional view taken along the line IV—IV in FIG. 3,
- FIG. 5 is a flowchart illustrating the main operation of the single-tube cylindrical reformer of the present invention.
- FIG. 6 is a longitudinal sectional view showing a schematic configuration of a single-tube cylindrical reformer according to a third embodiment of the present invention.
- FIG. 7 is a longitudinal sectional view showing a schematic configuration of a single-tube cylindrical reformer according to a fourth embodiment of the present invention.
- FIG. 2 is a longitudinal sectional view showing a schematic configuration of the single-tube cylindrical reformer according to the first embodiment of the present invention.
- the illustrated reformer according to the first embodiment has an elongated outer cylinder 1 having a circular cross section, which is arranged upright, and an inner cylinder having the same central axis inside the outer cylinder 1 and having a circular cross section. 3 are located. Further, an intermediate cylinder 2 surrounding the inner cylinder 3 is provided at a certain distance from the inner cylinder 3 inside the outer cylinder 1, and an intermediate gap is formed between the inner cylinder 3 and the intermediate cylinder 2. Catalyst 5 is packed. Further, a radiation tube 4 is arranged inside the inner tube 3 with the same central axis as the inner tube 3, and above a combustion chamber 9 formed inside the radiation tube 4 via a parner mount 6. Pana 7 is installed.
- lid plates (bottom plates) lb, 3a are hermetically fixed by welding or the like to lower ends in the axial direction of the outer cylinder 1 and the inner cylinder 3 facing the parner 7, respectively. There is a certain gap between the lid 1b of the outer cylinder 1 and the lid 3a of the inner cylinder 3. In other words, the lid plates lb and 3a have a double structure with respect to the center direction of the outer cylinder 1 and the inner cylinder 3 (instead of a common single disk).
- the wrench 7 and the wrench mount 6 are arranged at the upper part of the combustion chamber 9, and the lid plate (bottom plate) lb, 3 a is attached to the lower end of the outer cylinder 1 and the inner cylinder 3, respectively. It has a double structure.
- the wrench 7 and the wrench mount 6 may be arranged in the lower part of the combustion chamber 9.
- the lid plates of the inner cylinder 3 and the outer cylinder 1 are also provided. (In this case both ceiling plates) have a double structure (rather than a common single disk).
- the axial distance between the lid plate 1b and the lid plate 3a is determined in consideration of the axial thermal displacement difference between the outer cylinder 1 and the inner cylinder 3, and from the viewpoint that the reformed gas does not cause natural convection there. It is determined appropriately.
- a steam generator for generating and supplying steam introduced into the reformer together with the reforming raw material gas such as city gas is provided inside the reformer. Or it is provided outside.
- the reformer shown in FIG. 2 operates as follows.
- the temperature of the reforming catalyst reaches its maximum near the lower end of the annular flow path that fills the reforming catalyst, that is, near the lower end of the intermediate cylinder 2.
- the reformed gas flowing out from the lower end of the annular flow path reverses and turns into an ascending flow.
- the sensible heat of the reformed gas is recovered by the inner reforming process and the temperature drops (about 200 ° C), is taken out from the upper end portion of the reformer as a hydrogen-rich reformed gas (mixed gas of hydrogen, such as CO and C_ ⁇ 2).
- the present invention in addition to the first embodiment, has a low concentration of C ⁇ , is efficient, has good start-up properties, is small and lightweight, and is thermally stable. It also provides a single-tube cylindrical reformer without any.
- FIG. 3 shows a schematic configuration of an example of a small and light single-tube cylindrical reformer.
- the reformer 81 includes a circular outer cylinder 10, an intermediate group 60 provided concentrically inside the outer cylinder 10, and an inner group concentrically provided inside these intermediate cylinder groups.
- the cylinder 68, the reforming catalyst layer 13 provided in the annular space formed between the inner cylinder 68 and the innermost intermediate cylinder 67, the intermediate cylinders 65 and 64, Between the CO conversion catalyst layer 11 (hereinafter also referred to as shift layer 11) provided in the annular space formed between the intermediate cylinder 61 provided on the outermost side and the next intermediate cylinder 62.
- C ⁇ selective oxidation catalyst layer 12 (hereinafter also referred to as PROX layer 12) provided in the annular space formed between them. It is composed of
- a heat transfer partition 14 (radiation tube) provided concentrically with the inner tube 68 is disposed inside the inner tube 68, and a parner mounting base 16 is provided inside the heat transfer partition 14.
- Banner 18 is attached via.
- the outer cylinder 10 is a bottomed cylinder with a circular cross section and has a saturated or superheated steam outlet 20, wet steam outlet 21, water supply 22, and flue gas outlet on the upper side. 24, a supply port 26 for the combined fluid of the reforming raw material gas and steam, an outlet 28 for the reformed gas, and a supply port 30 for the air for the PROX layer are provided.
- the intermediate cylinder group 60 is composed of a plurality of intermediate cylinders from a first intermediate cylinder 61 to a seventh intermediate cylinder 67, and forms annular gaps between the respective intermediate cylinders.
- An air passage 42 for supplying air to the PROX layer 12 is formed between the first intermediate cylinder 61 and the outer cylinder 10. The air passages 42 are connected to the entire periphery at the bottom to form a jacket structure surrounding the whole with an air layer.
- the first intermediate cylinder 61 has an air introduction hole for introducing air to the bottom 71 and side surfaces. 4 3 is formed.
- a PROX layer 12 is formed in two upper and lower stages.
- Each PROX layer 12 is composed of a PROX catalyst layer 44 and an air mixing layer 46.
- the lower PR ⁇ X layer 12a communicates with the inner shift layer 11 at the bottom, and the upper PROX layer 1 2b is connected to the reformed gas outlet 28 at the upper part.
- the reformed gas outlet 28 is connected to, for example, a fuel gas supply pipe 102 of the polymer electrolyte fuel cell 100, and has a predetermined concentration extracted from the reformed gas outlet 28.
- the reformed gas d (fuel gas) containing hydrogen is supplied to the fuel electrode side (not shown) of the polymer electrolyte fuel cell 100, thereby generating power.
- the surplus reformed gas e in the polymer electrolyte fuel cell 100 may be used as a combustion gas in the parner 18.
- the inside of the air mixing layer 46 is filled with ceramic spheres of a predetermined diameter, and when the air passes through the inside of the air mixing layer 46, the ceramic sphere bends the flow path and is mixed efficiently. It has become so.
- the air introduction hole 43 is formed below the air mixing layer 46, that is, near the upstream end of the air mixing layer 46. Ceramics P 025 1
- the diameter of the ball is set to 1Z3 to 110, which is the width of the flow path of the air mixing layer 46, in consideration of the increase in the flow rate and the quality of mixing. If the diameter of the ceramic spheres is 1 to 3 or more, the mixing is not sufficient. If the diameter is 1 to 10 or less, the passage resistance increases, which is not preferable. Between the second intermediate cylinder 62 and the fourth intermediate cylinder 64, there is a cooling fluid passage 48 through which a cooling fluid passes with the third intermediate cylinder 63 interposed therebetween. Connected to combination fluid supply port 26.
- the cooling fluid passage 48 is divided in the radial direction at the boundary of the third intermediate cylinder 63, and the outside is the PROX layer 1 2 is a descending passage, and the inside is an ascending passage contacting the shift layer 11. Note that the main cooling fluid flowing into the cooling fluid passage 48 is a combined fluid of the reforming raw material gas and the reforming water. A little bit.
- a shift layer (C ⁇ shift catalyst layer) 11 is formed between the fourth intermediate cylinder 64 and the fifth intermediate cylinder 65.
- the shift layer 11 has a C ⁇ conversion catalyst filled therein, and is connected to the heat recovery layer 50 at the upper portion and connected to the PROX layer 12 at the lower portion to perform a CO conversion reaction.
- the fifth intermediate cylinder 65 is connected to the bottom of the first intermediate cylinder 61 at the lower part.
- the fifth intermediate cylinder 65 is the inner wall of the shift layer 11, and the sixth intermediate cylinder 66 is the outer wall of the heat recovery layer 50, and a space is formed between the two to insulate them.
- the heat insulating layer 49 serves as a buffer mechanism for relaxing the thermal stress of both.
- the ceramic sphere has a function of transmitting the heat of the gas passing through the heat recovery layer 50 to the reforming catalyst layer 13 in contact therewith via the seventh intermediate cylinder 67.
- a bottom plate 76 is attached to the lower portion of the sixth intermediate cylinder 66, and a space is formed between the bottom plate 78 and the bottom plate 78 attached to the lower portion of the inner cylinder 68.
- the annular space formed between the seventh intermediate cylinder 67 and the inner cylinder 68 is preheated upstream.
- the preheating layer 51 is also provided with a filler for improving the heat transfer effect, for example, a ceramic ball having a diameter of 1/2 to 1/5 of the passage width. ing.
- a reforming catalyst layer 13 is formed downstream of the preheating layer 51.
- the preheating layer 51 communicates with the cooling fluid passage 48 on the upstream side.
- the reforming catalyst layer 13 is filled with a reforming catalyst for steam reforming the reforming raw material gas.
- the reforming catalyst layer 13 is formed at the lower end of the heat recovery layer 50 through a space formed between the bottom plate 78 of the inner cylinder 68 and the bottom plate 76 of the sixth intermediate cylinder 66 at its lower part. Communicating.
- the gap between the bottom plate 78 and the bottom plate 76 also has a function as a heat insulating layer for the combustion part of the parner 18.
- a cylindrical heat transfer partition 14 is attached with an appropriate interval between the inner cylinder 68 and the bottom plate 78.
- the gap between the heat transfer bulkhead 14 and the inner cylinder 68 is formed as an exhaust gas passage through which the combustion exhaust gas in the parner 18 flows, and is connected to a combustion exhaust gas outlet 24 at the upper portion.
- a steam generator 34 is provided inside the upper part of the heat transfer partition 14.
- the steam generator 34 is a space having a heat transfer partition 14 on one side, and is partitioned inside and outside by providing a partition 35 inside, and each of the partitioned sections has a steam extraction port 20 and water.
- Supply port 22 is connected.
- a wet steam outlet 21 is installed on the side of the water supply port 22 opposite to the outlet, and the steam outlet 20 and the wet steam outlet 21 regulate the flow rate respectively. It is connected to the combined fluid supply port 26 of the reforming raw material gas and steam via the regulating valve B (see FIG. 4).
- Pana 18 is located at a position where the height of the crater is lower than the lower end of the steam generator 34, and even when the flame is emitted from the crater by being ignited by Pana 18, the flame is steam It is arranged so that it does not directly hit the generator 34.
- FIG. 4 is a horizontal sectional view taken along line IV-IV in FIG. However, supply ports and discharge ports that are unnecessary for the explanation here are excluded.
- Reforming water a is supplied to the steam generator 34 of the reformer 81 via a water supply valve A and a supply port 22.
- a certain time is required from the ignition of the burner 18 to the heating by the burner 18 until the steam generator 34 saturates or superheated steam b 1 is taken out from the steam outlet 20.
- a predetermined amount of saturated or superheated steam b 1 is taken out from the steam outlet 20.
- the reforming raw material gas c to be reformed is supplied via the reforming raw material gas supply control valve C, and is operated together with the superheated steam b1 which is merged by operating the regulating valve B. It is introduced into the reformer from 26 and steam reforming of the reforming raw material gas c in the reformer is started.
- the supply of saturated or superheated steam b1 is stopped and the supply of saturated or superheated steam b1 is stopped in order to advance the operation of the reformer from the start-up operation state to the steady operation state.
- the regulating valve B is operated so that wet steam b2 containing liquid water discharged from the wet steam supply port 21 communicating with the steam generator 34 is supplied.
- the water supply valve A is opened, and the water a is supplied from the water supply port 22 to the steam generator 34 in the reformer (F-1). Subsequently, the burner 18 provided in the reformer is ignited to start the reformer (F-2), and the reforming raw material gas undergoing reforming mixed with superheated steam b1 c is introduced into the reformer.
- the temperature inside the reformer gradually increases due to the combustion by the burner 18, the temperature T at the turning point P of the shift layer 11 is detected as a measure for shifting to the steady operation (F-3). It is determined whether the turning point temperature T is higher than 200 ° C (F_4), and when the turning point temperature T becomes higher than 200 ° C, the regulating valve B is gradually opened ( F-5) Instead of the superheated steam b1, wet steam b2 containing liquid water is mixed with the reforming raw material gas c and supplied. The introduction of wet steam b 2 lowers the temperature inside the reformer, but the turning point is between 170 ° C and 230 ° C (1 70 ° C ⁇ T ⁇ 230 ° C) C) is checked (F-6).
- reforming water a is supplied from the water supply port 22, and water is supplied into the steam generator 34.
- the burner 18 is ignited to heat the inside of the reformer 81. Heating by the burner 18 heats the heat transfer partition 14 by radiant heat from the flame, and the combustion exhaust gas passes between the heat transfer partition 14 and the inner cylinder 68 and is exhausted from the combustion exhaust gas outlet 24. As a result, the reforming catalyst layer 13 and the preheating layer 51 are heated from the inside.
- the steam generator 34 is gradually heated by the combustion exhaust gas passing between the heat transfer partition 14 and the inner cylinder 68, the temperature rise in the combustion chamber of the parner 18, and the heat transfer from the heat transfer partition 14. It is.
- steam b 1 is taken out from the steam outlet 20 and steam b 1 is added to the raw material gas c. Supplied from the reforming material gas supply port 26.
- the steam generator 34 is heated by the combustion of the parner 18, the steam b 1 required for starting the reformer 81 can be obtained in a relatively short time.
- the heat contained in the flue gas can be absorbed and effectively used to improve efficiency. it can.
- the reforming raw material gas c is a hydrocarbon-based fuel such as city gas, and is formed between the second intermediate cylinder 62 and the fourth intermediate cylinder 64 when supplied from the supply port 26 together with the steam bl. It is sent to the preheating layer 51 through the cooled cooling fluid path 48. In the meantime, in the cooling fluid passage 48, the temperature of the shift layer 11 and the PR ⁇ X layer 12 in contact with the cooling fluid passage 48 is low. Supply heat to PROX layer 12. In particular, the steam bl is liquefied to supply latent heat, whereby the temperature rise of the shift layer 11 and the PROX layer 12 can be accelerated.
- the ceramic spheres filled in the preheating layer 51 are heated by the heat from the panner 18, so that the reforming raw material gas' c The heat is absorbed, heated to a predetermined temperature or higher required for the reforming reaction, and enters the reforming catalyst layer 13. Further, since the preheating layer 51 is supplied with the low-temperature reforming raw material gas c and the steam b1, the temperature can be kept low near the inlet.
- the reforming raw material gas c that has entered the reforming catalyst layer 13 is, for example, reformed by the following reaction in the case of methane gas.
- the reaction proceeds by absorbing the combustion heat of the parner 18. Specifically, when the flue gas from the parner 18 passes between the heat transfer partition wall 14 and the reforming catalyst layer 13, the heat of the flue gas is absorbed by the reforming catalyst layer 13 and reformed. In the catalyst layer 13, a reforming reaction is carried out with increasing temperature. When the reaction becomes substantially equilibrium, the reformed gas exits from the lower portion of the reforming catalyst layer 13, reverses at the lower end, and enters the heat recovery layer 50.
- the inside of the heat recovery layer 50 is filled with ceramic spheres, and the heat of the reformed gas is supplied to the reforming catalyst layer 13 via the ceramic spheres.
- the upper end of the heat recovery layer 50 is It comes into contact with the preheating layer 51 into which the relatively low-temperature reforming raw material gas c and water vapor b1 flow, and as a result, the temperature drops further and exits from the top at a temperature suitable for the CO shift reaction and inverts to form a shift layer. 1 Enter within 1.
- the CO shift reaction in the shift layer 11 is an exothermic reaction, but since the shift layer 11 and the heat recovery layer 50 are formed with a gap, the heat in the heat recovery layer 50 is transmitted directly and the shift layer 1 1 is not heated, and the temperature of the shift layer 11 can be kept low.
- the reformed gas discharged from the lower part of the shift layer 11 reverses at the lower end and enters the PROX layer 12.
- the PROX layer 12 is composed of a PR ⁇ X catalyst layer 44 and an air mixing layer 46, and is first mixed with air introduced from the air introduction holes 43 while passing through the air mixing layer 46, 44 causes a CO selective oxidation reaction.
- the air for the C ⁇ selective oxidation reaction also oxidizes the force H 2 that converts C ⁇ to C ⁇ 2 , consuming H 2 . Therefore, in order to minimize the oxidation of H 2 , an air mixing layer 46 is installed in the preceding stage to supply the necessary minimum amount of oxygen to the reformed gas to selectively perform the CO oxidation reaction. To cause a reaction. Further, since the cooling fluid passage 48 is formed between the shift layer 11 and the PR ⁇ X layer 12, the time required for the reaction to reach the temperature required for the reaction by the heat from the steam b1 at the time of startup is obtained. Is shortened.
- the regulating valve communicating with the wet steam outlet 21 is gradually opened to release the wet steam b 2 containing liquid water. It is supplied from the reforming material gas supply port 26 together with the reforming material gas c. Then, the liquid water contained in the wet steam b 2 absorbs the heat of reaction between the shift layer 11 and the PROX layer 12 in the cooling fluid passage 48 and evaporates. Endothermic due to evaporation of this moisture By the action, the temperature rise of the shift layer 11 and the PROX layer 12 due to the exothermic reaction is suppressed, and the temperature in the reformer can be maintained at a predetermined temperature.
- the fuel in the parner 18 is throttled and heated by the steam generator 34.
- the reforming raw material gas c is introduced into the reforming catalyst layer 13 via the preheating layer 51 together with the steam heated in the cooling fluid path 48.
- the temperature required for the reforming catalyst layer 13 It is not necessary to provide a separate preheating device or the like to raise the temperature of the reforming raw material gas c, and the thermal efficiency can be increased.
- the reforming raw material gas c is not supplied at a high temperature in advance, the temperature near the inlet of the preheating layer 51, for example, the outlet temperature of the heat recovery layer 50 can be reduced.
- the shift layer 11, which becomes a reaction at a temperature lower than the reaction temperature of the reforming catalyst layer 13, can be continuously connected to the reforming catalyst layer 13 via the.
- the reforming raw material gas c heated in the preheating layer 51 is further heated in the reforming catalyst layer 13 to undergo a reforming reaction, and flows out from the lower portion of the reforming catalyst layer 13.
- the relatively high temperature reformed gas flowing out from the lower portion of the reforming catalyst layer 13 rises inside the heat recovery layer 50, and the heat transfer promoting effect of the ceramic spheres provided inside the reforming catalyst layer 13 causes the reforming catalyst to flow.
- Heat exchange with layer 13 reduces temperature. That is, the heat recovery layer 50 has a temperature gradient in which the temperature decreases as going upward from below, and the reformed gas absorbs heat as it rises in the heat recovery layer 50, and the temperature decreases. This is the same between the heat recovery layer 50 and the preheating layer 51, and the heat absorbed by the heat recovery layer 50 from the reformed gas is preheated from the heat recovery layer 50 using the temperature difference. Communicated to layer 51.
- the preheating layer 51 is provided before the reforming catalyst layer 13 and the inlet of the preheating layer 51 and the outlet of the heat recovery layer 50 are arranged close to each other, so that the preheating layer 51 has no preheating.
- the reforming raw material gas c is introduced, the rise in the inlet temperature of the preheating layer 51 and, consequently, the rise in the outlet temperature of the heat recovery layer 50 are suppressed, and the shift layer 11 continues for the first time. It can be configured as follows.
- the reformed gas which has been cooled to a temperature suitable for the CO conversion reaction in the heat recovery layer 50, enters the shift layer 11 from above, and CO contained in the reformed gas is converted to carbon dioxide. Although this reaction is an exothermic reaction, the temperature is reduced to a temperature suitable for the C ⁇ selective oxidation reaction by heat exchange with the cooling fluid passage 48, and enters the next PROX layer 12.
- the reformed gas at this stage contains about 0.5% ( ⁇ ).
- the heat insulating layer 49 is formed between the heat recovery layer 50 and the shift layer 11, the heat of the heat recovery layer 50 is blocked by the heat insulating layer 49.
- the temperature of the shift layer 11 can be maintained at a predetermined temperature. Also, thermal stress due to the temperature difference between the two can be eliminated, and damage can be prevented.
- the cooling fluid passage 48 provided on the outer periphery of the shift layer 11 vaporizes the wet water vapor b2, so that the boiler section is integrated into the inside, so to speak, and the heat generated by the burner 18
- the shift layer 11 and the PROX layer 12 can be cooled by heat of vaporization, and the shift layer 11 and the PROX layer 12 can be suppressed to a predetermined temperature.
- the conversion can be increased, and the PROX layer 12 can suppress the undesired side reactions such as the metanalysis reaction and the reverse shift reaction. Further, since the heat of reaction and the sensible heat in the shift layer 11 and the PROX layer 12 can be recovered in this way, the thermal efficiency can be improved.
- the cooling fluid flowing into the cooling fluid passage 48 may include combustion air, water for reforming gas or liquid, and reforming material gas. Etc., or a combination of a plurality of these methods may be used.
- the cooling fluid passage 48 is dedicated to the combustion air, or the passage of the cooling fluid passage 48 is divided to allow the combustion air to pass through.
- reforming water, reforming raw material gas, and the like are provided separately from these passages, and are introduced into the reformer 81.
- liquid reforming water provides a sufficient cooling capacity and can arbitrarily lower the temperature as compared with gas.
- the cooling fluid inflow nozzle and the reforming raw material gas c inflow nozzle can also be used. Since the exit nozzle can be made unnecessary, the configuration can be simplified.
- the amount of cooling heat in the cooling fluid passage 48 can be increased or decreased, and the temperatures of the shift layer 11 and the PROX layer 12 important for the reaction can be maintained at predetermined values.
- the reformed gas discharged from the shift layer 11 enters the inside of the air mixing layer 46 into which the air from the air supply port 30 is mixed. Since the reformed gas is mixed with air while passing through the air mixing layer 46, it can be sufficiently stirred without installing a separate stirrer or the like, and enters the PRO X catalyst layer 44 in a stirred state. In the reaction in the X catalyst layer 44, unnecessary loss of hydrogen due to local high oxygen concentration can be prevented. In addition, since the holes 43 can be set arbitrarily, air can be introduced from any position in the PROX layer 12, thereby reducing the amount of air required for selective oxidation and removal of CO, and Hydrogen loss due to air can be suppressed.
- the reaction in the first-stage PROX layer 12 When the reaction in the first-stage PROX layer 12 is completed, it enters the next-stage PROX layer 12 and lowers the CO concentration again.
- the reformed gas is, for example, hydrogen 7
- the gas containing 5%, 5% methane, 19% carbon dioxide, 1% nitrogen, and 10 ppm or less carbon monoxide is taken out from the reformed gas outlet 28. Since the reformed gas has a carbon monoxide concentration of 10 ppm or less, it can be supplied to a polymer electrolyte fuel cell and used as a fuel gas for a polymer electrolyte fuel cell.
- a space is formed between the PROX layer 12 and the outer cylinder 10, through which air to be introduced into the PROX layer 12 is circulated. Air can be retained, the heat insulation effect is high, the internal temperature can be maintained, and heat loss can be prevented.
- the amount of hydrogen generated is changed by adjusting the amount of the reforming raw material gas supplied from the supply port 26.
- the temperature of each part it is necessary to keep the temperature of each part almost constant. For example, if the required amount of reforming gas decreases and the inflow of reforming raw material gas decreases, the supply amount of reforming water also needs to be reduced, so the shift layer 11 and the PROX layer 12 In such a case, the temperature may increase due to a decrease in cooling water.
- the regulating valve communicating with the outlet 21 of the wet steam in the steam generator 34 is opened, and the steam outlet 20 is opened.
- Reduce the intake of saturated or superheated steam from the system. the amount of heat absorbed by the latent heat increases because the wetness of the steam flowing from the supply port 26 increases, and the temperature rise in the shift layer 11 and the PROX layer 12 can be prevented. It is possible to maintain the temperature of each part without generating unnecessary heat loss and without replenishing heat from others.
- the steam generator 34 is heated via the heat transfer of the heat transfer bulkhead 14 and is not directly heated by the flame of the burner 18, the water for reforming the steam generator 34 is not used.
- the steam generator 34 is not overheated even when the supply amount is reduced and the inside becomes dry.
- the regulating valve B communicating with the wet steam outlet 21 is throttled, and the saturated or superheated steam from the saturated or superheated steam outlet 20 is squeezed.
- b Increase incorporation of 1.
- FIG. 6 Another example of the small and light single-tube cylindrical reformer of the present invention is shown in FIG. 6 as a third embodiment of the present invention.
- the reformer 82 has an inner bottom opened inside the inner cylinder 65 and a closed upper part between the inner cylinder 65 and the inner cylinder 66.
- Other configurations are the same as those of the reformer 81 shown in FIG. With this configuration, the air passage 42 that supplies oxygen to the PROX layer 12 is connected to the gap between the heat recovery layer 50 and the shift layer 11. As a result, the heat insulating effect on the shift layer 11 can be improved. Further, since the bottom of the heat recovery layer 50 and the bottom of the shift layer 11 are not brought close to each other, heat radiation from the bottom of the reformer 82 can be suppressed.
- the PR ⁇ X layer 12 may be one stage or three or more stages, and further a shift layer 11 may also be provided in the outermost layer, and the shift layer 11 and the PROX layer 12 may be provided in two layers in the outermost layer.
- a CO remover as the PROX layer 12 may be provided separately from the reformer 82, and the outermost layer of the reformer 82 may be the shift layer 11 alone.
- FIG. 7 Yet another example of the small and light single-tube cylindrical reformer of the present invention is shown in FIG. 7 as a fourth embodiment of the present invention.
- the reformer 83 is provided with a sub-shift layer 27 above (downstream of) the heat recovery layer 50.
- the second shift layer 11b is also provided in the outermost annular flow path, and the shift layer 11b and the PR ⁇ X layer 12 are provided in the outermost layer in two stages.
- the axial length of the annular flow path between the shift layer 11a and the PROX layers 12 and Z or the second shift layer 11b is shorter than the axial length of the heat recovery layer 50. Their lower ends do not reach near the bottom of the outer cylinder 10.
- the heat insulating material 53 is filled between the layer 50 and the shift layer 11, that is, between the sixth inner cylinder 66 and the fifth inner cylinder 65.
- the outermost annular flow path formed between the first inner cylinder 61 and the second inner cylinder 62, that is, the partition plate 1 is provided between the second shift layer 11b and the PROX layer 12.
- a shift layer 1 lb and a PROX layer 12 are separated by a partition plate 17.
- Eight outlets 23 are formed almost uniformly in the circumferential direction on the outer wall downstream of the shift layer 11b.
- one inlet 25 is formed on the outer wall upstream of the PROX layer 12 so as to face the mounting position of the air supply port 30 for PROX.
- Insulation material fills between outer cylinder 10 and bottom plate 76 and between bottom plate 76 and bottom plate 78 As a result, heat can be prevented from dissipating from near the bottom, wasteful heat loss from the reformer 83 can be prevented, and thermal efficiency can be improved. Further, since the heat insulating material is filled between the periphery of the heat recovery layer 50 and the outer cylinder 10 and between the heat recovery layer 50 and the shift layer 11, heat from the heat recovery layer 50 is removed. The transfer can be prevented, the heat loss in the heat recovery layer 50 can be reduced, and the temperature rise of the shift layer 11 can be suppressed, and the temperature can be maintained at a predetermined temperature.
- Providing the heat insulating material 53 near the bottom is not limited to the above example, and may be used in the reformers 81 and 82 shown in FIG. 3 or FIG. Since the axial length of the annular flow path consisting of the shift layer 11a, the second shift layer 11b, and the PROX layer 12 has been shortened, the shift layers 11a and the (2) The amount of heat transferred to the shift layer (11b) can be reduced, the heat from the conventional heat recovery layer (50) can be easily overheated, and the shift layer can be maintained at an appropriate temperature. The drop can be prevented.
- the temperature rise of the sub-shift layer 27 can be accelerated.
- the catalytic action of 27 can be performed quickly, and the starting time of the reformer 83 can be shortened.
- the length of the sub-shift layer 27 is appropriately selected according to the shortening of the start-up time by installing the sub-shift layer 27 and the degree of overheating of the sub-shift layer 27 during steady operation.
- the sub-shift layer 27 is provided continuously on the upstream side of the shift layer 11a.
- the present invention is not limited to such a configuration. It may be configured as up to the shift layer 27.
- a catalyst device having a main shift layer or the like may be connected to a separate single-tube cylindrical reformer. Also in this case, the temperature rise of the sub-shift layer 27 in the single-tube cylindrical reformer is accelerated, and the catalytic reaction in the sub-shift layer 27 becomes possible at an early stage, and the start-up time and the like can be shortened.
- the reformed gas that has passed through the second shift layer 11 surely merges with the air, and since the inlet 25 is only one place, the reformed gas and the air are introduced when the gas is introduced from the inlet 25. Is very well mixed. In this way, sufficient agitation with air is performed, and the reformed gas is introduced into the PROX layer 12, so that the selective oxidation reaction is performed efficiently and the hydrogen consumption in the selective oxidation reaction is reduced.
- the CO concentration can be reduced to a specified value or less by minimizing it.
- the second shift layer 11 b is provided below the PROX layer 12, but the second shift layer 11 b may not be provided below the PROX layer 12. Even in such a case, the reformed gas that has passed through the shift layer 11a is discharged into the gap 31 and is stirred with air before flowing into the PROX layer 12. Further, the entire structure may be the second shift layer 11 without providing the PROX layer 12. In such a case, connect a device having a CO selective oxidation function to the outside as necessary.
- the heat insulating material does not necessarily need to be filled in all of the above locations, and may be omitted as appropriate according to various conditions such as the length of each part of the reformer 83, the operating temperature, and the distance between the parts.
- the discharge port 23 is formed almost equally in the circumferential direction at eight force points, and the inlet port 25 is formed at one place.
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Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000612215A JP3625770B2 (ja) | 1999-04-20 | 2000-04-20 | 単管円筒式改質器およびその運転方法 |
EP00917380A EP1094031A4 (en) | 1999-04-20 | 2000-04-20 | MONOTUBE CYLINDRICAL REFORMER AND METHOD FOR OPERATING THE SAME |
AU38404/00A AU774857B2 (en) | 1999-04-20 | 2000-04-20 | Single-pipe cylindrical reformer and operation method therefor |
CA002335483A CA2335483C (en) | 1999-04-20 | 2000-04-20 | Single-pipe cylindrical reformer and operation method therefor |
US09/750,490 US6481207B2 (en) | 1999-04-20 | 2000-12-20 | Single-pipe cylinder type reformer and method of operating the same |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11/112267 | 1999-04-20 | ||
JP11226799 | 1999-04-20 | ||
JP24106899 | 1999-08-27 | ||
JP11/241068 | 1999-08-27 | ||
JP2000002080 | 2000-01-11 | ||
JP2000/2080 | 2000-01-11 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/750,490 Continuation US6481207B2 (en) | 1999-04-20 | 2000-12-20 | Single-pipe cylinder type reformer and method of operating the same |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000063114A1 true WO2000063114A1 (fr) | 2000-10-26 |
Family
ID=27312222
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2000/002581 WO2000063114A1 (fr) | 1999-04-20 | 2000-04-20 | Reformeur cylindrique monotube et procede pour faire fonctionner ledit reformeur |
Country Status (6)
Country | Link |
---|---|
US (1) | US6481207B2 (ja) |
EP (1) | EP1094031A4 (ja) |
JP (1) | JP3625770B2 (ja) |
AU (1) | AU774857B2 (ja) |
CA (1) | CA2335483C (ja) |
WO (1) | WO2000063114A1 (ja) |
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- 2000-04-20 CA CA002335483A patent/CA2335483C/en not_active Expired - Fee Related
- 2000-04-20 JP JP2000612215A patent/JP3625770B2/ja not_active Expired - Lifetime
- 2000-04-20 AU AU38404/00A patent/AU774857B2/en not_active Ceased
- 2000-04-20 EP EP00917380A patent/EP1094031A4/en not_active Withdrawn
- 2000-04-20 WO PCT/JP2000/002581 patent/WO2000063114A1/ja active Application Filing
- 2000-12-20 US US09/750,490 patent/US6481207B2/en not_active Expired - Fee Related
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Cited By (39)
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JP2003531085A (ja) * | 2000-04-17 | 2003-10-21 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | 燃料プロセッサ |
EP1197261A2 (en) * | 2000-10-10 | 2002-04-17 | Tokyo Gas Co., Ltd. | Single-Pipe cylinder type reformer |
US7037472B2 (en) | 2000-10-10 | 2006-05-02 | Tokyo Gas Co., Ltd. | Single-pipe cylinder-type reformer |
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JP2002326805A (ja) * | 2001-04-27 | 2002-11-12 | Daikin Ind Ltd | 改質装置及びこれを備える燃料電池システム |
JP2004535350A (ja) * | 2001-05-30 | 2004-11-25 | ヌベラ フュエル セルズ インコーポレイテッド | 多段シェル型改質装置における熱伝達の最適化 |
WO2002098790A1 (fr) * | 2001-06-04 | 2002-12-12 | Tokyo Gas Company Limited | Unite de reformage a vapeur d'eau cylindrique |
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JP2005231965A (ja) * | 2004-02-20 | 2005-09-02 | Matsushita Electric Ind Co Ltd | 一酸化炭素除去装置、および燃料電池発電装置 |
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JP2008243709A (ja) * | 2007-03-28 | 2008-10-09 | Aisin Seiki Co Ltd | 燃料電池用改質装置 |
JP2007335413A (ja) * | 2007-08-06 | 2007-12-27 | Toyota Motor Corp | 燃料電池システムおよび水素生成装置 |
WO2009087955A1 (ja) | 2008-01-08 | 2009-07-16 | Tokyo Gas Company Limited | 円筒式水蒸気改質器 |
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Also Published As
Publication number | Publication date |
---|---|
US6481207B2 (en) | 2002-11-19 |
AU774857B2 (en) | 2004-07-08 |
EP1094031A1 (en) | 2001-04-25 |
CA2335483A1 (en) | 2000-10-26 |
US20010029735A1 (en) | 2001-10-18 |
EP1094031A4 (en) | 2005-02-02 |
AU3840400A (en) | 2000-11-02 |
JP3625770B2 (ja) | 2005-03-02 |
CA2335483C (en) | 2005-03-29 |
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