WO2003050214A1

WO2003050214A1 - Fuel gas odorant for fuel cell

Info

Publication number: WO2003050214A1
Application number: PCT/JP2002/012894
Authority: WO
Inventors: Hitoshi Hatada
Original assignee: Soda Aromatic Co.,Ltd.
Priority date: 2001-12-11
Filing date: 2002-12-10
Publication date: 2003-06-19
Also published as: AU2002354128A1; JPWO2003050214A1

Abstract

A fuel gas odorant, especially, a novel fuel gas odorant for fuel cells which is suitable for use in a fuel gas for fuel cells which comprises hydrogen or another gas. The fuel gas odorant for fuel cells comprises at least one of compounds represented by the following general formula (1): R1-S-R2 (wherein R1 and R2 each represents optionally branched C1-4 alkyl or alkenyl) and/or cyclic compounds represented by the following general formula (2): (2) (wherein R3 represents a C2-5 (un)saturated carbon chain optionally substituted by C1-3 alkyl or alkenyl).

Description

Specification

Fuel gas odorant for fuel cells

Technical field

The present invention particularly relates to a fuel gas odorant suitably used for a fuel gas for a fuel cell.

Background art

Conventionally, to prevent accidents such as poisoning, ignition or explosion due to fuel gas such as liquefied natural gas (LNG), city gas, and LP gas, if a fuel gas leaks, it will promptly and easily appeal to the sense of smell. A fuel gas odorant is added to the fuel gas so that it can be detected.

Conventionally, sulfur-containing compounds have been known as odorants used in these fuel gases (see Patent Document 1 below). However, when these conventional sulfur-containing compounds are applied to fuel gas for fuel cells, which is being developed recently, the activity of the catalyst used in the fuel cell may be reduced. There is a problem in that a desulfurizer is required to remove odorant components.

Various non-sulfur odorants have been known. For example, a odorant containing a mixture of valeric acid and ethyl acrylate (see Patent Document 2 below), a hexene hexene (see Patent Document 3 below), and 5-ethylidene_2-norbornene ( Patent Literature 4 below), an odorant containing 2-methoxy-3-isobutyl virazine as a non-sulfur component and combining it with mercaptan or sulfide (see Patent Literature 5 below), and pyrazine (See Patent Document 6 below). Further, as an excellent fuel gas odorant with odor characteristics as yet odorant does not contain sulfur, 5 Echi V Den one 2- norbornene and 2-alkoxy one ₃ - alkyl Vila Jin has been proposed ( See Patent Document 7 below). However, among these odorants, for example, acrylate-based odorants are chemically unstable, and the amount of added hexene-ethylidene-norpolene is higher than that of mercaptan. There is such a problem.

As described above, fuel cells have recently been developed, and fuel gas such as methane gas, propane gas, butane gas, LNG and hydrogen gas is used as fuel gas. The number of types is also increasing, and applications are beginning to expand. Therefore, a new odorant for fuel gas is required.

(Patent Document 1)

Japanese Patent Application Laid-Open No. 2-20596

(Patent Document 2)

Japanese Unexamined Patent Publication No. 48-79804

(Patent Document 3)

Japanese Patent Application Laid-Open No. 54-58701

(Patent Document 4)

Said Japanese Unexamined Patent Publication No. 55-56190

(Patent Document 5)

Japanese Patent Application Laid-Open No. 60-92396

(Patent Document 6)

Japanese Patent Laid-Open No. 55-59190

(Patent Document 7)

Japanese Patent Application Laid-open No. Hei 8-60167

Disclosure of the invention

Accordingly, an object of the present invention is to provide a fuel gas odorant which is suitably used particularly for a fuel gas such as hydrogen gas used for a fuel cell or the like.

The present inventors have conducted intensive studies with the aim of developing an odorant suitable for a fuel gas for a fuel cell, which has little effect on a catalyst used in a fuel cell and has excellent odor characteristics. As a result, they have found that among the sulfur compounds, a compound selected in particular exhibits the intended effect. That is, the inventors have found that the reaction efficiency does not decrease only when a specific sulfur compound is used, particularly when a platinum catalyst is used, and have solved the above-mentioned problem.

The fuel gas odorant for a fuel cell of the present invention has the following general formula 1

R 1-S-R 2

(Wherein, R 1 and R 2 represent an alkyl or alkenyl group having 1 to 4 carbon atoms which may be branched) and / or the following general formula 2

(Wherein, R 3 represents a saturated or unsaturated carbon chain having 2 to 5 carbon atoms which may be substituted by an alkyl group having 1 to 3 carbon atoms or an alkaryl group) It contains at least one compound.

The fuel gas odorant for a fuel cell of the present invention, for example, is less likely to be poisonous to a fuel cell catalyst, and thus can be suitably used for a fuel gas for a fuel cell. Conventionally, it has been said that a desulfurization device is required when a sulfur-based compound is contained.However, depending on the combination of the fuel gas and the selected sulfur compound of the present invention, these devices can be omitted. The device can be miniaturized. BEST MODE FOR CARRYING OUT THE INVENTION

R 1— S— R 2

(Wherein, R 1 and R 2 each represent an alkyl group or an alkenyl group having 1 to 4 carbon atoms which may be branched) and Z or the following general formula 2

(Wherein, R 3 represents a saturated or unsaturated carbon chain having 2 to 5 carbon atoms which may be substituted by an alkyl group or an alkenyl group having 1 to 3 carbon atoms). Contains one.

As the compounds represented by the above general formulas 1 and 2 used in the fuel gas odorant for a fuel cell of the present invention, the following compounds can be exemplified.

That is, specifically, dimethyl sulfide, getyl sulfide, dipropinoresnosulfide, diisopropinoresnosulfide, dibutyl sulfide, diisopeptide Nores / Ref, Disecondary Petit / Resulfide, Jittershear Butyl Sulfide, Gibienoresnorefide, Giarenoresnorefide, Gipopeninoresnorefide,

(1 butul) sulfide, di (2 butul) sulfide, di (3 butte ninore) sulfide, di (1,3 buttageninole) sulfide, methylethyls / sulfide, methylpropinoresphenol, methyl isopropyl Snoresulfide, Methylbutyl Sulfide, Methyl Isobutyl Sulfide, Methyl Secondary Butyl Snosulfide, Metino Letter Shaributinoresnosulfide, Methyl Biel Sulfide, Methyl Norealyl Sulfide, Methyl Propenyl Sulfide, Methyl (2-butenyl) Snorefide, etinolepropisolesnorefide, etylbutinoresnorefide, ethylenoletarshaliptylsolefide, ethilaryl sulfide, propylbutyls Sulfide, propyl tert-butyl sulfide, Linolepropinoresphenol sulfide, isopropyl tertiary liptylsulfone sulfide, arylisopropinolesulfide, butyl tertiary butyl sulfide, aryl butyl sulfide, isoptino oletanella V butyl sulfide, aryl isobutyls Sulfide, secondary butyl tertiary butyl sulfide, butyl tertiary butyl sulfide, butyl tertiary butyl sulfide, butyl tertiary butyl sulfide, butyl tertiary butyl sulfide Desserts, tersialibutinore (11-buten-nore) Snorefido, tersiyaribuchinore (21-buteninore) s / ref, tersiyaribuchinore (3-butenir) snorefido, tersiyaributinore (1) , 3-butadienyl) sulfide, arylprodenyls Sulfide, aryl (1-butenyl) sulfide, aryl (2-butenyl) sulfide, aryl (3-butenyl) sulfide, aryl (1,3-butagenyl) sulfide, and other sulfides, thiirane, 2-methinoretez Iran, 2,3-Dimethylthiirane, 2-Ethylthiirane, 2,3-Getylthiirane, 2-Propinorethiirane, 2,3-Dipropinoretiiran, 2-Isopropinoretiirane, 2-Echinolini 3-Methi / retirane, 2 Thipropane, 3-methylthiirane, 2-isopropyl-13-methylthiirane, 2-propyl-13-ethylthiirane, thiirane such as 2-isopropyl-13-ethylthiirane, thiylene, 2-methylthiirane, 2,3-dimethylthiirane Len, 21-ethylthiylene, 2,3-getinolethylene, 2-propynolethiylene Down, 2, 3 Jipuropinore Thiirenes such as thylene, 2-isopropinoretylene, 2-ethyl-3-methinoretylene, 2-propyl-13-methylthiylene, 2-isopropyl-13-methylthiylene, 2-propyl-13-ethylthiylene, 2-isopropyl-13-ethylethylylene , Chetan, 2-Methyl Chetan, 2-Echinorethetane, 2-Ipropinolethetane, 2-Isopropinolethetane, 3-Methinolethietane, 3-1-Ethylthetane, 3-Propyl Chetan, 3-Propyl Chetan, 3-Isopropyl Chetan , 2,3 dimethinolechetan, 2,3_diethylenochetan, 2,3-dipropylchetan, 3-ethylo-2-methinolechetan, 2-ethylomethyl-3-ethane, 2-propyl-1-methylmethane, 3- Propyl-1-Methyl Chetan, 2-Isopropyl-1-Methyl Chetan, 3- 2-isopropyl-1-methylethane, 2-propynole 3-ethylethylethane, 3-propyl-12-ethylethylethane, 2-isopropyl-1-ethylethyleethane, 3-isopropyl-1,2-ethylethylethane, 2-isopropyl-1-ethylpropyl ethane, 3 Chetans such as —isopropyl-1-2-propinolechetane, 2,4-dimethylchetan, 2,3,4-trimethinolechetane, 2,4-jetinolechetane, 2,3,4-trietie / lechetan, 2 H—Chete, 2-Methyl-2 H—Chete, 3-Methyl-2 H—Chete, 2,3-Dimethinole 2 H—Chete, 2-Echinoleh 2 H—Chete, 3-Echinore 2 H—Chete, 2, 3 —Jetinole 2H—Cetet, 2—Propyl 2H—Cetet, 3—Propyl 1 2H—Cetet, 2,3-Dipropyl—2H—Cetet, 2—Isopropyl-1 2 H-Chete, 3-Isopropyl- 1H-Chete, 2,4-Dimethyl-2H-Chete, 2,4-Jethyl-2H-Chete, 2-Echinolée 4-Methyl-2H-Chete, 2,3,4 —Trimethyl-2H—Chete, 2,3,4—Triethyl-2H—Chete, 2,3,4-Tripropyl-12H—Cetet and other teets, thiophene, 2,3-dihidrothofen, 2,5— Dihydrothiophene, Tetrahydrothiophene, 2-Methylthiophene, 3-Methylthiophene, 2,3-Dimethinorethiophene, 2,4 Dimethinorethiophene, 2,5 Dimethinorethiophene, 2, 3, 4- Trimethylthiophene, 2,3,5-trimethylthiophene, 2,3,4,5-tetramethylthiophene, 2-ethylthiophene, 3-ethinorethiophene, 2,3-jeti / rethiophene, 2,4 one Jetinoretifen, 2,5—Jetinoretifen, 2,3,4_Trietinoretifen, 2,3,5-Trietinoretifen, 2,3,4,5-tetraethinorethiophene, 2-propizolethiophene, 3-propinorethiophene, 2,3-dipropylthiophene, 2,4-dipropylthiophene, 2,5-dipropylthiophene, 2,3,4-tripropylthiophene, 2 , 3,5-Tripropizolethiophene, 2,3,4,5-tetrapropy / rethiophene, 2-isopropylthiophene, 3-isopropylthiophene, 3-methyl-2,3-dihydrothiophene, 4-methyl-2,3-dihydrothiophene Fen, 3-methyltetrahydrothiophene, 3-ethinolethiophene, 3-ethinole 2,3-dihydrothiophene, 3-ethylethylhydrohydrofen Thiophenes, such as 3,4-dimethylthiophene, 3,4-dimethyltetrahydrothiophene, 3,4-dimethinolay 2,3-dihydrothiophene, 2H-chopyran, 4H-thiopyran, and 3,4-dihydrodraw 2 H-thiopyran, 3,6-dihydro-2H-thiopyran, tetrahydrothiopyran, 2-methyltetrahydrothiopyran, 3-methyltetrahydrothiopyran, 4-methyltetrahydrothiopyran, 2-methyl-3,4-dihydro2H— Thiopyran, 3-methyl-3,4-dihydro 2H—Chopyran, 4-methyl-3,4-dihydro 2H—Chopyran, 5-methyl-3,4 dihydro-1 2H—Chopyran, 6-methyl-3,4 dihydro 2H-thiopyran, 2-methyl-3,6-dihydro-2H-thiopyran, 3-methylone-3,6-dihydro-2H Thiopyran, 4-methyl-3,6-dihydro 2H-chopyran, 5-methyl-3,6-dihydro-2H-chopyran, 6-methinolay 3, 6-dihydro-2H-chopyran, 2-ethinolay 3,4-dihydro 2 H-Chopyran, 3-Echinolée 3, 4-dihydro 2 H-Chopyran, 4-Echinolean 3, 4 Jihi-Draw 2 H-Chopyran, 5-Echinolée 3, 4 Ji-Hiderow 2 H-Chopyran, 6-Echileun 3, 4 —Jihi Draw 2 H—Chovilan, 2—Echiro 3, 6—Jihi Draw 2 H—Chopyran, 3—Echinole 3, 6 Jihi Draw 2 H—Chopyran, 4—Echiru 3,6—Jihi Draw 2 H—Chopyran, 5-Echinolé 3, 6-dihydro-2H-chopyran, 6-ethynole 3, 6-dihydro_2H-chopyran, 2-propyl-1,3,4-dihydro-2H— Thiopyran, 3-propyl-1,3,4-dihydro-2H-thiopyran, 4-propyl-1,3,4-dihydro-2H-thiopyran, 5-propyl-1,3,4-dihydro 2 H-thiopyran, 6-propyl-13 , 4-dihydro-2H-chopyran,

2-Propyl-1,3,6-dihydro 2H-chopyran, 3-Propyl 3,6 dihydro 2H-chopyran, 4-Propyl-1,3,6-dihydro 2H-chopyran, 5-Propyl-3 , 6-dihydro 2H-chopyran, 6-propyl 3, 6-dihydro-2H-chopyran, 2-methyl-2H-chopyran,

3-methyl-2H-chopyran, 4-methyl-2H-chopyran, 5-methyl-1H-chopyran, 6-methyl-2H-chopyran, 2-methyl-4H-thipyran, 3-methyl-4H-chopyran, 4-Methyl-4H-chopyran, 2-ethylinotetrahydrothiopyran, 3-ethylethylhydrohydropyran, 4-ethyl / letetrahydrothiopyran, 2-ethylino 2H-chopyran, 3-ethyleno 2H-chopyran, 4-ethylinopyran 2H—Chopyran, 5 ー Chyrupan 2H—Chopyran, 6—Ethyl 1 2H—Chopyran, 2—Ethyl 4H—Chopyran, 3 ェ Cytylan 4H—Chopylan, 4 ー Chypyran, 4 ー Chopirane, etc. be able to.

Among these, particularly preferred sulfur compounds are sulfides and 5- to 6-membered ring compounds having no side chains in view of stability and low boiling point, and more specifically, dimethyl sulfone. Feed, getyl sulfide, dipropyl snoresulfide, dibutinoresnorefide, disecondary butyl snoresulfide, ditanjaributyl snoresulfide, divininoles / refide, giary / resnorefide, methinolle methinolebutinoresulfide, bul Methyl sulfide, arylmethyl snosulfide, ethyl propyl sulfide, ethyl butyl sulfide, propyl butyl sulfide, thiophene, 2,3-dihydrothiophene, 2,5-dihydrothiophene , Tetrahydrothiophene, Tetrahydriclotiopyran, 2H-H Pyran, and 4 H- Chiopiran can be cited as preferred compounds.

Further, from the viewpoint of stability in a fuel cell, sulfides are particularly preferable, and more specifically, dimethyl sulfide, getyl sulfide, and dipropyl sulfide. , Diptide / residue, disecondary ptinoles ^^, ditertiary chinoresnorefide, methinolethienoresnorefide, methylpropylsnolefide, methyl isopropyl sulphide, divinyl sulphide, divinyl sulphide, Vinyl methyl sulfide and aryl methyl sulfide are particularly preferred compounds.

The following general formula 1 used in the present invention:

R 1-S-R 2

(Wherein, R 1 and R 2 each represent an alkyl group or an alkenyl group having 1 to 4 carbon atoms which may be branched) can be obtained by a known method. For example, the sulfur compound can be obtained by a method of reacting an alkyl halide or an alkyl halide with a sulfur sulfide or sodium sulfide. Furthermore, a method is also known in which a sodium alkyl mercaptide is reacted with an alkyl iodide to obtain methylethyl sulfide.

The following general formula 2 used in the present invention:

(Wherein, R 3 represents a saturated or unsaturated carbon chain having 2 to 5 carbon atoms which may be substituted by an alkyl group having 1 to 3 carbon atoms or an alkaryl group) Can also be obtained by a known method.

For example, as a method for obtaining thiirane, there is a method of treating 3-chloroethyl thiocyanate or ethylene dithiocyanate with sodium sulfide. Thiofen can also be industrially produced from butane and sulfur. Other methods include the method of reacting sodium succinate with diphosphorus trisulfide, the method of passing acetylene through boiling sulfur, or It can be obtained by passing a mixed gas of acetylene and hydrogen sulfide through a heating tube filled with alumina, or reacting butadiene or butene with sulfur. In addition, tetrahydrothiophene is obtained by reacting 1,4-dibromobutane or 1,4-jodobutane with aluminum sulfide. And tetrahydrothiopyran can be obtained by a method in which potassium sulfide acts on 1,5-jodopentane.

Some of these sulfur-containing compounds are commercially available, and they can also be used. For example, the chain compound represented by the above general formula 1 can be obtained from Aldrich (dimethyl sulfide, dibutyl sulfide, diaryl sulfide, etc.), Nippon Wako Pure Chemical Industries (getyl sulfide, ditertiary). Butyl sulfide, etc.) or International Flavor and Fragrance (dibutyl sulfide).

In addition, the cyclic compound represented by the above general formula 2 is available as a reagent, for example, Aldrich (Thilan, methylthiirane, Chetan, tetrahydrothiofen, etc.), Fluka (Tiophen, etc.) It is commercially available at.

In the present invention, these compounds may be used alone, or a plurality of these compounds may be mixed and used at an arbitrary ratio.

Further, in the fuel gas odorant for a fuel cell of the present invention, a non-sulfur compound may be used in addition to the sulfur compound used in the present invention.

The odorant of the present invention is added to the fuel gas at a concentration exceeding at least the recognition threshold value at a normal temperature and normal pressure with a mixing ratio in the air of 1 / 1,000 or less by volume.

The perception threshold value of the fuel gas odorant for a fuel cell in the present invention is the lower limit concentration at which the odor can be easily sensed based on the volume ratio in air (vol./vol.). This figure indicates that, for example, after stirring the test substance in an odorless chamber until the concentration of the test substance in the atmosphere becomes constant, several panelists enter the room and reduce the odor intensity to the value of the odor pollution reported by the Central Pollution Control Council. It can be measured by evaluating with a six-stage odor intensity display method.

As an example of the specific method of the recognition threshold, an odorant is placed in a petri dish or the like in an odorless room, allowed to stand for a certain period of time, and then the air in the odorless room is thoroughly stirred until uniform, and then left for 1 minute After that, the panelists enter the room and evaluate it by the 6-step odor intensity display method. This is done by changing the concentration of the odorant in the fuel gas to determine the odorant concentration that can be easily perceived as easily understood as what odor corresponds to “2” in the six-step odor intensity display method. Thus, the recognition threshold value of the fuel gas odorant can be obtained.

"6-step odor intensity indication method J

0: Odorless

1: I don't know what it smells, but it smells barely

2: You know what smell, smell feels easy

3: The smell that you feel clearly

4: Bow smell

5: intolerable smell

Further, it is preferable that the fuel gas odorant can be distinguished from a living odor, and it is particularly desirable that the odorant functions as a warning odor. Here, the living odor is a odor that is felt daily in a normal living space, and is used to mean a odor that is not recognized as foreign or abnormal in daily life. In addition, the warning odor is an unpleasant odor that is generally recognized as indicating an unusual situation, and can be clearly distinguished from the above-mentioned life odor, and can be used as a signal indicating danger. Used in a meaning. Since the odorant of the present invention has the same odor as the odorant conventionally used for liquefied natural gas and the like, it has an odor highly recognized as a warning odor.

Further, the fuel gas odorant for a fuel cell preferably has low corrosiveness. The amount of odorant used in fuel gas is very small, but the corrosiveness of resin such as metal and packing used for cylinders, pipes, valves, etc., is an effect that accumulates. Therefore, it is desirable that it be as small as possible. Since the odorant of the present invention has low corrosiveness, it has very little influence such as a decrease in the activity of the catalyst in the fuel cell, and other materials such as fuel gas cylinders, valves, and packings. Deterioration of organic polymer materials that form pipes, fuel cells or stacks of fuel cells is unlikely to occur.

Examples of the fuel gas to which the fuel gas odorant for a fuel cell of the present invention is applied include hydrogen gas, but the present invention is not limited thereto.

The fuel gas odorant for a fuel cell of the present invention can be added to the fuel gas by a known method using an odor device or the like.

Example (Evaluation method of fuel gas odorant)

Concentration in the atmosphere of the test substance in the odorless chamber of 8m ³ is discharged with the test substance to be one thousandth, was stirred until its concentration is constant, odor and enter after standing a certain time The strength is evaluated. The odor intensity is determined using a panel of six skilled persons according to the six-step odor intensity display method described above, and the average value is used as the measured value.

(Evaluation of material corrosion test)

The experiment was conducted in the following manner according to JI SK2234 (Test method for corrosion of radiator with antifreeze).

1) Platinum plate is measured vertically and horizontally with a vernier caliper. The height is measured three times at each of three locations, and the average is used as the representative length.

2) Wash the platinum plate in 1) above with detergent and methanol and dry it in a dryer at 50 ° C for 2 hours. Then, let cool in a desiccator.

3) Weigh the platinum plate of 1) above to 0.000 lg with a precision balance.

4) Immerse the platinum plate in 1) above in the sample.

5) After 40 days, take out the platinum plate in 4) above, wash (detergent and methanol), and measure (weigh).

(Example 1)

Inject 200 zg of dimethyl sulfide (recognition threshold: 3.2 ppb) into a small cylinder (LPG, W3.3), and then inject 1.33 g of hydrogen gas into the small cylinder. At this time, the concentration of the odorant (dimethyl sulfide) in the hydrogen gas is about 150 ppm by mass. The contents of the small cylinder after shaking for 30 seconds, to release half of its contents to room 8m ³ (room temperature 20 ° C), the indoor gas concentration and 1 1, 000 min . After that, the room air was stirred with a fan for 3 minutes and then left for 1 minute.Evaluation was performed by six panelists using the six-step odor intensity display method. It has the function of:

(Example 2)

Inject 250 / g of tetrahydrothiophene (cognition threshold: 2.36 ppb) into a small bomb (LPG, W3.3), followed by 1.33 g of hydrogen gas. At this time, the concentration of the odorant (tetrahydrothiophene) in the hydrogen gas is about 188 ppm. The contents of the small cylinder after shaking for 30 seconds, to release half of its contents to room 8m ³ (room temperature 20 ° C), the indoor gas concentration and 1 1, 00 0 minutes. After that, the indoor air was stirred with a fan for 3 minutes and then left for 1 minute, and evaluated by six panelists using the six-step odor intensity display method. It has a function as.

(Example 3)

Surface area of about 8 cm ^2, weight of about 1. 5 g~l. 7 g prepared platinum plate size described in Table 1, leave these platinum plate was immersed in the sample according to Table 1 The samples were allowed to stand at room temperature (average temperature: 29.9 ° C) for 40 days to conduct a material corrosion test. Ethanthiol was used as a control.

≠, Material Vertical Width Thickness Surface area Before immersion After immersion Weight difference

c) \ cm) (cm; (cm ² ) weight (g) weight (g) (g)

1 4.04 0.01 8.28 1.5532 1.5532 0 Ethancio 0.98 4.03 0.01 8.10 1.6294 1.6290 -0.0004 THT 0.99 4.04 0.01 8.44 1.7433 1.7433 0

Diethyl sulfide 1.03 4.03 0.01 8.50 1.7025 1.7025 0 Di-t-butyl sulfide 0.99 4.03 0.01 8.18 1.6532 1.6532 0 As a result, as shown in Table 1, the weight difference of the platinum plate before and after immersion in each sample for 40 days was weighed. As a result, the amount of ethanethiol used as a control for corrosive substances was reduced by 0.0004 g, whereas blank (untreated), tetrahydrothiophene (THT), dimethyl sulfide and ditertiary sulfide were used. Weight change was not observed for butyl sulfide (Di-t-butyl sulfide). As a result, tetrahydrothiophene, getyl sulfide, and di-tert-butyl sulfide, which are generally used as platinum plates for fuel cell catalysts, are non-corrosive, do not become catalyst poisons, and are suitable for fuel cell fuels. What can be used for It was judged.

Industrial applicability

Since the fuel gas odorant of the present invention has a desirable odor as a warning odor, it can be used as various fuel gas odorants such as liquefied natural gas (LNG), city gas, and LP gas. Since it does not become a catalyst poison to the catalyst for use and has a desirable odor as a warning odor, it can be suitably used particularly for fuel gas for fuel cells.

Claims

The scope of the claims

1. The sulfur compound contained in the fuel gas odorant has the following general formula 1

R 1-S-R 2

(Wherein, R 1 and R 2 each represent an alkyl group or an alkenyl group having 1 to 4 carbon atoms which may be branched) or a compound represented by the following general formula 2

(Wherein, R 3 represents a saturated or unsaturated carbon chain having 2 to 5 carbon atoms which may be substituted with an alkyl group or an alkenyl group having 1 to 3 carbon atoms). A fuel gas odorant for a fuel cell.

2. The sulfur compound contained in the fuel gas odorant has the following general formula 1

R 1-S-R 2

(Wherein, R 1 and R 2 represent an alkyl group or an alkenyl group having 1 to 4 carbon atoms which may be branched). Odorant.

3. The sulfur compound contained in the fuel gas odorant has the following general formula 2

4. Sulfur compounds are dimethyl sulfide, getyl sulfide, dipropinoles norfide, diptinoles phenol sulfide, ditertiary rib chin oleno sulfide, divininoles / refide, diaryl sulfide, methylethyl sulfide, methyl propyl sulfide Nolefide, methinoleisopropinoresnolefide, methylbutyl sulfide, bininole methylsnolefide, arylmethyl sulphide, ethylpropyl sulphide, head, propylbutyl sulphide, thiirane, 2- Methylthio Iran, Chetan, 2-Methyl Chetan, 3-Methinolechetan, Chi-Shi Feng, 2,3-Dihi-Drothiophene, 2,5-Dihi-Drothiophene, Tetrahi-Drothiophene, 3-Methino-Rethiophene, 3-Methinole 2,3-Dihydrothio Phen, 4-methinole-1,2,3-dihydrothiophene, 3-methinoletetrahydrodrothiophene, 3-ethylthiophene, 3-ethylethyl 2,3-dihydrothiophene, 3-ethinoletetrahydrodrothiophene, 3,4-dimethinolethiophene, 3,4-Dimethyltetrahydrodrothiophene, 3,4-dimethynorethone 2,3-dihydrodrothiophene, tetrahydrodrothiopyran, 2H-thiopyran, 4H-thiopyran, 2-methyl-2H-thiopyran, 3-methyltetrahydrothiopyran And 3,4 dihydro-2H-chopyran Selected from the group, the fuel gas odorant for fuel cell according to claim 1, characterized in that at least one horn of compounds.

5. Sulfur compounds are dimethyl sulfide, getyl sulfide, dipropyl sulfide, diptide / less / sulfide, disecondary butyl sulfide, ditertiary butyltinolene sulfide, gibiel sulfide, diaryl sulfide, methyl ethyl phenol sulfide , Methyl propyl snore sulfide, methyl isopropyl sulfide, methyl butyl sulfide, butyl methyl sulfide, aryl methyl sulfide, ethyl propinores sulfide, ethynolebutinolesulfide, propyl Selected from the group consisting of norebutinoresolefide, thiophene, 2,3-dihydrothiophene, 2,5-dihydrothiophene, tetrahydrothiophene, tetrahydrothiopyran, 2H-thiopyran and 4H-thiopyran. At least one Fuel gas odorant for fuel cell according to claim 1, wherein the compound der Rukoto.

6. Sulfur compounds are dimethyl sulfide, getyl sulfide, dipropyl sulfide, dibutyl sulfide, disecondary butyl sulfide, ditertiary liptylsnolesulfide, methylethinolesulfide, methinolepropinolesno At least one disulfide selected from the group consisting of sulfide, methyl isopropyl sulfide, dibininoresno sulfide, diaryl sulfide, vinyl methyl sulfide and aryl methyl sulfide. Item 2. The fuel gas odorant for a fuel cell according to Item 1.

7. The sulfur compound is thiophene, 2,3-dihydrothiophene, 2,5-dithiophene 2. The fuel gas for a fuel cell according to claim 1, wherein the gaseous fuel is at least one cyclic compound selected from the group consisting of drothiophene, tetrahydrothiophene, tetrahydrothiopyran, 2 H-chopyran, and 4 H-thiopyran. 3. Attached

8. The fuel gas odorant according to any one of claims 1 to 7, wherein the fuel gas is hydrogen.