JP5229525B2 - Fuel cell fuel cartridge, fuel cell fuel cartridge using the same, gelled fuel reliquefaction method, reliquefied fuel takeout method, and fuel cell fuel storage soft case used therefor - Google Patents

Description

The present invention relates to a fuel soft cartridge for a fuel cell, a fuel cartridge for a fuel cell using the same, a method for taking out reliquefied fuel from which gelled fuel is taken out again, and a soft case for storing fuel cell fuel used therein. .

  Fuel cells are attracting attention as next-generation power supply systems. This is because the fuel cell emits almost no environmental pollutant gas during power generation, can use biofuel, and is excellent as clean energy. In addition, it has sufficient advantages such as sufficient power generation and easy weight reduction and miniaturization. Against this background, research and development of fuel cell systems and their applications have been energetically advanced recently.

  On the other hand, the fuel used in the fuel cell usually requires attention in handling. For example, methanol is a volatile combustible substance as it is, and requires careful management against ignition. For example, there are cases where it is restricted in railways and air transportation, and if it is inhaled by the human body, it may have an effect. Therefore, there is a demand for the development of a fuel cell fuel that can be handled safely and a highly fail-safe system for using the fuel.

  In order to meet this demand, it has been proposed to include methanol by inclusion with an inclusion compound to solidify and store (see Patent Document 1). However, what is disclosed here does not have a high fuel take-out property, and the fuel that cannot be taken out from the inside of the solidified product tends to remain during power generation. Also, a large amount of eluent such as water is required to elute the fuel, and it is difficult to separate the fuel and the adsorbent. As a cartridge for handling the solid fuel, a cartridge using a sponge containing moisture, a syringe for sucking water, or the like has been proposed (see Patent Documents 2 to 5), but the above problems remain.

  Recently, a fuel mixture has been developed in which fuel can be gelled and stored, and brought into contact with a reliquefaction agent to reliquefy (Patent Document 5). This greatly increases the safety of fuel handling and can achieve high power generation efficiency, but there is no effective cartridge that can be suitably used therefor.

  On the other hand, a disinfecting kit is disclosed in which a disinfecting chemical solution and a cotton swab are placed in separate storage chambers, and a weak seal portion provided between the disinfecting chemical solution is peeled off to impregnate the cotton with the chemical solution (Patent Document 6). If this is used, the disinfectant does not adhere to the hands or fingers of doctors or nurses, and although it is a convenient kit, there is no disclosure regarding fuel cells.

JP 2005-203335 A JP 2006-302039 A JP 2006-156197 A JP 2006-156198 A JP 2006-236969 A JP 2004-001784 A

It is an object of the present invention to provide a fuel soft cartridge for a fuel cell that can be handled safely and can be quickly liquefied and taken out from a fuel once gelled and stored in high yield and high purity.
The present invention also provides a fuel soft fuel cartridge for a fuel cell that maintains the above-described excellent performance, further suppresses deterioration of the stored fuel, and has a structure suitable as a replaceable cartridge, and a fuel cartridge for a fuel cell using the same Another object of the present invention is to provide a method for taking out reliquefied fuel that is taken out by reliquefying the gelled fuel and a soft case for storing fuel cell fuel used in the method.

The above object has been achieved by the following means.
[1] The interior of the soft case is separated into two storage chambers by a partition, gelled fuel is stored in one storage chamber, a reliquefying agent is stored in the other storage chamber, and the soft case partition A fuel take-out port is provided in a portion other than the above, the partition portion is broken by an external force, the gelled fuel and the reliquefying agent are brought into contact with each other, the fuel is reliquefied, and the fuel can be taken out from the take-out port. a fuel fuel software cartridge for batteries in,
The combination of the gelled fuel and the reliquefaction agent is any one of the following AC:
A fuel soft cartridge for a fuel cell, wherein the fuel outlet is provided in a storage chamber on the reliquefying agent side.
<A>
Gelled fuel: Mixture of methanol and electrolyte gelling agent
Reliquefaction agent: at least one selected from the group consisting of polyelectrolytes, proteins, peptides, collagen, gelatin, and agar
<B>
Gelled fuel: at least one selected from the group consisting of methanol, electrolyte gelling agent, polymer electrolyte, ascorbic acid, stearic acid, protein, peptide, collagen, gelatin, agar, and other solid or liquid organic acids Mixture of
Reliquefaction agent: water or aqueous medium
<C>
Gelled fuel: Mixture of methanol, polymer electrolyte and gelling auxiliary resin
Reliquefaction agent: Reliquefaction ion generating resin [2] The fuel soft cartridge for a fuel cell according to [1], wherein an internal filter is provided in a path for taking out the reliquefied fuel from the fuel outlet.
[3] The fuel soft cartridge for a fuel cell according to [1] or [2], wherein a screwing type or fitting type connecting means is provided at the fuel outlet.
[4] The fuel soft cartridge for a fuel cell according to [ 2] or [ 3], wherein the internal filter is a combination of an ion exchange resin and a filter paper made of Teflon (registered trademark).
[5] The fuel soft cartridge for a fuel cell according to any one of [1] to [4], wherein the soft case is made of a laminate of an ultraviolet blocking resin and an aluminum sheet.
[6] The fuel soft cartridge for a fuel cell according to any one of [1] to [5], wherein the breaking strength of the partition is lower than the breaking strength of the soft case.
[7] The fuel soft cartridge for a fuel cell according to any one of [1] to [6], wherein the partition portion is formed such that the inner surface of the soft case is detachably bonded.
[8] The fuel soft cartridge for a fuel cell according to any one of [1] to [7], wherein the reliquefaction agent is in a gel form.
[9] The fuel soft cartridge for the fuel cell according to any one of [1] to [8], wherein an inner opening end of the fuel outlet port reaches a position close to a partition of the soft case .
[10] A fuel cartridge for a fuel cell, wherein the soft cartridge according to any one of [1] to [9] is stored in a hard case.
[11] A check valve is provided on the hard case side so as to be in contact with and in close contact with the fuel outlet of the soft cartridge, or an external filter and a check valve are provided on the hard case side as viewed from the soft cartridge side. The fuel cartridge for a fuel cell according to [10], wherein the fuel cartridges are provided in that order.
[12] The fuel cartridge for a fuel cell according to [10] or [11], wherein the hard case has elastic pressing means for pressing the soft cartridge housed therein.
[13] A method for taking out a reliquefied fuel by using the fuel soft cartridge for a fuel cell according to any one of [1] to [10], wherein the gelled fuel is reliquefied and taken out.
The gelled fuel and the reliquefaction agent are respectively contained in a storage chamber separated into two by a partition, and the gel is broken by applying a pressing force from the outside of the soft case. A method for taking out a reliquefied fuel, wherein the reliquefied fuel and the reliquefying agent are brought into contact with each other.
[14] The soft case containing the gelled fuel and the reliquefying agent is pressed by hand, or the soft case is stored in a hard case and pressed by an elastic pressing means provided in the hard case. extraction method of re liquid fuels having the constitution to retrieve and re-liquefy the fuel (13).
[15] The fuel take-out port is provided at a position opposite to a portion of the soft case other than a portion of the storage chamber on the reliquefying agent side , [13] or [14] How to take out liquefied fuel .
[16] A soft case for storing fuel cell fuel, characterized by being used in the method for taking out the reliquefied fuel according to [13] to [ 15] ,
The interior is separated into two storage chambers by a partition, gelled fuel is stored in one storage chamber, and a reliquefying agent is stored in the other storage chamber,
The combination of the gelled fuel and the reliquefaction agent is any one of the following AC:
A fuel outlet is provided on the side of the soft case other than the partition where the reliquefier is stored, the partition is broken by an external force, the gelled fuel and the reliquefier are brought into contact, and the fuel is removed. A soft case for storing fuel for a fuel cell that can be re-liquefied and fuel can be removed from the outlet.
<A>
Gelled fuel: Mixture of methanol and electrolyte gelling agent
Reliquefaction agent: at least one selected from the group consisting of polyelectrolytes, proteins, peptides, collagen, gelatin, and agar
<B>
Gelled fuel: at least one selected from the group consisting of methanol, electrolyte gelling agent, polymer electrolyte, ascorbic acid, stearic acid, protein, peptide, collagen, gelatin, agar, and other solid or liquid organic acids Mixture of
Reliquefaction agent: water or aqueous medium
<C>
Gelled fuel: Mixture of methanol, polymer electrolyte and gelling auxiliary resin
Reliquefaction agent: Reliquefaction ion generating resin

Further, according to the soft cartridge of the present invention, the fuel for fuel cells stored after gelation can be stored and handled safely, the gelled fuel can be quickly re-liquefied, and the re-liquefied fuel can be obtained in high yield and high purity. Can be taken out with. In addition, the soft cartridge of the present invention can be handled more safely as a fuel cartridge for a fuel cell in combination with a hard case, and more various functions can be given.
Furthermore, the soft cartridge of the present invention maintains the above-mentioned excellent performance, further suppresses the deterioration of the gelled fuel stored therein, and is stable as a replaceable cartridge without requiring a good structure, that is, a complicated mechanism. It has an excellent effect of being able to be produced efficiently and in large quantities with quality.

Hereinafter, the fuel soft cartridge for a fuel cell of the present invention will be described in detail with reference to the drawings. However, the present invention is not construed as being limited to the embodiments shown in the drawings.
FIG. 1 is a perspective view schematically showing a preferred embodiment of a fuel soft cartridge for a fuel cell of the present invention. FIG. 2 is a sectional view showing a section taken along line II-II in FIG. In the soft cartridge 10 of this embodiment, the gelled fuel 11 and the reliquefying agent 12 are accommodated in the soft case 1 (see FIG. 2). Here, the soft case 1 is provided with a partition (easy peel seal) 3 and the inside thereof is divided into a storage chamber 9a on the left side of the drawing and a storage chamber 9b on the right side of the drawing. The storage chamber 9b is filled with the gelled fuel 11 and the storage chamber 9a is filled with the reliquefying agent 12 so as not to mix. Further, an extraction port 2 is provided in a portion other than the partition portion 3 of the soft case 1, and in the illustrated example, the extraction port 2 is provided in a part of the storage chamber 9a.

In the present invention, (the ones illustrated housing chamber 9a) Ri out port 2 is provided with side storage room preparative you housing reliquefaction agent 12. By doing so, when the gelled fuel 11 and the reliquefying agent 12 are mixed as will be described later, the gelled fuel 11 is surely brought into contact with the reliquefying agent 12, and from the reliquefaction to removal of the fuel, Further, it can be carried out efficiently and quickly without leaving any unloading.

In the present invention, the form of the partition part 3 is not particularly limited, but before the partition part 3 is broken, the gelled fuel 11 and the reliquefaction agent 12 do not contact each other, and the partition part 3 is formed by applying a predetermined external force. It is preferable that the gelled fuel 11 and the reliquefying agent 12 be brought into contact with each other. More specifically, it is preferable to use an easy peel seal in which the inner surface of the soft case 1 is bonded with an appropriate adhesive force as in this embodiment. In the present invention, the section formed by bonding the inner surface of the soft case 1 is used to mean not only the bonding interface but also the soft case portion of the bonded region.
The soft case cartridge of the present invention may have three or more storage chambers to which additional functional storage chambers are added as necessary. Moreover, the collar part 3 may be a wall-shaped collar part that can be broken, for example, a partition wall, other than the collar part formed by adhering the inner surface of the soft case.

Here, the soft case 1 is formed of a normal sheet material, and includes both the take-out port seal portion 4 (see FIG. 1) and both sides in the longitudinal direction (X direction) of the soft cartridge 10 of the present embodiment (the take-out port 2 and the opposite side). Side seals may be provided on the side edges. It is preferable that the side seal portion is firmly bonded and bonded so as not to cause leakage of contents.
The adhesive strength of the side seal portion is not particularly limited, but it is preferable to withstand pressure application of 5 kg / 1 cm ² , and more preferably withstand pressure application of 10 kg / 1 cm ² .
On the other hand, in the easy peel seal that forms the above-described separation part 3, it is preferable that the adhesive force is weaker than that of the side seal part, and when the contents are pressed by the gripping force, due to the compression force of the contents It is more preferable that the degree of rupture (peeling) occurs. By doing in this way, the side seal part including the outlet seal part 4 is not peeled off, but only the easy peel seal part is selectively peeled off, and the gelled fuel 11 and the reliquefaction agent 12 are separated from the outside. Can be reliably mixed without leakage. The adhesive strength of the easy peel seal is not particularly limited, but is preferably opened when a force of 0.5N to 2N is applied to the container, and is opened when a force of 0.8N to 1N is applied. More preferably.

  When the partition part 3 is formed by an easy peel seal, the width of the easy peel seal part (the length in the X direction in FIGS. 1 and 2) is not particularly limited. Considering the peelability due to external force, it is practical to set it to about 3 to 10 mm.

  The easy peel seal is not limited as long as it is formed by a normal sealing method, but when using a resin material as a soft case, a method of providing an easy peel film or agent at the adhesive interface, or a method of heat bonding Is mentioned. When heat bonding, it is preferable that the above-mentioned strong side seal portion is adjusted so as to have a relatively weak adhesive force by changing the heat bonding conditions (for example, pressure and temperature).

  The fuel soft cartridge for a fuel cell of the present invention can be produced efficiently and at low cost and is suitable for mass production. Fuel cartridges are usually used as replacement parts in electronic devices and the like. In view of such usage, a low-priced and simple structure is preferable, and according to the present invention, these needs can be sufficiently met. Furthermore, if it is a fuel cartridge for a fuel cell combined with a hard case described later, functional parts are arranged on the hard case side and only the soft case is replaced, so that it is suitable for replacement even if it is multifunctional. It can correspond as a cartridge.

  In the soft cartridge according to the present embodiment, it is preferable that a take-out tube 7 is disposed in the take-out port 2 as shown in the drawing. The take-out tube 7 may be provided as necessary, but is preferable in that the external open end 7b is extended to a predetermined location and the reliquefied fuel can be reliably delivered to that location. Further, it is preferable that the tube 7 is inserted deeply into the storage chamber 9a as shown in the figure, and the internal opening end 7c is arranged to reach the vicinity of the partition portion 3. In other words, considering that the mixing of the gelled fuel and the reliquefaction agent spreads from the vicinity of the partition portion 3, the reliquefied fuel is not directly moved from the inner opening end 7c as it is inside the case. It is preferable because it can be taken out.

  Moreover, it is preferable to provide the internal filter 8 in the inner hole of the tube 7 like what was illustrated (refer FIG. 2). As a result, the internal filter 8 is disposed in a path through which the reliquefied fuel is taken out from the takeout port 2 or the opening end 7b, and other than the reliquefied fuel can be blocked and only the fuel can be taken out with high purity. As the internal filter, it is preferable to use a filter made of a combination of an ion exchange resin and a filter paper made of Teflon (registered trademark). As the ion exchange resin, a cation exchange resin, an anion exchange resin or the like as described later can be used.

  The take-out port 2 and the take-out tube 7 are attached as separate members in the soft cartridge 10 of the present embodiment, and are sealed and bonded on the tube bonding surface 4a. At this time, the adhesive force on the adhesive surface 4a (see FIG. 2) is preferably a strong adhesive force similar to that of the side seal described above. This can prevent inadvertent leakage of contents. However, unlike the present embodiment, the extraction port 2 and the extraction tube 7 may be integrated. Therefore, in the present invention, the term “fuel outlet” means only the “outlet 2” provided in the soft case so as to include the outlets in both the separate outlet and the integral outlet. Instead, it includes the meaning of the outlet structure portion formed by the combination with the “tube 7”.

  The fuel outlet is preferably provided with a screw-type or fitting-type connecting means. In the illustrated case, a screw-type connecting means (male thread portion) 7a is provided in the vicinity of the external opening end 7b of the tube 7. (See FIG. 1). By doing in this way, it can connect so that it may contact | abut and contact | abut with the non-return valve and external filter which are mentioned later.

  The material of the soft case is not particularly limited, but is preferably a material having bending flexibility, for example, a material and a thickness that can be freely deformed by an external force such as a gripping force. Moreover, it is preferable that it is a material which has thermal adhesiveness considering sealing a predetermined location so that it may mention later. The material of the soft case generally includes materials usually used as a sheet or film of a packaging case. A single or laminated sheet of polyolefin such as polyethylene or polypropylene, or a stretched sheet of polyester or polyamide, etc. And a laminated material in which a gas barrier layer such as an aluminum foil, a silica vapor deposition layer, an ethylene-vinyl alcohol copolymer, or polyvinylidene chloride is laminated.

  Further, from the viewpoint of suppressing deterioration of the gelled fuel and / or the reliquefaction agent, it is preferable to use an ultraviolet blocking soft case, and it is preferable to use a laminate sheet made of an ultraviolet blocking resin and an aluminum sheet. Specifically, the ultraviolet shielding laminate case can be constructed by incorporating aluminum foil (7 μm, 9 μm) for shielding oxygen and light, polyethylene terephthalate on which aluminum is deposited, and the like.

  Since the gelled fuel is gelled and stored, the safety of the gelled fuel is higher than that of the liquid fuel. For example, in the case of methanol, the evaporation rate can be greatly reduced by gelation as compared with liquid. In the present invention, since the gelled fuel is further enclosed by the above-mentioned soft case, the safety is further improved, and it is possible to suitably cope with a wide range of distribution means and transportation. For example, if a sealing cap is attached to the above-described screw-type and / or fitting-type connecting means of the take-out port, and the leakage prevention property is further improved, the fuel can be handled as an extremely safe and reliable aspect.

  The sheet thickness of the soft case is not particularly limited, but it is practical that the thickness of the soft case is about 100 μm to 5 mm in consideration of bending flexibility and the sealing property of the contents. The size of the soft case is not particularly limited, but when it is a cartridge of a size used for a mobile phone or a portable computer as a typical application, for example, it is about 100 mm long × about 50 mm wide, about 200 mm long × about 100 mm wide, etc. It is preferable.

  In the fuel soft cartridge for a fuel cell according to the present invention, the partition portion is broken by an external force so that the gelled fuel and the reliquefying agent are brought into contact with each other to reliquefy the fuel. FIG. 3 is a cross-sectional view schematically showing a mixed form of the gelled fuel and the reliquefaction agent in the fuel soft cartridge for the fuel cell of the present invention. As shown in the figure, in the fuel soft cartridge for a fuel cell according to the present invention, pressing is performed with a force about the gripping force of a person (in the illustrated case, the pressing action is indicated by the fingers 31 and 32, but pressing is performed with the finger. It is not limited to the embodiment, and it may be pressed more strongly including the palm.) It is preferable that the contents are pressed and flowed, and the partition 3 is broken (peeled) by the pressing force. In the mixing mode shown in FIG. 3, the easy peel seal of the partition 3 is peeled off by the pressing force of the gelled fuel 11 pressed, and the gelled fuel 11 is brought into contact with the reliquefying agent 12 while moving. It has been. 3 shows a state in which the mixing of the gelled fuel 11 and the reliquefying agent 12 has progressed somewhat, and the mixed fuel 33 spreads around the portion where the partition portion 3 was present, A reliquefied fuel (not shown) is generated in the region of the mixed fuel 33.

  At this time, in order to further promote the mixing of the two agents, it is preferable to press the entire soft cartridge at many positions by hand. As a result, a quick reliquefaction that cannot be realized with a hard cartridge having a solid structure can be realized, and a high fuel extraction yield can be achieved (in the present invention, the “fuel extraction yield” is once gelled and stored. The percentage of the value obtained by dividing the mass of the fuel removed after re-liquefaction by the mass of the recovered fuel, sometimes simply referred to as “yield.” The higher the “fuel extraction yield” is, the higher the “yield” is 100%. If so, it means that all of the fuel that has been gelled and stored has been removed.) In addition, the speed of reliquefaction can be adjusted according to the use and needs depending on the degree of manual handling. In addition, it is not necessary to carry a special device such as a handcuff in this way, and fuel can be supplied easily, so that the need for a replacement cartridge that can quickly secure liquid fuel at the required place when needed is met. Can do.

  The fuel soft cartridge for a fuel cell of the present invention is preferably housed in a hard case to form a fuel cartridge for the fuel cell. FIG. 4 is an exploded perspective view schematically showing a preferred embodiment of the fuel cartridge for a fuel cell of the present invention. In the form shown in the figure, the soft cartridge is housed in a hard case including a pedestal 43 and a lid 44. Here, the pedestal 43 is formed with a carved portion 43 c that is substantially matched to the outer dimensions of the soft cartridge 10. Then, the edge 43a on the upper surface of the pedestal and the rear surface 44a of the lid are combined, and if necessary, both can be fixed and sealed by a fixing means (not shown). As a result, the soft cartridge 10 does not move in the engraving portion 43c unnecessarily, and an appropriate installation and fixing state of the soft cartridge 10 can be maintained also by vibrations when mounted in the portable device, for example.

  In the present invention, the soft cartridge is housed in a hard case, and a check valve is provided in the hard case so that the soft cartridge comes into contact with and closely contacts the fuel outlet of the soft cartridge, or an external filter as viewed from the soft cartridge side. It is preferable to provide a check valve in that order. In the form shown in FIG. 4, the check valve cap 42 is shown as being attached to the take-out tube 7 of the soft cartridge via a cap 41 with rubber.

  FIG. 5 is an enlarged cross-sectional view schematically showing a cross section taken along the line VV of FIG. 4 (note that the check valve cap 42 is partially cut away and shown in a partial cross-sectional view). In the present embodiment, the male screw portion 7a provided on the tube 7 and the female screw portion 41c provided on the inner side of the rubber cap can be screwed and connected. Thereby, the opening end 7b of the tube 7 and the opening 41b of the cap with rubber are connected and hermetically fixed. Further, a male screw portion 41 a is provided on the outer side of the rubber cap 41, and can be connected by screwing with a female screw portion 42 c provided on the inner side of the check valve cap 42. As a result, the rubber cap 41 is connected to the opening 42b of the check valve cap 42 and hermetically fixed. With each of the above connections, the soft cartridge outlet tube 7, the cap 41 with rubber, and the check valve cap 42 come into contact with each other and are in close contact with each other.

  The cap 41 is provided with a rubber 52 so that the contents of the soft case do not leak to the outside in an unused state (a state before a needle to be described later is inserted). Therefore, for example, leakage is prevented with the cap 41 attached, and the high handling safety as described above is ensured. Then, when the fuel is taken out and used, the cap 42 is screwed, whereby the needle 53 pierces the rubber 52 and the liquid fuel can be taken out from the narrow mouth opened there.

The liquid fuel that has passed through the rubber 52 passes through a check valve structure (not shown) of the check valve 42 and is taken out from the outlet 57. In this way, the extracted fuel can be supplied to a fuel cell (not shown).
By adopting such a structure, it is possible to accurately take out the reliquefied fuel only when necessary while maintaining high safety when not in use. Furthermore, it is possible to perform a good fuel supply in which the fuel reversion is suppressed.

  FIG. 6 is a cross-sectional view schematically showing an aspect in which an elastic pressing means (spring material) is provided in a hard case in the fuel cartridge for a fuel cell of the present invention by a cross section taken along line VI-VI shown in FIG. However, although the VI-VI cross section in FIG. 4 is an exploded view, it is shown in an assembled state. As shown in FIG. 6, it is preferable to apply a pressing force in the pressing direction 61 by disposing a plate-shaped spring material in the hard case so as to sandwich the soft cartridge. By doing so, the partition portion is broken in the soft case 1 so that the gelled fuel 11 and the reliquefying agent 12 are mixed, and the fuel re-liquefied in the mixed fuel 33 is taken out in the direction 34. Can increase the discharge power. It is sufficient if there is a fuel suction means on the side of the fuel cell or device to which the cartridge is mounted so that the fuel output can be obtained. However, even if there is no such suction means, the spring material as described above can be used. By pressing, an appropriate amount of fuel can be continuously supplied without requiring a complicated mechanism.

Fuel used in the present invention is methanol.

  The above-mentioned gaseous fuel including hydrogen can be liquefied and used. For liquefaction of the gaseous fuel, for example, it is preferable to obtain a dispersed fluid fuel in which an occlusion material is occluded in advance and further dispersed in a dispersion medium. Examples of the gaseous fuel storage material include hydrogen storage alloys, hydrogen absorbents such as carbon nanotubes, chemical hydrides (organic hydride, borohydride, sodium hydride), metal complexes, and the like. Examples of the dispersion medium for dispersing the hydrogen storage material that has stored the gaseous fuel include water and organic solvents such as methanol, ethanol, dimethyl ether, formic acid, formalin, and hydrazine.

[Reliquefaction Aspect 1-1]
In this reliquefaction mode, the gelling agent used for the gelled fuel may be any gelling agent that can co-gel with the fuel, and may be a chemical gel in which the fuel is absorbed by an organic polymer or the like. A physical gel that exhibits thixotropic properties due to the interaction between the fluid fuel and the gelling agent may be used. At this time, the gelling agent should form a gel structure in a state in which the fuel is incorporated into the network structure by crosslinking, hydrogen bonding, molecular entanglement, etc. alone or together with the fuel etc. Is preferred.

  Examples of the gelling agent include an electrolyte gelling agent that constitutes an electrolyte gel. When the gelling agent is a polymer compound, even if it is a crosslinkable polymer gelling agent, a non-crosslinking polymer gelling agent is used. It may be. In the case of a cross-linked polymer gelling agent, the absorption power (affinity and osmotic pressure, etc. with the substance serving as the fuel) that attempts to incorporate the fuel into the gel by adjusting the cross-linking density, and the power to stop the absorption action The amount of absorption may be controlled by balancing (such as elastic force based on the network structure).

  Examples of the non-crosslinking type polymer gelling agent include polymer compounds having acidic and / or basic polar groups, and polyacrylic acid, polyacrylamide, polyethylene glycol, or derivatives thereof are preferable. An acid or a derivative thereof is more preferable, and polyacrylic acid is particularly preferable.

Examples of the cross-linking polymer gelling agent include those obtained by cross-linking the non-cross-linking polymer gelling agent and derivatives thereof (cross-linking polyacrylic acid and derivatives thereof, cross-linking polyacrylamide, etc.). Reticulated products, Reticulated products by introducing crosslinkable monomers, Reticulated products by self-crosslinking, Reticulated products by light / radiation irradiation, Insolubilized (crosslinked) products by copolymerization of hydrophobic monomers, Insolubilized (crosslinked) products by introducing crystalline polymer blocks , Cross-linked products with polyvalent metal cations, cross-linked products by introducing secondary bonds such as hydrogen bonds, and the like.
The molecular weight of the gelling agent is not particularly limited, but is preferably 100 or more, and more preferably 1000 to 8000000 (in the present invention, the molecular weight refers to a mass average molecular weight unless otherwise specified). However, a gelling agent having a higher molecular weight that is cross-linked using a cross-linking agent or the like can also be used.

  Fuel usually increases in viscosity by decreasing the fuel evaporation rate due to interaction with the gelling agent. The addition amount of the gelling agent is not particularly limited, but the viscosity of the gelled fuel (in the present invention, the viscosity represents the viscosity at room temperature (25 ° C. unless otherwise specified)) is 0.02 Pa · sec or more. Thus, it is preferable to adjust appropriately according to the kind of gelling agent. For example, when polyacrylic acid or a cross-linked polyacrylic acid is used as the gelling agent, 3 to 30 parts by mass with respect to 100 parts by mass of fuel It is preferable that it is 3-10 mass parts. The addition amount of the gelling agent is preferably small so as not to reduce the content ratio of the fuel, but if it is too small, it becomes difficult to ensure the gelation / reliquefaction reactivity. If the viscosity of the gelled fuel is 0.02 Pa · sec or more, fluid scattering can be prevented when the tank is broken or carried, so that high safety can be ensured.

The reliquefaction agent is not particularly limited, and examples thereof include a substance that forms a hydrogen bond with a part of the gelled fuel and a substance that forms an ionic bond with a part of the gelled fuel mixture. It is preferably an ionic polymer compound containing a nonionic group, a cationic group, or both in the chain.), Protein, peptide, collagen, gelatin, agar and the like.
The reliquefying agent acts to cause a reliquefaction of the fuel by acting with a gelled product comprising at least a fuel and a gelling agent. The affinity for the gelling agent in the gelled product (hydrogen bonding force, ionic bond strength, fan) It is preferable that the fuel is unbound and reliquefied in the gelled product by the action of insoluble salt formation, pH fluctuation, molecular entanglement, and combinations thereof through Delwars force and the like.
The reliquefaction agent can be determined by the relationship between the polar group possessed by itself and the polar group possessed by the gelling agent. The reliquefaction agent polarity (side chain polarity in the case of a polymer compound) and the gelling agent polarity ( In the case of a polymer compound, the side chain polarity) can be used to cause reliquefaction even if either one has amphoteric polarity. The polarity of the agent is preferably opposite to that of the agent, and the reactivity of these polar groups is more preferable.
The average molecular weight of the reliquefaction agent is preferably 100 or more, more preferably 1000 to 8000000. However, it is also possible to use a reliquefying agent having a higher molecular weight that has been crosslinked using a crosslinking agent or the like.
If the average molecular weight of the reliquefaction agent is too small, when only the fuel is taken out after reliquefaction, it becomes difficult to separate it from low molecular weight compounds such as fuel, making it difficult to obtain an inexpensive filter. If the molecular weight is too large, the reliquefaction agent may not easily penetrate into the gelled product composed of the gelling agent.

  Furthermore, the reliquefaction agent is preferably in the form of a gel. The gel-like reliquefaction agent preferably has a viscosity of 0.01 Pa · sec or more.

  In the present invention, there is no particular limitation on the amount of the reliquefaction agent added (the total amount in the case of a plurality of the reliquefaction agents), but it is preferable that the amount is sufficient to reliquefy the gelled product. When it says, it is preferable that it is 1-30 mass parts, and it is more preferable that it is 1-10 mass parts. The addition amount of the reliquefaction agent is preferably small so as not to decrease the fuel content, but if it is too small, it becomes difficult to ensure the reliquefaction reactivity. Therefore, it is preferable to determine in consideration of the fuel content and reliquefaction reactivity.

[Reliquefaction Aspect 1-2]
In this reliquefaction mode, the reliquefaction aid is dispersed in advance in the gelled fuel, and the reliquefaction agent is added to reliquefy the fuel. The reliquefaction aid is preferably one that can be dispersed in a substantially insoluble state in the mixture, or one that can be dispersed in a slightly dissolved state. Furthermore, the reliquefaction aid acts on the reliquefaction aid by the addition of the reliquefaction agent, and specifically increases the solubility of the reliquefaction aid in the gelation mixture. It is preferable to cause an action through the affinity generated between the auxiliary agent and break the network structure of the gel structure so that the fuel can be taken out from the network structure of the gel structure.

The reliquefaction aid is preferably composed of an electrolyte, and before reliquefaction, the electrolyte is preferably dispersed in the gel structure in a low ionization state. The electrolyte reliquefaction auxiliary agent is preferably a polyelectrolyte, ascorbic acid (for example, L-ascorbic acid (vitamin C), D-ascorbic acid, isoascorbic acid, erythorbic acid, redox derivatives thereof (dehydroascorbine) Acid) and the like, stearic acid, protein, peptide, collagen, gelatin, agar, and other solid or liquid organic acids. These electrolytes are also preferably used as salts containing metal ion groups and the like. It is also preferable to use sodium hydrogen carbonate as a reliquefaction aid.
The reliquefaction aid may be used alone or in combination of two or more. When used alone, an electrolyte containing a peptide, protein, metal ion, etc. is preferred, and when used in combination of two kinds, ascorbine A combination of acids and proteins, a combination of ascorbic acids and peptides, and the like are preferable.

  In the present invention, when the reliquefaction aid is dispersed in the fuel mixture in advance, the form is not particularly limited, but it is preferable to use powder or fine particles, for example, inorganic metal fine particles, polymer beads, etc. May be used to make fine particles. The particle diameter of the fine particles is not particularly limited, but the average particle diameter is preferably 0.01 mm to 1 mm, and more preferably 0.1 mm to 1 mm. The larger the particle size, the easier it is to separate from the fuel by a filter.

  Although there is no restriction | limiting in particular in the quantity which adds a reliquefaction adjuvant (when there are two or more), when it says with respect to 100 mass parts of fuel, it is preferable that it is 1-30 mass parts, and is 1-10 mass parts. It is more preferable. The amount of the reliquefaction auxiliary added is preferably small so as not to reduce the fuel content, but if it is too small, it becomes difficult to ensure the reliquefaction reactivity. Therefore, it is preferable to determine in consideration of the fuel content and reliquefaction reactivity.

  The reliquefaction agent in this embodiment using a reliquefaction auxiliary agent is not particularly limited as long as it can promote reliquefaction, but water or an aqueous medium is preferable, and in the case of an aqueous medium, a low molecular weight ( For example, a pH adjuster (for example, an amino acid solution, a peptide solution, an acid substance or an alkali substance similar to a fuel cell electrolyte, such as sulfuric acid for a separator of a perfluorosulfone membrane) having a molecular weight of 100 to 1000), an organic acid A solution (for example, stearic acid solution, ascorbic acid solution, etc.) is preferable, and ascorbic acid is more preferable because it functions as a fuel depending on the type of fuel cell.

  Although there is no restriction | limiting in particular regarding the quantity which adds the reliquefaction agent in this aspect using the reliquefaction adjuvant, When it says with respect to 100 mass parts of fuel, it is preferable that it is 1-30 mass parts, and is 1-10 mass parts. More preferably. The amount of the reliquefying agent added in this embodiment is preferably small so as not to lower the fuel content, but if it is too small, it becomes difficult to ensure the reactivity of the reliquefaction induction reaction. Therefore, it is preferable to determine in consideration of the fuel content and reliquefaction reactivity.

  Further, when the gaseous fuel is used as a fluid, for example, when using a dispersed fluid fuel in which a hydrogen storage material or the like is dispersed, the gelation and reliquefaction can be performed in the same manner as described above. After re-liquefaction, gaseous fuel (eg, hydrogen) can be extracted from the occluded material by hydrolysis, dehydration, and dehydrogenation and used for power generation. Takashi Saida, Kanae Yanase et al., “Passive using metal hydride Development of small fuel cell ", Seiko Instruments, 12th Fuel Cell Symposium Lecture Collection; Yasuyuki Tsutsumi, Liuiwa et al.," Dehydrogenation Fuel Cell ", Proc. can do.

The viscosity of the reliquefied fuel is not particularly limited, but is preferably adjusted as appropriate according to the type of the reliquefaction agent so as to be less than 0.02 Pa · sec. If the viscosity of the reflowed fuel is too high, the fuel cannot be taken out efficiently.
In addition, JP, 2006-236969, A can be referred to for the above-mentioned aspects of gelled fuel, a reliquefaction agent, and a reliquefaction adjuvant.

[Reliquefaction Aspect 2]
In this re-liquefaction mode, the addition of re-liquefied ions (re-liquefaction agent) increases in the gelled fuel in which methanol, polymer electrolyte, and gelled ions coexist to increase the degree of dissociation of the polymer electrolyte. The dissociation degree of the molecular electrolyte can be reduced to reliquefy (in the present invention, “agent” is used to mean not only a single compound but also a resin, composition and ions).
Here, the polyelectrolyte can adjust the strength of the polarity depending on the type of the functional group, the amount of the functional group in the resin, etc., and its strength is, for example, strong polarity (strongly acidic, strongly basic) and weak polarity ( We can distinguish between weakly acidic and weakly basic. As a scale representing the dissociation property of a functional group, there are indices such as a dissociation constant K and pK derived using the dissociation constant. It is known that an acidic group is dissociated in a solution having a pH higher than its pK value, and a basic group is dissociated at a pH lower than its pK value. Although the exact pK value of the functional group of the polyelectrolyte cannot be measured, the apparent pK value can be obtained by calculation. In the present invention, for the acid-base strength, for example, a predetermined polymer electrolyte is put into a methanol aqueous solution having a predetermined concentration and the degree of ionization is measured, and the acid-base strength can be generally substituted. Specifically, it can be determined from the pH when 1 g of polymer electrolyte is added to 1 L (liter) of water. You may consider the exchange capacity of a polymer electrolyte, a solution composition, etc. as needed. In the present invention, unless otherwise specified, strong acidity is an acid strength generally corresponding to a resin having a —SO ³ group as a functional group (for example, strongly acidic ion exchange resin PK212 (trade name) manufactured by Mitsubishi Chemical Corporation). acid corresponding to roughly corresponding acid strength resin having a group (e.g., manufactured by Nippon Shokubai Co., Ltd. polymeric absorbent AQUALIC CA (trade name) ^- refers to acidic strength), the weakly acidic -COO as a functional group to Strength). On the other hand, strong basicity refers to a base strength substantially equivalent to a resin having a —NR ₃ ⁺ group (R is a methyl group or an ethyl group) (for example, a basic ion exchange resin PA308 (trade name) manufactured by Mitsubishi Chemical Corporation). refers to the corresponding basic strength), -NR ₂ group as a functional group is a weak base (R bases intensity corresponding approximately to a resin having a methyl group or an ethyl group) (for example, basic ion exchange Dow Chemical Basic strength corresponding to resin marathon WBA (trade name). In addition, the chelate type resin described later can be used as a resin having a weaker polarity than that of the above weak polarity.
In the re-liquefied gel fuel, at least one selected from the group consisting of polyacrylic acid, polyacrylic acid cross-linked product, polyethylene glycol, polyethylene glycol derivative, polyacrylamide, and polyethyleneimine is used as the polymer electrolyte. It is preferable to use two polymer electrolytes.

Among materials obtained by crosslinking polyacrylic acid, what is called a polymer absorbent that has become a bead-like huge molecule can be preferably used. The polymer absorbent is one of widely used materials used for diapers and the like, and is supplied stably and can be obtained at a relatively low cost. Examples of the polymer absorbent include those having a functional group such as a carboxyl group in the main chain. The cationic polymer absorbent is in the form of an ammonium salt or sodium salt at the time of shipment, and is inherently weakly acidic, but is often neutralized with sodium hydroxide or aqueous ammonia. At this time, it is preferable to perform pretreatment for removing ammonium ions and sodium ions bonded to the polymer absorbent. This process is similar to a process called ion-exchange resin conditioning. Since the polymer absorbent that has been subjected to the conditioning treatment is swollen, it is preferably dried at room temperature.
The polymer absorbent is preferably a macromolecule having a high molecular weight, for example, a molecular weight of 100,000 to 10,000,000 is preferable, and a molecular weight of 1,000,000 or more is more preferable. By using such an absorbent having a high molecular weight, for example, a hard gelled fuel that does not sag even when the container is turned upside down can be obtained. Here, the hard gel refers to a gel having a high viscosity, a high volatilization inhibitory property, a high flash point, a low spinnability, a low adhesiveness and the like. If such a polymer absorbent is used, it will not gel when it is mixed with methanol fuel, and it may take too long even if gelled. Can be efficiently gelled.

  The gelled ions that coexist in the fuel composition may be appropriately determined according to the type of the polymer electrolyte (for example, fuel gelled resin), the methanol concentration, and the like. Examples include ions, potassium ions, lithium ions, ammonium ions, strontium ions, lead ions, barium ions, calcium ions, and zinc ions. Examples of anions include oxonium ions, sulfate ions, phosphate ions, and the like. Among them, the cation generated from water is preferably a proton, and the anion is preferably an oxonium ion. Adding water is preferred for reducing crossover in certain fuel cells. Even in the case of the same type of gelling ions, the gelling acceleration state varies depending on the type of fuel gelling resin and the methanol concentration.

  Gelling ions are ions that promote gelation by the polymer electrolyte (for example, fuel gelling resin). Here, since the amount of the salt composed of the gelled resin and the gelled ions in the methanol aqueous solution varies depending on the combination of the gelled resin and the gelled ions, the type and concentration of the gelled ions are It depends not only on the type of gelled resin but also on the concentration of the aqueous methanol solution used. In many cases, the polarity of the gelled ions is determined in relation to the polarity of the polymer electrolyte of the fuel gelled resin. In general, a polyelectrolyte is composed of a functional group bound to a main chain of a resin and a counter ion bonded to the functional group. Therefore, the gelled ion is an ion that promotes ionization between the functional group and the counter ion, and the ion having the same polarity as the functional group of the polymer electrolyte is used. Specifically, when a cationic polymer electrolyte (polyacrylic acid or the like) is used as the polymer electrolyte, the gelling ion becomes an anion because the functional group fixed to the main chain is a carboxyl group. More specifically, it becomes an anion (such as oxonium) that separates the proton bonded to the carboxyl group from the carboxyl group. Conversely, when an anionic polymer electrolyte (such as polyacrylamide) is used as the polymer electrolyte, the gelled ions become cations (such as protons).

The method for allowing gelling ions to coexist in the fuel composition is not particularly limited. For example, gelling ions are generated after mixing methanol fuel and fuel gelling resin even if gelling ions are charged in methanol fuel. An agent may be added to supply and generate gel ions to coexist. At this time, even if the gelling ions are directly supplied from the gelling ion generator and generated (for example, protons dissociated from the COOH group), the group of the gelling ion generator is water (H ₂ O ions generated indirectly by reaction with O) (for example, an oxonium ion generated by the NH ₂ group pulling a proton from water to become an NH ₃ ⁺ group and thus generated).

  Examples of the gelling ion generator include agents containing gelling ions (specifically, neutral salts, acidic salts, alkaline salts, polymer electrolyte resins, aqueous solutions thereof, and methanol solutions thereof). It is done. In particular, it is preferable to use an aqueous solution, a resin that generates gelling ions (hereinafter referred to as “gelling auxiliary resin”), or the like, and it is more preferable to use a gelling auxiliary resin. That is, for example, when a low molecular weight salt or electrolyzed water thereof is used as a gelling ion generator, counter ions are generated and diffused in the fuel composition together with the gelling ions. For example, when ammonium chloride is generated as gelling ions using ammonium chloride, chlorine ions are generated as counter ions. This counter ion is mixed in the methanol fuel when reliquefied, and its removal is difficult. Such counter ions (by-products) may deteriorate the durability of the fuel cell electrodes and the like when methanol fuel is taken out and used for power generation. Therefore, it is preferable to remove. On the other hand, if a gelling auxiliary resin is used as the gelling ion generator, the resin portion after the gelling ion release will not diffuse into the composition, and can be easily removed without mixing. Therefore, it is preferable.

  The swelling strength of the gelling auxiliary resin is not particularly limited, but is preferably lower than the swelling strength of the fuel gelling resin. By doing in this way, also when gelling resin swells, swelling of gelling auxiliary resin is suppressed and it is maintained in a fixed shape. Therefore, for example, when it is removed, it can be easily separated from the fuel gelled product. In general, the swelling strength of the resin can be adjusted by the composition of the resin, and in particular by the type of functional group and the amount of crosslinking. That is, a resin having a desired swelling strength can be obtained by reducing the amount of swelling by changing the type of functional group of the gelling auxiliary resin or increasing the amount of crosslinking. In the present invention, the swelling strength (absorption capacity) of a resin in an aqueous methanol solution is a value measured by the tea bag method (JIS standard K7223). Specifically, it is a value obtained by adding a predetermined resin and measuring the swelling strength with an aqueous methanol solution in which the amount of protons is adjusted. The larger the value, the easier the swelling.

When a gelling auxiliary resin is used as the gelling ion generator, its polarity is determined by the relationship with the polarity of the gelling ions, and preferably has a functional group having a polarity opposite to that of the gelling ions. The acid-base strength of the gelling auxiliary resin is not particularly limited, and even if it is a strongly polar ion exchange resin (strongly acidic cation exchange resin, strongly basic anion exchange resin), a weakly polar ion exchange resin (weakly acidic cation exchange resin, It may be a weakly basic anion exchange resin) or a chelate resin (the acid-base strength here is the same as that described above for the fuel gelled resin). In particular, a combination using a weakly polar polymer electrolyte as the fuel gelling resin and a strongly polar ion exchange resin having the opposite polarity as the gelation auxiliary resin is preferable, and a weakly acidic polymer electrolyte and a strongly basic anion exchange resin are preferably used. A combination is more preferred. The gelling auxiliary resin may be used alone, in combination with a plurality of resins, or in combination with other additives as long as it does not interfere with the gelation of methanol fuel.
The molecular weight of the gelling auxiliary resin is not particularly limited, but a mass average molecular weight of 100,000 to 10,000,000 is preferable, and 1,000,000 or more is more preferable. A crosslinked resin is particularly desirable. This range of resin not only facilitates filtering out of the gelation auxiliary resin to the outside after re-liquefaction, but also aids gelation before storing the gelled fuel in a cartridge, etc. It is also possible to remove only the resin.

  In this embodiment, the amount of the fuel gelled resin added is not particularly limited, but the viscosity of the fuel gelled product (in the present invention, the viscosity represents the viscosity at room temperature (25 ° C.) unless otherwise specified) is 8 Pa · sec or more. It is preferable to adjust as appropriate according to the type of the fuel gelled resin so that, for example, when polyacrylic acid or a cross-linked polyacrylic acid is used as the gelling agent, It is preferable that it is 1-100 mass parts, and it is more preferable that it is 0.1-10 mass parts. At this time, the amount of the fuel gelled resin added is preferably small so as to ensure the fuel content, but if it is too small, the gelation / reliquefaction reactivity will be low. The higher the viscosity of the gelled fuel, the higher the safety.

  The amount of gelled ions to coexist in the fuel composition is not particularly limited, but is preferably in the range of 0.1 to 10 times the equivalent of neutralizing and reacting the functional group of the fuel gelled resin, A range of 0.5 to 2 times is more preferable. By setting the amount of gelling ions in the above range, the pH of the fuel composition can be prevented from inadvertently increasing or decreasing due to the addition of gelling ions, and as a buffer solution during the reaction. Can be expected.

When reliquefied ions are generated in the gelled fuel, the action reduces the degree of dissociation of the polymer electrolyte in the gelled product, causing the fuel gelled resin to shrink, and methanol fuel to be reliquefied and released. It is.
The polarity of the re-liquefied ions is not particularly limited. However, in order to reduce the degree of dissociation of the functional group of the polymer electrolyte, a polarity opposite to that of the functional group of the polymer electrolyte is desirable. For example, when a chaotic polymer electrolyte is used as the fuel gelled resin, the reliquefied ion becomes chaotic, and when the anionic polymer electrolyte is used as the fuel gelled resin, the reliquefied ion becomes an anion. Of these, protons or oxonium ions generated from water are preferred. When the reliquefied ion is chaotic, it is preferably a proton. When the reliquefaction ion is an anion, it is preferably an oxonium ion. Adding water is preferred for reducing crossover in certain fuel cells.

  The amount of reliquefied ions generated in the gelled product is not particularly limited, but is preferably in the range of 0.1 to 10 times the equivalent of neutralizing the functional group of the fuel gelled resin, It is more preferable that the range be ˜2 times. Considering the use of gelling ions, it is preferably in the range of 0.1 to 10 times the equivalent of neutralizing both the functional groups and gelling ions of the fuel gelling resin, It is more preferable that the range be ˜2 times. By setting it as the said range, it is prevented that pH of a fuel composition raises carelessly or becomes low, and the effect as a buffer solution at the time of reaction can be anticipated.

  The method for generating reliquefied ions in the gelled product is not particularly limited. For example, agents containing reliquefied ions (specifically, neutral salts, acidic salts, alkaline salts, polymer electrolyte resins, aqueous solutions thereof) And their methanol solutions). In particular, it is preferable to use an aqueous solution, a resin that generates reliquefied ions (hereinafter, referred to as “reliquefied ion generating resin”), and more preferably a reliquefied ion generating resin. By using the resin in this way, the resin portion after releasing the reliquefied ions without generating and diffusing counter ions of the reliquefied ions in the reliquefied fuel, as described in the gelation auxiliary resin. Can be separated and recovered as a solid. The reliquefied ions may be generated directly from the reliquefied ion generator or indirectly generated as in the case of gelling ions.

  The type of reliquefied ion generating resin is not particularly limited, but from the viewpoint of the reliquefied action of reliquefied ions as described above, a resin that generates reliquefied ions having a polarity opposite to the functional group of the polymer electrolyte in the gelled product, That is, a resin having a functional group having the same polarity as the polymer electrolyte is desirable. In order to increase the reliquefaction efficiency, it is preferable to use a resin having a polarity stronger than that of the polymer electrolyte in the gelled product. Specifically, for example, when a weakly acidic polymer electrolyte is used as the gelling resin, it is preferable to use a strongly acidic chaotic exchange resin as the reliquefied ion generating resin. When a weakly basic polymer electrolyte is used as the gelling resin, it is preferable to use a strongly basic anion exchange resin as the reliquefied ion generating resin. Here, the polarity is the same as that described for the polymer electrolyte.

  The molecular weight of the reliquefied ion generating resin is not particularly limited, but a mass average molecular weight of 100,000 to 10,000,000 is preferable, and 1,000,000 or more is more preferable. In particular, a crosslinked resin is preferred. By setting it as resin of such a range, it becomes easy to filter the loss of reliquefied ion generation resin to the outside after reliquefaction.

  The swelling strength of the reliquefied ion generating resin is not particularly limited, but is preferably lower than the swelling strength of the fuel gelled resin. By doing so, as described above with respect to the gelling auxiliary resin, even when the gelled resin swells, the swelling of the reliquefied ion generating resin is suppressed and kept in a certain shape. Sometimes it can be easily separated from the fuel gelled product. Adjustment of the swelling strength of the resin, measurement method, and the like are the same as those described for the gelation auxiliary resin.

  The amount of the reliquefied ion generating resin is not particularly limited, but is an amount that generates reliquefied ions in a range of 0.1 to 10 times the equivalent of neutralizing and reacting the functional group of the fuel gelled resin. The amount is preferably such that the amount of reliquefied ions in the range of 0.5 to 2 times is generated. In consideration of the use of gelled ions, it is preferable that the amount is such that reliquefied ions in the above range are generated with respect to the equivalent of neutralizing and reacting both the functional group and gelled ions of the fuel gelled resin. . The mass of the resin is derived from the required amount of reliquefied ions generated and the ion exchange capacity of the resin.

The mode of adding the reliquefied ion generating resin to the fuel gelled product is not particularly limited. Even if the reliquefied ion generating resin is added alone, the reliquefied ion generating resin is mixed with other compounds, and the mixture is used. It may be added to the gelled product. Among them, it is preferable to add a low-concentration methanol aqueous solution containing the re-liquefied ion generating resin to the fuel gelled product, release the high-concentration methanol fuel as the fuel is removed, and control the methanol concentration to supply the fuel cell. .
In a specific fuel cell, the concentration of methanol is diluted with water generated during power generation to obtain an optimal methanol concentration for the fuel cell. In such a fuel cell, when methanol having a high concentration is supplied at the time of startup, the power generation capacity may be reduced. By supplying low-concentration methanol at the time of startup, it is possible to prevent such a decrease in performance. Furthermore, methanol is supplied quickly during reliquefaction. At this time, the mixing ratio of the reliquefied ion generating resin and the low-concentration aqueous methanol solution is not particularly limited, but the reliquefied ion generating resin is preferably 10% by mass or less, and more preferably 1% by mass or less. The methanol concentration of the low-concentration methanol aqueous solution is not particularly limited, but is preferably 3% by mass or less, for example. The methanol concentration of the high-concentration methanol thus extracted is not particularly limited as long as it is higher than the concentration of the low-concentration methanol aqueous solution. Is preferred.

  In general, commercially available ion exchange resins can be used as the gelling auxiliary resin or the reliquefaction ion generating resin, and are classified as follows, for example.

ここで、基体とは高分子化合物の骨格をいい、例えば、「スチレン系」とはスチレン骨格を有する高分子化合物を意味する。Ｉ型とは、ＩＩ型よりも塩基度がやや高い樹脂をいう。また、Ｉ型はＩＩ型より化学的に安定であり、交換吸着する力（イオンの選択性）が強いという特徴があり、Ｉ型を最強塩基性陰イオン交換樹脂ということもある。
ゲル型とは粒子内部が均一な架橋高分子で構成されているもので、もっとも一般的なものである。透明感のある外観をしており、粒子の内部は橋架けされた高分子が均一な網目状の構造となっており、この編目の隙間を通って水やイオン、溶質分子が粒子内部まで自由に拡散できる。
ポーラス型は粒子内部に微細な粗密構造を有するもので、高分子の編目以外に、イオンや分子の拡散を促進する細孔が存在する。
ハイポーラス型は細孔をさらに発達させた構造を持っており、反応速度が向上する。

Here, the substrate refers to a skeleton of a polymer compound. For example, “styrene-based” means a polymer compound having a styrene skeleton. Type I refers to a resin having a slightly higher basicity than type II. In addition, type I is chemically more stable than type II and has a strong exchange-adsorption force (ion selectivity), and type I is sometimes referred to as the strongest basic anion exchange resin.
The gel type is the most common type in which the inside of the particle is composed of a uniform crosslinked polymer. It has a transparent appearance, and the inside of the particles has a uniform network structure with bridged polymers, and water, ions, and solute molecules can freely pass through the gaps inside the particles. Can diffuse.
The porous type has a fine and dense structure inside the particle, and in addition to the polymer stitches, there are pores that promote the diffusion of ions and molecules.
The high porous type has a structure in which pores are further developed, and the reaction rate is improved.

  Specific examples of the repeating unit having a functional group constituting the ion exchange resin are shown below (however, the present invention is not construed as being limited thereto). Here, C-1 and C-2 are strongly acidic cation exchange resins, C-5 and C-6 are weakly acidic ion exchange resins, K-1 to K-3 are chelate resins, and A-1 and A-2 are Strongly basic anion exchange resins (A-1 is type I, A-2 is type II), and A-6 to A-8 are classified as weakly basic anion exchange resins. Although K-2 and K-7 have the same structural formula, the base strength can be changed by adjusting n in the formula, the number of functional groups in the molecule, etc., for example, reducing the total exchange capacity. Even if it is used as a chelate resin, it may be used as a weakly basic ion exchange resin by increasing the amount thereof.

The chelate resin may be coordinated with the central metal to form a complex, and the metal ions include Cr ³⁺ , In ³⁺ , Fe ³⁺ , Ce ³⁺ , Al ³⁺ , La ³⁺ , Hg ³⁺ , UO ²⁺ , Cu ²⁺ , VO ²⁺ , Pb ²⁺ , Ni ²⁺ , Cd ²⁺ , Cd ²⁺ , Zn ²⁺ , Co ²⁺ , Fe ²⁺ , Mn ²⁺ , Be ²⁺ , Ca ²⁺ , Mg ²⁺ , St ^{2+ and the} like.
In addition, some resin functional groups are described as metal ion salts, but they can be used as desired by conditioning treatment, if necessary.
In addition, the gelling auxiliary resin and the reliquefied ion generating resin preferably have a bead shape having a size that allows a ratio of passing through a mesh structure with an interval of 150 μm to be 20% or less. However, a sheet shape, a fiber shape, or a powder shape is preferable. It may be.

  Next, one example of swelling (fuel storage) and shrinkage (reliquefaction) of the fuel storage gel of this embodiment will be described in detail using the following schematic reaction scheme. However, the present invention is not construed as being limited thereby.

  For example, when a fuel gelling resin having a carboxyl group as a functional group of the polymer electrolyte is used, for example, a strongly basic anion exchange resin having an amino group can be used as the gelling auxiliary resin. Here, since the polarities of both are opposite, dissociation and proton release of the polymer electrolyte in the methanol solution are promoted. That is, since anionic ion exchange resin is strongly basic, it dissociates in a methanol solution and releases hydroxide ions. Protons released from the polymer electrolyte react with the hydroxide ions in methanol. In order to maintain the equilibrium, proton dissociation is promoted. As a result, the degree of dissociation of the functional group of the polymer electrolyte is increased by the addition of the gelling auxiliary resin, and the fuel gelled resin swells more effectively in methanol to become a gelled product (left side of the reaction scheme).

  An acidic cation exchange resin is added there as a reliquefied ion generating resin. Then, protons are released into the gelled product, and the degree of dissociation of the functional group of the polymer electrolyte swollen in methanol by the action of the protons decreases and contracts. At this time, when the acidic cation exchange resin is a stronger acid than the polymer electrolyte, the action is further promoted. As a result, the polymer electrolyte contracts and methanol is effectively reliquefied and released (right side of reaction scheme).

  Here, the strong base anion exchange resin used for swelling of the polymer electrolyte is preferably removed after the swelling as described above. For example, a strong base anion exchange resin is packed in a bag made of nylon or Teflon (registered trademark), mixed with a polymer electrolyte, and methanol fuel is added. Since the hydroxide ions released from the strongly basic anion exchange resin are released to the outside through the gaps between the fibers, the fuel gelled resin swells. In this way, after the fuel gelling resin is sufficiently swollen, the gelling auxiliary resin can be taken out together with the bag.

  Japanese Patent Application No. 2006-203600 can be referred to for the reliquefaction mode utilizing the acid-base reaction between the gelled ions and the reliquefied ions as described above.

[Reliquefaction Aspect 3]
As another embodiment of reliquefaction, a cationic polymer electrolyte (fuel gelled resin) and methanol are further contained to form a gelled fuel, and reliquefied ions are added to the gelled fuel, The aspect which forms a salt with a polymer electrolyte and reliquefies is mentioned.

  As for the cationic polymer electrolyte (fuel gelation resin) and the gelation auxiliary resin used in the reliquefaction mode 3, and the gelled fuel using them, those previously mentioned in the reliquefaction mode 2 may be used. (However, in the present liquefaction mode 3, the polymer electrolyte is cationic.)

  The polarity of the re-liquefied ions at this time is not particularly limited. However, in order to reduce the degree of dissociation of the functional group of the polymer electrolyte, the polarity opposite to the functional group of the polymer electrolyte is desirable. That is, in this embodiment, a chaotic polymer electrolyte is used as the fuel gelled resin, and therefore, katine is desirable as the reliquefied ion. Specific examples of the reliquefied ions include sodium ions, potassium ions, lithium ions, ammonium ions, strontium ions, lead ions, barium ions, calcium ions, zinc ions, and the like. Ammonium ions are preferred.

  The amount of reliquefied ions generated in the gelled product is not particularly limited, but is preferably in the range of 0.1 to 10 times the equivalent of neutralizing the functional group of the fuel gelled resin, It is more preferable that the range be ˜2 times. Considering the use of gelling ions, it is preferably in the range of 0.1 to 10 times the equivalent of neutralizing both the functional groups and gelling ions of the fuel gelling resin, It is more preferable that the range be ˜2 times. By setting it as the said range, it is prevented that pH of a fuel composition raises carelessly or becomes low, and the effect as a buffer solution at the time of reaction can be anticipated.

The method for generating the reliquefied ions in the gelled product is not particularly limited, but is the same as the reliquefying mode 2 described above, and it is preferable to use an agent containing reliquefied ions, a reliquefied ion generating resin, or the like. Among these, it is more preferable to use a reliquefied ion generating resin. By using the resin in this way, the resin portion after releasing the reliquefied ions without generating and diffusing counter ions of the reliquefied ions in the reliquefied fuel, as described in the gelation auxiliary resin. Can be separated and recovered as a solid. The reliquefied ions may be generated directly from the reliquefied ion generator or indirectly generated as in the case of gelling ions.
The kind and preferred range of the reliquefaction ion generating resin are the same as those described in the reliquefaction aspect 2 (however, in the reliquefaction aspect 3, the reliquefaction ion generation resin is acidic).

  Next, examples of swelling (fuel storage) and shrinking (reliquefaction) of gelled fuel in this embodiment (an example of adding a compound salt such as ammonium chloride to the fuel storage gel, an ion exchange resin (ammonium salt) Hereinafter, the embodiment example in which “resin salt” is also added to the fuel storage gel will be described in detail. However, the present invention is not construed as being limited thereby.

  When a compound salt containing reliquefied ions is added to an acidic polyelectrolyte in a methanol solution or aqueous solution and free cations (eg, ammonium ions) are generated and coexisted, the free cations are highly acidic (negative charge). Reacts with molecular electrolytes. In this reliquefaction mode, such an ion exchange action is utilized. At this time, as described above, instead of the compound salt containing the reliquefied ions, the aqueous solution containing the reliquefied ions by adding the resin salt, the methanol containing the reliquefied ions by adding the resin salt It is also preferable to use a solution or an aqueous methanol solution containing a reliquefied ion by adding a resin salt.

  The above ion exchange can be performed between ion exchange resins. For example, an acidic ion exchange resin that has become a free cation salt (for example, an ammonium salt) is added to a methanol-swelled gelled polymer electrolyte having a stronger acidity that has been protonated by conditioning treatment. Then, free cations are selectively substituted from the acidic ion exchange resin (resin salt) to a stronger acidic polymer electrolyte. By this ion exchange action, the fuel gelled resin shrinks and solidifies, and the methanol fuel is released, thereby realizing reliquefaction.

This will be described more specifically with the following reaction scheme (however, the present invention is not limited thereto). In this exemplary scheme, the polyelectrolyte has a carboxyl group. This is swollen in methanol as a fuel gelled resin to form a gelled product (state 1). At this time, as described above, the gelled resin may not swell in methanol, such as when a high molecular weight absorbent is used to obtain a hard gel. In such a case, gelling ions may be generated in a mixture of methanol fuel and fuel gelling resin in the presence of a gelling auxiliary resin that assists swelling to promote swelling gelation. At this time, gelling ions having a polarity opposite to that of the polymer electrolyte are used. In this exemplary scheme, oxonium ions generated by a strongly basic ion exchange resin are used.
An ammonium salt of an acidic ion exchange resin that is weaker than the polymer electrolyte (a chelate resin ammonium salt is used in the present exemplary scheme) is added to the gelled product. Then, ammonium ions are substituted into the polymer electrolyte from the weaker acidic chelate resin. The polymer electrolyte in the form of an ammonium salt is insoluble in methanol, and the resin contracts to release methanol fuel (state 2).

本再液化態様については特願２００６−２０３６０１号明細書の記載を参考にすることができる。

Regarding the reliquefaction mode, the description in Japanese Patent Application No. 2006-203601 can be referred to.

1 is a perspective view schematically showing a preferred embodiment of a fuel soft cartridge for a fuel cell of the present invention. It is sectional drawing which shows the II-II line cross section of FIG. It is sectional drawing which showed typically the mixing form of the gelatinized fuel and the reliquefaction agent in the fuel soft cartridge for fuel cells of this invention. It is a disassembled perspective view which shows typically the preferable embodiment of the fuel cartridge for fuel cells of this invention. FIG. 5 is an enlarged cross-sectional view schematically showing a cross section taken along line VV in FIG. 4. FIG. 5 is a cross-sectional view schematically showing a mode in which a spring material for pressing a soft cartridge provided in the fuel cartridge for the fuel cell shown in FIG. 4 is provided by a cross section taken along line VI-VI shown in FIG. 4.

Explanation of symbols

1 soft case 2 outlet 3 separation (easy peel seal)
DESCRIPTION OF SYMBOLS 4 Outlet port sealing part 4a Sealing surface of extraction port and tube 7 Tube 7a Male screw part 7b External opening end 7c Internal opening end 8 Internal filter 9a, 9b Storage chamber 10 Fuel soft fuel cartridge for fuel cell 11 Gelled fuel 12 Reliquefaction Agents 31, 32 Fingers 33 Mixed fuel 34 Extraction direction of reliquefied fuel 41 Cap with rubber 41a Male thread part 41b Opening part 41c Female thread part 42 Check valve cap 42b Opening part 42c Female thread part 52 Rubber 53 Needle 57 Outlet 61 Press Direction 63 Plate-like pressing elastic material

Claims (16)

The inside of the soft case is separated into two storage chambers by a partition, the gelled fuel is stored in one storage chamber, the reliquefying agent is stored in the other storage chamber, and the portions other than the partition of the soft case Provided with a fuel outlet, the partition portion is broken by an external force, the gelled fuel and the reliquefier are brought into contact with each other, the fuel is reliquefied, and the fuel can be taken out from the outlet. A fuel soft cartridge for a battery ,
The combination of the gelled fuel and the reliquefaction agent is any one of the following AC:
A fuel soft cartridge for a fuel cell, wherein the fuel outlet is provided in a storage chamber on the reliquefying agent side.
<A>
Gelled fuel: Mixture of methanol and electrolyte gelling agent
Reliquefaction agent: at least one selected from the group consisting of polyelectrolytes, proteins, peptides, collagen, gelatin, and agar
<B>
Gelled fuel: at least one selected from the group consisting of methanol, electrolyte gelling agent, polymer electrolyte, ascorbic acid, stearic acid, protein, peptide, collagen, gelatin, agar, and other solid or liquid organic acids Mixture of
Reliquefaction agent: water or aqueous medium
<C>
Gelled fuel: Mixture of methanol, polymer electrolyte and gelling auxiliary resin
Reliquefaction agent: Reliquefaction ion generating resin   2. The fuel soft cartridge for a fuel cell according to claim 1, wherein an internal filter is provided in a path for taking out the re-liquefied fuel from the fuel outlet.   3. The fuel soft cartridge for a fuel cell according to claim 1, wherein a screw-type or fitting-type connecting means is provided at the fuel outlet. 4. The fuel soft cartridge for a fuel cell according to claim 2, wherein the internal filter is a combination of an ion exchange resin and a filter paper made of Teflon (registered trademark).   The fuel soft cartridge for a fuel cell according to any one of claims 1 to 4, wherein the soft case is made of a laminate material of an ultraviolet blocking resin and an aluminum sheet.   The fuel soft cartridge for a fuel cell according to any one of claims 1 to 5, wherein a breaking strength of the partition portion is lower than a breaking strength of the soft case.   The fuel soft cartridge for a fuel cell according to any one of claims 1 to 6, wherein the partition part is formed so that the inner surface of the soft case can be peeled off.   The fuel soft cartridge for a fuel cell according to any one of claims 1 to 7, wherein the reliquefaction agent is in a gel form. The fuel soft cartridge for a fuel cell according to any one of claims 1 to 8, wherein an inner opening end of the fuel take-out port reaches a position close to a partition portion of the soft case . A fuel cartridge for a fuel cell, wherein the soft cartridge according to any one of claims 1 to 9 is housed in a hard case.   A check valve is provided on the hard case side so as to come into contact with and in close contact with the fuel outlet of the soft cartridge, or an external filter and a check valve are arranged in that order on the hard case side as viewed from the soft cartridge side. The fuel cartridge for a fuel cell according to claim 10, wherein the fuel cartridge is provided.   The fuel cartridge for a fuel cell according to claim 10 or 11, wherein the hard case has an elastic pressing means for pressing the soft cartridge housed therein. A method for taking out a reliquefied fuel by reliquefying and taking out the gelled fuel using the fuel soft cartridge for a fuel cell according to any one of claims 1 to 10,
The gelled fuel and the reliquefaction agent are respectively contained in a storage chamber separated into two by a partition, and the gel is broken by applying a pressing force from the outside of the soft case. A method for taking out a reliquefied fuel, wherein the reliquefied fuel and the reliquefying agent are brought into contact with each other. The soft case containing the gelled fuel and the reliquefying agent is pressed by hand, or the soft case is stored in a hard case and pressed by elastic pressing means provided on the hard case to regenerate the gelled fuel. extraction method of re liquid fuels according to claim 13, wherein the retrieving is liquefied. And providing a fuel outlet at a position opposed to隔部of the portion other than隔部reliquefaction agent side of the housing chamber of said soft case, extraction of the re-liquefied fuel according to claim 13 or 14 Method. A soft case for storing fuel cell fuel, characterized in that it is used in the method for taking out reliquefied fuel according to claim 13 to claim 15 ,
The interior is separated into two storage chambers by a partition, gelled fuel is stored in one storage chamber, and a reliquefying agent is stored in the other storage chamber,
The combination of the gelled fuel and the reliquefaction agent is any one of the following AC:
A fuel outlet is provided on the side of the soft case other than the partition where the reliquefier is stored, the partition is broken by an external force, the gelled fuel and the reliquefier are brought into contact, and the fuel is removed. A soft case for storing fuel for a fuel cell that can be re-liquefied and fuel can be removed from the outlet.
<A>
Gelled fuel: Mixture of methanol and electrolyte gelling agent
Reliquefaction agent: at least one selected from the group consisting of polyelectrolytes, proteins, peptides, collagen, gelatin, and agar
<B>
Gelled fuel: at least one selected from the group consisting of methanol, electrolyte gelling agent, polymer electrolyte, ascorbic acid, stearic acid, protein, peptide, collagen, gelatin, agar, and other solid or liquid organic acids Mixture of
Reliquefaction agent: water or aqueous medium
<C>
Gelled fuel: Mixture of methanol, polymer electrolyte and gelling auxiliary resin
Reliquefaction agent: Reliquefaction ion generating resin

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