WO2015166854A1 - Filter for fuel cell - Google Patents

Filter for fuel cell Download PDF

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Publication number
WO2015166854A1
WO2015166854A1 PCT/JP2015/062224 JP2015062224W WO2015166854A1 WO 2015166854 A1 WO2015166854 A1 WO 2015166854A1 JP 2015062224 W JP2015062224 W JP 2015062224W WO 2015166854 A1 WO2015166854 A1 WO 2015166854A1
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Prior art keywords
activated carbon
fuel cell
filter
filter layer
layer
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PCT/JP2015/062224
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French (fr)
Japanese (ja)
Inventor
理沙子 野田
洋平 武田
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株式会社ブリヂストン
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Priority to JP2016516335A priority Critical patent/JP6534653B2/en
Publication of WO2015166854A1 publication Critical patent/WO2015166854A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C3/00—Separating dispersed particles from gases or vapour, e.g. air, by electrostatic effect
    • B03C3/017—Combinations of electrostatic separation with other processes, not otherwise provided for
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C3/00—Separating dispersed particles from gases or vapour, e.g. air, by electrostatic effect
    • B03C3/28—Plant or installations without electricity supply, e.g. using electrets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to an air filter (filter for fuel cell) that is used in a power generator (fuel cell stack) of a fuel cell system and has dust removal performance and chemical adsorption performance.
  • a fuel cell generates electricity by an electrochemical reaction between hydrogen and oxygen, and oxygen is generally supplied from the atmosphere at that time, but SO X , NO X, etc. are supplied into the supplied atmosphere. If the impurities and dust are included, the electrocatalyst deteriorates and the electromotive force is lowered, so the power generation device (fuel cell stack) in the fuel cell system has dust removal performance, chemical adsorption performance, etc. An air filter is installed.
  • the chemical adsorption performance means the performance of adsorbing harmful substances such as SO x , NO x, toluene, H 2 S, etc.
  • activated carbon is generally used for a filter having this chemical adsorption performance. That is, as shown in FIG. 1, a fuel cell filter in which an activated carbon filter layer 1 and a charged filter layer 2 are combined is known. This air filter is activated carbon for the atmosphere flowing in the direction of the arrow in the figure.
  • the filter layer 1 adsorbs and removes impurity gases such as SO x and NO x, and the charged filter layer 2 removes dust.
  • the activated carbon filter layer 1 for example, a filter or sheet made of activated carbon processed into a fibrous form or a net-like base material or activated carbon processed into a fibrous form is used, and SO X or H 2 S.
  • a technique has been proposed in which a chemical such as an alkaline substance is previously impregnated on activated carbon.
  • the present invention has been made in view of the above circumstances, and is intended to obtain a fuel cell filter capable of maintaining the chemical adsorption performance of sulfur oxides or the like for a long time and extending the life of the fuel cell. Objective.
  • the present inventors have combined an activated carbon filter and a charge filter to remove impurity gases (SO X , NO X, etc.) and dust in the atmosphere, and a fuel cell filter.
  • the activated carbon filter is disposed on the gas inflow side and the charging filter is disposed on the gas discharge side, and an additive containing an alkaline substance and an oxidizing agent is previously attached to the activated carbon of the activated carbon filter layer.
  • SO x sulfur oxide
  • the present invention provides the following fuel cell filters [1] to [4].
  • [1] In the fuel cell filter in which the activated carbon filter layer is disposed on the gas inflow side and the charged filter layer is disposed on the gas exhaust side, the activated carbon of the activated carbon filter layer is attached with an additive containing an alkaline substance and an oxidizing agent.
  • [2] The fuel cell filter according to [1], wherein the concentration of the alkaline substance in the activated carbon is 1 to 10% by mass and the concentration of the oxidizing agent is 1 to 10% by mass.
  • [3] The fuel cell filter according to [1] or [2], wherein the oxidizing agent is a halogen-based oxidizing agent.
  • [4] The fuel cell filter according to [3], wherein the halogen-based oxidizing agent is potassium iodide.
  • the fuel cell filter of the present invention can maintain the chemical adsorption performance well over a long period of time, and can realize a long life of the fuel cell.
  • the fuel cell filter of the present invention has an activated carbon filter layer, a charged filter layer, and a urethane foam layer (or activated carbon container) as described above, and purifies the air supplied to the fuel cell stack of the fuel cell system.
  • the fuel cell filter shown in FIG. 1 or 2 is exemplified.
  • FIG. 1 shows an activated carbon filter layer 1 on the gas inflow side and a charged filter layer 2 on the discharge side.
  • FIG. 2 shows a urethane foam layer 3 disposed between the activated carbon filter layer 1 and the charged filter layer 2.
  • the activated carbon filter layer 1 adsorbs and removes impurities such as SO x and NO x contained in the atmosphere.
  • activated carbon is supported on a filter substrate having a three-dimensional network structure or a honeycomb structure, or is crushed.
  • a filter base material having a three-dimensional network structure on which activated carbon is supported is preferably used.
  • the three-dimensional network structure of the filter substrate is not particularly limited, but a polyurethane foam having a three-dimensional network skeleton structure in which the cell membrane is removed by a blast treatment or the like is preferably used.
  • This polyurethane foam has low pressure loss and good contact efficiency with air.
  • ether-based materials have better hydrolysis resistance than ester-based materials, and suppress hydrolysis degradation of the filter substrate due to the alkali-adhesion treatment described below. This is more preferable.
  • the number of pores of the polyurethane foam of the filter base material varies depending on the relationship with the activated carbon particles attached to the base material. However, it is usually preferable that the number of pores is 4 to 14 / inch, particularly 6 to 12 / inch. When the number of pores is less than 4 / inch, the pressure loss of the filter is lowered, but the contact efficiency with the passing gas is lowered, so that the removal performance of impurities may be lowered, and the number of pores is 14 / If it exceeds 1 inch, the contact efficiency with the gas becomes high, but the pressure loss becomes high, which may cause disadvantages such as an increased load of the air supply fan of the fuel cell system.
  • the activated carbon supported on the filter substrate examples include coconut shell activated carbon, wood activated carbon, petroleum pitch-based activated carbon, coal-based granulated coal, and other molded activated carbon. Among these, coal-based granulated coal is preferably used. .
  • the activated carbon is not particularly limited, but preferably has a BET specific surface area of 500 m 2 / g or more, particularly about 1000 to 2000 m 2 / g. Considering the adsorption capacity, the larger the specific surface area, the better. However, increasing the specific surface area tends to lower the hardness of the adsorbent, which may cause dust generation depending on the type of adsorbent.
  • the activated carbon mesh of the activated carbon filter layer is preferably # 20 or more and 40 or less.
  • the reason for this is that when it is # 20 or less, the gas adsorption capacity of a low molecular weight is lowered, and when it is # 40 or more, activated carbon is buried in the binder, and there is a possibility that a sufficient BET specific surface area cannot be secured.
  • the activated carbon of the activated carbon filter layer is attached with an additive (medicine) containing an alkaline substance and an oxidizing agent.
  • the purpose of adding an alkaline substance to the additive is to efficiently remove sulfur-based compounds in the atmosphere that lower the electromotive force.
  • the alkaline substance include potassium carbonate, sodium carbonate, hydroxide Alkali metal salts, alkali metal hydroxides, alkaline earth metal salts, and alkaline earth metal hydroxides such as potassium, sodium hydroxide, magnesium carbonate, calcium carbonate, magnesium hydroxide, and calcium hydroxide 1 type or 2 types or more chosen from the group which consists of are mentioned.
  • the concentration of the alkaline substance is not particularly limited, but is preferably adjusted to 1 to 10% by mass with respect to the activated carbon.
  • the purpose of adding an oxidizing agent to the additive is to maintain the chemical adsorption performance well for a long time.
  • the oxidizing agent include halogens, permanganates, peroxides, and the like.
  • a halogen-based oxidizing agent such as potassium iodide is used. It is preferable to adopt.
  • the concentration of the oxidizing agent is not particularly limited, but is preferably adjusted to 1 to 10% by mass with respect to the activated carbon.
  • the adsorbent may be added to the activated carbon in advance, or the activated carbon may be retained on the filter base material, and then the additive may be subjected to an addition treatment. If the amount of the additive added to the activated carbon is excessively large, the adsorption performance by the activated carbon is impaired. Therefore, the amount of the additive added is preferably 20% by mass or less with respect to the activated carbon. Even if the amount of the additive is too small, the effect of improving the sulfur compound removal performance due to the addition of the additive containing an alkaline substance or the like cannot be obtained sufficiently. Therefore, the additive is preferably 0.1 to 20% by mass, particularly 5 to 10% by mass, from the viewpoint of maintaining the adsorption performance of activated carbon and ensuring the removal performance of sulfur compounds.
  • the charging filter layer 2 adsorbs and removes dust of about 1 to 2 ⁇ m contained in the atmosphere.
  • a nonwoven fabric or a woven fabric made of a charged fiber can be used, and in particular, a spun pond nonwoven fabric, a melt blown nonwoven fabric, a needle punched nonwoven fabric made of a charged fiber.
  • Embossed nonwoven fabrics are preferably used, and various shapes such as a pleated shape, a honeycomb shape, and a flat shape can be used.
  • the kind of the fiber subjected to the charging treatment is not particularly limited, but organic fibers such as polypropylene, polyester, and polyamide are preferably used, and polypropylene is particularly preferably used from the viewpoint of repair efficiency.
  • the basis weight of the nonwoven fabric or the woven fabric is not particularly limited, but is preferably 15 to 500 g / m 2 , particularly 50 to 200 g / m 2 in terms of dust removal performance and flow resistance.
  • the fuel cell filter of the present invention can be provided with a urethane foam layer 3 as shown in FIG. 2 if necessary.
  • the urethane foam layer 3 removes clogging substances such as ammonium sulfate from the gas that has passed through the activated carbon filter layer 1 to prevent clogging of the charging filter layer 2.
  • a polyurethane foam having a three-dimensional network skeleton without a cell membrane is preferably used.
  • a polyether-based polyurethane foam is hydrolyzed even when used in a high humidity environment. It is preferably used because it can maintain good durability without causing decomposition.
  • the urethane foam for forming the urethane foam layer 3 is not particularly limited, but preferably has a pore number of 30 to 60 / inch, particularly 40 to 50 / inch, and has a pore number of 30 / If it is less than inches, ammonium sulfate may not be sufficiently collected. On the other hand, if it exceeds 60 inches / inch, there may be a problem that the urethane foam layer 3 itself is clogged.
  • This urethane foam layer 3 can be formed by laminating or laminating a plurality of the above polyurethane foams formed in a sheet shape or block shape, and the number of the polyurethane foam layers can be increased or decreased to adjust the adsorption capacity, air permeability, life, etc. can do.
  • the activated carbon filter layer 1 and the charge filter layer 2 may be formed by laminating a plurality of filters or a plurality of filters, and the same adjustment may be performed by increasing or decreasing the number or the number of the filters.
  • an activated carbon container 3 ′ filled with specific activated carbon can be disposed between the activated carbon filter layer 1 and the charged filter layer 2 instead of the urethane foam layer 3.
  • the activated carbon filled in the activated carbon container 3 ′ can reliably adsorb and remove siloxane gas contained in the atmosphere from the gas that has passed through the activated carbon filter layer 1.
  • Examples of the activated carbon used in the activated carbon container 3 ′ include coconut shell activated carbon, wood activated carbon, petroleum pitch-based activated carbon, coal-based granulated coal, and other molded activated carbon. Is preferably used.
  • the BET specific surface area of the above activated carbon in order to effectively adsorb the siloxane gas, it is preferable to use one having about 500 to 2000 m 2 / g, particularly about 1000 to 1500 m 2 / g. .
  • the activated carbon mesh used for the activated carbon container 3 ′ is coarser than the activated carbon used for the activated carbon filter layer.
  • the mesh may be # 6 or more and less than 20. More preferably, the mesh is not less than # 8 and less than 15 inclusive. If it deviates from the range of the mesh of the activated carbon, the siloxane gas cannot be reliably adsorbed and removed, so that it may become saturated immediately and the siloxane gas may flow to the discharge side.
  • the volume of the activated carbon container 3 ′ is not particularly limited. However, in order to ensure the adsorption / removal effect of the siloxane gas which is the object of the present invention, the occupied volume of the activated carbon container 3 ′ is: It is desirable that the volume of the entire filter including the activated carbon filter layer 1, the charging filter layer 2, and the activated carbon container 3 ′ is 1/5 to 1/15, more preferably 1/12 to 1/14.
  • the volume ratio of the activated carbon filter layer 1 / charged filter layer 2 / active carbon container 3 ′ is 5 to 15 / 0.5 to 5 / 0.5 to 10, more preferably 9 to 11 / 0.5. ⁇ 2/1 ⁇ 3.
  • the fuel cell filter of the present invention purifies the air supplied by being attached to the fuel cell stack of the fuel cell system, but there is no particular limitation on the fuel cell system, and the polymer electrolyte fuel cell, alkaline Any one of an aqueous electrolyte fuel cell, a phosphoric acid aqueous electrolyte fuel cell, a molten carbonate electrolyte fuel cell, a solid oxide electrolyte fuel cell and the like may be used.
  • This fuel cell may be a stationary type or a portable type for mounting on a vehicle.
  • Example 1 Each of the following filter materials was used to form an activated carbon filter layer 1, a charged filter layer 2 and a urethane foam layer 3 to which a chemical was attached, thereby producing a fuel cell filter having the structure shown in FIG.
  • the charging filter layer 2 is formed by laminating 24 sheets of the following charging filter materials
  • the activated carbon filter layer 1 is formed by laminating 24 sheets of the following activated carbon filter materials
  • the urethane foam layer 3 is composed of 4 of the following urethane foam materials. It was formed by laminating.
  • [Material of activated carbon filter layer 1] A polyurethane foam having a three-dimensional network skeleton without cell membrane (10 pores / inch, 5 mm in thickness) fixed with 60 mesh coconut shell activated carbon to an adhesion amount of 300 g / m 2 (( DEO filter “OQ-10K” manufactured by Bridgestone Corporation). Size is ⁇ 60mm, thickness 5mm
  • Example 1 uses an agent (additive) that has a concentration of 3% by mass of potassium carbonate and a concentration of 2% by mass of potassium iodide with respect to the activated carbon.
  • a chemical agent (additive) having a concentration of 6% by mass potassium carbonate is used with respect to activated carbon.
  • the fuel cell filter of Example 1 has an adsorption removal rate of SO 2 contained in the atmosphere of about 1.5 to about 1 to that of Comparative Example 1 (conventional product). It can be seen that it can be satisfactorily maintained over a long period of time, twice or more. In particular, when the air condition is a relative humidity of 30 to 50%, the SO 2 removal time is doubled or more, and the life effect is further increased.
  • Example 2 Each of the following filter materials was used to form an activated carbon filter layer 1, a charged filter layer 2 and a urethane foam layer 3 to which a chemical was attached, thereby producing a fuel cell filter having the structure shown in FIG.
  • the charging filter layer 2 is formed by laminating 24 sheets of the following charging filter materials
  • the activated carbon filter layer 1 is formed by laminating 14 sheets of the following activated carbon filter materials
  • the urethane foam layer 3 is composed of 4 of the following urethane foam materials. It was formed by laminating.
  • [Material of activated carbon filter layer 1] A polyurethane foam having a three-dimensional network skeleton without cell membrane (10 pores / inch, 5 mm in thickness) fixed with 60 mesh coconut shell activated carbon to an adhesion amount of 300 g / m 2 (( DEO filter “OQ-10K” manufactured by Bridgestone Corporation). Size is ⁇ 14mm, thickness 5mm
  • Example 2 uses a chemical agent (additive) having a concentration of 3 mass% potassium carbonate and a concentration of 2 mass% potassium iodide with respect to the activated carbon. In Comparative Example 2, a chemical agent (additive) having a concentration of 6% by mass potassium carbonate is used with respect to the activated carbon.
  • Example 2 can maintain the SO 2 adsorption removal rate well over a long period of about three times or more compared with Comparative Example 2 (conventional product).

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Abstract

　The purpose of the present invention is to provide a filter for a fuel cell, with which adsorption of sulfur oxides can be maintained for a long period of time, and the life of the fuel cell extended. Provided is a filter for a fuel cell, having an activated carbon filter layer (1) at the gas inflow side and an electrostatic filter layer (2) at the gas discharge side, wherein the filter for a fuel cell is characterized in that an additive that contains an alkaline substance and an oxidant is added to the activated carbon of the activated carbon filter layer (1).

Description

燃料電池用フィルターFuel cell filter
　本発明は、燃料電池システムの発電装置（燃料電池スタック）に用いられ、除塵性能や化学吸着性能を有するエアフィルター（燃料電池用フィルター）に関する。 The present invention relates to an air filter (filter for fuel cell) that is used in a power generator (fuel cell stack) of a fuel cell system and has dust removal performance and chemical adsorption performance.
　燃料電池は、水素と酸素の電気化学反応により発電を行なうものであり、その際に酸素は大気中から供給されるのが一般的であるが、供給される大気中にＳＯXやＮＯX等の不純物や塵埃が含まれていると電極触媒を劣化させて起電力を低下させる不都合が生じるため、燃料電池システム内の発電装置（燃料電池スタック）には、除塵性能や化学吸着性能等を有するエアフィルターが取り付けられている。 A fuel cell generates electricity by an electrochemical reaction between hydrogen and oxygen, and oxygen is generally supplied from the atmosphere at that time, but SO X , NO X, etc. are supplied into the supplied atmosphere. If the impurities and dust are included, the electrocatalyst deteriorates and the electromotive force is lowered, so the power generation device (fuel cell stack) in the fuel cell system has dust removal performance, chemical adsorption performance, etc. An air filter is installed.
　化学吸着性能とは、ＳＯX、ＮＯX、トルエン、Ｈ2Ｓ等の有害物質を吸着する性能を意味し、この化学吸着性能を有するフィルターには、一般的には活性炭が用いられている。即ち、図１に示したように、活性炭フィルター層１と帯電フィルター層２とを組み合わせた燃料電池用フィルターが知られており、このエアフィルターは、図中矢印の方向に流入する大気につき、活性炭フィルター層１によりＳＯX，ＮＯXなどの不純物ガスを吸着除去し、更に帯電フィルター層２で塵埃を除去するように構成される。 The chemical adsorption performance means the performance of adsorbing harmful substances such as SO x , NO x, toluene, H 2 S, etc., and activated carbon is generally used for a filter having this chemical adsorption performance. That is, as shown in FIG. 1, a fuel cell filter in which an activated carbon filter layer 1 and a charged filter layer 2 are combined is known. This air filter is activated carbon for the atmosphere flowing in the direction of the arrow in the figure. The filter layer 1 adsorbs and removes impurity gases such as SO x and NO x, and the charged filter layer 2 removes dust.
　上記活性炭フィルター層１としては、例えば繊維状やネット状の基材に活性炭を付着させたものや繊維状に加工した活性炭からなるフィルターやシートが用いられており、更に、ＳＯXやＨ2Ｓの吸着のために、アルカリ性物質等の薬剤を予め活性炭に添着させた技術が提案されている。 As the activated carbon filter layer 1, for example, a filter or sheet made of activated carbon processed into a fibrous form or a net-like base material or activated carbon processed into a fibrous form is used, and SO X or H 2 S. In order to adsorb these substances, a technique has been proposed in which a chemical such as an alkaline substance is previously impregnated on activated carbon.
　しかしながら、燃料電池の高性能化が課題となっている現在においては、燃料電池用フィルターの小型化や長寿命化が強く求められており、化学吸着性能を長時間に亘り良好に維持できる燃料電池用フィルターを開発することが望まれている。 However, at present, where high performance of fuel cells is an issue, there is a strong demand for miniaturization and long life of fuel cell filters, and fuel cells that can maintain good chemisorption performance over a long period of time. It is desired to develop a filter for use.
　なお、本発明に関連する先行技術としては、下記特許文献を挙げることができる。 Note that the following patent documents can be cited as prior art related to the present invention.
国際公開第２００７／０６０９２３号International Publication No. 2007/060923 特開２００６－１０７９８０号公報JP 2006-107980 A 国際公開第２００５／０６２４１１号International Publication No. 2005/062411 特開２００３－２９７４１０号公報JP 2003-297410 A 特開２０１３－２５１１１６号公報JP 2013-251116 A
　本発明は、上記事情に鑑みなされたもので、硫黄酸化物等の化学吸着性能を長時間に亘り維持することができ、燃料電池の長寿化を図ることができる燃料電池用フィルターを得ることを目的とする。 The present invention has been made in view of the above circumstances, and is intended to obtain a fuel cell filter capable of maintaining the chemical adsorption performance of sulfur oxides or the like for a long time and extending the life of the fuel cell. Objective.
　本発明者らは、上記目的を達成するため鋭意検討を重ねた結果、活性炭フィルターと帯電フィルターとを組み合わせて大気中の不純物ガス（ＳＯX，ＮＯXなど）及び塵埃を除去する燃料電池用フィルターにおいて、気体の流入側に上記活性炭フィルターを、気体排出側に上記帯電フィルターをそれぞれ配設すると共に、上記活性炭フィルター層の活性炭に、アルカリ性物質と酸化剤とを含有する添着剤を予め添着することにより、硫黄酸化物（ＳＯX）等の化学吸着性能を長時間に亘り維持することができ、燃料電池の長寿化を図ることができることを見出し、本発明を完成したものである。 As a result of intensive studies to achieve the above object, the present inventors have combined an activated carbon filter and a charge filter to remove impurity gases (SO X , NO X, etc.) and dust in the atmosphere, and a fuel cell filter. In the above, the activated carbon filter is disposed on the gas inflow side and the charging filter is disposed on the gas discharge side, and an additive containing an alkaline substance and an oxidizing agent is previously attached to the activated carbon of the activated carbon filter layer. Thus, the present inventors have found that the chemical adsorption performance of sulfur oxide (SO x ) or the like can be maintained for a long time, and the life of the fuel cell can be extended.
　従って、本発明は、下記［１］～［４］の燃料電池用フィルターを提供する。
［１］
　気体の流入側に活性炭フィルター層、気体の排出側に帯電フィルター層が配設された燃料電池用フィルターにおいて、上記活性炭フィルター層の活性炭には、アルカリ性物質と酸化剤とを含有する添着剤が添着されてなることを特徴とする燃料電池用フィルター。
［２］
　上記活性炭中のアルカリ性物質の濃度が１～１０質量％であり、酸化剤の濃度が１～１０質量％である［１］記載の燃料電池用フィルター。
［３］
　上記酸化剤がハロゲン系酸化剤である［１］又は［２］記載の燃料電池用フィルター。
［４］
　上記ハロゲン系酸化剤がヨウ化カリウムである［３］記載の燃料電池用フィルター。 Accordingly, the present invention provides the following fuel cell filters [1] to [4].
[1]
In the fuel cell filter in which the activated carbon filter layer is disposed on the gas inflow side and the charged filter layer is disposed on the gas exhaust side, the activated carbon of the activated carbon filter layer is attached with an additive containing an alkaline substance and an oxidizing agent. A fuel cell filter characterized by being made.
[2]
The fuel cell filter according to [1], wherein the concentration of the alkaline substance in the activated carbon is 1 to 10% by mass and the concentration of the oxidizing agent is 1 to 10% by mass.
[3]
The fuel cell filter according to [1] or [2], wherein the oxidizing agent is a halogen-based oxidizing agent.
[4]
The fuel cell filter according to [3], wherein the halogen-based oxidizing agent is potassium iodide.
　本発明の燃料電池用フィルターは、化学吸着性能を長時間に亘り良好に維持でき、燃料電池の長寿命化を実現することができる。 The fuel cell filter of the present invention can maintain the chemical adsorption performance well over a long period of time, and can realize a long life of the fuel cell.
燃料電池用フィルターの構造の一例を示す概略断面図である。It is a schematic sectional drawing which shows an example of the structure of the filter for fuel cells. 燃料電池用フィルターの構造の他の例を示す概略断面図である。It is a schematic sectional drawing which shows the other example of the structure of the filter for fuel cells. 第１実施例における二酸化硫黄（ＳＯ2）吸着除去の実験結果を示すグラフである。Is a graph showing experimental results of sulfur dioxide (SO 2) adsorbed and removed in the first embodiment. 第２実施例における二酸化硫黄（ＳＯ2）吸着除去の実験結果を示すグラフである。Is a graph showing experimental results of sulfur dioxide (SO 2) adsorbed and removed in the second embodiment.
　本発明の燃料電池用フィルターは、上記のように、活性炭フィルター層、帯電フィルター層及びウレタンフォーム層（または活性炭収容体）を有し、燃料電池システムの燃料電池スタックに供給される大気を浄化するものである。その具体的構成としては、図１又は図２に示した燃料電池用フィルターが例示される。 The fuel cell filter of the present invention has an activated carbon filter layer, a charged filter layer, and a urethane foam layer (or activated carbon container) as described above, and purifies the air supplied to the fuel cell stack of the fuel cell system. Is. As the specific configuration, the fuel cell filter shown in FIG. 1 or 2 is exemplified.
　図１は、気体の流入側に活性炭フィルター層１、排出側に帯電フィルター層２をそれぞれ配設したものである。図２は、活性炭フィルター層１と帯電フィルター層２との間に、ウレタンフォーム層３を配設したものである。 FIG. 1 shows an activated carbon filter layer 1 on the gas inflow side and a charged filter layer 2 on the discharge side. FIG. 2 shows a urethane foam layer 3 disposed between the activated carbon filter layer 1 and the charged filter layer 2.
　上記活性炭フィルター層１は、大気中に含まれるＳＯX，ＮＯXなどの不純物を吸着除去するものであり、例えば三次元網状構造やハニカム構造のフィルター基材に活性炭が担持されたものや、破砕状又は粒状の活性炭を通気性容器に収容したものなどで形成することができるが、本発明では、三次元網状構造を有するフィルター基材に活性炭を担持させたものが好適に用いられる。 The activated carbon filter layer 1 adsorbs and removes impurities such as SO x and NO x contained in the atmosphere. For example, activated carbon is supported on a filter substrate having a three-dimensional network structure or a honeycomb structure, or is crushed. In the present invention, a filter base material having a three-dimensional network structure on which activated carbon is supported is preferably used.
　この場合、フィルター基材の三次元網状構造体としては、特に制限されるものではないが、ポリウレタンフォームが特に爆破処理等によりセル膜を除去した三次元網状骨格構造を有するポリウレタンフォームが好ましく用いられ、このポリウレタンフォームは低圧力損失で、空気との接触効率が良い。更に、除膜処理を施したポリウレタンフォームとしては、エーテル系素材の方がエステル系素材に比べて耐加水分解性に優れ、後述のアルカリ添着処理等によるフィルター基材の加水分解劣化を抑制することができることから、より好適である。 In this case, the three-dimensional network structure of the filter substrate is not particularly limited, but a polyurethane foam having a three-dimensional network skeleton structure in which the cell membrane is removed by a blast treatment or the like is preferably used. This polyurethane foam has low pressure loss and good contact efficiency with air. Furthermore, for polyurethane foams that have undergone film removal treatment, ether-based materials have better hydrolysis resistance than ester-based materials, and suppress hydrolysis degradation of the filter substrate due to the alkali-adhesion treatment described below. This is more preferable.
　このフィルター基材のポリウレタンフォームの気孔数は、基材に付着させる活性炭粒子との関係で異なるが、通常は、気孔数４～１４個／インチ、特に６～１２個／インチとすることが好ましく、気孔数が４個／インチ未満であるとフィルターの圧力損失は低下するが、通過する気体との接触効率が低下するため不純物の除去性能が低下する場合があり、また気孔数が１４個／インチを超えると気体との接触効率は高くなるが、圧力損失が高くなり、燃料電池システムの空気供給ファンの負荷増大などの不利を生じる場合がある。 The number of pores of the polyurethane foam of the filter base material varies depending on the relationship with the activated carbon particles attached to the base material. However, it is usually preferable that the number of pores is 4 to 14 / inch, particularly 6 to 12 / inch. When the number of pores is less than 4 / inch, the pressure loss of the filter is lowered, but the contact efficiency with the passing gas is lowered, so that the removal performance of impurities may be lowered, and the number of pores is 14 / If it exceeds 1 inch, the contact efficiency with the gas becomes high, but the pressure loss becomes high, which may cause disadvantages such as an increased load of the air supply fan of the fuel cell system.
　このフィルター基材に担持される活性炭としては、例えば椰子殻活性炭、木質活性炭、石油ピッチ系活性炭、石炭系造粒炭、その他の成型活性炭などが例示され、中でも石炭系造粒炭が好ましく用いられる。また、活性炭は特に制限されるものではないが、ＢＥＴ比表面積が５００ｍ2／ｇ以上、特に１０００～２０００ｍ2／ｇ程度のものが好ましい。吸着能を考えると比表面積は大きい程よいが、比表面積を大きくすると吸着体の硬度が下がる傾向にあり、吸着体の種類によっては発塵要因となる可能性がある。更に、上記活性炭フィルター層の活性炭のメッシュは＃２０以上４０以下であることが好適である。その理由は、＃２０以下となると低分子量のガス吸着能力が低くなり、＃４０以上になるとバインダーに活性炭が埋もれてしまい、ＢＥＴ比表面積を十分に確保することができないおそれがあるからである。 Examples of the activated carbon supported on the filter substrate include coconut shell activated carbon, wood activated carbon, petroleum pitch-based activated carbon, coal-based granulated coal, and other molded activated carbon. Among these, coal-based granulated coal is preferably used. . The activated carbon is not particularly limited, but preferably has a BET specific surface area of 500 m 2 / g or more, particularly about 1000 to 2000 m 2 / g. Considering the adsorption capacity, the larger the specific surface area, the better. However, increasing the specific surface area tends to lower the hardness of the adsorbent, which may cause dust generation depending on the type of adsorbent. Furthermore, the activated carbon mesh of the activated carbon filter layer is preferably # 20 or more and 40 or less. The reason for this is that when it is # 20 or less, the gas adsorption capacity of a low molecular weight is lowered, and when it is # 40 or more, activated carbon is buried in the binder, and there is a possibility that a sufficient BET specific surface area cannot be secured.
　本発明では、上記活性炭フィルター層の活性炭には、アルカリ性物質と酸化剤とを含有する添着剤（薬剤）が添着されるものである。前記添着剤にアルカリ性物質を含有させた目的は、起電力低下となる大気中の硫黄系化合物を高効率で除去するためであり、アルカリ性物質の具体例としては、炭酸カリウム、炭酸ナトリウム、水酸化カリウム、水酸化ナトリウム、炭酸マグネシウム、炭酸カルシウム、水酸化マグネシウム、水酸化カルシウムなどの、アルカリ金属の塩、アルカリ金属の水酸化物、アルカリ土類金属の塩、及びアルカリ土類金属の水酸化物よりなる群から選ばれる１種又は２種以上が挙げられる。上記アルカリ性物質の濃度は、特に制限はないが、活性炭に対して、１～１０質量％となるように調整されることが好適である。 In the present invention, the activated carbon of the activated carbon filter layer is attached with an additive (medicine) containing an alkaline substance and an oxidizing agent. The purpose of adding an alkaline substance to the additive is to efficiently remove sulfur-based compounds in the atmosphere that lower the electromotive force. Specific examples of the alkaline substance include potassium carbonate, sodium carbonate, hydroxide Alkali metal salts, alkali metal hydroxides, alkaline earth metal salts, and alkaline earth metal hydroxides such as potassium, sodium hydroxide, magnesium carbonate, calcium carbonate, magnesium hydroxide, and calcium hydroxide 1 type or 2 types or more chosen from the group which consists of are mentioned. The concentration of the alkaline substance is not particularly limited, but is preferably adjusted to 1 to 10% by mass with respect to the activated carbon.
　また、上記添着剤に酸化剤を含有させる目的は、化学吸着性能を長時間に亘り良好に維持するためである。この酸化剤としては、ハロゲン、過マンガン酸塩、過酸化物等が挙げられ、特に、本発明の上記効果をより効果的に発揮し得るためには、ヨウ化カリウム等のハロゲン系酸化剤を採用することが好適である。また、上記酸化剤の濃度は、特に制限はないが、活性炭に対して、１～１０質量％となるように調整されることが好適である。 The purpose of adding an oxidizing agent to the additive is to maintain the chemical adsorption performance well for a long time. Examples of the oxidizing agent include halogens, permanganates, peroxides, and the like. In particular, in order to exhibit the above-described effects of the present invention more effectively, a halogen-based oxidizing agent such as potassium iodide is used. It is preferable to adopt. The concentration of the oxidizing agent is not particularly limited, but is preferably adjusted to 1 to 10% by mass with respect to the activated carbon.
　上記添着剤を添着させた添着活性炭を用いる態様としては、活性炭に予め添着剤を添着して用いるほか、活性炭をフィルター基材に保持させた後、添着剤の添着処理を行っても良い。活性炭への添着剤の添着が過度に多いと、活性炭による吸着性能が損なわれることから、この添着剤の添着量は活性炭に対して２０質量％以下とすることが好ましい。添着剤の添着量が少な過ぎても、アルカリ性物質等を含む添着剤を添着したことによる硫黄化合物の除去性能の向上効果を十分に得ることができない。従って、添着剤は、活性炭の吸着性能の維持と、硫黄化合物の除去性能の確保の面から、０．１～２０質量％、特に５～１０質量％とすることが好ましい。 As an aspect of using the impregnated activated carbon in which the above-mentioned additive is impregnated, the adsorbent may be added to the activated carbon in advance, or the activated carbon may be retained on the filter base material, and then the additive may be subjected to an addition treatment. If the amount of the additive added to the activated carbon is excessively large, the adsorption performance by the activated carbon is impaired. Therefore, the amount of the additive added is preferably 20% by mass or less with respect to the activated carbon. Even if the amount of the additive is too small, the effect of improving the sulfur compound removal performance due to the addition of the additive containing an alkaline substance or the like cannot be obtained sufficiently. Therefore, the additive is preferably 0.1 to 20% by mass, particularly 5 to 10% by mass, from the viewpoint of maintaining the adsorption performance of activated carbon and ensuring the removal performance of sulfur compounds.
　上記帯電フィルター層２は、大気中に含まれる１～２μｍ程度の塵埃を吸着除去するものである。この帯電フィルター層２を形成するフィルターとしては、帯電処理された繊維からなる不織布や織布を用いることができ、特に帯電処理された繊維からなるスパンポンド不織布、メルトブロー不織布、ニードルパンチ加工された不織布、エンボス加工された不織布などが好ましく用いられ、形状もプリーツ形状、ハニカム形状、フラット形状等、種々の形状のものを用いることができる。また、帯電処理された繊維の種類としては、特に制限されるものではないが、ポリプロピレン、ポリエステル、ポリアミド等の有機繊維が好ましく用いられ、中でもポリプロピレンが補修効率の点で特に好ましく用いられる。また、不織布や織布目付としては、特に制限はないが、除塵性能及び流通抵抗の面から１５～５００ｇ／ｍ2、特に５０～２００ｇ／ｍ2であることが好ましい。 The charging filter layer 2 adsorbs and removes dust of about 1 to 2 μm contained in the atmosphere. As the filter for forming the charge filter layer 2, a nonwoven fabric or a woven fabric made of a charged fiber can be used, and in particular, a spun pond nonwoven fabric, a melt blown nonwoven fabric, a needle punched nonwoven fabric made of a charged fiber. Embossed nonwoven fabrics are preferably used, and various shapes such as a pleated shape, a honeycomb shape, and a flat shape can be used. The kind of the fiber subjected to the charging treatment is not particularly limited, but organic fibers such as polypropylene, polyester, and polyamide are preferably used, and polypropylene is particularly preferably used from the viewpoint of repair efficiency. Further, the basis weight of the nonwoven fabric or the woven fabric is not particularly limited, but is preferably 15 to 500 g / m 2 , particularly 50 to 200 g / m 2 in terms of dust removal performance and flow resistance.
　本発明の燃料電池用フィルターは、必要により、図２に示されるように、ウレタンフォーム層３を配設することができる。このウレタンフォーム層３により、活性炭フィルター層１を通過した気体から硫酸アンモニウムなどの目詰まり原因物質を除去し、帯電フィルター層２の目詰まりを防止するものである。 The fuel cell filter of the present invention can be provided with a urethane foam layer 3 as shown in FIG. 2 if necessary. The urethane foam layer 3 removes clogging substances such as ammonium sulfate from the gas that has passed through the activated carbon filter layer 1 to prevent clogging of the charging filter layer 2.
　このウレタンフォーム層３を形成するウレタンフォームとしては、セル膜のない三次元網状骨格を有するポリウレタンフォームが好適に用いられ、特にポリエーテル系のポリウレタンフォームが、湿度の高い環境で使用しても加水分解が生じることなく良好な耐久性を維持し得ることから好ましく用いられる。 As the urethane foam for forming the urethane foam layer 3, a polyurethane foam having a three-dimensional network skeleton without a cell membrane is preferably used. Particularly, a polyether-based polyurethane foam is hydrolyzed even when used in a high humidity environment. It is preferably used because it can maintain good durability without causing decomposition.
　このウレタンフォーム層３を形成するウレタンフォームは、特に制限されるものではないが、気孔数が３０～６０個／インチ、特に４０～５０個／インチであることが好ましく、気孔数が３０個／インチ未満では十分に硫酸アンモニウムを捕集できない場合があり、一方６０個／インチを超えるとウレタンフォーム層３自体に目詰まりが発生する不都合を生じる場合がある。 The urethane foam for forming the urethane foam layer 3 is not particularly limited, but preferably has a pore number of 30 to 60 / inch, particularly 40 to 50 / inch, and has a pore number of 30 / If it is less than inches, ammonium sulfate may not be sufficiently collected. On the other hand, if it exceeds 60 inches / inch, there may be a problem that the urethane foam layer 3 itself is clogged.
　このウレタンフォーム層３は、シート状又はブロック状に形成された上記ポリウレタンフォームを複数枚又は複数個積層して形成することができ、その枚数を増減して吸着能力や通気性、寿命などを調整することができる。なお、上記活性炭フィルター層１及び帯電フィルター層２も同様に、複数枚又は複数個のフィルターを積層して形成すると共に、その枚数又は個数を増減して同様の調整を行なうことができる。 This urethane foam layer 3 can be formed by laminating or laminating a plurality of the above polyurethane foams formed in a sheet shape or block shape, and the number of the polyurethane foam layers can be increased or decreased to adjust the adsorption capacity, air permeability, life, etc. can do. Similarly, the activated carbon filter layer 1 and the charge filter layer 2 may be formed by laminating a plurality of filters or a plurality of filters, and the same adjustment may be performed by increasing or decreasing the number or the number of the filters.
　また、本発明では、活性炭フィルター層１と帯電フィルター層２との間に、上記ウレタンフォーム層３に代えて、特定の活性炭を充填した活性炭収容体３’を配設することもできる。この活性炭収容体３’に充填された活性炭により、活性炭フィルター層１を通過した気体から大気中に含まれるシロキサンガスを確実に吸着・除去できるものである。 In the present invention, an activated carbon container 3 ′ filled with specific activated carbon can be disposed between the activated carbon filter layer 1 and the charged filter layer 2 instead of the urethane foam layer 3. The activated carbon filled in the activated carbon container 3 ′ can reliably adsorb and remove siloxane gas contained in the atmosphere from the gas that has passed through the activated carbon filter layer 1.
　上記の活性炭収容体３’において、使用される活性炭については、例えば椰子殻活性炭、木質活性炭、石油ピッチ系活性炭、石炭系造粒炭、その他の成型活性炭などが例示され、中でも石炭系造粒炭が好ましく用いられる。また、上記の活性炭のＢＥＴ比表面積としては、シロキサンガスを効果的に吸着させるためには、５００～２０００ｍ2／ｇ、特に、１０００～１５００ｍ2／ｇ程度のものを使用することが好適である。 Examples of the activated carbon used in the activated carbon container 3 ′ include coconut shell activated carbon, wood activated carbon, petroleum pitch-based activated carbon, coal-based granulated coal, and other molded activated carbon. Is preferably used. In addition, as the BET specific surface area of the above activated carbon, in order to effectively adsorb the siloxane gas, it is preferable to use one having about 500 to 2000 m 2 / g, particularly about 1000 to 1500 m 2 / g. .
　また、上記の活性炭収容体３’に使用される活性炭のメッシュは上記活性炭フィルター層に使用される活性炭よりもメッシュ粗いものであり、具体的には、メッシュが＃６以上２０未満であることが好適であり、より好ましくは、メッシュが＃８以上１５以下未満である。上記の活性炭のメッシュの範囲を逸脱すると、シロキサンガスを確実に吸着・除去することができず、すぐに飽和状態になり排出側にシロキサンガスが流れてしまうおそれがある。 The activated carbon mesh used for the activated carbon container 3 ′ is coarser than the activated carbon used for the activated carbon filter layer. Specifically, the mesh may be # 6 or more and less than 20. More preferably, the mesh is not less than # 8 and less than 15 inclusive. If it deviates from the range of the mesh of the activated carbon, the siloxane gas cannot be reliably adsorbed and removed, so that it may become saturated immediately and the siloxane gas may flow to the discharge side.
　上記活性炭収容体３’の容積は、特に制限はないが、本発明の目的であるシロキサンガスの吸着・除去効果をより確実なものにするためには、活性炭収容体３’の占有容積が、活性炭フィルター層１、帯電フィルター層２及び活性炭収容体３’からなるフィルター全体の容積の１／５～１／１５とし、より好ましくは、１／１２～１／１４とすることが望ましい。 The volume of the activated carbon container 3 ′ is not particularly limited. However, in order to ensure the adsorption / removal effect of the siloxane gas which is the object of the present invention, the occupied volume of the activated carbon container 3 ′ is: It is desirable that the volume of the entire filter including the activated carbon filter layer 1, the charging filter layer 2, and the activated carbon container 3 ′ is 1/5 to 1/15, more preferably 1/12 to 1/14.
　また、本発明の目的及び効果は、大気中のシロキサンガスを確実に除去するほか、不純物ガス（ＳＯX，ＮＯXなど）及び塵埃を除去することにより燃料電池の性能低下や寿命低下の発生をより効果的に防止し得るものである。このため、活性炭フィルター層１／帯電フィルター層２／活性炭収容体３’の容積比は、５～１５／０．５～５／０．５～１０、より好ましくは、９～１１／０．５～２／１～３である。 The objects and advantages of the present invention, in addition to reliably remove the siloxane gases in the atmosphere, the impurity gases (SO X, NO X, etc.) the occurrence of performance degradation or reduction of the service life of the fuel cell by removing and dust This can be prevented more effectively. Therefore, the volume ratio of the activated carbon filter layer 1 / charged filter layer 2 / active carbon container 3 ′ is 5 to 15 / 0.5 to 5 / 0.5 to 10, more preferably 9 to 11 / 0.5. ~ 2/1 ~ 3.
　本発明の燃料電池用フィルターは、燃料電池システムの燃料電池スタックに取り付けて供給される大気を浄化するものであるが、その燃料電池システムには特に制限はなく、固体高分子型燃料電池、アルカリ水溶液電解質型燃料電池、リン酸水溶液電解質型燃料電池、溶融炭酸塩電解質型燃料電池、固体酸化物電解質型燃料電池などのいずれのものであっても良い。この燃料電池は静置型であっても良く、車両搭載用などの可搬型のものであっても良い。 The fuel cell filter of the present invention purifies the air supplied by being attached to the fuel cell stack of the fuel cell system, but there is no particular limitation on the fuel cell system, and the polymer electrolyte fuel cell, alkaline Any one of an aqueous electrolyte fuel cell, a phosphoric acid aqueous electrolyte fuel cell, a molten carbonate electrolyte fuel cell, a solid oxide electrolyte fuel cell and the like may be used. This fuel cell may be a stationary type or a portable type for mounting on a vehicle.
　以下、実施例，比較例を示し、本発明をより具体的に説明する。なお、本発明は下記実施例に制限されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. In addition, this invention is not restrict | limited to the following Example.
［実施例１，比較例１］
　下記フィルター材をそれぞれ用いて、薬剤が添着された活性炭フィルター層１、帯電フィルター層２及びウレタンフォーム層３を形成して、図２に示した構造の燃料電池用フィルターを作製した。この場合、帯電フィルター層２は下記帯電フィルター材を２４枚積層して形成し、活性炭フィルター層１は下記活性炭フィルター材を２４枚積層して形成し、ウレタンフォーム層３は下記ウレタンフォーム材料を４枚積層して形成した。 [Example 1, Comparative Example 1]
Each of the following filter materials was used to form an activated carbon filter layer 1, a charged filter layer 2 and a urethane foam layer 3 to which a chemical was attached, thereby producing a fuel cell filter having the structure shown in FIG. In this case, the charging filter layer 2 is formed by laminating 24 sheets of the following charging filter materials, the activated carbon filter layer 1 is formed by laminating 24 sheets of the following activated carbon filter materials, and the urethane foam layer 3 is composed of 4 of the following urethane foam materials. It was formed by laminating.
［活性炭フィルター層１の材料］
　セル膜のない三次元網状骨格を有するポリウレタンフォーム（気孔数１０個／インチ、厚さ５ｍｍ）の骨格に６０メッシュの椰子殻活性炭を付着量３００ｇ／ｍ2となるように固着させたもの（（株）ブリヂストン製、ＤＥＯフィルター「ＯＱ－１０Ｋ」）。サイズはφ６０ｍｍ、厚さ５ｍｍ
　実施例１は、活性炭に対して、濃度３質量％炭酸カリウム，濃度２質量％ヨウ化カリウムとなる薬剤（添着剤）を用いる。
　比較例１は、活性炭に対して、濃度６質量％炭酸カリウムとなる薬剤（添着剤）を用いる。
［帯電フィルター層２の材料］
　φ６４．３ｍｍ、厚さ０．５ｍｍのポリプロピレン系エレクトレット不織布（東レファインケミカル（株）「ＳＢ０５０Ｎ」）
［ウレタンフォーム層３の材料］
　セル膜のない三次元網状骨格を有するポリエーテル系ポリウレタンフォーム（気孔数５０個／インチ）（（株）ブリヂストン製、ＳＦフィルター「ＱＯＫ－５０」）。サイズはφ６３．６ｍｍ、厚さ５ｍｍ。 [Material of activated carbon filter layer 1]
A polyurethane foam having a three-dimensional network skeleton without cell membrane (10 pores / inch, 5 mm in thickness) fixed with 60 mesh coconut shell activated carbon to an adhesion amount of 300 g / m 2 (( DEO filter “OQ-10K” manufactured by Bridgestone Corporation). Size is φ60mm, thickness 5mm
Example 1 uses an agent (additive) that has a concentration of 3% by mass of potassium carbonate and a concentration of 2% by mass of potassium iodide with respect to the activated carbon.
In Comparative Example 1, a chemical agent (additive) having a concentration of 6% by mass potassium carbonate is used with respect to activated carbon.
[Material of Charged Filter Layer 2]
Polypropylene electret nonwoven fabric with a diameter of 64.3 mm and a thickness of 0.5 mm (Toray Fine Chemicals Co., Ltd. “SB050N”)
[Material of urethane foam layer 3]
Polyether polyurethane foam having a three-dimensional network skeleton without cell membrane (50 pores / inch) (manufactured by Bridgestone Corporation, SF filter “QOK-50”). The size is φ63.6mm, thickness 5mm.
［二酸化硫黄（ＳＯ2）吸着性能試験］
　上記により得られた実施例１，比較例１の燃料電池用フィルターについて、下記の（Ｉ），（ＩＩ）の２種類のエアー条件により、大気をフィルターの上流側から導入し、通過させ、帯電フィルター層が近傍に位置する気体の排出側のＳＯ2の濃度から二酸化硫黄（ＳＯ2）除去率を計算した。その結果を下記の表１及び図３に示す。
・吸着測定機：ガステック社製校正ガス調製装置「パーミエーター」
　条件：流量１Ｌ／ｍｉｎ、ＳＯ2濃度１０～２０ｐｐｍ
　（Ｉ）　チッ素（Ｎ2）１００％・相対湿度０％（ドライ条件）
　（ＩＩ）　大気・相対湿度３０～５０％（実際の使用条件） [Sulfur dioxide (SO 2 ) adsorption performance test]
For the fuel cell filters of Example 1 and Comparative Example 1 obtained as described above, the atmosphere was introduced from the upstream side of the filter under the following two types of air conditions (I) and (II), passed through, and charged. The sulfur dioxide (SO 2 ) removal rate was calculated from the SO 2 concentration on the gas discharge side where the filter layer was located in the vicinity. The results are shown in Table 1 below and FIG.
・ Adsorption measuring device: Gas Tech's calibration gas preparation device "Permeator"
Conditions: Flow rate 1L / min, SO 2 concentration 10 ~ 20ppm
(I) Nitrogen (N 2 ) 100%, relative humidity 0% (dry conditions)
(II) Air / relative humidity 30-50% (actual usage conditions)
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１及び図３の測定結果から、実施例１の燃料電池用フィルターは、比較例１（従来品）のものに比べると、大気中に含まれるＳＯ2の吸着除去率を約１．５～２倍以上と長期間に亘り良好に維持できることが分かる。
　特に、エアー条件が、相対湿度３０～５０％の場合には、ＳＯ2の除去時間が２倍以上となり、寿命効果がより大きくなる。 From the measurement results in Table 1 and FIG. 3, the fuel cell filter of Example 1 has an adsorption removal rate of SO 2 contained in the atmosphere of about 1.5 to about 1 to that of Comparative Example 1 (conventional product). It can be seen that it can be satisfactorily maintained over a long period of time, twice or more.
In particular, when the air condition is a relative humidity of 30 to 50%, the SO 2 removal time is doubled or more, and the life effect is further increased.
［実施例２，比較例２］
　下記フィルター材をそれぞれ用いて、薬剤が添着された活性炭フィルター層１、帯電フィルター層２及びウレタンフォーム層３を形成して、図２に示した構造の燃料電池用フィルターを作製した。この場合、帯電フィルター層２は下記帯電フィルター材を２４枚積層して形成し、活性炭フィルター層１は下記活性炭フィルター材を１４枚積層して形成し、ウレタンフォーム層３は下記ウレタンフォーム材料を４枚積層して形成した。 [Example 2, Comparative Example 2]
Each of the following filter materials was used to form an activated carbon filter layer 1, a charged filter layer 2 and a urethane foam layer 3 to which a chemical was attached, thereby producing a fuel cell filter having the structure shown in FIG. In this case, the charging filter layer 2 is formed by laminating 24 sheets of the following charging filter materials, the activated carbon filter layer 1 is formed by laminating 14 sheets of the following activated carbon filter materials, and the urethane foam layer 3 is composed of 4 of the following urethane foam materials. It was formed by laminating.
［活性炭フィルター層１の材料］
　セル膜のない三次元網状骨格を有するポリウレタンフォーム（気孔数１０個／インチ、厚さ５ｍｍ）の骨格に６０メッシュの椰子殻活性炭を付着量３００ｇ／ｍ2となるように固着させたもの（（株）ブリヂストン製、ＤＥＯフィルター「ＯＱ－１０Ｋ」）。サイズはφ１４ｍｍ、厚さ５ｍｍ
　実施例２は、活性炭に対して、濃度３質量％炭酸カリウム，濃度２質量％ヨウ化カリウムとなる薬剤（添着剤）を用いる。
　比較例２は、活性炭に対して、濃度６質量％炭酸カリウムとなる薬剤（添着剤）を用いる。
［帯電フィルター層２の材料］
　φ１４．３ｍｍ、厚さ０．５ｍｍのポリプロピレン系エレクトレット不織布（東レファインケミカル（株）「ＳＢ０５０Ｎ」）
［ウレタンフォーム層３の材料］
　セル膜のない三次元網状骨格を有するポリエーテル系ポリウレタンフォーム（気孔数５０個／インチ）（（株）ブリヂストン製、ＳＦフィルター「ＱＯＫ－５０」）。サイズはφ１４．６ｍｍ、厚さ５ｍｍ。 [Material of activated carbon filter layer 1]
A polyurethane foam having a three-dimensional network skeleton without cell membrane (10 pores / inch, 5 mm in thickness) fixed with 60 mesh coconut shell activated carbon to an adhesion amount of 300 g / m 2 (( DEO filter “OQ-10K” manufactured by Bridgestone Corporation). Size is φ14mm, thickness 5mm
Example 2 uses a chemical agent (additive) having a concentration of 3 mass% potassium carbonate and a concentration of 2 mass% potassium iodide with respect to the activated carbon.
In Comparative Example 2, a chemical agent (additive) having a concentration of 6% by mass potassium carbonate is used with respect to the activated carbon.
[Material of Charged Filter Layer 2]
φ14.3mm, 0.5mm thick polypropylene electret non-woven fabric (Toray Fine Chemicals Co., Ltd. “SB050N”)
[Material of urethane foam layer 3]
Polyether polyurethane foam having a three-dimensional network skeleton without cell membrane (50 pores / inch) (manufactured by Bridgestone Corporation, SF filter “QOK-50”). The size is φ14.6mm, thickness 5mm.
［二酸化硫黄（ＳＯ2）吸着性能試験］
　上記により得られた実施例２，比較例２の燃料電池用フィルターについては、上記実施例１と同様に、ガステック社製校正ガス調製装置「パーミエーター」を使用し、下記のエアー条件により、大気をフィルターの上流側から導入し、通過させ、帯電フィルター層が近傍に位置する気体の排出側のＳＯ2の濃度から二酸化硫黄（ＳＯ2）除去率を計算した。その結果を図４のグラフに示す。 [Sulfur dioxide (SO 2 ) adsorption performance test]
About the fuel cell filter of Example 2 and Comparative Example 2 obtained as described above, in the same manner as in Example 1 above, using a calibration gas preparation device "Permeator" manufactured by GASTEC, under the following air conditions, Air was introduced from the upstream side of the filter and allowed to pass through, and the sulfur dioxide (SO 2 ) removal rate was calculated from the SO 2 concentration on the gas discharge side where the charged filter layer was located nearby. The result is shown in the graph of FIG.
　〔エアー条件〕
・ＳＯ2濃度　・・・　５００ｐｐｂ
・ガス　・・・　チッ素（Ｎ2）ガス
・流量　・・・　１Ｌ／ｍｉｎ
・空間速度　・・・　５６００ｈｒ-1 [Air condition]
・ SO 2 concentration ・ ・ ・ 500ppb
· Gas ··· Nitrogen (N 2 ) gas · Flow rate ··· 1 L / min
・ Space velocity: 5600hr -1
　図４に示されるように、二酸化硫黄（ＳＯ2）の吸着率を９９％以上維持することができる時間について、実施例２では「１３５０時間」、比較例１（従来品）では「４２０時間」となった。この実験結果から、実施例２は、比較例２（従来品）と比べると、ＳＯ2吸着除去率を約３倍以上と長期間に亘り良好に維持できることが分かる。 As shown in FIG. 4, regarding the time during which the adsorption rate of sulfur dioxide (SO 2 ) can be maintained at 99% or more, “1350 hours” in Example 2 and “420 hours” in Comparative Example 1 (conventional product). It became. From this experimental result, it can be seen that Example 2 can maintain the SO 2 adsorption removal rate well over a long period of about three times or more compared with Comparative Example 2 (conventional product).
１　活性炭フィルター層
２　帯電フィルター層
３　ウレタンフォーム層 1 Activated carbon filter layer 2 Charged filter layer 3 Urethane foam layer

Claims (4)

  1. 　気体の流入側に活性炭フィルター層、気体の排出側に帯電フィルター層が配設された燃料電池用フィルターにおいて、上記活性炭フィルター層の活性炭には、アルカリ性物質と酸化剤とを含有する添着剤が添着されてなることを特徴とする燃料電池用フィルター。 In the fuel cell filter in which the activated carbon filter layer is disposed on the gas inflow side and the charged filter layer is disposed on the gas exhaust side, the activated carbon of the activated carbon filter layer is attached with an additive containing an alkaline substance and an oxidizing agent. A fuel cell filter characterized by being made.
  2. 　上記活性炭中のアルカリ性物質の濃度が１～１０質量％であり、酸化剤の濃度が１～１０質量％である請求項１記載の燃料電池用フィルター。 The fuel cell filter according to claim 1, wherein the concentration of the alkaline substance in the activated carbon is 1 to 10% by mass and the concentration of the oxidizing agent is 1 to 10% by mass.
  3. 　上記酸化剤がハロゲン系酸化剤である請求項１又は２記載の燃料電池用フィルター。 The fuel cell filter according to claim 1 or 2, wherein the oxidizing agent is a halogen-based oxidizing agent.
  4. 　上記ハロゲン系酸化剤がヨウ化カリウムである請求項３記載の燃料電池用フィルター。 The fuel cell filter according to claim 3, wherein the halogen-based oxidizing agent is potassium iodide.
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CN110026052A (en) * 2019-05-13 2019-07-19 江苏优冠汽车配件有限公司 Hydrogen energy source fuel cell chemical filter
CN114725454A (en) * 2022-04-06 2022-07-08 山东工业陶瓷研究设计院有限公司 SOFC (solid oxide Fuel cell) and preparation method thereof
WO2024052574A1 (en) * 2022-09-09 2024-03-14 Bayerische Motoren Werke Aktiengesellschaft Means of transportation and method for determining a state of an air filter of a fuel cell system

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JPH02139035A (en) * 1988-08-17 1990-05-29 Hitachi Plant Eng & Constr Co Ltd Air purification agent
JPH0938605A (en) * 1995-07-27 1997-02-10 Toshiba Eng & Constr Co Ltd Method for rinsing and drying substrate and device therefor
JP2003297410A (en) * 2002-04-05 2003-10-17 Bridgestone Corp Fluid purifier for fuel cell
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JP2013251116A (en) * 2012-05-31 2013-12-12 Bridgestone Corp Fuel cell filter

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JPH02139035A (en) * 1988-08-17 1990-05-29 Hitachi Plant Eng & Constr Co Ltd Air purification agent
JPH0938605A (en) * 1995-07-27 1997-02-10 Toshiba Eng & Constr Co Ltd Method for rinsing and drying substrate and device therefor
JP2003297410A (en) * 2002-04-05 2003-10-17 Bridgestone Corp Fluid purifier for fuel cell
WO2005062411A1 (en) * 2003-12-24 2005-07-07 Bridgestone Corporation Method and apparatus for purifying air for fuel cell and fuel cell
JP2013251116A (en) * 2012-05-31 2013-12-12 Bridgestone Corp Fuel cell filter

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110026052A (en) * 2019-05-13 2019-07-19 江苏优冠汽车配件有限公司 Hydrogen energy source fuel cell chemical filter
CN114725454A (en) * 2022-04-06 2022-07-08 山东工业陶瓷研究设计院有限公司 SOFC (solid oxide Fuel cell) and preparation method thereof
WO2024052574A1 (en) * 2022-09-09 2024-03-14 Bayerische Motoren Werke Aktiengesellschaft Means of transportation and method for determining a state of an air filter of a fuel cell system

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