Various embodiments of the present invention will be described with reference to the accompanying drawings. It is to be noted that the same or similar reference numerals are applied to the same or similar parts and elements throughout the drawings, and the description of the same or similar parts and elements will be omitted or simplified.
In the following descriptions, numerous details are set forth such as specific signal values, etc. to provide a thorough understanding of the present invention. However, it will be obvious to those skilled in the art that the present invention may be practiced without such specific details.
As shown in
The inner tube 101 can be made of such metal that endures a high temperature environment and that can be easily machined to form joints for example (e.g., aluminum, copper, steel, stainless steel). However, when the inner tube 101 is used for a small reaction system in which hydrogen-containing fluid or the like flows, the inner tube 101 is preferably made of stainless steel having lower thermal conductivity than those of aluminum, copper, and the like. A member having a high thermal conductivity is preferably required to have a minimized cross section. Thus, the inner tube 101 is preferably designed so as to implement a minimized thickness (thickness d2 of
For example, a mobile device application requires the inner tube 101 to have a structure that can withstand an impact (e.g., drop). Under the circumstances, the inner tube 101 is required to have a thick thickness with increased weight in despite of the smaller weight requirement. When the inner tube 101 is used for a stationary system, on the other hand, consideration of an impact (e.g., drop) is not required and thus the thickness may be modified appropriately. The inner tube 101 is also required to have a thickness to endure a differential pressure between fluid flowing at the inner side of the inner tube 101 and an outer environment of the outer tube 103. Thus, the thickness of the inner tube 101 is preferably optimized depending on a system to be used.
The inner tube 101 can be made of material chosen in terms of easiness of making joints between the inner tube 101 and the reactor, or the like. For example, when the reactor or the like is made of SUS316L (JIS standard), SUS316L is selected as material for the inner tube 101 to provide an identical linear expansion coefficient characteristic and thus provides an improved joint reliability.
An example of the inner tube 101 preferred for a hydrogen generation apparatus (which will be described later) includes, for example, a stainless-steel tube having an internal withstand-pressure of 5.88×105 Pa (6 kgf/cm2), a length (length 1a of
The outer tube 103 can be made of material that has a lower thermal conductivity than that of metal, or the like, and that has a high workability (i.e., fluorinated resin, epoxy resin, polyimide resin). Here, it is understood that fluorinated resin has an upper limit of the working temperature of about 180° C. and epoxy resin has an upper limit of the working temperature of about 250° C., respectively. When the outer tube 103 is used for a small reaction system for generating hydrogen-containing fluid for example, the outer tube 103 may be preferably made of polyimide resin that can be used under a high temperature environment of 250° C. or more.
Polyimide has a thermal conductivity λ of about 0.29 W/(m·K) at 300 K for example. Thus, polyimide has an effect of suppressing thermal conduction compared with silica glass having the thermal conductivity λ of 1.38 W/(m·K) at 300 K, alumina having the thermal conductivity λ of 36.0 W/(m·K) at 300 K, or stainless steel (SUS304 (JIS standard)) having the thermal conductivity λ of 16.0. W/(m·K) at 300 K. The outer tube 103 preferred for a hydrogen generation apparatus (which will be described later) may be, for example, a polyimide resin-made tube having an outer diameter (diameter D1 of
The intermediate layer 102 preferably includes polyimide resin that has a lower thermal conductivity than that of the inner tube 101 and that has a higher thermal conductivity than that of the outer tube 103 (e.g., polyimide resin foam and polyimide adhesive agent). An the interface between the inner tube 101 having a high thermal conductivity and the outer tube 103 having a low thermal conductivity has thermal stress due to a difference in the linear expansion coefficient due to temperature gradient. When the intermediate layer 102 is composed of polyimide resin having an intermediate thermal conductivity, thermal stress due to a difference in the linear expansion coefficient can be reduced and a highly-reliable connecting member can be provided. Furthermore, the intermediate layer 102 suppresses thermal conduction in the radial direction of the connecting member shown in
In order to provide the intermediate layer 102 with a lower thermal conductivity than that of the inner tube 101 and a higher thermal conductivity than that of the outer tube 103, the intermediate layer 102 may include therein a plurality of foams. For example, the intermediate layer 102 may be made of polyimide resin having a plurality of closed cells. The closed cells are filled with gas having a lower thermal conductivity than that of drying air. This can suppress thermal conduction in the tube radial direction when compared with a case where a closed cell is filled with air, thus providing a higher thermal efficiency. It is noted that the closed cell-type resin foam also may be substituted by an interconnected cell-type resin foam.
Foams may be preferably filled with inert gas such as argon, carbon dioxide, nitrogen, or krypton. The intermediate layer 102 can be filled with inert gas by mixing liquid-like polyimide resin foam with polyimide adhesive agent to heat the mixture to have an increased temperature so that carbon dioxide gas, nitrogen or the like is generated and retained in polyimide resin foam, or by actively filling inert gas (argon) in polyimide adhesive agent to subsequently disperse the inert gas to cure the polyimide adhesive agent.
The foam of the intermediate layer 102 filled with inert gas can prevent, even when the inner tube 101 is broken in the worst case, inert gas from reacting with fluid flowing in the flow path 100 at the inner side of the inner tube 101, thus providing safety. Furthermore, even when inert gas filled in the intermediate layer 102 flows in the flow path 100 in the inner tube 101, the gas does not have a major impact on the chemical reaction in the respective reactors and thus the entire system can have a high reliability.
The linkage sections 104a and 104b may be made of stainless steel as in the inner tube 101. The linkage sections 104a and 104b may have a length 1b (see
To facilitate a laser welding architecture, for example, connecting members 23 and 24 and a reactor 50 are prepared firstly, as shown in
The linkage sections 234 and 244 may have a tapered shape (not shown) to provide an easier welding in a case where the connecting members 23 and 24 are joined by the welding of tungsten inert gas (TIG). When soldering or brazing is used, the linkage sections 234 and 244 as well as the engagement sections 51 and 52 are preferably shaped so as to be easily surrounded by solder or brazing material.
As shown in
When the connecting members shown in
In order to suppress the thermal conduction in the axial direction of a connecting member, any of the following approaches can be used based on the heat transfer engineering:
(1) To increase a distance between small reactors at different temperature conditions;
(2) To reduce the thermal conductivity of a connecting member; and
(3) To reduce the size of the cross section of a connecting member.
In order to realize a smaller system, the methodology (1) cannot be used. Thus, a connecting member considering the methodologies (2) and (3) are required to be examined. According to the connecting members shown in
However, polyimide resin poorly endures when the composition includes water vapor or water. Thus, it is not preferable to implement a connecting member by using polyimide resin only. According to the connecting member shown in
Furthermore, the connecting member shown in
As described above, the connecting member according to the embodiment of the present invention can achieve different reaction temperature conditions between reactors, while reducing a distance between the reactors, the difference in the temperature between the reactors facilitates an easy temperature control. Furthermore, the reduced thermal conduction can suppress the thermal dissipation in the respective reactors to provide the respective reactors with an improved thermal efficiency.
As shown in
In order to manufacture the connecting member shown in
The intermediate layer 102 also may be obtained by mixing polyimide adhesive agent with polyimide film 106 or polyimide resin foam (not shown). Specifically, commercially-available polyimide resin foam or foamed polyimide film also may be wound around the outer side of the inner tube 101 and the resultant inner tube 101 is externally engaged with the outer tubes 103a and 103b to flow liquid-like polyimide adhesive agent between the inner tube 101 and the outer tubes 103a and 103b to cure the agent at predetermined temperature. Alternatively, polyimide resin foam or polyimide film also may be placed at the intermediate layer 102 to use polyimide adhesive agent to join the outer tube 103 only.
As can be seen from tables of
The container 1 stores therein organic raw material and water as fuel. Organic raw material may be alcohol (e.g., methanol, ethanol), fossil fuel (e.g., ethane, propane, gasoline, kerosene), ether (e.g., dimethyl ether), or liquid raw material containing hydrogen atoms. When methanol is used as organic raw material, fluid supplied to the vaporizer 3 preferably contains methanol and water with a molar ratio of 1:1 to 1:2. When liquefied gas such as dimethyl ether is used as organic raw material, the material is desirably obtained by adding methanol of a weight ratio of 5 to 10% to a mixture of dimethyl ether and water. Organic raw material and water also may not be mixed in the container 1 and also may be mixed in connecting members 21a and 21b leading to the vaporizer 3 or in the vaporizer 3 or also may be previously mixed in the container 1.
The container 1 is connected to a flow rate controller 2 via the piping 21a. The flow rate controller 2 may be, for example, a diaphragm pump, a plunger pump, a gear pump, a tube pump, an orifice, a needle valve, a bellows valve, a diaphragm valve, or a butterfly valve. The flow rate controller 2 also may be a combination of a plurality of orifices having different shapes or a temperature variable orifice by which a temperature is adjusted to change the viscosity of fluid to adjust a flow rate for example.
Liquid organic raw material passing through the flow rate controller 2 is supplied to the vaporizer 3 via the connecting member 21b. The vaporizer 3 heats at least one of organic raw material or water at 150 to 200° C. to vaporize organic raw material or water to generate organic matter-containing gas. The organic matter-containing gas generated by the vaporizer 3 is supplied to the reformer 4 via the connecting member 22 and is heated to about 350° C. The reformer 4 includes therein a flow path through which organic matter-containing gas passes. The inner wall face of the flow path 5 includes reforming catalyst for promoting a reforming reaction of organic raw material to reform the organic matter-containing gas to hydrogen-containing fluid (reforming gas).
The hydrogen-containing fluid generated by the reformer 4 is supplied to a carbon monoxide shift unit (CO shift unit) 5 via a piping 23. The CO shift unit 5 includes therein a flow path through which hydrogen-containing fluid passes. A shift catalyst for promoting the shift reaction of carbon monoxide included in hydrogen-containing fluid is provided with the inner wall face of the flow path. The CO shift unit 5 is heated to about 275° C. so that carbon monoxide included in hydrogen-containing fluid reacts with water to cause a shift reaction of carbon dioxide and hydrogen to reduce the amount of carbon monoxide in the hydrogen-containing fluid.
The hydrogen-containing fluid having reduced carbon monoxide at the CO shift unit 5 is supplied to a methanation unit 6 via the connecting member 24. The hydrogen-containing fluid supplied from the CO shift unit 5 still includes carbon monoxide of about 1%. Thus, the methanation unit 6 allows a methanation reaction to proceed at about 250° C. to allow carbon monoxide remaining in hydrogen-containing fluid to react with hydrogen to convert hydrogen-containing fluid to methane and water, thereby removing carbon monoxide. The methanation unit 6 includes therein a flow path through which hydrogen-containing fluid passes. The inner wall face of the flow path includes a methanation catalyst for promoting the methanation reaction of carbon monoxide included in hydrogen-containing fluid.
The hydrogen-containing fluid discharged from the methanation unit 6 is supplied to the power generation unit 7 via the connecting member 25. The power generation unit 7 includes a fuel electrode (anode) 7a; an air electrode (cathode) 7b; and an ion exchange type polymer electrolyte membrane (polymer electrolyte membrane: PEM) 7c sandwiched between the fuel electrode 7a and the air electrode 7b. Hydrogen in hydrogen-containing fluid reacts with oxygen in air to generate water and power generation is performed in the fuel electrode 7a. Gas including unused hydrogen discharged from the fuel electrode 7a is supplied to a combustion section 8 via the connecting member 26 and is subjected to catalytic combustion. Heat generated by the catalytic combustion is used as reforming reaction heat for fuel in the reformer 4. Heat required for reforming reaction also may be supplied from a heater 35 as shown in
The upstream side of the air electrode 7b is connected with the connecting member 29 to supply air to the air electrode 7b of the power generation unit 7. Air supplied from the pump 14 is supplied to the heat exchanger 13 for heating air via the connecting member 28 connected to the pump 14 and is supplied to the air electrode 7b via the connecting member 29 connected to the heat exchanger 13. The outlet side of the air electrode 7b is connected with the connecting member 30. Fluid discharged from the air electrode 7b passes through the connecting member 30 and is introduced into the heat exchanger 13 connected to the connecting member 30. Then, water in the fluid is condensed in the heat exchanger 13 and water is collected in the water collection unit 15 and the rest is discharged to outside. The ion exchange type polymer electrolyte membrane 7c may be, for example, a fluorinated ion exchange film, a polybenzoimidazol porous film (PBI), or a polyimide porous film (PI).
As shown in
In particular, in the hydrogen generation apparatus shown in
By using the connecting member according to the embodiment in the hydrogen generation apparatus shown in
An SUS316L special thin tube as the inner tube 101 in a first example (outer diameter of 1.5 mm, thickness of 0.10 mm, inner diameter of 1.3 mm, length of 20 mm, both ends of 5 mm where the tube is welded with the reactor) was surrounded by polyimide adhesive agent (KYOCERA Chemical Corporation: CT4150) as the intermediate layer 102 and was fixed. The special thin tube fixed with the polyimide adhesive agent was sandwiched by VESPEL® (made by Dupont: SP1 and length of 20 mm)) as the outer tube 103 having an outer diameter of 3.06 mm and an inner diameter of 1.8 mm. Then, the special thin tube sandwiched by VESPEL® was placed in a furnace at 300° C. to cure the polyimide adhesive agent, thereby preparing a connecting member according to the first example.
One end of the connecting member according to the first example was connected with a reactor at 300° C. and the temperature of the other end of the connecting member was measured. The result was that the temperature of the other end was 40° C. or less (about 27 to 32° C.). On the other hand, when a hitherto known SUS316L-made connecting member having identical outer diameter and inner diameter as those of a connecting member according to the first example was subjected to the same measurement, the other end showed a temperature of about 80° C. (78 to 87° C.). Thus, in the first example, a reactor at higher temperature can have an improved thermal efficiency when compared with a conventional case.
When the connecting member according to the first example was connected between a high temperature reactor having a reaction temperature of about 300° C. and a reactor having a reaction temperature of about 200° C. to operate the hydrogen generation apparatus, the connecting member having a length of about 2.5 cm allowed the operation at the respective predetermined temperatures. On the other hand, when a hitherto known SUS316L-made connecting member having identical outer diameter and inner diameter as those of the connecting member according to the first example was subjected to the same measurement, the connecting member was required to have a length of 80 mm in order to allow the reactor having a higher temperature to operate at reaction temperature of about 300° C. and the reactor having lower temperature to operate at reaction temperature of about 200° C. Thus, the hitherto known connecting member required to have a larger size than that required by the system according to the first example. Furthermore, when the connecting member according to the first example is applied for the hydrogen generation apparatus shown in
An SUS316L special thin tube as the inner tube 101 in a second example (outer diameter of 1.5 mm, thickness of 0.10 mm, inner diameter of 1.3 mm, length of 20 mm, both ends of 5 mm where the tube is welded with the reactor) was surrounded by polyimide adhesive agent (KYOCERA Chemical Corporation: CT4150) as the intermediate layer 102 and was fixed. The special thin tube fixed with the polyimide adhesive agent was sandwiched by VESPEL® (made by Dupont: SP1 and length of 20 mm)) as the outer tube 103 having an outer diameter of 3.06 mm and an inner diameter of 1.8 mm in an argon gas atmosphere. Then, the special thin tube sandwiched by VESPEL® was placed in a furnace of argon atmosphere at 300° C. to cure the polyimide adhesive agent.
One end of the connecting member according to the second example was connected with a reactor at 250° C. (CO removal unit 9 in
The outer tube 103 of VESPEL® (made by Dupont: outer diameter of 3.16 mm, thickness of 0.80 mm, inner diameter of 1.56 mm, and length of 20 mm) is divided to two parts in the axial direction to engage the parts to each other. Then, an SUS316L special thin tube as the inner tube 101 in a third example (outer diameter of 1.5 mm, thickness of 0.10 mm, inner diameter of 1.3 mm, length of 20 mm, both ends of 5 mm where the tube is welded with the reactor) was sandwiched by the VESPEL. Commercially available polyimide adhesive agent as the intermediate layer 102 is provided in a space between the inner tube 101 and the outer tube 103. Then, the special thin tube sandwiched by the VESPEL was placed in a furnace to cure the polyimide adhesive agent, thereby preparing a connecting member according to the third example.
One end of the connecting member according to the third example was connected with a reactor at 300° C. and the temperature of the other end of the connecting member was measured. The result was that the temperature of the other end was 40° C. or less (about 27 to 32° C.).
Furthermore, one end of the connecting member according to the third example was connected with a reformer at 300° C. and the other end of the connecting member was connected with a heat exchanger at 1000C. In such a condition, when the hydrogen that provides electric power of about 50 W is generated, the reactors were properly operated at predetermined temperatures, respectively.
Connecting members according to the first to third examples were used as the piping 23 between the reformer 4 of the hydrogen generation apparatus shown in
Various modifications will become possible for those skilled in the art after receiving the teachings of the present disclosure without departing from the scope thereof.
In the above-described embodiments, connecting members are provided between reactors. However, applicable examples are not limited thereto. For example, housings of reactors may be made of the same materials as the connecting members of the present embodiment to decrease the heat capacity of the reactors themselves.
Number | Date | Country | Kind |
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2006-223827 | Aug 2006 | JP | national |