JP2003155488A - Odorant for fuel hydrogen of fuel cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a novel and useful odorant added to the fuel hydrogen of a fuel cell utilizing hydrogen as the fuel. SOLUTION: This odorant is the one added to the fuel hydrogen of a fuel cell utilizing hydrogen as the fuel and comprising at least one or more substances selected from 1-pentene, 2-methyl-1-butene, allene, ethylallene, 1, 4-pentadiene, 1-butyne, styrene, vinylacetylene, octene, decene, propylene, isobutene, diisobutylene, isopropylene, cyclopentene, cyclopentadiene, 1, 3- cyclohexadiene, 1-vinylcyclohexene-1, 5-ethylidene-2-norbornene, cyclohexene, 1-methylpyrrole, pyrazine, 2, 3-dimethylpyrazine, 2-propylpyrazine, 2-picoline, α, p-dimethylstyrene, cumene, limonen, mesitylene, 2-methylnaphthalene, 3- methylindole, myrcene, α-pinene, and the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an odorant for fuel hydrogen of a fuel cell, that is, an odorant to be used by adding to fuel hydrogen for a fuel cell using hydrogen as a fuel.

[0002]

2. Description of the Related Art Hydrogen is a basic raw material used for various purposes, and is a polymer electrolyte fuel cell (PEFC).
ectrolyte Fuel Cell) and phosphoric acid fuel cell (PAF)
It is also used as fuel for fuel cells such as C: Phosphoric Acid Fuel Cell). In a fuel cell using hydrogen as a fuel, until now, as the fuel hydrogen, hydrocarbons and alcohols have been reformed by a steam reforming method or a partial combustion method via a reforming catalyst to improve hydrogen-rich reforming. As a quality gas, by-products such as CO are removed and used.

[0003] City gas and LP gas are used as the above-mentioned raw material hydrocarbons because they are familiar sources of hydrocarbons. However, these gases are used for leakage security purposes, that is, to the user etc. at the time of leakage. Sulfur compounds such as mercaptans, sulfides, and thiophene are added as odorants to make them notice. However, since these sulfur compounds poison the reforming catalyst and deteriorate the catalytic performance, it is necessary to remove them in advance. As described above, when city gas or LP gas is used as a raw material, the reforming operation is not sufficient, and the desulfurization operation is required as a pre-process, which is a very troublesome operation.

Therefore, as fuel hydrogen for fuel cells,
It is conceivable to use hydrogen produced in advance and purified as a fuel without undergoing such hydrocarbon reforming, and research and development from this viewpoint are also underway. However, even when hydrogen is produced using preliminarily manufactured and purified hydrogen itself as fuel hydrogen for a fuel cell, the hydrogen fuel must be used for the same purpose as in the case of city gas or LP gas for the purpose of leakage security. It is necessary to add an odorant.

However, it is known that a catalyst used in an electrode of a fuel cell such as PEFC is poisoned by a sulfur compound. Therefore, if hydrogen compounds such as mercaptans, sulfides, or sulfur compounds such as thiophene that are conventionally used as odorants for city gas and LP gas are added to fuel hydrogen, the catalyst may be poisoned as well. There is a nature. When the catalyst is poisoned, the catalyst performance is deteriorated, and as a result, the performance of the fuel cell is deteriorated, which is a fatal result of the fuel cell.

For this reason, for example, in JP-A-8-60167, an odorant containing 5-ethylidene-2-norbornene and 2-alkoxy-3-alkylpyrazine as essential components as a sulfur gas-free odorant for fuel gas. Agents have been proposed. However, even if an odorant that does not contain sulfur is applied to fuel hydrogen for fuel cells, it may adversely affect the dissolution of the electrolyte membrane of the fuel cell, which is also fatal to the fuel cell. It will be a result.

Therefore, the conventionally known odorant cannot be immediately applied as the fuel hydrogen odorant for the fuel cell, and any substance can be used as the fuel hydrogen odorant for the fuel cell. There is no choice but to explore and develop such things individually. However, no research or study focusing on this point has been performed so far, and no report has been found so far regarding the effect of hydrogen containing an odorant on the fuel cell.

[0008]

SUMMARY OF THE INVENTION From the above facts and viewpoints, the present inventors have proposed a number of substances that can be added as odorants to fuel hydrogen for fuel cells using hydrogen as a fuel. We conducted a thorough experiment to determine whether the substances could be applied as an odorant for fuel hydrogen in fuel cells, and found a substance that can be used as an odorant for fuel hydrogen in fuel cells. That is, an object of the present invention is to provide a novel and useful odorant for fuel hydrogen of a fuel cell, that is, an odorant to be added to hydrogen for fuel cell fueled with hydrogen.

[0009]

The present invention provides an odorant to be added to hydrogen fuel for a fuel cell, wherein the odorant is one or more selected from the following substances. Provided is an odorant for fuel hydrogen of a fuel cell, which is composed of a substance. In the present specification, the following substances are referred to as X group substances. In the following description of the substance, for example, cyclopentadiene (dicyclopentanediene) in the description, the dicyclopentanediene in parentheses following the cyclopentadiene is an alias for the substance cyclopentadiene, and in this respect, The same applies to the parentheses in the table and claims. 1-pentene, cis-2-pentene, trans-2-pentene, 2-methyl 1-butene, 3-methyl 1-butene, 2-methyl 2-butene,
Allene, methyl allene, ethyl allene, 1,3-pentadiene, 2-methyl 1,3-butadiene, 2,3-dimethyl 1,3-butadiene, 1,4-pentadiene, 1,
5-hexadiene, 1,6-heptadiene, 1,3,5
-Hexatriene, 1-butyne, 2-butyne, styrene, vinylacetylene, heptene, octene, nonene,
Decene, propylene, 1-butene, isobutene, tra
ns-2-butene, cis-2-butene, 1,5-hexadiene-3-yne, diisobutylene, 1-hexene, isoprene, 1,3-butadiene, 1,2-butadiene,
Cyclopentene, cyclopentadiene (dicyclopentanediene), 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,5-cyclooctadiene, 1,
5,9-cyclododecatriene, 4-vinylcyclohexene-1,1-vinylcyclohexene-1,5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, bicyclopentadiene, cyclohexene, 1-methylpyrrole, pyrazine, 2-methylpyrazine, 2-methyl-3-isobutylpyrazine, 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine, 2,3,5-trimethylpyrazine, 2-ethylpyrazine, 2 -Propylpyrazine, 2-vinylpyrazine,
2-allylpyrazine, 2-picoline, α. p-Dimethyl-styrene, cumene, 2,5-diethylpyrazine, limonene, mesitylene, 2-methylnaphthalene, 3-methylindole (skatole), myrcene, α-pinene.

The present invention also provides an odorant used by adding it to fuel hydrogen for a fuel cell using either a graft polymerization resin film or a hydrocarbon resin film as an electrolyte membrane. 1 or 2 selected from the following substances
There is provided an odorant for fuel hydrogen of a fuel cell, characterized by comprising at least one kind of substance. In the present specification, the following substances are referred to as Y group substances. 1-octen-3-one, 2,3
-Butanedione, pentane-2,3-dione, hexane-2,5-dione, heptane-2,5-dione, ethylidene diethyl ether, isopropanol, n-butanol, isobutanol, amyl alcohol, propargyl alcohol, β, γ -Hexenol (cis-hexen-1-ol), formaldehyde, acetaldehyde, propionaldehyde, hexanal (caproaldehyde), cumin aldehyde, acetone, 2-octanone, 3-octanone, diacetyl (2,3-butanedione), acetophenone, Methyl formate, methyl acetate, methyl propionate, methyl phenyl acetate, ethyl formate, ethyl acetate, isopropyl formate, isoamyl acetate, n-amyl acetate, phenyl ether Chill formate, 2-isopentenyl acetate, ethyl propionate, butyl acetate, isobutyl acetate, amyl propionate,
Ethyl caproate, amyl butyrate, ethyl caprylate, ethyl caprate, hexyl butyrate, ethyl cinnamate, benzyl acetate, ethyl crotonate, ethyl 3,3-dimethyl acrylate, ethyl-
4-methyl-4-pentenoate, ethyl-4-methyl-3-pentenoate, ethylhept-3-enoate, ethylpyruvate, propylcrotonate, methyl acrylate, butyl acrylate, allyl acrylate, methyl methacrylate, menthyl acetate, bornyl Acetate, β-phenylethyl acetate, allyl caproate, ethylmethylphenylglycidate, p-cresyl acetate, acetol acetate,
Ethyl 9-decenoate, 2,3 octanedione, methyl-3-acetoxy-butanoate, propionoin,
2-methyl-2-pentenal, acetoin acetate, methyl 3-hydroxy-butyrate, 2-methyl-
1-hepten-3-ol, 8-nonen-2-one, acetoin, 3-methyl-3-butenyl acetate, tetrahydrocitral, allyl alcohol, butanal (butyraldehyde), 2,3-butanedione (diacetyl), iso Butyl cellosolve, isobutyraldehyde, carbitol acetate, 2-decenal, decanal, diisobutylcarbinol, dodecanal (lauryl aldehyde), ethyl acrylate, ethyl butyrate, ethyl valerate, ethyl vinyl ketone, ethyl 2-methylbutyrate, heptanal, 1 -Heptanol, 2-heptanone, 2-heptenal, 2-hexenol, mesityl oxide, 2-methylbutanal-
1,3-methylbutanal-1,2-methylbutanol, methylisoamylketone (5-methyl-2-hexanone), 2-methyl-1-pentanol, 2-methylbutylacetate, 2-methylpropanal (isobutyl Aldehyde), 2-nonanal, n-nonanal (pelargone aldehyde), 2-octenal, octanal (n-capryl aldehyde), octyl acetate, 1
-Penten-3-one (ethyl vinyl ketone), isopentanal, pentanal (valeraldehyde),
2,4-Pentanedione (acetylacetone), isopentyl acetate (isoamyl acetate), pentyl acetate (n-amyl acetate), propanal (propionaldehyde), propanoic acid, propylbutyrate, undecanal, butyroin, tetrahydrofuran, 2- Methyltetrahydrofuran, cyclohexene oxide, m-cresol, N- (2'-furfuryl) pyrrole, 2-pyrrolealdehyde, 5-methyl-
2-pyrrolealdehyde, N-ethylpyrrolealdehyde, 2-acetyl-N-methylpyrrole, diketene, 5
-Acetyl 2-methyloxazole, 2-acetylfuran, 2-methylfuran, furfural, furfurylacetone, 5-methyl-2-furfural, dihydrofuranone, cyclopentanone, phenyl n-butyrate, 2-
Phenyl-2-butenal, difurfuryl ether, chrysanthenone, 2-butene-4-olide, 2-methoxyphenol (Gaiacol), 2-methoxy-3-ethylpyrazine, 2-methoxy-3-isobutylpyrazine,
2-methoxy-3-isobutylpyridine, 2-methoxy-3-isopropylpyrazine, 2-methoxy-3-propylpyrazine, anisole, benzaldehyde, 1,8
-Cineol, cyclopentyl acetate, 2-ethoxy-3-ethylpyrazine, 2-hydroxy-3-methoxybenzaldehyde (o-vanillin), phenyl ether.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Among fuel cells using hydrogen as a fuel, for example, a polymer electrolyte fuel cell (PEFC) is characterized in that an ionic conductor, that is, an electrolyte is a solid and a polymer. In PEFC, both electrodes of a negative electrode (anode) and a positive electrode (cathode) are arranged with a polymer electrolyte membrane sandwiched, and fuel hydrogen is supplied to the negative electrode side and oxygen or air is supplied to the positive electrode side to cause an electrochemical reaction. By doing so, electric power can be obtained. The principle of PAFC is similar to that of PEFC.

FIG. 1 is a diagram showing an outline of a configuration example of a PEFC (single cell). In FIG. 1, 1 is a polymer electrolyte membrane, 2 is a cathode electrode (positive electrode), 3 is an anode electrode (negative electrode), and the polymer electrolyte membrane 1 is arranged in contact with both the positive and negative electrodes 2 and 3 facing each other. Has been done. Reference numeral 4 is a cathode electrode side current collector, and 5 is an anode electrode side current collector, which are in contact with the positive and negative electrodes 2 and 3, respectively. As the electrode material, for example, a white metal metal such as platinum or an alloy thereof,
Carbon or the like carrying a white metal such as platinum or an alloy thereof is used.

A groove for supplying oxygen or air is provided on the electrode 2 side of the cathode electrode side current collector 4, and a hydrogen supplying groove is provided on the electrode 3 side of the anode electrode side current collector 5 as well. There is. The groove of the positive electrode side current collector 4 communicates with oxygen (or oxygen-enriched air) or the air supply pipe 6, and the groove of the negative electrode side current collector 5 communicates with the hydrogen supply pipe 7. Reference numeral 8 is a cathode terminal plate provided in contact with the positive electrode side current collector 4, and 9 is an anode terminal plate provided in contact with the negative electrode side current collector 5, through which electric power is taken out during operation of the battery. Be done.

As the electrolyte membrane for PEFC, various ion exchange resin membranes are used, and these are generally described in the following (A) to (A).
It can be classified as in (C). (A) Perfluorocarbon sulfonic acid type resin film. As a typical example of the polymer electrolyte membrane of this system, there is a resin membrane represented by the following formula (1).

[0015]

[Chemical 1]

(B) Graft polymerization resin film. As a typical example of the polymer electrolyte membrane of this system, a polymer membrane having a basic skeleton represented by the following formula (2) (a resin membrane such as a tetrafluoroethylene-ethylene copolymer is reacted with trifluorostyrene and sulfonated) A treated graft polymerized membrane), an ion exchange resin membrane in which a sulfonic acid group, a phosphonic acid group or the like is introduced into a copolymer of trifluorostyrene and a trifluorostyrene derivative. In this specification, a polymer electrolyte membrane of a system represented by these is referred to as a graft polymerization resin membrane.

[0017]

[Chemical 2]

(C) Hydrocarbon resin film (heat-resistant resin film containing no fluorine). Electrolyte membranes of this system include resin membranes in which aromatic polyether ketone, polybenzimidazole, etc. are added with sulfonic acid groups or impregnated with phosphoric acid. Typical examples are Is an ion exchange resin membrane having a basic skeleton represented by the following formula (3). Since the polymer electrolyte membrane of this system does not contain fluorine [above (A)
And (B) contains fluorine], and is referred to as a hydrocarbon resin film in this specification.

[0019]

[Chemical 3]

The substance of the X group according to the present invention is any one of the electrolyte membrane (A) perfluorocarbon sulfonic acid type resin membrane, (B) graft polymerization type resin membrane and (C) hydrocarbon type resin membrane. It can also be used as an odorant with respect to fuel hydrogen for fuel cells using the same, without degrading the cell performance. The reason for this is unknown, but it is probably because it has no adverse effects such as dissolving these electrolyte membranes, and does not adversely affect the catalyst used in the electrodes of fuel cells. .

The substance of the Y group according to the present invention has a cell performance against fuel hydrogen for a fuel cell using an electrolyte membrane comprising the above (B) graft polymerization resin membrane and (C) hydrocarbon resin membrane. Can be used as an odorant without deteriorating. However, with respect to fuel hydrogen for a fuel cell using the electrolyte membrane composed of the above-mentioned (A) perfluorocarbon sulfonic acid type resin membrane, it deteriorates the cell performance and cannot be used as an odorant. Although the details of the reason are unknown, it is considered that it is probably caused by adverse effects such as dissolution of the electrolyte membrane (A) made of perfluorocarbon sulfonic acid resin membrane.

In the present invention, one or two or more kinds (that is, at least one or more kinds) of the odorant composed of the substance of the X group is used by adding it to the fuel hydrogen for the fuel cell. Fuel using one or two or more types (that is, at least one or more types) of odorants composed of Y group substances and an electrolyte membrane composed of the above (B) graft polymerization resin film or (C) hydrocarbon resin film It is used by adding it to fuel hydrogen for batteries.

Hydrogen is used for reforming (transforming) hydrocarbons such as natural gas, petroleum gas and petroleum, separating from water gas, electrolyzing water, separating from coke oven gas and waste gas from petroleum refineries, etc. Although produced by various methods, the odorant of the present invention can be produced by PEFC or P
Used for hydrogen used as fuel hydrogen for fuel cells that use hydrogen as fuel, such as AFC. It should be noted that the fuel hydrogen may contain any component that is harmless or substantially harmless to the fuel cell, and the fuel hydrogen in the present invention is meant to include such a case.

The hydrogen added with the odorant of the present invention is used for a fuel cell using hydrogen as a fuel. A vehicle equipped with a fuel cell that uses hydrogen as fuel has a hydrogen tank, piping, etc., and is parked in a parking lot or garage when the vehicle is stopped. Further, as related equipment, a hydrogen station, a transportation pipe or a tank truck to the hydrogen station, a pipe to or from the tank truck, and a meter are required. By adding the odorant according to the present invention to hydrogen,
Even if hydrogen leaks from the hydrogen tank, piping, and other facilities such as hydrogen stations, piping, and meters, the user can be made aware of it and the purpose of leakage security can be achieved.

[0025]

The present invention will be described in more detail based on the following examples, but it goes without saying that the present invention is not limited to these examples.

As the electrolyte membrane, each PEFC using three types of solid polymer electrolyte membranes having different systems was constructed as a single cell as shown in FIG. Carbon supporting platinum was used as the electrode material. In this way, many individual cells using electrolyte membranes of different systems were produced,
The following battery performance tests were performed.

Here, as the three different types of solid polymer electrolyte membranes, a perfluorocarbon sulfonic acid type electrolyte membrane represented by the above formula (1) [Nafion 1 manufactured by DuPont]
17 membranes (trade name, Nafion = registered trademark)], the graft polymerization type electrolyte membrane represented by the above formula (2) (where n≈
1) and the hydrocarbon-based electrolyte represented by the above formula (3) were used. Of these, the graft polymerization electrolyte membrane is a graft polymerization membrane obtained by reacting a tetrafluoroethylene-ethylene copolymer membrane with trifluorostyrene and then subjecting it to a sulfonation treatment.

First, as an initial performance of each of the above single cells, a battery performance test using pure hydrogen gas (purity = 99.99%) as a fuel was carried out as follows. There was no change. 1. Hydrogen was introduced into the fuel electrode and air was introduced into the air electrode, the current value was set so that the voltage value was about 0.75 V, and the voltage value before continuous operation was measured. 2. A continuous power generation test was performed for 1000 hours (over 41 days) at the same current value as before continuous operation. 3. After continuous operation at the same current value as in the test before continuous operation, the voltage value was measured.

Next, a battery performance test was conducted in the same manner as above using hydrogen gas (hydrogen gas before addition = the same pure hydrogen gas as above) to which various substances having an odor (= smell) were added as a fuel. The odor and the like of each substance was evaluated, that is, the odor intensity and odor of each substance were measured by the odorless chamber method in accordance with the "Gas Odor Concentration Measurement Method" of the Japan Gas Association. The amount of each substance added was set at a concentration 1,000,000 times higher than the odor recognition threshold value (the lowest concentration at which a person can recognize an odor). In the test, hydrogen gas to which each substance was added was used as a fuel in the same manner as above, and a continuous power generation test for 1000 hours (more than 41 days) was conducted to examine the influence on the battery performance. It should be noted that the reason why the addition ratio with respect to the recognition threshold value is increased and the conditions are set to be harsh as described above is to see, in a short period of time, whether or not the fuel cell has an effect over a long period of several months to several years.

Table 1 shows the test methods (that is, including the recognition threshold value of each substance, the amount added to hydrogen gas, etc.) and the results of some of them (7 types). In Table 1, the three types of electrolyte membranes are abbreviated as perfluorocarbon sulfonic acid type, graft polymerization type, and hydrocarbon type, respectively, and the same applies to the description in the following tables. For the threshold (= recognition threshold) and addition amount columns in Table 1, for example, 5
In the case of ethylidene-2-norbornene, the recognition threshold is 7.
Since it is 3 ppb (capacity, the same below), 7,300 ppm (capacity, the same below) is added to hydrogen gas, and for ethyl acrylate, the recognition threshold is 0.30 ppb.
Therefore, it means that 30 ppm was added to the hydrogen gas. Other substances are shown in Table 1.

<Determination Method of Appropriateness as Odorant> In the judgment column of Table 1, the mark ◯ indicates that the following items (1) and (2) were confirmed for the substance. is there. (1) The odors can be clearly distinguished from daily odors, a unique odor is recognized even at low concentrations, and there is no harm to humans and no toxicity, and the requirements to be met as an odorant are satisfied. Was it. And (2) no change in cell performance is observed even after 1000 hours of continuous power generation test, the substance has no adverse effect on the fuel cell, and the substance has an odorant added to hydrogen fuel for fuel cells. Can be used as.

The cross mark in the judgment column of Table 1 indicates that the following items (1) and (2) were confirmed for the substance. (1) It can be clearly distinguished from daily odor,
The requirements that must be met as an odorant must be satisfied, such as the fact that a peculiar odor is recognized even at low concentrations, that it is harmless to humans and has no toxicity. However, (2) the cell performance after 1000 hours of continuous power generation test has deteriorated by 5% or more, and the substance cannot be used as an odorant added to hydrogen fuel for fuel cells.

As shown in Table 1, for 5-ethylidene-2-norbornene and 2,3-dimethylpyrazine,
It has no adverse effect on the fuel cell using any of the perfluorocarbon sulfonic acid type electrolyte membrane, the graft polymerization type electrolyte membrane and the hydrocarbon type electrolyte membrane, showing that these substances can be used as odorants. . It has been shown that isopropanol and ethyl acrylate have no effect on fuel cells using graft polymerization type electrolyte membranes and hydrocarbon type electrolytes, and that they can be used as odorants, but perfluorocarbon sulfonic acid type electrolyte membranes are used. It has an adverse effect on the fuel cell used and indicates that it cannot be used as an odorant. It has been shown that monoallylpyrazine, piperidine and dimethyl sulfide adversely affect fuel cells using an electrolyte membrane of any of these three systems and cannot be used as odorants.

Tables 2 to 11 show the results obtained by the same test method and judgment method as in Table 1. The substances in Table 2, the substances in Table 3, and the substances up to picric acid in Table 4 are perfluorocarbon sulfonic acid-based electrolyte membranes,
It has an adverse effect on fuel cells using either a graft polymerization electrolyte membrane or a hydrocarbon electrolyte electrolyte membrane, and these substances cannot be used as odorants added to fuel hydrogen for fuel cells. Shows.

The substances from 1-octen-3-one in Table 4 to the substances in Table 5, the substances in Table 6, the substances in Table 7, the substances in Table 8 and the phenyl ethers in Table 9 are: , It can be used as an odorant with no effect on a fuel cell using a graft polymerization electrolyte membrane and a hydrocarbon electrolyte electrolyte membrane, but for a fuel cell using a perfluorocarbon sulfonic acid electrolyte membrane. It has an adverse effect and indicates that it cannot be used as an odorant to be added to fuel hydrogen for a fuel cell using an electrolyte membrane of this system.

From 1-pentene in Table 9, the substances in Table 10 and the substances in Table 11 correspond to any one of perfluorocarbon sulfonic acid type electrolyte membrane, graft polymerization type electrolyte membrane and hydrocarbon type electrolyte membrane. It has been shown that the fuel cell used has no adverse effect and can be used as an odorant to be added to fuel hydrogen for fuel cells using any electrolyte membrane.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

[Table 4]

[0041]

[Table 5]

[0042]

[Table 6]

[0043]

[Table 7]

[0044]

[Table 8]

[0045]

[Table 9]

[0046]

[Table 10]

[0047]

[Table 11]

[0048]

EFFECTS OF THE INVENTION According to the present invention, a novel and useful odorant can be obtained as an odorant to be used by adding it to fuel hydrogen for fuel cells using hydrogen as a fuel.

[Brief description of drawings]

FIG. 1 is a diagram showing an outline of a configuration example of PEFC (single cell).

[Explanation of symbols]

1 polymer electrolyte membrane 2 cathode electrode (positive electrode) 3 anode electrode (negative electrode) 4 cathode electrode side current collector 5 anode electrode side current collector 6 oxygen or air supply pipe 7 hydrogen supply pipe 8 positive electrode side current collector 4 Cathode terminal plate 9 provided in contact with it Anode terminal plate provided in contact with the negative electrode side current collector 5

Claims (3)

[Claims] 1. An odorant used by adding to fuel hydrogen for a fuel cell, wherein the odorant is selected from the following substances:
Odorant for fuel hydrogen of a fuel cell, characterized in that it is composed of one or more substances. 1-pentene, cis-2-
Pentene, trans-2-pentene, 2-methyl 1-
Butene, 3-methyl 1-butene, 2-methyl 2-butene, allene, methyl allene, ethyl allene, 1,3-pentadiene, 2-methyl 1,3-butadiene, 2,3-
Dimethyl 1,3-butadiene, 1,4-pentadiene,
1,5-hexadiene, 1,6-heptadiene, 1,
3,5-hexatriene, 1-butyne, 2-butyne, styrene, vinylacetylene, heptene, octene, nonene, decene, propylene, 1-butene, isobutene, t
rans-2-butene, cis-2-butene, 1,5-
Hexadiene 3-yne, diisobutylene, 1-hexene, isoprene, 1,3-butadiene, 1,2-butadiene, cyclopentene, cyclopentadiene (dicyclopentanediene), 1,3-cyclohexadiene, 1,
3-cycloheptadiene, 1,5-cyclooctadiene, 1,5,9-cyclododecatriene, 4-vinylcyclohexene-1,1-vinylcyclohexene-1,5
-Ethylidene-2-norbornene, 5-vinyl-2-norbornene, bicyclopentadiene, cyclohexene,
1-methylpyrrole, pyrazine, 2-methylpyrazine,
2-methyl-3-isobutylpyrazine, 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine, 2,3,5-trimethylpyrazine, 2-
Ethylpyrazine, 2-propylpyrazine, 2-vinylpyrazine, 2-allylpyrazine, 2-picoline, α. p-
Dimethyl-styrene, cumene, 2,5-diethylpyrazine, limonene, mesitylene, 2-methylnaphthalene, 3
-Methylindole (skatole), myrcene, α-pinene. 2. An odorant used by being added to fuel hydrogen for a fuel cell using either a graft polymerization resin film or a hydrocarbon resin film as an electrolyte membrane, wherein the odorant is the following substance. An odorant for fuel hydrogen of a fuel cell, comprising one or more substances selected from the following. 1
-Octen-3-one, 2,3-butanedione, pentane-2,3-dione, hexane-2,5-dione, heptane-2,5-dione, ethylidene diethyl ether,
Isopropanol, n-butanol, isobutanol,
Amyl alcohol, propargyl alcohol, β, γ-hexenol (cis-hexen-1-ol), formaldehyde, acetaldehyde, propionaldehyde, hexanal (caproaldehyde), cumin aldehyde, acetone, 2-octanone, 3-octanone, diacetyl (2,3-butanedione), acetophenone,
Methyl formate, methyl acetate, methyl propionate, methylphenyl acetate, ethyl formate, ethyl acetate, isopropyl formate, isoamyl acetate, n-amyl acetate, phenylethyl formate, 2-isopentenyl acetate, ethyl propionate , Butyl acetate, isobutyl acetate, amyl propionate, ethyl caproate,
Amyl butyrate, ethyl caprylate, ethyl caprate, hexyl butyrate, ethyl cinnamate, benzyl acetate, ethyl crotonate, ethyl 3,3-
Dimethyl acrylate, ethyl-4-methyl-4-pentenoate, ethyl-4-methyl-3-pentenoate, ethyl hept-3-enoate, ethyl pyruvate, propyl crotonate, methyl acrylate, butyl acrylate, allyl acrylate, methyl methacrylate, Menthyl acetate, bornyl acetate,
β-phenylethyl acetate, allyl caproate,
Ethylmethylphenylglycidate, p-cresyl acetate, acetol acetate, ethyl 9-decenoate, 2,3 octanedione, methyl-3-acetoxy-
Butanoate, propionoin, 2-methyl-2-pentenal, acetoin acetate, methyl 3-hydroxy-butyrate, 2-methyl-1-hepten-3-ol, 8-nonen-2-one, acetoin, 3-methyl-
3-butenyl acetate, tetrahydrocitral, allyl alcohol, butanal (butyraldehyde),
2,3-butanedione (diacetyl), isobutyl cellosolve, isobutyraldehyde, carbitol acetate, 2-decenal, decanal, diisobutylcarbinol, dodecanal (lauryl aldehyde), ethyl acrylate, ethyl butyrate, ethyl valerate,
Ethyl vinyl ketone, ethyl 2-methylbutyrate, heptanal, 1-heptanol, 2-heptanone, 2-
Heptenal, 2-hexenol, mesityl oxide, 2-methylbutanal-1,3-methylbutanal-1,2-methylbutanol, methylisoamylketone (5-methyl-2-hexanone), 2-methyl-1- Pentanol, 2-methylbutylacetate, 2-methylpropanal (isobutyraldehyde), 2-nonanal, n-nonanal (pelargonaldehyde), 2-octenal, octanal (n-caprylaldehyde), octyl acetate, 1-pentene- 3-one (ethyl vinyl ketone), isopentanal, pentanal (valeraldehyde), 2,4-pentanedione (acetylacetone), isopentyl acetate (isoamyl acetate), pentyl acetate (n-amyl acetate), propaner (Propionaldehyde), propanoic acid, propylbutyrate, undecanal, butyroin, tetrahydrofuran, 2-methyltetrahydrofuran, cyclohexene oxide, m-cresol, N- (2'-furfuryl) pyrrole, 2-pyrrolealdehyde, 5-methyl- 2-pyrrolealdehyde, N-ethylpyrrolealdehyde, 2-acetyl-N
-Methylpyrrole, diketene, 5-acetyl 2-methyloxazole, 2-acetylfuran, 2-methylfuran, furfural, furfurylacetone, 5-methyl-
2-furfural, dihydrofuranone, cyclopentanone, phenyl n-butyrate, 2-phenyl-2-butenal, difurfuryl ether, chrysanthenone, 2-
Butene-4-olide, 2-methoxyphenol (Gaiacol), 2-methoxy-3-ethylpyrazine, 2-methoxy-3-isobutylpyrazine, 2-methoxy-3-
Isobutylpyridine, 2-methoxy-3-isopropylpyrazine, 2-methoxy-3-propylpyrazine, anisole, benzaldehyde, 1,8-cineole, cyclopentyl acetate, 2-ethoxy-3-ethylpyrazine, 2-hydroxy-3-methoxy. Benzaldehyde (o-vanillin), phenyl ether. 3. The odorant for fuel hydrogen of a fuel cell according to claim 1, wherein the fuel cell is a polymer electrolyte fuel cell.