JP2001286753A - Adsorbent for sulfur compound in fuel gas and method for removing the same - Google Patents
Adsorbent for sulfur compound in fuel gas and method for removing the sameInfo
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- JP2001286753A JP2001286753A JP2000232780A JP2000232780A JP2001286753A JP 2001286753 A JP2001286753 A JP 2001286753A JP 2000232780 A JP2000232780 A JP 2000232780A JP 2000232780 A JP2000232780 A JP 2000232780A JP 2001286753 A JP2001286753 A JP 2001286753A
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- Prior art keywords
- fuel gas
- adsorbent
- sulfur compound
- gas
- sulfur
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- Separation Of Gases By Adsorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、都市ガスやＬＰガ
スなどの燃料ガス中の硫黄化合物の吸着除去に用いる硫
黄化合物除去用吸着剤、及び、該硫黄化合物除去用吸着
剤による硫黄化合物含有燃料ガス中の硫黄化合物の除去
方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sulfur compound-removing adsorbent used for adsorbing and removing sulfur compounds in fuel gas such as city gas and LP gas, and a sulfur compound-containing fuel by the sulfur compound-removing adsorbent. The present invention relates to a method for removing a sulfur compound in a gas.
【０００２】[0002]
【従来の技術】メタン、エタン、エチレン、プロパン、
ブタン等の低級炭化水素ガス、あるいはこれらを含む天
然ガス、都市ガス、ＬＰガス等のガスは、工業用や家庭
用などの燃料として用いられるほか、燃料電池用燃料や
雰囲気ガスなどとして利用される水素の製造用原料とし
ても使用される。水素の工業的製造方法の一つである水
蒸気改質法では、それらの低級炭化水素ガスを、Ｎｉ
系、Ｒｕ系等の触媒の存在下、水蒸気を加えて改質し、
水素を主成分とする改質ガスが生成される。2. Description of the Related Art Methane, ethane, ethylene, propane,
Gases such as butane and other low-grade hydrocarbon gases, or natural gas, city gas, and LP gas containing them, are used as fuels for industrial and domestic uses, as well as fuels for fuel cells and atmosphere gases. It is also used as a raw material for producing hydrogen. In the steam reforming method, which is one of the industrial methods for producing hydrogen, the lower hydrocarbon gas is converted to Ni
System, reforming by adding steam in the presence of a catalyst such as Ru system,
A reformed gas containing hydrogen as a main component is generated.
【０００３】都市ガスやＬＰガス等の燃料ガスには漏洩
保安を目的とする付臭剤として、サルファイド類やチオ
フェン類、あるいはメルカプタン類などの硫黄化合物が
含まれている。具体的には、サルファイド類としてジメ
チルサルファイド（本明細書中ＤＭＳと略称する）やエ
チルメチルサルファイドやジエチルサルファイド、チオ
フェン類としてテトラヒドロチオフェン（同じくＴＨＴ
と略称する）、メルカプタン類としてターシャリーブチ
ルメルカプタン（同じくＴＢＭと略称する）やイソプロ
ピルメルカプタンやノルマルプロピルメルカプタンやタ
ーシャリーアミルメルカプタンやターシャリーヘプチル
メルカプタンやメチルメルカプタンやエチルメルカプタ
ンなどである。[0003] Fuel gases such as city gas and LP gas contain sulfur compounds such as sulfides, thiophenes, and mercaptans as odorants for the purpose of leak protection. More specifically, sulfides such as dimethyl sulfide (abbreviated as DMS in the present specification), ethyl methyl sulfide and diethyl sulfide, and thiophenes such as tetrahydrothiophene (also THT)
Tertiary butyl mercaptan (also abbreviated as TBM), isopropyl mercaptan, normal propyl mercaptan, tertiary amyl mercaptan, tertiary heptyl mercaptan, methyl mercaptan, ethyl mercaptan, and the like.
【０００４】一般に添加される付臭剤としてはＤＭＳ、
ＴＨＴ及びＴＢＭが多く用いられ、その濃度はいずれも
数ｐｐｍである。とりわけ、都市ガスにおいてはＤＭＳ
及びＴＢＭの両方を用いるケースがほとんどである。上
記のように水蒸気改質法で用いられる触媒は、これらの
硫黄化合物により被毒し、性能劣化を来たしてしまう。
このため燃料ガス中のそれらの硫黄化合物は、燃料ガス
から予め除去しておく必要がある。また、硫黄化合物を
除去した燃料ガス中に、たとえ残留硫黄化合物が少量含
まれていても、その残留硫黄化合物の量はできるだけ低
濃度であることが望ましい。[0004] Commonly added odorants are DMS,
THT and TBM are often used, and their concentrations are several ppm. Especially in city gas, DMS
In most cases, both TBM and TBM are used. As described above, the catalyst used in the steam reforming method is poisoned by these sulfur compounds, resulting in performance deterioration.
For this reason, those sulfur compounds in the fuel gas need to be removed from the fuel gas in advance. Further, even if a small amount of the residual sulfur compound is contained in the fuel gas from which the sulfur compound has been removed, it is desirable that the amount of the residual sulfur compound be as low as possible.
【０００５】従来、燃料ガスに含まれる硫黄化合物の除
去方法としては、水添脱硫法や吸着剤による方法が知ら
れている。水添脱硫法は、燃料ガスに水素を添加し、Ｃ
ｏーＭｏ系触媒等の触媒の存在下、硫黄化合物を硫化水
素に分解させ、分解生成物である硫化水素を酸化亜鉛、
酸化鉄等の脱硫剤に吸着させて脱硫する方法であり、こ
の場合水素の添加や加熱が必要である。一方、吸着剤に
よる方法は、活性炭、金属酸化物、あるいはゼオライト
等を主成分とする吸着剤に燃料ガスを通過させることに
より、硫黄化合物を吸着させて除去する方法である。こ
の吸着剤による方法では、加熱することで、吸着能力を
増加させる方法もあるが、常温で吸着させる方がシステ
ムがより簡易になるので望ましい。Conventionally, as a method for removing a sulfur compound contained in a fuel gas, a hydrodesulfurization method and a method using an adsorbent are known. In the hydrodesulfurization method, hydrogen is added to fuel gas, and C
In the presence of a catalyst such as an o-Mo catalyst, a sulfur compound is decomposed into hydrogen sulfide, and hydrogen sulfide as a decomposition product is converted into zinc oxide,
This is a method of desulfurization by adsorption to a desulfurizing agent such as iron oxide. In this case, addition of hydrogen and heating are required. On the other hand, the method using an adsorbent is a method in which a sulfur gas is adsorbed and removed by passing a fuel gas through an adsorbent mainly composed of activated carbon, metal oxide, zeolite, or the like. In the method using the adsorbent, there is a method of increasing the adsorption capacity by heating, but it is preferable to perform adsorption at room temperature because the system becomes simpler.
【０００６】吸着剤を用いて常温で硫黄化合物を除去す
る方法は、水添脱硫法や加熱吸着法のように熱や水素等
を必要としないため簡易な脱硫方法である。しかし、吸
着剤がこれに吸着された硫黄化合物で飽和してしまうと
ガス中の硫黄化合物を除去することができなくなるの
で、再生や交換が必要である。したがって、吸着剤の吸
着能力の大小により吸着剤の必要量、交換頻度が大きく
左右されることになるため、より高い吸着能力を有する
吸着剤が望まれる。吸着剤の場合、その性能は、特に硫
黄化合物の性質に左右される。付臭剤として使用される
ケースが多いＤＭＳ、ＴＢＭでは、特にＤＭＳがより吸
着され難いため破過が早い。このためＤＭＳの吸着量を
増加させることが重要となってくる。[0006] The method of removing sulfur compounds at room temperature using an adsorbent is a simple desulfurization method which does not require heat, hydrogen or the like unlike the hydrodesulfurization method and the heat adsorption method. However, if the adsorbent is saturated with the sulfur compound adsorbed by the adsorbent, the sulfur compound in the gas cannot be removed, so that regeneration or replacement is required. Therefore, the required amount of the adsorbent and the frequency of replacement are greatly influenced by the magnitude of the adsorbing capacity of the adsorbent. Therefore, an adsorbent having a higher adsorbing capacity is desired. In the case of an adsorbent, its performance depends in particular on the nature of the sulfur compound. DMS and TBM, which are often used as odorants, break down quickly because DMS is particularly difficult to be adsorbed. Therefore, it is important to increase the amount of DMS adsorbed.
【０００７】これまでガス中の硫黄化合物の吸着剤とし
ては各種吸着剤が提案されている。例えば特開平６ー３
０６３７７号では、都市ガス、ＬＰガス等の燃料ガスの
付臭成分であるメルカプタン類を無酸素雰囲気下、選択
的に、水素及び／又はアルカリ土類金属以外の多価金属
イオン交換ゼオライトにより除去するというもので、こ
こでの多価金属イオンとしてはＭｎ、Ｆｅ、Ｃｏ、Ｎ
ｉ、Ｃｕ、Ｓｎ、Ｚｎが好ましいとされている。この技
術での吸着対象硫黄化合物は吸着の容易なメルカプタン
類だけであり、その吸着能の確認は、その実施例に記載
のとおり、上記ゼオライトを入れたサンプリングバッグ
に３５０ｐｐｍのＴＢＭ（都市ガスバランス）を導入す
ることで行われている。Various adsorbents have been proposed as adsorbents for sulfur compounds in gas. For example, JP-A-6-3
No. 06377, mercaptans, which are odorous components of fuel gas such as city gas and LP gas, are selectively removed by a polyvalent metal ion-exchanged zeolite other than hydrogen and / or alkaline earth metal under an oxygen-free atmosphere. Thus, the polyvalent metal ions here are Mn, Fe, Co, N
i, Cu, Sn and Zn are preferred. Sulfur compounds to be adsorbed by this technique are only mercaptans which can be easily adsorbed, and the adsorption ability thereof is confirmed by the sampling bag containing zeolite having 350 ppm TBM (city gas balance) as described in the example. It is done by introducing.
【０００８】本発明者等は、ゼオライト、活性炭、金属
化合物、活性アルミナ、シリカゲル、活性白土、粘土系
鉱物等の各種多孔質物質、各種金属酸化物など、市販の
数多くの吸着剤を用いて、燃料ガス中の硫黄化合物を除
去する実験を実施した。このうち、一部は表２に示して
いる。その結果、それらのうち特定の活性炭、特定の金
属酸化物（特公平５ー５８７６８号）、特定のゼオライ
ト（特開平１０ー２３７４７３号）だけが燃料ガス中の
硫黄化合物の吸着に有効であることを確認することがで
きた。[0008] The present inventors have made use of a number of commercially available adsorbents such as various porous substances such as zeolite, activated carbon, metal compounds, activated alumina, silica gel, activated clay, clay minerals, and various metal oxides. An experiment was conducted to remove sulfur compounds in the fuel gas. Some of them are shown in Table 2. As a result, only specific activated carbon, specific metal oxides (Japanese Patent Publication No. 5-58768), and specific zeolites (Japanese Patent Application Laid-Open No. Hei 10-237473) are effective in adsorbing sulfur compounds in fuel gas. Could be confirmed.
【０００９】ところで、燃料ガス中には、その製造過程
あるいは供給過程において、微量の水分が含まれている
ケースがある。特に、ゼオライトにより水分を含有した
燃料ガスを処理した場合、水分を選択的に吸着してしま
い、水分が含まれていないか、あるいはそれが極微量で
ある場合に比べ、硫黄化合物の吸着性能が大幅に低下し
てしまう。この理由は、吸湿剤としても利用されている
ゼオライトはそれ自身が親水性であり、極性分子である
水分を優先的に吸着するためであると推認される。この
ことからしても、硫黄化合物除去用の吸着剤は、燃料ガ
ス中の硫黄化合物のみを選択的に吸着する必要があり、
燃料ガス中の水分の有無に関わらず硫黄化合物を吸着す
る選択性が必要であるが、従来技術の吸着剤において
は、上記公報の吸着剤を含め、この点に関して何も配慮
されていない。In some cases, a trace amount of water is contained in the fuel gas during its production or supply process. In particular, when a fuel gas containing water is treated with zeolite, water is selectively adsorbed, and the adsorption performance of sulfur compounds is lower than when water is not contained or the amount is very small. It will drop significantly. This is presumed to be because zeolite, which is also used as a hygroscopic agent, is itself hydrophilic and preferentially adsorbs water, which is a polar molecule. Even from this, the adsorbent for removing sulfur compounds needs to selectively adsorb only sulfur compounds in the fuel gas,
Selectivity for adsorbing sulfur compounds is required regardless of the presence or absence of moisture in the fuel gas, but no consideration is given to this point in the prior art adsorbents, including the adsorbents described in the above publications.
【００１０】前述のとおり、硫黄化合物を除去した燃料
ガス中に含まれる残留硫黄化合物濃度は、燃料ガスを水
蒸気改質などに使用する場合、出来るだけ低濃度である
ことが望ましい。これは、水蒸気改質触媒が硫黄により
被毒されるのを防ぐためである。これまで、ガス中の硫
黄化合物を極低濃度まで除去する吸着剤として銅系吸着
剤（特開平６ー２５６７７９号）が報告されている。し
かしながら、この吸着剤は、その性能を満足させるため
には、２００〜２５０℃の加熱が必要である。これま
で、常温付近においてガス中の硫黄化合物を極低濃度ま
で除去する吸着剤は報告されていない。As described above, the concentration of the residual sulfur compound contained in the fuel gas from which the sulfur compound has been removed is desirably as low as possible when the fuel gas is used for steam reforming or the like. This is to prevent the steam reforming catalyst from being poisoned by sulfur. A copper-based adsorbent (JP-A-6-256779) has been reported as an adsorbent for removing sulfur compounds in a gas to an extremely low concentration. However, this adsorbent requires heating at 200 to 250 ° C. to satisfy its performance. So far, no adsorbent has been reported that removes sulfur compounds in a gas to an extremely low concentration at around normal temperature.
【００１１】そこで、本発明者等は、このような観点か
ら、燃料ガス中に水分が含まれていてもなお有効に機能
する吸着剤について追求し、ゼオライトのうちでも特に
疎水性ゼオライトに着目して各種検討、実験を続けたと
ころ、疎水性ゼオライトを用い、且つ、これに特定の遷
移金属をイオン交換により担持させてなる吸着剤が、燃
料ガス中に水分が含まれていても、有効な硫黄化合物の
吸着性能を有することを見い出し、本発明に到達するに
至ったものである。In view of the above, the present inventors have pursued an adsorbent which functions effectively even when fuel gas contains moisture, and pay particular attention to hydrophobic zeolites among zeolites. As a result of various studies and experiments, the adsorbent using hydrophobic zeolite and carrying a specific transition metal by ion exchange was effective even if the fuel gas contained moisture. The inventors have found that they have the ability to adsorb sulfur compounds, and have reached the present invention.
【００１２】[0012]
【発明が解決しようとする課題】本発明は、疎水性ゼオ
ライトに対して特定の遷移金属をイオン交換により担持
させることにより、燃料ガス中の水分濃度に関わらず、
硫黄化合物除去用として有効に機能する硫黄化合物除去
用吸着剤を提供することを目的とし、また本発明は、該
硫黄化合物除去用吸着剤による硫黄化合物含有燃料ガス
中の硫黄化合物の除去方法を提供することを目的とす
る。SUMMARY OF THE INVENTION The present invention provides a method for carrying a specific transition metal on a hydrophobic zeolite by ion exchange, regardless of the water concentration in the fuel gas.
It is an object of the present invention to provide a sulfur compound removal adsorbent that functions effectively for sulfur compound removal, and the present invention also provides a method for removing sulfur compounds in a sulfur compound-containing fuel gas by the sulfur compound removal adsorbent. The purpose is to do.
【００１３】[0013]
【課題を解決するための手段】本発明は、（１）燃料ガ
ス中の硫黄化合物除去用吸着剤であって、疎水性ゼオラ
イトにＡｇ、Ｃｕ、Ｚｎ、Ｆｅ、Ｃｏ及びＮｉから選ば
れた１種又は２種以上の遷移金属をイオン交換により担
持させてなることを特徴とする燃料ガス中の硫黄化合物
吸着剤を提供し、また、本発明は（２）硫黄化合物含有
燃料ガスを、疎水性ゼオライトにＡｇ、Ｃｕ、Ｚｎ、Ｆ
ｅ、Ｃｏ及びＮｉから選ばれた１種又は２種以上の遷移
金属をイオン交換により担持させてなる硫黄化合物除去
用吸着剤に通すことを特徴とする硫黄化合物含有燃料ガ
ス中の硫黄化合物の除去方法を提供する。The present invention provides (1) an adsorbent for removing sulfur compounds in fuel gas, wherein the hydrophobic zeolite is selected from Ag, Cu, Zn, Fe, Co and Ni. The present invention provides a sulfur compound adsorbent in a fuel gas characterized by carrying one or more kinds of transition metals by ion exchange. Ag, Cu, Zn, F in zeolite
e, one or more transition metals selected from Co and Ni are passed through a sulfur compound removal adsorbent carried by ion exchange to remove sulfur compounds in a sulfur compound-containing fuel gas. Provide a way.
【００１４】[0014]
【発明の実施の形態】ゼオライトには各種数多くの種類
があるが、本発明においては特に疎水性のゼオライトを
使用することが重要である。本発明は、この点と合わせ
て、この疎水性ゼオライトに、Ａｇ、Ｃｕ、Ｚｎ、Ｆ
ｅ、Ｃｏ及びＮｉから選ばれた１種又は２種以上の遷移
金属をイオン交換により担持させてなることが重要であ
る。こうしてなる本発明の吸着剤は、いずれも燃料ガス
中の水分濃度に関わらず、該燃料ガス中に含まれている
硫黄化合物を有効に除去することができる。それら遷移
金属の中でもＡｇ又はＣｕを担持させた吸着剤が特に有
効である。DETAILED DESCRIPTION OF THE INVENTION There are many types of zeolites. In the present invention, it is particularly important to use hydrophobic zeolites. The present invention, in conjunction with this point, provides the hydrophobic zeolite with Ag, Cu, Zn, F
It is important that one or more transition metals selected from e, Co and Ni are supported by ion exchange. The adsorbent of the present invention thus configured can effectively remove the sulfur compounds contained in the fuel gas regardless of the moisture concentration in the fuel gas. Among these transition metals, an adsorbent supporting Ag or Cu is particularly effective.
【００１５】本発明の吸着剤を製造するには、先ず、上
記Ａｇ、Ｃｕ、Ｚｎ、Ｆｅ、Ｃｏ及びＮｉから選ばれた
各遷移金属を疎水性ゼオライトに対してイオン交換法に
より担持させる。具体的には、それら金属の化合物を水
に溶解して水溶液とする。各金属の化合物としては、疎
水性ゼオライトの陽イオンとイオン交換させる必要があ
るため、水に溶解し、その水溶液中、金属が金属イオン
として存在し得る金属化合物が用いられる。この水溶液
を疎水性ゼオライトと後述図２に示すような一撹拌
法、含浸法、流通法等により接触させることによ
り、疎水性ゼオライト中の陽イオンをこれら金属イオン
と交換させる。次いで、水等で洗浄した後、乾燥、焼成
することにより得られる。In order to produce the adsorbent of the present invention, first, each transition metal selected from Ag, Cu, Zn, Fe, Co and Ni is supported on a hydrophobic zeolite by an ion exchange method. Specifically, these metal compounds are dissolved in water to form an aqueous solution. As the compound of each metal, a metal compound which can be dissolved in water and in which the metal exists as a metal ion in an aqueous solution is used because it is necessary to perform ion exchange with the cation of the hydrophobic zeolite. The aqueous solution is brought into contact with the hydrophobic zeolite by a stirring method, an impregnation method, a flow method or the like as shown in FIG. 2 to exchange cations in the hydrophobic zeolite with these metal ions. Next, it is obtained by washing with water or the like, followed by drying and baking.
【００１６】本発明に係る硫黄化合物除去用吸着剤は、
各種燃料ガス中の前述サルファイド類、チオフェン類及
びメルカプタン類のうちの１種又は２種以上の硫黄化合
物を吸着除去するのに適用できるが、特に都市ガスやＬ
Ｐガス等の燃料ガスからそれら硫黄化合物を吸着除去す
るのに好適に適用することができる。The adsorbent for removing sulfur compounds according to the present invention comprises:
The present invention can be applied to adsorb and remove one or more sulfur compounds of the above-mentioned sulfides, thiophenes and mercaptans in various fuel gases.
The present invention can be suitably applied to adsorptive removal of such sulfur compounds from fuel gas such as P gas.
【００１７】また、本発明に係る硫黄化合物除去用吸着
剤による硫黄化合物を含む燃料ガスの処理は、該吸着剤
に硫黄化合物含有燃料ガスを接触させることにより行う
が、従来の吸着剤によるガス処理と同様にして行うこと
ができる。図１は本発明を実施する装置の一態様例を示
す図である。図１中、１は硫黄化合物含有燃料ガス導入
管、２は硫黄化合物吸着剤充填層（反応管）、３は処理
済み燃料ガス導出管である。導入管１から導入される硫
黄化合物含有燃料ガス中の硫黄化合物は、吸着剤充填層
２で吸着除去され、処理済み燃料ガスとして導出管３か
ら排出される。The treatment of the fuel gas containing a sulfur compound with the adsorbent for removing a sulfur compound according to the present invention is performed by bringing the fuel gas containing the sulfur compound into contact with the adsorbent. Can be performed in the same manner as described above. FIG. 1 is a diagram showing an example of an embodiment of an apparatus for implementing the present invention. In FIG. 1, reference numeral 1 denotes a sulfur compound-containing fuel gas inlet tube, 2 denotes a sulfur compound adsorbent packed bed (reaction tube), and 3 denotes a treated fuel gas outlet tube. Sulfur compounds in the sulfur compound-containing fuel gas introduced from the introduction pipe 1 are adsorbed and removed in the adsorbent packed bed 2 and discharged from the discharge pipe 3 as a treated fuel gas.
【００１８】[0018]
【実施例】以下、実施例に基づき本発明をさらに詳しく
説明するが、本発明がこれら実施例により制限されない
ことは勿論である。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but it is needless to say that the present invention is not limited by these Examples.
【００１９】〈供試吸着剤の調製〉ゼオライトとして、
市販のβ型ゼオライト（東ソー社製、商品名：ＨＳＺー
９３０ＨＯＤ１Ａ）を用いた。このゼオライトの化学組
成はＮａ2Ｏ＝０．０３ｗｔ％、ＳｉＯ2／Ａｌ2Ｏ3＝２
７．４（モル比）であり、バインダーとしてアルミナ２
０ｗｔ％を用いて円柱形のペレット（直径１．５ｍｍ、
長さ＝３〜４ｍｍ）に成形したものである。一方、塩化
ナトリウム、硝酸銀、酢酸銅、硫酸亜鉛、硫酸鉄、酢酸
コバルト、酢酸ニッケルの各金属塩を蒸留水に溶解し
て、これら各金属塩の水溶液を得た。<Preparation of sample adsorbent> As zeolite,
A commercially available β-type zeolite (trade name: HSZ-930HOD1A, manufactured by Tosoh Corporation) was used. The chemical composition of this zeolite is Na 2 O = 0.03 wt%, SiO 2 / Al 2 O 3 = 2
7.4 (molar ratio) and alumina 2 as a binder.
Using 0 wt%, a cylindrical pellet (1.5 mm in diameter,
(Length = 3-4 mm). On the other hand, each metal salt of sodium chloride, silver nitrate, copper acetate, zinc sulfate, iron sulfate, cobalt acetate, and nickel acetate was dissolved in distilled water to obtain an aqueous solution of each of these metal salts.
【００２０】これら各金属塩水溶液を用いて、図２に示
す各種イオン交換方法により、上記ゼオライト中の水素
イオンをこれら金属イオンと交換させた後、１００ｍｌ
蒸留水（図２中ＤＩＷ）にて５回洗浄し、次いで乾燥、
焼成した。表１にこれに用いた各条件等をまとめて示し
ている（表１中、吸着剤名の欄には略号「元素記号（Ｃ
ｕ等）ーβ」で示しているが、同欄中、例えば「Ｃｕー
β」とはβ型ゼオライトにＣｕをイオン交換により担持
させたものの意味であり、この点表２についても同じで
ある）。なお、乾燥及び焼成条件は各吸着剤とも共通で
あり、乾燥は空気中において１００℃で１日行い、また
焼成は乾燥窒素中において４００℃で２時間行った。こ
うして、上記ゼオライトに各金属Ｎａ、Ａｇ、Ｃｕ、Ｚ
ｎ、Ｆｅ、Ｃｏ、Ｎｉをイオン交換により担持させた各
供試吸着剤を得た。The hydrogen ions in the zeolite were exchanged with these metal ions by various ion exchange methods shown in FIG.
Wash 5 times with distilled water (DIW in FIG. 2), then dry,
Fired. Table 1 summarizes the conditions and the like used for this (in the column of adsorbent name in Table 1, the abbreviation "element symbol (C
u, etc.)-β ”, for example, in the same column,“ Cu-β ”means that β-type zeolite carries Cu by ion exchange, and the same applies to this point table 2. ). The drying and firing conditions were the same for each adsorbent. Drying was performed in air at 100 ° C. for 1 day, and firing was performed in dry nitrogen at 400 ° C. for 2 hours. Thus, each of the metals Na, Ag, Cu, Z is added to the zeolite.
Each sample adsorbent in which n, Fe, Co, and Ni were supported by ion exchange was obtained.
【００２１】[0021]
【表 １】 [Table 1]
【００２２】〈硫黄化合物の吸着試験１〉図３に示す試
験装置を用いて硫黄化合物の吸着試験を実施した。図３
中、４が充填塔（円筒反応管）であり、これに上記で得
た各供試吸着剤を充填し、それぞれについて硫黄化合物
の吸着試験を実施した。各供試吸着剤による硫黄化合物
の吸着量は充填塔の出口から経時的にサンプリングし、
ＧＣーＦＰＤ（炎光光度検出器付きのガスクロマトグラ
フ）により連続的に測定して濃度を求めた。この測定
は、供試吸着剤による硫黄化合物除去性能を破過試験
（ｂｒｅａｋーｔｈｒｏｕｇｈーｔｅｓｔ）によって調
べた。<Sulfur Compound Adsorption Test 1> A sulfur compound adsorption test was carried out using the test apparatus shown in FIG. FIG.
Among them, reference numeral 4 denotes a packed tower (cylindrical reaction tube), which was filled with each of the test adsorbents obtained above, and subjected to a sulfur compound adsorption test for each. The amount of sulfur compounds adsorbed by each test adsorbent was sampled over time from the outlet of the packed tower,
The concentration was determined by continuous measurement using a GC-FPD (gas chromatograph equipped with a flame photometric detector). In this measurement, the ability of the test adsorbent to remove sulfur compounds was examined by a break-through test.
【００２３】試験条件は以下のとおりとした。充填塔：
２８．４ｍｍ（直径）×６３．２ｍｍ（高さ）、試験ガ
ス：都市ガス（１３Ａ）、試験ガス中の硫黄化合物濃
度：４．４ｍｇーＳＮｍ3（ＤＭＳ＝５０ｗｔ％、ＴＢ
Ｍ＝５０ｗｔ％、これはＤＭＳ＝１．８ｐｐｍ、ＴＢＭ
＝１．２ｐｐｍに相当する）、ガス流量：３４０Ｌ／
ｈ、ＬＶ（ガスの線速度）＝１５ｃｍ／ｓｅｃ、ＳＶ
（空間速度）＝８５００ｈ-1、試験ガス中の水分濃度：
露点−３０℃（≒３７６ｐｐｍ：水分量）、温度：室
温、圧力：常圧。本吸着試験は比較例を含めてすべて同
一装置、同一条件で実施した。The test conditions were as follows. Packing tower:
28.4 mm (diameter) × 63.2 mm (height), test gas: city gas (13 A), sulfur compound concentration in test gas: 4.4 mg-SNm 3 (DMS = 50 wt%, TB
M = 50 wt%, which is DMS = 1.8 ppm, TBM
= 1.2 ppm), gas flow rate: 340 L /
h, LV (linear velocity of gas) = 15 cm / sec, SV
(Space velocity) = 8500 h −1 , moisture concentration in test gas:
Dew point -30 ° C (≒ 376 ppm: water content), temperature: room temperature, pressure: normal pressure. This adsorption test was performed under the same apparatus and under the same conditions, including the comparative examples.
【００２４】表２は上記吸着試験の結果である。表２に
は、各供試吸着剤及び市販のβ型ゼオライト自体（Ｈ
型、比較例１）のほか、比較例として、市販の各種吸着
剤及び吸着作用を有すると思われる各種多孔質材料につ
いて、上記と同じく吸着試験を行った結果も示してい
る。表２中の硫黄吸着容量（硫黄化合物吸着量）は、吸
着塔出口における各硫黄化合物濃度が０．１ｐｐｍに達
した時点までの吸着量を示し、式〔吸着量（ｗｔ％）＝
吸着した硫黄化合物中の硫黄量（ｇ）／吸着剤の重量
（ｇ）×１００〕により算出したものである。Table 2 shows the results of the above adsorption test. Table 2 shows each test adsorbent and commercially available β-type zeolite itself (H
In addition to the mold and Comparative Example 1), as a comparative example, the results of the same adsorption test performed on various commercially available adsorbents and various porous materials that are considered to have an adsorption action are also shown. The sulfur adsorption capacity (sulfur compound adsorption amount) in Table 2 indicates the adsorption amount up to the time when each sulfur compound concentration at the outlet of the adsorption tower reaches 0.1 ppm, and is expressed by the formula [Adsorption amount (wt%) =
The amount of sulfur in the adsorbed sulfur compound (g) / the weight of the adsorbent (g) × 100].
【００２５】[0025]
【表 ２】 [Table 2]
【００２６】表２のとおり、β型ゼオライトは疎水性の
ゼオライトの一種であるが、イオン種がＨである基本形
（比較例２）では、硫黄化合物吸着量は０．０５４ｗｔ
％であるに過ぎない。このようにゼオライトが疎水性で
あるだけでは、水分を含む燃料ガス中の硫黄化合物を除
去できないことを示している。イオン種がアルカリ金属
のＮａである比較例１ではさらに劣っており、水分を含
む燃料ガス中の硫黄化合物用の吸着剤としては有用でな
いことを示している。As shown in Table 2, the β-type zeolite is a kind of hydrophobic zeolite, but in the basic form in which the ionic species is H (Comparative Example 2), the adsorption amount of the sulfur compound is 0.054 wt.
It is only a percentage. Thus, the fact that zeolite is merely hydrophobic cannot remove sulfur compounds in fuel gas containing water. Comparative Example 1, in which the ionic species is alkali metal Na, is even worse, indicating that it is not useful as an adsorbent for sulfur compounds in fuel gas containing water.
【００２７】これに対して、β型ゼオライトに対してＣ
ｕをイオン交換担持した場合（実施例１）の硫黄化合物
吸着量は１．１ｗｔ％、同じくＡｇをイオン交換により
担持させた場合（実施例２）の硫黄化合物吸着量は１．
７ｗｔ％であり、格段に改善されていることが分かる。
またβ型ゼオライトに対してＺｎをイオン交換担持した
場合（実施例３）の硫黄化合物吸着量は０．２４ｗｔ
％、同じくＦｅ、Ｎｉ、Ｃｏをイオン交換担持した場合
（実施例４〜６）の硫黄化合物吸着量は０．１４〜０．
１３ｗｔ％であり、Ａｇ、Ｃｕの場合に比べれば少ない
が、硫黄化合物吸着能がそれぞれ有効改善されているこ
とが分かる。On the other hand, for β-zeolite, C
The amount of sulfur compound adsorbed when u was supported by ion exchange (Example 1) was 1.1 wt%, and the amount of sulfur compound adsorbed when Ag was supported by ion exchange (Example 2) was 1.
It is 7 wt%, which indicates that it is significantly improved.
When Zn was ion-exchanged and supported on β-zeolite (Example 3), the amount of sulfur compound adsorbed was 0.24 wt.
%, And when Fe, Ni, and Co are ion-exchanged and supported (Examples 4 to 6), the sulfur compound adsorption amount is 0.14 to 0.1%.
It is 13 wt%, which is smaller than that of Ag and Cu, but it can be seen that the sulfur compound adsorption ability is effectively improved.
【００２８】表２中、比較例３〜１０はβ型以外のゼオ
ライト、比較例１１〜１８はゼオライト以外の吸着剤種
を用いた例であるが、いずれにおいても０．１ｗｔ％以
下の硫黄化合物吸着量に過ぎない。以上のとおり、本発
明に係る吸着剤における優れた硫黄化合物の吸着効果は
明らかである。In Table 2, Comparative Examples 3 to 10 are examples using zeolite other than β-type, and Comparative Examples 11 to 18 are examples using adsorbents other than zeolite. It is only the amount of adsorption. As described above, the excellent sulfur compound adsorption effect of the adsorbent according to the present invention is apparent.
【００２９】〈硫黄化合物の吸着試験２：実施例７〉硫
黄化合物の吸着試験１は試験ガスに水分を含む条件での
試験であるが、本吸着試験２では、β型ゼオライトに対
してＣｕをイオン交換担持した吸着剤（実施例１）につ
いて、試験ガス中の水分濃度を異ならせて試験した。試
験条件は、試験ガス中の水分濃度：露点−６０℃（≒１
０ｐｐｍ：水分量）とした以外は、吸着試験１と同じ条
件で試験した。表３はその結果である。対比のため実施
例１を併記している。表３のとおり、硫黄化合物吸着量
は１．６ｗｔ％であり、露点−６０℃、すなわちドライ
条件下での硫黄化合物吸着量はさらに優れていることが
分かる。実施例１の硫黄化合物吸着量は１．１ｗｔ％で
あり、水分を含む条件でも格段に改善されているが、ド
ライ条件下での硫黄化合物吸着量は、水分を含む条件下
である実施例１に比べて約４割の性能向上である。<Sulfur Compound Adsorption Test 2: Example 7> Sulfur compound adsorption test 1 is a test under the condition that the test gas contains moisture. In this adsorption test 2, Cu was added to β-type zeolite. The ion-exchanged adsorbent (Example 1) was tested with different moisture concentrations in the test gas. The test conditions were as follows: moisture concentration in test gas: dew point −60 ° C. ($ 1
The test was performed under the same conditions as in the adsorption test 1 except that the amount was 0 ppm: water content). Table 3 shows the results. Example 1 is also shown for comparison. As shown in Table 3, the sulfur compound adsorption amount is 1.6 wt%, and it is understood that the sulfur compound adsorption amount under the dew point of -60 ° C, that is, the dry condition, is further excellent. The adsorption amount of the sulfur compound in Example 1 was 1.1 wt%, which was remarkably improved even under the condition including water. However, the adsorption amount of the sulfur compound under the dry condition was the condition under the condition including water. Approximately 40% of the performance is improved.
【００３０】[0030]
【表 ３】 [Table 3]
【００３１】〈硫黄化合物の吸着試験３：実施例８〉硫
黄化合物の吸着試験１〜２は硫黄成分としてＤＭＳ（サ
ルファイド類）とＴＢＭ（メルカプタン類）を含む試験
ガスについての試験であるが、本吸着試験３では、β型
ゼオライトに対してＣｕをイオン交換担持した吸着剤
（実施例１）について、試験ガス中の硫黄成分を異なら
せ、ＴＨＴ（チオフェン類）を含む試験ガスについて試
験した。試験条件は以下のとおりとした。充填塔：１５
ｍｍ（直径）×６６ｍｍ（高さ）、試験ガス：都市ガス
（１３Ａ）、試験ガス中の硫黄化合物濃度：１０ｍｇー
ＳＮｍ3（これはＴＨＴ＝７．０ｐｐｍに相当する）、
ガス流量：６５Ｌ／ｈ、ＬＶ（ガスの線速度）＝１０ｃ
ｍ／ｓｅｃ、ＳＶ（空間速度）＝５５００ｈ-1、試験ガ
ス中の水分濃度：露点−６０℃（≒１０ｐｐｍ：水分
量）、温度：室温、圧力：常圧。表４はその結果であ
る。対比のため実施例７を併記している。表４のとお
り、硫黄化合物（ＴＨＴ）吸着量は２．２ｗｔ％であ
り、本発明の吸着剤はＴＨＴ吸着能にも優れていること
が分かる。これはＤＭＳ＋ＴＢＭ吸着量よりさらに優れ
た性能である。<Sulfur Compound Adsorption Test 3: Example 8> Sulfur compound adsorption tests 1 and 2 are tests on test gases containing DMS (sulfides) and TBM (mercaptans) as sulfur components. In the adsorption test 3, the adsorbent (Example 1) in which Cu was ion-exchanged and supported on β-type zeolite was tested with a test gas containing THT (thiophenes) with different sulfur components in the test gas. The test conditions were as follows. Packing tower: 15
mm (diameter) × 66 mm (height), test gas: city gas (13 A), sulfur compound concentration in test gas: 10 mg-SNm 3 (this corresponds to THT = 7.0 ppm),
Gas flow rate: 65 L / h, LV (linear velocity of gas) = 10 c
m / sec, SV (space velocity) = 5500 h -1 , moisture concentration in test gas: dew point −60 ° C. (≒ 10 ppm: moisture content), temperature: room temperature, pressure: normal pressure. Table 4 shows the results. Example 7 is also shown for comparison. As shown in Table 4, the amount of sulfur compound (THT) adsorbed was 2.2 wt%, and it can be seen that the adsorbent of the present invention is also excellent in THT adsorption ability. This is a performance superior to the DMS + TBM adsorption amount.
【００３２】[0032]
【表 ４】 [Table 4]
【００３３】〈硫黄化合物の吸着試験４：実施例９〉硫
黄化合物の吸着試験１〜３は、吸着剤充填塔出口から経
時的にサンプリングをし、ＧＣーＦＰＤ（炎光光度検出
器付きのガスクロマトグラフ）により分析してその吸着
性能を評価したが、本吸着試験４では、β型ゼオライト
に対してＣｕをイオン交換担持した吸着剤（実施例１：
実施例７も同じ）について、より高感度で極低硫黄濃度
分析が可能なＧＣーＳＣＤ（硫黄化学発光検出器付きの
ガスクロマトグラフ）により吸着剤充填塔出口ガスの分
析を行った。試験条件は吸着試験２と同じ条件で試験し
た。表５はその結果である。対比のためＧＣーＦＰＤを
用いた実施例７における対応値を併記している。<Sulfur Compound Adsorption Test 4: Example 9> In the sulfur compound adsorption tests 1 to 3, the GC-FPD (gas chromatograph equipped with a flame photometric detector) was used for sampling over time from the outlet of the adsorbent packed tower. The adsorption performance was evaluated by analyzing the adsorbent by using an adsorbent obtained by ion-exchange-supporting Cu on β-zeolite (Example 1:
For Example 7), the gas at the outlet of the adsorbent-packed tower was analyzed by GC-SCD (gas chromatograph equipped with a sulfur chemiluminescence detector), which is capable of higher sensitivity and extremely low sulfur concentration analysis. The test conditions were the same as those in the adsorption test 2. Table 5 shows the results. For comparison, corresponding values in Example 7 using GC-FPD are also shown.
【００３４】[0034]
【表 ５】 [Table 5]
【００３５】前記のとおり、硫黄化合物を除去した燃料
ガス中に含まれている残留硫黄化合物濃度は、できるだ
け低濃度であることが望ましいが、表５から明らかなと
おり、本発明の吸着剤によれば、都市ガス中の硫黄成分
は７ｐｐｂ以下という極低濃度まで吸着除去されている
ことが分かる。As described above, it is desirable that the concentration of the residual sulfur compound contained in the fuel gas from which the sulfur compound has been removed be as low as possible. From this, it can be seen that the sulfur component in the city gas has been adsorbed and removed to an extremely low concentration of 7 ppb or less.
【００３６】[0036]
【発明の効果】本発明によれば、疎水性ゼオライトに特
定の金属をイオン交換により担持させることにより、燃
料ガス中の水分濃度に関わらず、燃料ガス中における硫
黄化合物の吸着特性を格段に改善することができる。こ
れにより、吸着剤の必要量を少なくできるだけでなく、
再生頻度、交換頻度を少なくでき、ＤＭＳ等の硫黄化合
物を含む燃料ガスから硫黄化合物を有効に除去すること
ができる。According to the present invention, by adsorbing a specific metal on a hydrophobic zeolite by ion exchange, the adsorption characteristics of sulfur compounds in the fuel gas are remarkably improved regardless of the water concentration in the fuel gas. can do. This not only reduces the amount of adsorbent needed,
The frequency of regeneration and replacement can be reduced, and sulfur compounds can be effectively removed from fuel gas containing sulfur compounds such as DMS.
【図１】本発明を実施する装置の一態様例を示す図。FIG. 1 is a diagram showing an example of an embodiment of an apparatus for implementing the present invention.
【図２】実施例でイオン交換に使用した撹拌法、含
浸法及び流通法の三法の概略を示す図。FIG. 2 is a diagram schematically illustrating three methods of a stirring method, an impregnation method, and a distribution method used for ion exchange in Examples.
【図３】実施例で使用した試験装置の概略を示す図。FIG. 3 is a diagram schematically illustrating a test apparatus used in the examples.
１ 付臭剤含有ガス導入管 ２ 吸着剤充填層（反応管） ３ 処理済みガス導出管 ４ 充填塔（円筒反応管） 1 Odorant-containing gas introduction tube 2 Adsorbent packed bed (reaction tube) 3 Treated gas outlet tube 4 Packing tower (cylindrical reaction tube)
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4D012 BA02 CA07 CB12 CE03 CG01 CG03 4G066 AA61B AA62B CA25 DA04 FA11 FA22 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4D012 BA02 CA07 CB12 CE03 CG01 CG03 4G066 AA61B AA62B CA25 DA04 FA11 FA22
Claims (9)
って、疎水性ゼオライトにＡｇ、Ｃｕ、Ｚｎ、Ｆｅ、Ｃ
ｏ及びＮｉから選ばれた１種又は２種以上の遷移金属を
イオン交換により担持させてなることを特徴とする燃料
ガス中の硫黄化合物除去用吸着剤。1. An adsorbent for removing sulfur compounds in fuel gas, wherein Ag, Cu, Zn, Fe, C are added to a hydrophobic zeolite.
An adsorbent for removing sulfur compounds in a fuel gas, wherein one or more transition metals selected from o and Ni are supported by ion exchange.
あることを特徴とする請求項１に記載の燃料ガス中の硫
黄化合物除去用吸着剤。2. The adsorbent for removing sulfur compounds in fuel gas according to claim 1, wherein the hydrophobic zeolite is a β-type zeolite.
る請求項１〜２のいずれかに記載の燃料ガス中の硫黄化
合物除去用吸着剤。3. The adsorbent for removing sulfur compounds in fuel gas according to claim 1, wherein the fuel gas is city gas or LP gas.
ド類、チオフェン類及びメルカプタン類のうちの１種又
は２種以上の硫黄化合物である請求項１〜３のいずれか
に記載の燃料ガス中の硫黄化合物除去用吸着剤。4. The fuel gas according to claim 1, wherein the sulfur compound in the fuel gas is one or more of a sulfide, a thiophene and a mercaptan. Adsorbent for removing sulfur compounds.
ス中の残留硫黄化合物濃度が数ｐｐｂ以下であることを
特徴とする請求項１〜４のいずれかに記載の燃料ガス中
の硫黄化合物除去用吸着剤。5. The sulfur compound in a fuel gas according to claim 1, wherein the concentration of the residual sulfur compound in the gas from which the sulfur compound in the fuel gas has been removed is several ppb or less. Adsorbent for removal.
イトにＡｇ、Ｃｕ、Ｚｎ、Ｆｅ、Ｃｏ及びＮｉから選ば
れた１種又は２種以上の遷移金属をイオン交換により担
持させてなる硫黄化合物除去用吸着剤に通すことを特徴
とする硫黄化合物含有燃料ガス中の硫黄化合物の除去方
法。6. A sulfur compound comprising a sulfur compound-containing fuel gas and one or more transition metals selected from Ag, Cu, Zn, Fe, Co and Ni supported on a hydrophobic zeolite by ion exchange. A method for removing a sulfur compound from a sulfur compound-containing fuel gas, wherein the sulfur compound is passed through a removal adsorbent.
あることを特徴とする請求項６に記載の硫黄化合物含有
燃料ガス中の硫黄化合物の除去方法。7. A method according to claim 6, wherein said hydrophobic zeolite is a β-type zeolite.
ド類、チオフェン類及びメルカプタン類のうちの１種又
は２種以上の硫黄化合物である請求項６〜７のいずれか
に記載の硫黄化合物含有燃料ガス中の硫黄化合物の除去
方法。8. A sulfur compound-containing fuel according to claim 6, wherein the sulfur compound in the fuel gas is one or more of a sulfur compound, a thiophene and a mercaptan. A method for removing sulfur compounds in a gas.
ス中の残留硫黄化合物濃度が数ｐｐｂ以下であることを
特徴とする請求項６〜８のいずれかに記載の硫黄化合物
含有燃料ガス中の硫黄化合物の除去方法。9. The sulfur compound-containing fuel gas according to claim 6, wherein the concentration of the residual sulfur compound in the gas from which the sulfur compound in the fuel gas has been removed is several ppb or less. Method for removing sulfur compounds.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000232780A JP3742284B2 (en) | 2000-02-01 | 2000-08-01 | Adsorbent for sulfur compounds in fuel gas and method for removing the same |
| DK01102061T DK1121977T3 (en) | 2000-02-01 | 2001-01-30 | Procedure for Removing Sulfur Compounds from Combustible Gases |
| DE60128016T DE60128016T2 (en) | 2000-02-01 | 2001-01-30 | Process for the removal of sulfur compounds from fuel gases |
| AT01102061T ATE360478T1 (en) | 2000-02-01 | 2001-01-30 | METHOD FOR REMOVAL OF SULFUR COMPOUNDS FROM FUEL GASES |
| EP01102061A EP1121977B1 (en) | 2000-02-01 | 2001-01-30 | Method for removing sulfur compound from fuel gases |
| CA002332818A CA2332818C (en) | 2000-02-01 | 2001-01-31 | Adsorbent for removing sulfur compounds from fuel gases and removal method |
| US09/774,966 US20010014304A1 (en) | 2000-02-01 | 2001-01-31 | Adsorbent for removing sulfur compouns from fuel gases and removal method |
| AU16772/01A AU759217B2 (en) | 2000-02-01 | 2001-02-01 | Adsorbent for removing sulfur compounds from fuel gases and removal method |
| US10/429,913 US6875410B2 (en) | 2000-02-01 | 2003-05-05 | Adsorbent for removing sulfur compounds from fuel gases and removal method |
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|---|---|---|---|
| JP2000023955 | 2000-02-01 | ||
| JP2000-23955 | 2000-02-01 | ||
| JP2000232780A JP3742284B2 (en) | 2000-02-01 | 2000-08-01 | Adsorbent for sulfur compounds in fuel gas and method for removing the same |
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| Publication Number | Publication Date |
|---|---|
| JP2001286753A true JP2001286753A (en) | 2001-10-16 |
| JP3742284B2 JP3742284B2 (en) | 2006-02-01 |
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| JP2005294089A (en) * | 2004-04-01 | 2005-10-20 | Idemitsu Kosan Co Ltd | Method of supplying liquefied petroleum gas to hydrogen production system for fuel cell and fuel cell system using it |
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