TW201231387A - Hydrogen production system for fuel cell, fuel cell system, deionization method for hydrocarbon fuel, and hydrogen production method - Google Patents

Abstract

This hydrogen production system for a fuel cell is provided with: a fuel supplying unit which supplies, to a later stage, a hydrocarbon fuel containing a sulfur compound and moisture having a conductivity of 0.05 to 500 μS/cm; a desulfurization unit which has a desulfurization catalyst for desulfurizing the hydrocarbon fuel; a hydrogen generating unit which generates hydrogen from the hydrocarbon fuel; and a deionization unit which is disposed between the fuel supplying unit and the desulfurization unit or between the desulfurization unit and the hydrogen generating unit and which brings the hydrocarbon fuel supplied from the fuel supplying unit or the hydrocarbon fuel that passed through the desulfurization unit into contact with a porous ion adsorbent.

Description

[Technical Field] The present invention relates to a hydrogen production system for a fuel cell, a fuel cell system, a deionization method for a hydrocarbon-based fuel, and a method for producing hydrogen. [Prior Art] In general, a fuel gas system for a fuel cell uses a gas containing hydrogen as a main component, and a natural gas, lpg (Iiquified petroleum gas), urban natural gas, and stone brain are used as raw materials. Hydrocarbons such as oil and lamp oil. The hydrogen obtained by the following method is used as the fuel hydrogen for the fuel cell: the raw material of the hydrocarbon containing (4) and the like is placed on the catalyst together with the water vapor for high temperature treatment, and partially oxidized by the oxygen-containing gas' or The self-heat recovery type reforming reaction is carried out in a system in which water vapor and an oxygen-containing gas coexist (for example, refer to the following patent document 丨). In the case of the use of the city natural gas, the gas is usually supplied to the fuel producing apparatus including the fuel cell through the existing piping (Example #, see Patent Document 2 below). CITATION LIST Patent Literature Patent Literature Patent Publication No. 2 〇〇 · · · 专利 专利 专利 专利 专利 专利 日本 日本 日本 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 供给 供给 供给 供给 供给 供给 供给 供给 供给 供给 供给 供给The pipeline is arbitrarily damaged by cracks and the like. Its shape. In this case, there is a decrease in the power generation efficiency of the hydrocarbon-based fuel mixed with the mineral fuel in the pipeline, such as underground 161172.doc 201231387, to the fuel-contaminated reforming catalyst or the electrode catalyst cell. The possibility inside. In the case of a battery system such as groundwater, it causes mineral formation and leads to hydrogen production efficiency or fuel power. The purpose of the invention is to provide a hydrogen production system and fuel for a fuel cell that can effectively remove hydrocarbon-derived water-derived ions. A battery system, a deionization method with a hydrocarbon-based fuel, and a method for producing hydrogen. Means for Solving the Problems In order to solve the above problems, a nitrogen production system for a fuel cell according to the present invention is a hydrogen production system for a fuel cell, and has a fuel supply portion that contains a conductivity of moisture and a sulfur compound. The flue-based fuel is supplied to the rear stage, and the melon #, which has a desulfurization catalyst 'hydrogen generating unit' for desulfurizing the hydrocarbon-based fuel, which generates hydrogen from the hydrocarbon-based fuel; and includes a deionization f' which is disposed on the fuel The hydrocarbon-based fuel supplied from the fuel supply unit or the hydrocarbon-based fuel supplied through the desulfurization unit is brought into contact with the porous ion adsorbent between the supply unit and the desulfurization unit or between the desulfurization unit and the nitrogen generation unit. The conductivity of the water contained in the hydrocarbon-based fuel can be jis (jap_se

InduStnal Standards, Japan Industrial Standards) is measured based on the "General Principles for Measuring Conductivity". According to the hydrogen production system of one aspect of the present invention, the deionization unit is provided between the fuel supply unit and the desulfurization unit or between the desulfurization unit and the hydrogen generation unit, and the inclusion can be efficiently removed. The moisture of the specific conductivity and the ions in the moisture of the hydrocarbon-based fuel can sufficiently prevent the modified catalyst from being contaminated by the incorporation of the water of the minerals such as the underground ruler. 161172.doc

S 201231387 In the hydrogen production system according to an aspect of the present invention, the deionization unit may be included between the fuel supply unit and the desulfurization unit. The above porous ion adsorbent may contain zeolite in terms of deionization performance, long life, and low cost. In the hydrogen production system for a fuel cell according to the aspect of the invention, the hydrocarbon-based fuel may contain a hydrocarbon compound having 4 or less carbon atoms from the viewpoint of easiness of obtaining the fuel and the like. Hydrogen manufacturing system. In the deionization method of the flue-based fuel of the present invention, the hydrocarbon-based fuel having a water content of 〇.05 to 500 #/cm is brought into contact with the porous ion adsorbent. According to the deionization method of the hydrocarbon-based fuel of the present invention, it is possible to efficiently remove the ions in the water; Therefore, even if the hydrocarbon-based fuel contains water containing minerals such as groundwater, it is possible to prevent the fuel cell system from repeating the description of the modified catalyst or electrode catalyst of the B# 3 :: the ionic sorbent Zeolite may be included in terms of deionization performance and long life. Further, in view of the ease of obtaining the hydrocarbon-based fuel of the present invention, the hydrocarbon compound is a fuel. m. The material may also contain a carbon number of 4 or less = the form of hydrogen in the form of hydrogen, and hydrogen may be obtained by the first deionization method of the present invention. In the case where the hydrocarbon-based fuel contains a sulfur compound, the deuterated hydrocarbon-based fuel can be desulfurized and modified to obtain hydrogen. Advantageous Effects of Invention According to the present invention, there can be provided a hydrogen system for fuel cell and a fuel cell system capable of effectively removing ions derived from moisture in a hydrocarbon (four) material, a deionization method with a hydrocarbon-based fuel, and a method for producing hydrogen . DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The preferred embodiments of the present invention will be described in detail with reference to the drawings. ® 1 You represent the reality of the invention. The fuel electric (4) system includes: a fuel supply unit 2, a decoupling unit, a desulfurization unit 3, a hydrogen generating unit 4, a battery stack 5, an exhaust gas combustion unit, a water vaporization unit 8, an oxidant supply unit 9, and a power conditioner. Second, the part u is supplied with a hydrocarbon-based fuel to the deionization unit 15 by piping (not shown) to the fuel supply unit 2 in a flow shown in FIG. The fuel containing the conductivity Α 〇 〇s can use the second: the moisture. Here, the other elements.../compounds (may also include potables such as oxygen, and biomass. As the flue-based fuel, for example, the former petroleum, rock mountain = white, and the flue-based fuels may be used as appropriate. From the synthetic fuels, come: chemical = 枓, synthetic gas, etc. List: methane, ethane, β p as a hydrocarbon can be said to say 'C-burn, Dingyuan, natural gas, lpg (liquefied stone 161l72.doc

S 201231387 oil gas), urban natural 惫, coal 、,,,,, α γ ^ ^ gravel / fly oil, naphtha, kerosene, light oil. Examples of the alcohols include methylcellulose and ethanol. As the screaming class, dimethyl ether can be cited. Examples of the raw fuel include enamel gas, raw ethanol, raw rubber, and raw fuel. In the present embodiment, it is preferable to use a gas (for example, urban natural gas (four)), gas (T_gas), natural gas (Natural), raw gas, or the like, which is supplied as a main component by a line feed, or LPG. . The conductivity of the water in the hydrocarbon-based fuel is 〇.5 5 〇〇 pS/em. Further, examples of the water-containing ions include magnesium ions, calcium ions, vanadium ions, potassium ions, sodium ions, iron ions, and copper ions. In the present embodiment, the hydrocarbon-based fuel preferably contains a hydrocarbon compound having 4 or less carbon atoms. Specific examples of the hydrocarbon compound having a carbon number of 4 or less include saturated aliphatic hydrocarbons such as methane 'ethane, propane and butane, and unsaturated aliphatic hydrocarbons such as ethylene, propylene and butylene. The hydrocarbon-based fuel is preferably a gas containing a hydrocarbon compound having a carbon number of 4 or less, that is, a gas containing more than one of methane, ethane, ethylene, propane, propylene, butane, and butene. In addition, the gas "containing a hydrocarbon compound having a carbon number of 4 or less is preferably a gas containing 8% by volume or more of decane", more preferably a gas containing methane of 85 vol / 〇 or more. The fe-based fuel generally contains a sulfur compound. The sulfur compound may be a sulfur compound originally mixed in a hydrocarbon or the like, or a compound contained in an odorant for detecting a gas. Examples of the sulfur compound which is originally mixed in a hydrocarbon or the like include hydrogen sulfide (H2s), carbonyl sulfide (COS, carbon oxide suifide), and carbon disulfide (Cs2). As an odorant, 161172.doc 201231387 uses sulphur mystery, thiol alone or in combination, for example, DES 'Diethyl sulfide, dimethyl sulfide (DMS, dimethyl sulfide), methyl ethyl EMS, ethyl methyl sulfide, THT, Tetrahydrothiophene, TBM, tert-butyl mercaptan, isopropyl mercaptan, dimercapto disulfide (DMDS ' Dimethyl disulfide), diethyl disulfide (DEds,

Diethyl disulfide). The sulfur compound is contained in an amount of 〇·1 to mass ppm in terms of a sulfur atom-equivalent concentration based on the total amount of the hydrocarbon-based fuel. In the hydrocarbon-based fuel, components other than the above-mentioned moisture and sulfur compounds may be contained in a range that does not adversely affect the characteristics of the fuel cell system. The hydrocarbon-based fuel supplied from the fuel supply unit 2 is supplied to the decoupling unit 15 . The deionization section 15 has a porous ion adsorbent, and the porous ion adsorbent adsorbs ions derived from moisture contained in the hydrocarbon-based fuel. Here, the temperature of the deionization portion is preferably 〇, more preferably 〇7吖, and still more preferably 〜30C. The temperature from the sub-portion is particularly good at room temperature. The porous ion absorbing material 2 preferably contains zeolite or a styrene-based cation exchange resin, and preferably contains zeolite having excellent adsorptivity. ^(10) Sub-exchange resin as a material for removing hydrocarbons (four) or a device, 1 has caused the operating cost of the fuel cell system to increase to a low level: the tendency to be ambiguous, but in the case of using zeolite, it can also be small The device is stably supplied with hydrogen. Stone work =: = boiling - type Buddha stone, mercerized type boiling is preferably not included (four) Ρΐ · 5, Μ (: Μ-41, etc. These zeolites 16U72.doc 201231387 / as styrene cation exchange resin, It is not particularly limited as long as it can capture ions derived from water contained in the soot fuel, and various commercially available ion exchange resins can be used. The amount of each zeolite or styrene cation exchange resin can be used according to the hydrocarbon-cut fuel. The hydrocarbon-based fuel from which the ions derived from water are removed from the deionization unit 15 is desulfurized in the desulfurization unit 3. The sulfur contained in the hydrocarbon-based fuel is desulfurized. The compound causes contamination of the reforming catalyst in the hydrogen generating unit 4 or the electrode catalyst in the battery stack 5, so it is removed by the desulfurizing catalyst in the desulfurizing section 3. The desulfurizing catalyst can be used as usual. As the sulfur catalyst, it is preferable to use a desulfurization catalyst containing a metal such as Ag'Cu, a & a metal, a desulfurization catalyst containing an active metal such as Ni, Zn, or the like. The desulfurization section 3 has Ag. In the case of the /X type zeolite, it is preferred to carry out the separation in the deionization section 15 The hydrocarbon-based fuel to be removed is contacted with the Ag/X-type zeolite under the conditions of 65 to 1 G5t. Further, when the desulfurization section 3 has a desulfurization catalyst containing an active metal such as Ni, Zn or Cu, it is preferred to The hydrocarbon-based fuel and the desulfurization catalyst which are ion-removed in the deionization section 15 are contacted at 200 to 30 G C. The desulfurization by such temperature conditions can be performed, for example, by the desulfurization section 3 having the heating section. The hydrocarbon-based fuel desulfurized by the desulfurization unit 3 is supplied to the hydrogen generation unit 4. The hydrogen generation unit 4, the fuel supply unit 2, the deionization unit 15, and the desulfurization unit 3 constitute a hydrogen production system 20. The generating unit 4 has a reformer that reforms the deionized and desulfurized hydrocarbon-based fuel by the modified catalyst, and generates a hydrogen-rich gas. The modification mode of the mouse generating unit 4 is not particularly limited, for example, It can be modified by steam, partial oxidation, self-heating, and other modification methods. I61172.doc 201231387 In addition, the upgrading temperature is usually 200~800. 〇, preferably 300~7〇〇〇c Further, there is also a case where the hydrogen generating portion 4 is rich in hydrogen gas required by the battery stack 5. In addition to the reformer that is modified by the modified catalyst, it has a configuration for adjusting the properties. For example, the type of the battery stack 5 is a solid polymer fuel cell (PEFC: P〇lymer Electr〇)丨yte Fuel Cell) or scaly fuel cell (PAFC: Ph〇Sph〇ric

In the case of Cell), the hydrogen generating unit 4 has a configuration for removing one of the hydrogen-rich gases (for example, a conversion reaction unit 'selective oxidation reaction unit'). The hydrogen generating unit 4 supplies the hydrogen rich gas to the anode 12 of the battery stack 5. The modified catalyst is not particularly limited. For example, it can be exemplified by a modified catalyst selected from the group consisting of aluminas and metals selected from the group consisting of nickel, austra, iron, bismuth and a metal.

A general modified catalyst can be used. Examples of the porous inorganic oxides such as Shi Xi, such as money, silver, and surface, are listed in Table VIII: Hydrogen generation. In the middle, it is preferable that the water vapor is supplied from the water vaporization unit 8 in order to reform the hydrocarbon-based fuel. The W gas is preferably heated by water vaporization by the water supplied from the water supply stage 7 and is caused to be heated. In the vaporized water vaporization unit 8, the skins of the stagnation a # + t 九 & 2, 'for example, the recovered iron generating unit 4, the scrap iron* burning portion 6, or the 妯屮々 ^ system ^ Production..., also;: The heat of the body is equal to other evaluations such as fuel cells, and U can also use a separate heater's burner, search for Dan,,., source and slave. The profit is from the exhaust gas. In Fig. 1, 'as an example, only this is described. The heat supplied from the UP 6 to the hydrogen generating unit 4 is not limited to the piping in which the fuel cell is connected (not shown in the drawings, and the gas manufacturing system_the battery stack 5 is connected), and the hydrogen-rich manufacturing system 20 supplies hydrogen-rich hydrogen. The gas m吏 uses I61172.doc 201231387 The hydrogen-rich gas and the oxidant generate electricity in the battery stack 5. The type of the battery stack 5 in the fuel cell system 1 is not particularly limited, and for example, a solid polymer fuel cell (PEFC) or a solid oxide fuel cell can be used: (S〇FC: S〇Hd 〇Xide Fue丨) Cell), Phosphoric Fuel Cell, (PAFC), Molten Carbonate Fuel Cell (MCFC : Mohen

Carbonate Fuei Cell), and other types. Further, depending on the type of the battery stack 5, the modification method, and the like, the constituent elements shown in the drawings may be omitted as appropriate. The oxidant is supplied from the oxidant supply unit 9 by a pipe connecting the oxidant supply unit 9 and the fuel cell system 1. As the oxidizing agent, for example, air, pure oxygen (including a substance which is not easily removed by a usual removal method), and oxygen-enriched air can be used. The battery stack 5 generates electric power using the hydrogen-rich gas from the hydrogen generating unit 4 and the oxidizing agent from the oxidizing agent supplying unit 9. The battery stack 5 includes an anode 12 supplied with a hydrogen-rich gas, a cathode 13 supplied with an oxidant, and an electrolyte 14 disposed between the anode 12 and the cathode 13. The battery stack 5 supplies electric power to the outside via a power conditioner. The battery stack 5 supplies a hydrogen-rich gas and an oxygen and a chemical agent which are not used for power generation to the exhaust gas burning unit 6 as exhaust gas. Further, a combustion portion including a hydrogen portion 4 (for example, a burner of a heating reformer) may be used in common with the exhaust gas burning portion 6. The exhaust gas burning unit 6 burns the exhaust gas supplied from the battery stack 5. The heat generated by the exhaust gas (four) portion 6 is supplied to the hydrogen generating portion 4, and is used for the generation of the wind gas by the hydrogen generating portion 4. X, the fuel supply unit 2, the water supply unit 7, and the oxidant supply unit 9 are configured by, for example, a pump, and are driven based on a control signal from the control unit & 161172.doc 201231387. The power conditioner ίο adjusts the power from the battery stack 5 in conjunction with the external power usage state. The power conditioner 1 is, for example, a process of converting a voltage or converting DC power into AC power. A control unit 11 performs control processing of the entire fuel cell system. The control unit 11 includes, for example, a CPU (Centrai Processing Unit)

A unit, a ROM (Read 〇nly Mem0ry), a RAM (Random Access Mem〇ry), and an input wheel interface. The control unit 丨丨 is electrically connected to the fuel supply unit 2, the water supply unit 7, the oxidant supply unit 9, the power conditioner 1A, and a sensor (not shown). The control unit acquires various signals generated in the fuel cell system and outputs control signals to the respective devices in the fuel cell system. As described above, according to the hydrogen production system and the fuel cell system of the present embodiment, even if a hydrocarbon-based fuel containing water containing minerals such as groundwater is used, stable supply of hydrogen and power generation can be performed. Further, the hydrogen production system and the fuel cell system of the present embodiment can sufficiently suppress the increase in size and operation cost of the apparatus while having the above-described deionization function. Next, the deionization method of the hydrocarbon-based fuel of the present embodiment and the method for producing hydrogen will be described. In the deionization method of the hydrocarbon-based fuel of the present embodiment, the hydrocarbon-based fuel containing water having a conductivity of 〇.05 to 500 #/cm is brought into contact with the porous ion adsorbent. The hydrocarbon-based fuel containing the water having a conductivity of 0.05 to 500 pS/cm can be exemplified. 16ll72.doc •12-

S 201231387 :: a specific mechanism for bringing the 4 series fuel into contact with the porous ion adsorbent, the fuel supply unit 2, the deionization unit 15 and the desulfurization unit 3. In other words, the fuel supply unit 2 supplies the hydrocarbon-based fuel to the deionization unit, and the ions derived from the water in the package-type 4 fuel are adsorbed and adsorbed by the porous ions. Thereafter, the ion-removing hydrocarbon-based fuel is supplied to the desulfurization section', and the supplied hydrocarbon-based (four) desulfurization section 3 is contacted with the de-synthesis medium and desulfurized. The hydrocarbon-based fuel of the above-described deionization method is modified to cover the gas (chlorine-rich gas). The modification is not particularly limited as described above. For example, it is possible to use steam reforming, 4-part oxidation modification, self-heat modification, and other modification methods. The reforming temperature is usually 200 to 800 ° C, preferably 300 to 7 Torr. The modified catalyst can be used as described above: generally, it is selected from the group consisting of alumina, ruthenium, etc., and is preferably selected from nickel, agar, iron, bismuth, and bismuth. The modified catalyst of the metal of the bond, the ruthenium, and the platinum (four) _. The metal of the group is in the middle of the modification. Since it is necessary to reform the fuel, it is preferable to supply the water from the water vaporization unit 8 to the hydrogen generation unit 4. It is preferable that the milk supplied from the water supply unit 7 is added to the water vaporization unit 8 to be vaporized, and the deionization method of the hydrocarbon-based fuel according to the present embodiment is used. , ... : Effectively removing the water contained in the hydrocarbon-based fuel, even when the hydrocarbon-based fuel contains minerals containing groundwater = when it can prevent the modified catalyst or electrode catalyst of the fuel cell system ^ I61l72.doc In addition, according to the 氲 氲 氲 方法 方法 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃 烃The description does not limit the invention. For example, The decoupling portion 5 is disposed between the desulfurization unit 3 and the hydrogen generating unit 4. In this case, sulfur contamination from the sub-portion can be avoided. Industrial Applicability According to the present invention, an inclusion can be provided which is effective A hydrogen production system for a fuel cell, a fuel cell system, a deionization method for a hydrocarbon-based fuel, and a hydrogen production method for removing a deionized portion of ions derived from water in a hydrocarbon-based fuel. [Simplified Schematic] FIG. A conceptual diagram showing an example of a fuel cell system according to an embodiment of the present invention. [Description of main components and symbols] 1 Fuel cell system 2 Fuel supply unit 3 Desulfurization section 4 Hydrogen generation section 5 Battery stack 15 Detachment section 20 Argon production system 161t72 .doc

Claims (1)

201231387 VII 1. 'Scope of application: A hydrogen production system for a battery, which is a hydrogen production system for a fuel cell, having: a fuel supply unit that will contain a hydrocarbon-based fuel having a conductivity of L and a sulfur compound. a desulfurization unit having a desulfurization catalyst for desulfurizing a hydrocarbon-based fuel; a hydrogen generation unit that generates hydrogen from the hydrocarbon-based fuel; and a deionization unit provided in the fuel supply unit and the Between the desulfurization sections or between the desulfurization section and the hydrogen generation section, the hydrocarbon-based fuel supplied from the fuel supply unit or the hydrocarbon-based fuel passing through the desulfurization section is brought into contact with the porous ion adsorbent. 2. The hydrogen production system for a fuel cell according to claim i, wherein the deionization unit is included between the fuel supply unit and the desulfurization unit. 3. The hydrogen production system for a fuel cell according to claim 2, wherein the porous ion adsorbent comprises zeolite. 4. The hydrogen production system for a fuel cell according to any one of the preceding claims, wherein the te-based fuel contains a hydrocarbon compound having a carbon number of 4 or less. A fuel cell system comprising the manufacturing system of any one of claims 1-4. Wind 6. A hydrocarbon-based fuel deionization method in which a hydrocarbon-based fuel containing water having a conductivity of 0 05 to 500 gS/em is brought into contact with a porous ion adsorbent. 7. The deionization method of the hydrocarbon-based fuel of claim 6, wherein the porous ion adsorbent comprises zeolite. 8. The deionization method of a hydrocarbon-based fuel according to claim 6 or 7, wherein the above-mentioned flue system 161l72.doc 201231387 fuel contains a hydrocarbon compound having a carbon number of 4 or less. 9. A method of hydrogen production, which can be carried out by, for example, requesting decoupling of ^1^^ nitrogen. In the method, the hydrocarbon-based fuel of the deionization is modified to obtain a hydrogen production method according to claim 9, wherein the hydrocarbon-based fuel contains a sulfur compound, and the hydrocarbon-based fuel that has undergone deionization is desulfurized. And upgraded to get gas. 16_〇C _2· s