JP2007091498A - Method of producing hydrogen - Google Patents

Method of producing hydrogen Download PDF

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JP2007091498A
JP2007091498A JP2005280342A JP2005280342A JP2007091498A JP 2007091498 A JP2007091498 A JP 2007091498A JP 2005280342 A JP2005280342 A JP 2005280342A JP 2005280342 A JP2005280342 A JP 2005280342A JP 2007091498 A JP2007091498 A JP 2007091498A
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adsorbent
adsorption
hydrogen
gas
adsorption tower
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Akitoshi Fujisawa
彰利 藤澤
Keita Yura
慶太 由良
Takeshi Yamashita
岳史 山下
Noboru Nakao
昇 中尾
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Kobe Steel Ltd
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    • 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

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing hydrogen which uses a membrane reactor type reformer and has excellent safety and by which the flow-in of CO to a fuel cell electrode is surely prevented while keeping high hydrogen yield even in the leakage of CO from the membrane reactor type reformer. <P>SOLUTION: A hydrogen enriched reformed gas B is produced by reforming a reforming raw material A in the membrane reactor type reformer 1 and the reformed gas B is cooled to ≤60°C by a heat exchanger 3 and is passed through a CO adsorption column 2a in which a CO adsorbent comprising a material prepared by supporting copper (I) halide and/or copper (II) halide or the reduced material of them on a support of one or more kinds selected from a group of silica, alumina, activated carbon, graphite and a polystyrene based resin is filled to adsorb and remove CO and the CO removed gas C obtained by completely adsorbing and removing CO is supplied to the fuel cell. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、リン酸形や固体高分子形等のプロトン伝導形燃料電池等に用いられる高純度水素の製造方法に関し、詳しくは、燃料電池のエネルギ源（燃料）である水素を製造する際に副生する一酸化炭素や二酸化炭素、水や、未反応のメタンなどのうち、特に燃料電池電極触媒への被毒性の高いＣＯを除去する方法に関する。   The present invention relates to a method for producing high-purity hydrogen used in proton conductive fuel cells and the like of phosphoric acid type and solid polymer type, and more specifically, in producing hydrogen which is an energy source (fuel) of a fuel cell. The present invention relates to a method for removing CO that is highly toxic to a fuel cell electrode catalyst, among carbon monoxide, carbon dioxide, water, and unreacted methane produced as by-products.

近年、地球温暖化防止対策ともあいまって、エネルギの原油依存体質からの脱却が世界的規模で重要課題となっており、環境保全に対する取組みが先行する欧州の先進国はもとより、米国や日本をはじめとするアジア諸国においても、水素ガスをエネルギ源とする燃料電池の実用化に向けての取組みが活発化している。   In recent years, coupled with measures to prevent global warming, the departure of energy from crude oil dependence has become an important issue on a global scale, and not only developed countries in Europe, where efforts for environmental conservation are ahead, but also the United States and Japan. In other Asian countries as well, efforts toward the practical application of fuel cells using hydrogen gas as an energy source have become active.

燃料電池の燃料として使用される水素ガスの製造方法についても多くの研究が進められているが、現時点で最も安価で実現性の高い製造方法は、原料として天然ガス、ＬＰＧ、灯油、ガソリン、メタノール、ジメチルエーテルなどを使用し、これらを改質して水素ガスを製造する方法である。   Much research has been carried out on the production method of hydrogen gas used as fuel for fuel cells, but the most inexpensive and highly feasible production methods are currently natural gas, LPG, kerosene, gasoline, methanol as raw materials. In this method, dimethyl ether or the like is used to reform these to produce hydrogen gas.

このような原料を改質して水素ガスを製造する方法、例えば天然ガスを改質して水素を製造するプロセスでは、通常水蒸気改質法が最もよく用いられている。天然ガスの主成分はメタン（ＣＨ４）であり、水蒸気改質法において以下のような２段階の反応で水素が生成する。 In a method for producing hydrogen gas by reforming such raw materials, for example, a process for producing hydrogen by reforming natural gas, the steam reforming method is usually used most often. The main component of natural gas is methane (CH 4 ), and hydrogen is generated by the following two-stage reaction in the steam reforming method.

（１）改質反応 ＣＨ４＋Ｈ２Ｏ → ＣＯ＋３Ｈ２
（２）変成反応 ＣＯ＋Ｈ２Ｏ → ＣＯ２＋Ｈ２ (1) Reforming reaction CH 4 + H 2 O → CO + 3H 2
(2) Metamorphic reaction CO + H 2 O → CO 2 + H 2

しかし、（１）の段階の改質反応は７００〜８００℃の反応温度で進行するため、多量の高温熱エネルギを要し、装置の効率が良いとはいえない。   However, since the reforming reaction in the stage (1) proceeds at a reaction temperature of 700 to 800 ° C., a large amount of high-temperature heat energy is required, and it cannot be said that the efficiency of the apparatus is good.

また、上記のような反応が理想的に進行すれば、生成物はＨ２とＣＯ２のみとなるが、実際にはメタンのコーキングによって炭素が生成するのを防止する観点から過剰の水蒸気を用いているため、改質反応を経て変性反応された後のガス（以下、「改質ガス」と呼ぶ。）中には水素（Ｈ２）と合わせて水蒸気（Ｈ２Ｏ）や未反応メタン（ＣＨ４）、一酸化炭素（ＣＯ）、および二酸化炭素（ＣＯ２）などの不純物が含まれることになる。これらの不純物の中でも、特にＣＯについては固体高分子形燃料電池の電極用触媒に用いられる白金（Ｐｔ）の被毒劣化防止の観点から１０ｐｐｍ以下の濃度に下げる必要があり、燃料電池の耐久性を考慮した場合、さらに０．２ｐｐｍ以下程度まで濃度を低減する必要があるとされている。 In addition, if the above reaction proceeds ideally, the products are only H 2 and CO 2 , but in actuality, excess water vapor is used from the viewpoint of preventing carbon from being generated by methane coking. Therefore, in the gas after the modification reaction through the reforming reaction (hereinafter referred to as “reformed gas”), together with hydrogen (H 2 ), water vapor (H 2 O) and unreacted methane ( CH 4), carbon monoxide (CO), and carbon dioxide (CO 2) will contain impurities such as. Among these impurities, in particular, CO must be reduced to a concentration of 10 ppm or less from the viewpoint of preventing poisoning deterioration of platinum (Pt) used as an electrode catalyst for a polymer electrolyte fuel cell. Is taken into consideration, it is said that the concentration needs to be further reduced to about 0.2 ppm or less.

従来から実施されている改質ガスからの水素の精製法としては、選択酸化触媒法、水素ＰＳＡ法が代表的である。選択酸化触媒法は、主に定置形燃料電池（家庭用燃料電池を含む）に対して開発が進められている技術であり、改質ガスに空気または酸素を添加し触媒を用いて改質ガス中のＣＯガスを選択的に酸化しＣＯ２にして除去し、燃料電池に対するＣＯの被毒を防止する技術である。常圧プロセスであること、比較的高い空塔速度（ＳＶ）で使用できることにより装置のコンパクト化が可能なことが本技術の特徴であるが、ＣＯ以外の不純物である、ＣＯ２、Ｈ２Ｏ、ＣＨ４の除去を行う技術ではないため、自動車用向けの燃料電池に対して要求される高純度水素を精製する方式としては利用できない。また 選択酸化触媒は耐久性が十分に確立されておらず、またＣＯの酸化のために酸素を導入するため、ＣＯだけでなく水素も酸化されるため水素収率が低下してしまう問題がある。 As a conventional method for purifying hydrogen from reformed gas, a selective oxidation catalyst method and a hydrogen PSA method are typical. The selective oxidation catalyst method is a technology that is being developed mainly for stationary fuel cells (including household fuel cells), and reformed gas using a catalyst by adding air or oxygen to the reformed gas. This is a technique for preventing CO poisoning of the fuel cell by selectively oxidizing the CO gas contained therein and removing it as CO 2 . The feature of the present technology is that the apparatus can be made compact by being a normal pressure process and being able to be used at a relatively high superficial velocity (SV), but it is an impurity other than CO, CO 2 , H 2 O. Since it is not a technique for removing CH 4 , it cannot be used as a method for purifying high purity hydrogen required for fuel cells for automobiles. In addition, the selective oxidation catalyst is not sufficiently durable, and since oxygen is introduced for the oxidation of CO, not only CO but also hydrogen is oxidized, resulting in a decrease in hydrogen yield. .

一方、水素ＰＳＡ法は、ゼオライトやカーボンモレキュラーシーブ、アルミナなどの複数の吸着剤を組み合わせ、圧力スイングを行いながら改質ガス中のＣＯ２、ＣＨ４、Ｈ２Ｏ、ＣＯを全て除去するプロセスである。自動車用の燃料電池に供給するための水素に対してはＣＯ以外の不純物の除去も要求されるため、水素供給ステーションで化石燃料を改質して燃料水素を製造する場合には、通常この水素ＰＳＡ法が採用されている。しかしながら、水素ＰＳＡ法に対する課題として、従来水素ＰＳＡ法では、粗製水素中に最大１％程度含まれるＣＯの除去が難しく、多量の吸着剤が必要になるため、水素ＰＳＡ設備のサイズ（吸着塔サイズ）が非常に大きくなるという問題や製品水素の回収率が十分ではないため、水素の精製コストが高くなるという問題がある。 On the other hand, the hydrogen PSA method is a process that removes all of CO 2 , CH 4 , H 2 O, and CO in the reformed gas while combining a plurality of adsorbents such as zeolite, carbon molecular sieve, and alumina while performing pressure swing. is there. Removal of impurities other than CO is also required for hydrogen supplied to fuel cells for automobiles. Therefore, when hydrogen is produced by reforming fossil fuel at a hydrogen supply station, this hydrogen is usually used. The PSA method is adopted. However, as a problem with the hydrogen PSA method, in the conventional hydrogen PSA method, it is difficult to remove CO contained in crude hydrogen at a maximum of about 1%, and a large amount of adsorbent is required. ) Becomes very large, and the recovery rate of product hydrogen is not sufficient, so that there is a problem that the cost of purifying hydrogen becomes high.

以上の問題を同時に解決する方法として、メンブレンリアクタ式改質器が提案されている。これは水蒸気改質触媒層の中に水素分離膜を設置し、改質反応で精製したＨ２、ＣＯ，ＣＯ２、未反応ＣＨ４の混合ガスから水素を選択的に分離する装置である。この装置を用いると生成した水素を水素分離膜によって抜き出すことにより、反応平衡を崩して水素生成側に反応を進めることができるため、７００〜８００℃の水蒸気改質反応温度を５００〜５５０℃に大幅に低下させることができる。また、水素分離膜によって水素のみを抜き出すことが可能なため、水素精製装置を省略することが可能となる。以上より、コンパクト、シンプルで高効率な水素製造装置が実現できると期待されている。 As a method for simultaneously solving the above problems, a membrane reactor type reformer has been proposed. This is an apparatus for selectively separating hydrogen from a mixed gas of H 2 , CO, CO 2 and unreacted CH 4 purified by a reforming reaction by installing a hydrogen separation membrane in a steam reforming catalyst layer. When this apparatus is used, the generated hydrogen is extracted by a hydrogen separation membrane, so that the reaction equilibrium can be broken and the reaction can proceed to the hydrogen generation side. Therefore, the steam reforming reaction temperature of 700 to 800 ° C. is increased to 500 to 550 ° C. It can be greatly reduced. Moreover, since only hydrogen can be extracted by the hydrogen separation membrane, the hydrogen purifier can be omitted. From the above, it is expected that a compact, simple and highly efficient hydrogen production apparatus can be realized.

しかしながら、メンブレンリアクタ式改質器内の水素分離膜に主に用いられているパラジウム膜・パラジウム合金膜などは極薄く柔らかいものであるため、熱応力や触媒との接触により破損し、ピンホールなどの欠陥が生じやすい。このため、不純物ガスのリークを完全に防止することが困難である。これを防ぐために水素分離膜の厚さを非常に厚く（例えば１００μｍ以上に）すると、パラジウム膜は高価な貴金属なため、装置の製造コストが過大となる。また、耐久性にも問題があり、膜の耐久性試験（圧力４．４ａｔｍ、改質器出口温度５９０℃、３００時間運転）の結果では運転時間にほぼ比例したガス漏れ量の増加が認められている（非特許文献１参照）。   However, since palladium membranes and palladium alloy membranes mainly used for hydrogen separation membranes in membrane reactor reformers are extremely thin and soft, they can be damaged by thermal stress or contact with catalysts, causing pinholes, etc. The defect is likely to occur. For this reason, it is difficult to completely prevent impurity gas leakage. In order to prevent this, if the thickness of the hydrogen separation membrane is very thick (for example, 100 μm or more), the palladium membrane is an expensive noble metal, and the manufacturing cost of the apparatus becomes excessive. In addition, there is a problem in durability, and in the results of the membrane durability test (pressure 4.4 atm, reformer outlet temperature 590 ° C., operation for 300 hours), an increase in gas leakage almost proportional to the operation time is recognized. (See Non-Patent Document 1).

これらの水素分離膜の欠陥を補うために、メンブレンリアクタ式改質器の後段にＣＯ選択酸化触媒やメタネーション触媒などを用いたＣＯ除去装置を配置した水素製造装置が提案されている（特許文献１参照）。しかし、ＣＯ選択酸化触媒およびメタネーション触媒による反応は発熱反応であり、また温度に非常に敏感な反応であるため、入放熱が非定常な状態では温度コントロールに不具合があると、ＣＯ除去装置通過後でもＣＯ濃度が数十〜数百ｐｐｍとなる恐れがある。また、触媒反応において水素を消費するため、水素収率が低下する問題がある。さらに、特にメタネーション触媒として用いられるニッケル系触媒は１５０℃以下で非常に有毒なニッケルカルボニルを生成するため、安全性にも問題がある。
石田政義監修：家庭用燃料電池の開発と課題、２００４年１２月２８日出版、ＣＭＣ出版、ｐ２０３〜２０８ 特開２００４−７５４３９号公報（特許請求の範囲など） In order to compensate for these defects in the hydrogen separation membrane, a hydrogen production apparatus has been proposed in which a CO removal apparatus using a CO selective oxidation catalyst, a methanation catalyst, or the like is arranged at the subsequent stage of the membrane reactor reformer (Patent Document). 1). However, the reaction by the CO selective oxidation catalyst and methanation catalyst is an exothermic reaction, and it is a very sensitive reaction to temperature. Even after this, the CO concentration may be several tens to several hundred ppm. Moreover, since hydrogen is consumed in the catalytic reaction, there is a problem in that the hydrogen yield decreases. Furthermore, since the nickel-based catalyst used as a methanation catalyst produces highly toxic nickel carbonyl at 150 ° C. or lower, there is a problem in safety.
Supervised by Masayoshi Ishida: Development and Challenges of Household Fuel Cells, Published December 28, 2004, CMC Publishing, p203-208 JP 2004-75439 A (Claims etc.)

本発明はこのような状況に鑑みてなされたものであって、その目的は、メンブレンリアクタ式改質器による水素製造方法において、高い水素収率を維持しつつ、たとえメンブレンリアクタ式改質器からＣＯがリークしても燃料電池電極へのＣＯの流入を確実に防止し得る、安全性にも優れた水素製造方法を提供することにある。   The present invention has been made in view of such a situation, and the object thereof is to maintain a high hydrogen yield in a hydrogen production method using a membrane reactor reformer, even from a membrane reactor reformer. An object of the present invention is to provide a hydrogen production method excellent in safety that can reliably prevent the inflow of CO into a fuel cell electrode even if CO leaks.

請求項１に記載の発明は、改質用原料をメンブレンリアクタ式改質器で改質して水素リッチな改質ガスを得る改質工程と、前記改質ガスをＣＯ吸着剤を充填したＣＯ吸着塔に通じてＣＯを吸着除去してＣＯ除去ガスを得るＣＯ除去工程を備えたことを特徴とする水素製造方法である。   The invention described in claim 1 includes a reforming step of reforming a reforming raw material with a membrane reactor type reformer to obtain a hydrogen-rich reformed gas, and a CO adsorbing the reformed gas with a CO adsorbent. A hydrogen production method comprising a CO removal step of obtaining CO removal gas by adsorbing and removing CO through an adsorption tower.

請求項２に記載の発明は、前記ＣＯ除去工程が、ＣＯを吸着除去するＣＯ吸着除去ステップと、前記ＣＯ吸着剤を再生するＣＯ吸着剤再生ステップとを有する請求項１に記載の水素製造方法である。   The invention according to claim 2 is the method for producing hydrogen according to claim 1, wherein the CO removal step includes a CO adsorption removal step for adsorbing and removing CO, and a CO adsorbent regeneration step for regenerating the CO adsorbent. It is.

請求項３に記載の発明は、前記ＣＯ除去工程が、前記ＣＯ吸着剤を充填してなるＣＯ吸着塔を複数備えたＣＯ除去装置を用いて行うものであり、１つのＣＯ吸着塔につき、前記ＣＯ吸着除去ステップと前記ＣＯ吸着剤ステップとを交互に行い、任意の時点において、少なくともいずれか１基のＣＯ吸着塔にて前記ＣＯ吸着除去ステップを行う請求項２に記載の水素製造方法である。   According to a third aspect of the present invention, the CO removal step is performed using a CO removal apparatus including a plurality of CO adsorption towers filled with the CO adsorbent. The hydrogen production method according to claim 2, wherein the CO adsorption removal step and the CO adsorbent step are alternately performed, and the CO adsorption removal step is performed in at least any one CO adsorption tower at an arbitrary time point. .

請求項４に記載の発明は、前記ＣＯ除去工程が、前記ＣＯ吸着剤を充填したＣＯ吸着塔を３塔以上備えたＣＯ除去装置を用いて行うものであり、下記の（１）および（２）の工程を繰り返すものである請求項３に記載の水素製造方法である。
（１）いずれか１塔のＣＯ吸着塔にて前記ＣＯ吸着剤再生ステップを行いつつ、残りのＣＯ吸着塔を直列に接続して前記ＣＯ吸着除去ステップを行う工程
（２）ついで前記直列に接続したＣＯ吸着塔のうち最上流側のＣＯ吸着塔を前記直列接続から分離するとともに、前記ＣＯ吸着剤再生ステップを終了したＣＯ吸着塔を前記直列接続の最下流側に接続する工程 In the invention according to claim 4, the CO removal step is performed using a CO removal apparatus including three or more CO adsorption towers filled with the CO adsorbent, and the following (1) and (2) The method for producing hydrogen according to claim 3, wherein the step (2) is repeated.
(1) A step of performing the CO adsorption removal step by connecting the remaining CO adsorption towers in series while performing the CO adsorbent regeneration step in any one CO adsorption tower. (2) Next, connecting in series Separating the most upstream CO adsorption tower from the series connection and connecting the CO adsorption tower having completed the CO adsorbent regeneration step to the most downstream side of the series connection.

請求項５に記載の発明は、前記ＣＯ吸着剤再生ステップにおいて、前記高純度水素ガスの一部を前記ＣＯ吸着塔に通じて前記ＣＯ吸着剤を再生する請求項２〜４のいずれか１項に記載の水素製造方法である。   According to a fifth aspect of the present invention, in the CO adsorbent regeneration step, the CO adsorbent is regenerated by passing a part of the high purity hydrogen gas through the CO adsorption tower. The hydrogen production method described in 1.

請求項６に記載の発明は、前記ＣＯ吸着剤再生ステップにおいて、燃料電池スタックオフガスの全部または一部を前記ＣＯ吸着塔に通じて前記ＣＯ吸着剤を再生する請求項２〜４のいずれか１項に記載の水素製造方法である。   According to a sixth aspect of the present invention, in the CO adsorbent regeneration step, the CO adsorbent is regenerated by passing all or part of the fuel cell stack off-gas through the CO adsorption tower. The method for producing hydrogen according to the item.

請求項７に記載の発明は、前記ＣＯ吸着剤再生ステップにおいて、前記改質工程における改質用原料の一部を前記吸着塔に通じて前記ＣＯ吸着剤を再生する請求項２〜４のいずれか１項に記載の水素製造方法である。   The invention according to claim 7 is the CO adsorbent regeneration step, wherein the CO adsorbent is regenerated by passing a part of the reforming raw material in the reforming step through the adsorption tower. The method for producing hydrogen according to claim 1.

請求項８に記載の発明は、前記ＣＯ吸着剤再生ステップで前記ＣＯ吸着塔から排出されたＣＯ吸着塔オフガスを、前記改質工程における改質ガス製造のための加熱用燃料の一部として用いる請求項５〜７のいずれか１項に記載の水素製造方法である。   The invention described in claim 8 uses the CO adsorption tower off-gas discharged from the CO adsorption tower in the CO adsorbent regeneration step as a part of heating fuel for producing reformed gas in the reforming step. It is a hydrogen production method of any one of Claims 5-7.

請求項９に記載の発明は、前記ＣＯ吸着剤再生ステップにおいて、前記ＣＯ吸着剤を再生するための熱量として、前記改質ガスの顕熱を用いる請求項５〜８のいずれか１項に記載の水素製造方法である。   According to a ninth aspect of the present invention, in the CO adsorbent regeneration step, the sensible heat of the reformed gas is used as the amount of heat for regenerating the CO adsorbent. This is a hydrogen production method.

請求項１０に記載の発明は、前記ＣＯ吸着剤が、シリカ、アルミナ、活性炭、グラファイトおよびポリスチレン系樹脂よりなる群から選択される１種以上の担体に、ハロゲン化銅（Ｉ）および／もしくはハロゲン化銅（ＩＩ）を担持させた材料、またはこれを還元処理したものである請求項１〜９に記載の水素製造方法である。   The invention according to claim 10 is characterized in that the CO adsorbent is applied to one or more kinds of carriers selected from the group consisting of silica, alumina, activated carbon, graphite and polystyrene-based resin, with copper (I) halide and / or halogen. The method for producing hydrogen according to any one of claims 1 to 9, wherein the copper (II) halide is supported on the material, or a reduction treatment of the material.

本発明によれば、たとえメンブレンリアクタ式改質器内の水素分離膜に存在する欠陥や劣化によってＣＯがリークしても、後段の吸着剤を充填したＣＯ吸着除去装置で安全かつ確実にＣＯをほぼ完全に除去することができ、燃料電池電極のＣＯ被毒を確実に防止できるようになった。   According to the present invention, even if CO leaks due to defects or deterioration existing in the hydrogen separation membrane in the membrane reactor reformer, the CO adsorption / removal device filled with the adsorbent in the subsequent stage can safely and reliably It can be almost completely removed, and CO poisoning of the fuel cell electrode can be surely prevented.

以下、本発明の実施の形態について図１〜４のフロー図を参照しつつ詳細に説明する。   Hereinafter, embodiments of the present invention will be described in detail with reference to the flowcharts of FIGS.

〔実施形態１〕
本発明の実施形態に係る水素製造プロセスの一例を図１のフロー図に示す。本実施形態では、メンブレンリアクタ式改質器内の水素分離膜に欠陥や劣化がほとんどない場合のバックアップとしてＣＯ除去装置を用いる例を示す。 Embodiment 1
An example of a hydrogen production process according to an embodiment of the present invention is shown in the flowchart of FIG. In the present embodiment, an example is shown in which a CO removal apparatus is used as a backup when there is almost no defect or deterioration in the hydrogen separation membrane in the membrane reactor reformer.

（改質工程）
水素リッチガスとしての改質ガスを製造するための改質工程には、メンブレンリアクタ式改質器１を用いる。メンブレンリアクタ式改質器１において天然ガスなどの改質用原料Ａを水蒸気にて改質してＨ２を主成分とする改質ガスＢとする。メンブレンリアクタ式改質器１内の水素分離膜の欠陥や劣化がほとんどない場合、改質ガスＢはほぼ全てＨ２である。この改質ガスＢの温度は５５０〜６５０℃であるが、ＣＯ吸着剤によるＣＯ吸着は吸着温度が低いほど吸着量が大きくなることから、後段のＣＯ除去工程における吸着温度は６０℃以下とするのが好ましい。このため、メンブレンリアクタ式改質器１の後段に熱交換器３を設置して改質ガスＢの顕熱を回収しつつ、ガス温度を６０℃以下に低下させた改質ガスＢ’とする。このとき熱交換器３で回収された排熱はコジェネレーションシステムにおける熱源等として利用できる。 (Reforming process)
The membrane reactor type reformer 1 is used in the reforming process for producing the reformed gas as the hydrogen rich gas. The reforming raw material A, such as natural gas is reformed by steam and reformed gas B composed mainly of H 2 in a membrane reactor-type reformer 1. If defects or deterioration of the hydrogen separation membrane of the membrane reactor-type reformer 1 is little, the reformed gas B is nearly all H 2. The temperature of the reformed gas B is 550 to 650 ° C. However, since the adsorption amount of CO adsorption by the CO adsorbent increases as the adsorption temperature decreases, the adsorption temperature in the subsequent CO removal step is set to 60 ° C. or less. Is preferred. For this reason, the heat exchanger 3 is installed in the subsequent stage of the membrane reactor reformer 1 to recover the sensible heat of the reformed gas B, and the reformed gas B ′ is reduced to 60 ° C. or lower. . At this time, the exhaust heat recovered by the heat exchanger 3 can be used as a heat source or the like in the cogeneration system.

（ＣＯ除去工程）
本実施例では、メンブレンリアクタ式改質器１内の水素分離膜に何らかの理由により欠陥が生じ、Ｈ２以外のＣＯ２，ＣＨ４，ＣＯ、Ｈ２Ｏ等のガスがリークしてきた際に、燃料電池電極に対して特に被毒性の強いＣＯのみを吸着除去するバックアップ装置としてＣＯ除去工程を設ける。このＣＯ除去工程には、ＣＯ吸着剤を充填した１基のＣＯ吸着塔２ａからなるＣＯ除去器２を用いる。ＣＯ吸着剤としては、シリカ、アルミナ、活性炭、グラファイトおよびポリスチレン系樹脂よりなる群から選択される１種以上の担体に、ハロゲン化銅（Ｉ）またはハロゲン化銅（II）を担持させた材料を用いるのが推奨される。このようなハロゲン化銅を担持させたＣＯ吸着剤は、ゼオライトモレキュラーシーブス、カーボンモレキュラーシーブス、活性炭、または活性アルミナといった従来の吸着剤に比べ数倍の吸着性能を発揮するため、ＣＯ除去器２が大幅に小型化できる。上述したように、ＣＯ吸着剤によるＣＯ吸着は吸着温度が低いほど吸着量が大きくなることから、高温の改質ガスＢを冷却するためにＣＯ除去器２の上流側に熱交換器３を設け、冷却後の改質ガスＢ’の温度を６０℃以下に低下させ、吸着温度をこの温度以下とするのが好ましい。ＣＯ吸着除去後のＣＯ除去ガスＣのＣＯ濃度は、燃料電池電極触媒の被毒を防ぐため、１０ｐｐｍ以下、さらには０．２ｐｐｍ以下とするのが好ましい。 (CO removal process)
In this example, when a hydrogen separation membrane in the membrane reactor reformer 1 has a defect for some reason and a gas such as CO 2 , CH 4 , CO, H 2 O other than H 2 has leaked, A CO removal step is provided as a backup device that adsorbs and removes only CO that is particularly toxic to the fuel cell electrode. In this CO removal step, a CO remover 2 comprising a single CO adsorption tower 2a filled with a CO adsorbent is used. As the CO adsorbent, a material in which copper (I) halide or copper (II) halide is supported on one or more carriers selected from the group consisting of silica, alumina, activated carbon, graphite, and polystyrene resin. Recommended to use. Such a CO adsorbent carrying copper halide exhibits adsorption performance several times that of conventional adsorbents such as zeolite molecular sieves, carbon molecular sieves, activated carbon, or activated alumina. The size can be greatly reduced. As described above, since the adsorption amount of CO adsorption by the CO adsorbent increases as the adsorption temperature decreases, the heat exchanger 3 is provided upstream of the CO remover 2 in order to cool the high-temperature reformed gas B. The temperature of the reformed gas B ′ after cooling is preferably lowered to 60 ° C. or lower, and the adsorption temperature is preferably lower than this temperature. The CO concentration of the CO removal gas C after CO adsorption removal is preferably 10 ppm or less, more preferably 0.2 ppm or less in order to prevent poisoning of the fuel cell electrode catalyst.

このようなＣＯ除去器２を後段に設置したことにより、万が一水素分離膜の欠陥によりメンブレンリアクタ式改質器１からＣＯを含む不純物がリークしてきても、ＣＯ除去器２で少なくともＣＯはほぼ完全に除去される。この結果、ＣＯ除去器２を通過したＣＯをほとんど含有しないＣＯ除去ガスＣが燃料電池に供給されるだけであるので、燃料電池電極にＣＯが流入することが防止され、装置全体の長寿命化・安定性の確保が可能となる。さらに、このようにバックアップとしてＣＯ除去器２を後段に設置することで、メンブレンリアクタ式改質器１内の高価な水素分離膜の厚さを必要最小限にすることができるので、ＣＯ除去器２を余分に設置するコストを考慮しても装置全体の製造コストを大幅に低減できる。   By installing such a CO remover 2 in the subsequent stage, even if impurities including CO leak from the membrane reactor reformer 1 due to a defect in the hydrogen separation membrane, at least CO is almost completely removed by the CO remover 2. Removed. As a result, since the CO removal gas C containing almost no CO that has passed through the CO remover 2 is only supplied to the fuel cell, it is possible to prevent CO from flowing into the fuel cell electrode and to prolong the life of the entire apparatus.・ Stability can be ensured. Furthermore, by installing the CO remover 2 as a back-up in this way, the thickness of the expensive hydrogen separation membrane in the membrane reactor reformer 1 can be minimized, so the CO remover Even considering the cost of installing 2 extra, the manufacturing cost of the entire apparatus can be greatly reduced.

なお、ＣＯ吸着塔２ａに充填されたＣＯ吸着剤の吸着性能を維持するために、定期的にＣＯ吸着剤を再生しておく必要があるが、たとえば、水素製造プロセスの定期点検の際に行うようにすればよい。   In order to maintain the adsorption performance of the CO adsorbent packed in the CO adsorption tower 2a, it is necessary to periodically regenerate the CO adsorbent. For example, it is performed at the periodic inspection of the hydrogen production process. What should I do?

〔実施形態２〕
本発明の別の実施形態に係る水素製造プロセスを図２のフロー図に示す。本実施形態では、メンブレンリアクタ式改質器の水素分離膜に欠陥が生じても継続して水素の製造を可能とするためにＣＯ除去装置を用いる例を示す。 [Embodiment 2]
A hydrogen production process according to another embodiment of the present invention is shown in the flow diagram of FIG. In the present embodiment, an example is shown in which a CO removal device is used in order to enable continuous production of hydrogen even if a defect occurs in the hydrogen separation membrane of the membrane reactor reformer.

（改質工程）
実施形態１と同様、メンブレンリアクタ式改質器１とその後段に熱交換器３を設置したものを用い、ガス温度が６０℃以下の改質ガスＢ’を得る。 (Reforming process)
As in the first embodiment, a reformed gas B ′ having a gas temperature of 60 ° C. or lower is obtained by using a membrane reactor type reformer 1 and a heat exchanger 3 installed in the subsequent stage.

（ＣＯ除去工程）
本実施形態のＣＯ除去工程には、ＣＯ吸着剤を充填したＣＯ吸着塔３基（２ａ、２ｂ、２ｃ）からなるＣＯ除去器２を用いる。以下、ＣＯ吸着除去ステップとＣＯ吸着剤再生ステップに分けて説明し、さらにそれらのステップの切り替え操作について説明を行う。 (CO removal process)
In the CO removal step of the present embodiment, a CO remover 2 comprising three CO adsorption towers (2a, 2b, 2c) filled with a CO adsorbent is used. Hereinafter, the CO adsorption removal step and the CO adsorbent regeneration step will be described separately, and the switching operation of those steps will be described.

［ＣＯ吸着除去ステップ］：改質ガスＢ’を、ＣＯ吸着剤を充填したＣＯ除去器２を通過させ、改質ガスＢ’中のＣＯを選択的に除去する。ＣＯ吸着剤としては、上記実施形態１と同様、シリカ、アルミナ、活性炭、グラファイトおよびポリスチレン系樹脂よりなる群から選択される１種以上の担体に、ハロゲン化銅（Ｉ）またはハロゲン化銅（II）を担持させた材料を用いるのが推奨される。ＣＯ吸着除去後のＣＯ除去ガスＣのＣＯ濃度は、上記実施形態１と同様、燃料電池電極触媒の被毒を防ぐため、１０ｐｐｍ以下、さらには０．２ｐｐｍ以下とするのが好ましい。     [CO Adsorption Removal Step]: The reformed gas B ′ is passed through the CO remover 2 filled with the CO adsorbent, and CO in the reformed gas B ′ is selectively removed. As the CO adsorbent, as in the first embodiment, copper (I) halide or copper halide (II) is used on one or more carriers selected from the group consisting of silica, alumina, activated carbon, graphite and polystyrene resin. ) Is recommended. The CO concentration of the CO removal gas C after CO adsorption removal is preferably 10 ppm or less, more preferably 0.2 ppm or less, in order to prevent poisoning of the fuel cell electrode catalyst, as in the first embodiment.

［ＣＯ吸着剤再生ステップ］：ＣＯ吸着剤の吸着性能を維持するために、ＣＯ吸着除去ステップにおいて所定の時間経過後に、ないしはＣＯ除去器２の出口側のＣＯ濃度が所定の濃度まで上昇（破過）したときにＣＯ吸着剤を再生する必要がある。ＣＯ吸着剤の再生は、吸着サイトに吸着したＣＯを脱離させ、この脱離したＣＯを再吸着させないで除去する必要があるため、キャリアガスとしてＣＯを実質的に含まないガスを流通させつつ行う。また、ＣＯの脱離は吸着とは逆に温度が高いほど促進されるため、ＣＯ吸着剤再生ステップにおける再生温度は、上記ＣＯ吸着除去ステップにおける吸着温度より高くする。このような条件を満足させるため、上記キャリアガスとして用いるＣＯを実質的に含まないガスとしては、ＣＯ吸着除去ステップで得られたＣＯ除去ガスＣの一部Ｃ’を利用し、これを上述の熱交換器３で改質ガスＢと熱交換し加熱して使用すればよい。ただし、２５０℃を超えて加熱すると、吸着剤に担持した活性種が不可逆的なダメージを受け、ＣＯ吸着剤の性能が低下するため２５０℃以下とする。とくに推奨される温度範囲は８０〜１５０℃である。そして、このＣＯ吸着剤を再生した後のガスＣ’’は、ＣＯを高濃度に含むため、例えばメンブレンリアクタ式改質器１の加熱用燃料Ｄの一部と代替して有効利用するとよい。     [CO adsorbent regeneration step]: In order to maintain the adsorption performance of the CO adsorbent, the CO concentration on the outlet side of the CO remover 2 rises to a predetermined concentration after elapse of a predetermined time in the CO adsorption removal step. It is necessary to regenerate the CO adsorbent. The regeneration of the CO adsorbent requires desorption of CO adsorbed on the adsorption site and removal of the desorbed CO without re-adsorption, so that a gas substantially free of CO is circulated as a carrier gas. Do. Further, since the desorption of CO is promoted as the temperature increases, the regeneration temperature in the CO adsorbent regeneration step is higher than the adsorption temperature in the CO adsorption removal step. In order to satisfy such conditions, as the gas substantially free of CO used as the carrier gas, a part C ′ of the CO removal gas C obtained in the CO adsorption removal step is used, and this is described above. What is necessary is just to heat-exchange with the reformed gas B with the heat exchanger 3, and to use it. However, when heated above 250 ° C., the active species carried on the adsorbent is irreversibly damaged, and the performance of the CO adsorbent is lowered. A particularly recommended temperature range is 80-150 ° C. The gas C ″ after the regeneration of the CO adsorbent contains CO at a high concentration, so that it may be effectively used instead of a part of the heating fuel D of the membrane reactor reformer 1, for example.

［ＣＯ吸着除去ステップとＣＯ吸着剤再生ステップとの切り替え操作］：それぞれのＣＯ吸着塔につき、上記ＣＯ吸着除去ステップとＣＯ吸着剤再生ステップとを交互に切り替える必要があるが、連続的に高純度水素を製造するためには（すなわち、連続的にＣＯ除去ガスＣを得るためには）、３塔のうち少なくとも１塔は常にＣＯ吸着除去ステップとしておく必要がある。なお、ＣＯ吸着除去ステップにあったＣＯ吸着塔をＣＯ吸着剤再生ステップに移行させ再生を十分に行うには、ＣＯ吸着剤をＣＯ脱離反応が活発化する温度まで昇温させるのに長時間を要することから、３塔のうち２塔をＣＯ吸着除去ステップとしておき、残りの１塔のみをＣＯ吸着剤再生ステップとするのが推奨される。そして、図３（ａ）に示すように、ＣＯ吸着除去ステップにある２塔（２ａ、２ｂ）を直列に接続し、改質ガスＢ’を２塔に分配して通過させるのでなく、２塔を順次通過させてＣＯを吸着除去するようにする。そして、所定時間経過後、上流側のＣＯ吸着塔２ａのＣＯ吸着容量が満杯になったとき、この上流側のＣＯ吸着塔２ａを直列接続から切り離すとともに、吸着剤の再生が完了したＣＯ吸着塔２ｃをＣＯ吸着塔２ｂの下流側に接続する。そして、同図（ｂ）に示すように、ＣＯ吸着塔２ａの吸着剤を再生しつつ、ＣＯ吸着塔２ｂ，２ｃからなる直列接続を用いてＣＯを吸着除去する。以下、同様の手順により、同図（ｃ）さらには同図（ａ）の状態へと戻り、このような切り替え操作が繰り返される。このように、２塔を直列に接続し、その上流側から順次再生を行うことにより、下流側のＣＯ吸着塔は常にＣＯ吸着容量を残した状態にあるので、破過（ＣＯ濃度の上昇）が発生することなく、常にＣＯが十分に取り除かれたＣＯ除去ガスＣが得られる。また、上流側のＣＯ吸着塔はその吸着容量をほぼ使い切った状態まで使用できるため、それぞれの吸着塔に吸着剤を過剰に充填する必要がなく、吸着剤コストの低減および設備の小型化を実現できる。     [Switching operation between CO adsorption removal step and CO adsorbent regeneration step]: For each CO adsorption tower, it is necessary to alternately switch the CO adsorption removal step and the CO adsorbent regeneration step. In order to produce hydrogen (that is, in order to obtain CO removal gas C continuously), at least one of the three towers must always be in the CO adsorption removal step. In order to perform the regeneration sufficiently by shifting the CO adsorption tower in the CO adsorption removal step to the CO adsorbent regeneration step, it takes a long time to raise the temperature of the CO adsorbent to a temperature at which the CO desorption reaction is activated. Therefore, it is recommended that two of the three columns be used as the CO adsorption removal step, and only the remaining one column be the CO adsorbent regeneration step. Then, as shown in FIG. 3 (a), the two towers (2a, 2b) in the CO adsorption removal step are connected in series, and the reformed gas B ′ is not distributed and passed through the two towers. In order to adsorb and remove CO. When the CO adsorption capacity of the upstream CO adsorption tower 2a is full after a predetermined time has elapsed, the upstream CO adsorption tower 2a is disconnected from the series connection, and the adsorbent regeneration is completed. 2c is connected to the downstream side of the CO adsorption tower 2b. Then, as shown in FIG. 5B, CO is adsorbed and removed using a series connection composed of the CO adsorption towers 2b and 2c while regenerating the adsorbent of the CO adsorption tower 2a. Thereafter, the same procedure is followed to return to the state shown in FIG. 5C and further to the state shown in FIG. In this way, by connecting two towers in series and performing regeneration sequentially from the upstream side, the downstream CO adsorption tower is always in a state of leaving the CO adsorption capacity, so breakthrough (CO concentration increase) Thus, the CO removal gas C from which CO has been sufficiently removed is always obtained. In addition, the upstream CO adsorption towers can be used up to the state where their adsorption capacity is almost used up, so there is no need to fill each adsorption tower with an excessive amount of adsorbent, reducing the adsorbent cost and downsizing the equipment. it can.

（変形例）
上記実施形態２では、ＣＯ吸着剤の再生に用いるＣＯを実質的に含まないガスとして、ＣＯ除去ガスＣの一部Ｃ’を用いたが、図４に示すように、固体高分子形燃料電池４のスタック部から排出されるオフガス（燃料電池スタックオフガス）Ｅの全部または一部Ｅ’を熱交換器３で改質ガスＢと熱交換し加熱して使用してもよい。この場合も、ＣＯ吸着剤を再生した後のガスＥ’’は、ＣＯを高濃度に含むため、例えばメンブレンリアクタ式改質器１の加熱用燃料Ｄの一部と代替して有効利用するとよい。 (Modification)
In the second embodiment, a part C ′ of the CO removal gas C is used as the gas that does not substantially contain CO used for the regeneration of the CO adsorbent. However, as shown in FIG. Alternatively, all or part of the off gas (fuel cell stack off gas) E ′ discharged from the stack portion 4 may be used by heat exchange with the reformed gas B in the heat exchanger 3. Also in this case, since the gas E ″ after the regeneration of the CO adsorbent contains CO at a high concentration, for example, it may be effectively used instead of part of the heating fuel D of the membrane reactor reformer 1. .

あるいは、上記ＣＯを実質的に含まないガスとして、図示を省略したが、メンブレンリアクタ式改質器１の改質用原料Ａの一部を用いてもよい。   Or although illustration was abbreviate | omitted as gas which does not contain the said CO substantially, you may use a part of raw material A for a reforming of the membrane reactor type | formula reformer 1. FIG.

また、上記実施形態２では、ＣＯ除去工程として３塔のＣＯ吸着塔を順次切り替えて用いる例を示したが、２塔または４塔以上のＣＯ吸着塔を順次切り替えて用いてもよい。なお、２塔の吸着塔を切り替えて用いる場合は、吸着操作に用いている１つの吸着塔がＣＯにより破過する前に（すなわち、ＣＯが漏れ出す前に）吸着操作を停止し、もう１つの再生ずみの吸着塔に切り替える必要があるため、ＣＯ吸着剤の吸着容量を全て用いることができない。これに対し、上記実施形態２で説明した３塔の吸着塔を切り替えて用いる場合は、上述したようにＣＯ吸着剤の吸着容量をほぼ全て用いることができ、吸着剤使用量が大幅に低減できるため、３塔切り替えのほうがより推奨される。   In the second embodiment, an example in which three CO adsorption towers are sequentially switched and used as the CO removal step has been described. However, two or four or more CO adsorption towers may be sequentially switched and used. When switching between two adsorption towers, the adsorption operation is stopped before one adsorption tower used for the adsorption operation breaks through with CO (that is, before CO leaks), Since it is necessary to switch to one regenerated adsorption tower, it is not possible to use all of the adsorption capacity of the CO adsorbent. In contrast, when the three adsorption towers described in the second embodiment are switched and used, almost all the adsorption capacity of the CO adsorbent can be used as described above, and the amount of adsorbent used can be greatly reduced. Therefore, switching to 3 towers is more recommended.

実施形態１に係る水素製造プロセスを示すフロー図である。FIG. 2 is a flowchart showing a hydrogen production process according to Embodiment 1. 実施形態２に係る水素製造プロセスを示すフロー図である。6 is a flowchart showing a hydrogen production process according to Embodiment 2. FIG. 実施形態２における、ＣＯ除去器の切り替え操作を説明するフロー図である。FIG. 6 is a flowchart for explaining a CO remover switching operation in the second embodiment. 実施形態２の変形例に係る水素製造プロセスを示すフロー図である。FIG. 6 is a flowchart showing a hydrogen production process according to a modification of the second embodiment.

符号の説明Explanation of symbols

１…メンブレンリアクタ式改質器
２…ＣＯ除去器
２ａ，２ｂ，２ｃ…ＣＯ吸着塔
３…熱交換器
４…固体高分子形燃料電池
Ａ…改質用原料
Ｂ…改質ガス
Ｃ…ＣＯ除去ガス
Ｄ…加熱用燃料
Ｅ…燃料電池スタックオフガス DESCRIPTION OF SYMBOLS 1 ... Membrane reactor type reformer 2 ... CO remover 2a, 2b, 2c ... CO adsorption tower 3 ... Heat exchanger 4 ... Polymer electrolyte fuel cell A ... Reforming raw material B ... Reformed gas C ... CO removal Gas D ... Heating fuel E ... Fuel cell stack off gas

Claims (10)

改質用原料をメンブレンリアクタ式改質器で改質して水素リッチな改質ガスを得る改質工程と、前記改質ガスをＣＯ吸着剤を充填したＣＯ吸着塔に通じてＣＯを吸着除去してＣＯ除去ガスを得るＣＯ除去工程を備えたことを特徴とする水素製造方法。   The reforming raw material is reformed with a membrane reactor reformer to obtain a hydrogen-rich reformed gas, and the reformed gas is passed through a CO adsorption tower filled with a CO adsorbent to remove CO by adsorption. And a CO removal step for obtaining a CO removal gas. 前記ＣＯ除去工程が、ＣＯを吸着除去するＣＯ吸着除去ステップと、前記ＣＯ吸着剤を再生するＣＯ吸着剤再生ステップとを有する請求項１に記載の水素製造方法。   The hydrogen production method according to claim 1, wherein the CO removal step includes a CO adsorption removal step for adsorbing and removing CO, and a CO adsorbent regeneration step for regenerating the CO adsorbent. 前記ＣＯ除去工程が、前記ＣＯ吸着剤を充填してなるＣＯ吸着塔を複数備えたＣＯ除去装置を用いて行うものであり、１つのＣＯ吸着塔につき、前記ＣＯ吸着除去ステップと前記ＣＯ吸着剤ステップとを交互に行い、任意の時点において、少なくともいずれか１基のＣＯ吸着塔にて前記ＣＯ吸着除去ステップを行う請求項２に記載の水素製造方法。   The CO removal step is performed by using a CO removal apparatus including a plurality of CO adsorption towers filled with the CO adsorbent, and the CO adsorption removal step and the CO adsorbent for one CO adsorption tower. The hydrogen production method according to claim 2, wherein the step is alternately performed, and the CO adsorption removal step is performed in at least one CO adsorption tower at an arbitrary time. 前記ＣＯ除去工程が、前記ＣＯ吸着剤を充填したＣＯ吸着塔を３塔以上備えたＣＯ除去装置を用いて行うものであり、下記の（１）および（２）の工程を繰り返すものである請求項３に記載の水素製造方法。
（１）いずれか１塔のＣＯ吸着塔にて前記ＣＯ吸着剤再生ステップを行いつつ、残りのＣＯ吸着塔を直列に接続して前記ＣＯ吸着除去ステップを行う工程
（２）ついで前記直列に接続したＣＯ吸着塔のうち最上流側のＣＯ吸着塔を前記直列接続から分離するとともに、前記ＣＯ吸着剤再生ステップを終了したＣＯ吸着塔を前記直列接続の最下流側に接続する工程 The CO removal step is performed using a CO removal device provided with three or more CO adsorption towers filled with the CO adsorbent, and the following steps (1) and (2) are repeated. Item 4. The method for producing hydrogen according to Item 3.
(1) A step of performing the CO adsorption removal step by connecting the remaining CO adsorption towers in series while performing the CO adsorbent regeneration step in any one CO adsorption tower. (2) Next, connecting in series Separating the most upstream CO adsorption tower from the series connection and connecting the CO adsorption tower having completed the CO adsorbent regeneration step to the most downstream side of the series connection. 前記ＣＯ吸着剤再生ステップにおいて、前記高純度水素ガスの一部を前記ＣＯ吸着塔に通じて前記ＣＯ吸着剤を再生する請求項２〜４のいずれか１項に記載の水素製造方法。   5. The hydrogen production method according to claim 2, wherein, in the CO adsorbent regeneration step, the CO adsorbent is regenerated by passing a part of the high-purity hydrogen gas through the CO adsorption tower. 前記ＣＯ吸着剤再生ステップにおいて、燃料電池スタックオフガスの全部または一部を前記ＣＯ吸着塔に通じて前記ＣＯ吸着剤を再生する請求項２〜４のいずれか１項に記載の水素製造方法。   5. The hydrogen production method according to claim 2, wherein in the CO adsorbent regeneration step, all or part of the fuel cell stack off gas is passed through the CO adsorption tower to regenerate the CO adsorbent. 前記ＣＯ吸着剤再生ステップにおいて、前記改質工程における改質用原料の一部を前記吸着塔に通じて前記ＣＯ吸着剤を再生する請求項２〜４のいずれか１項に記載の水素製造方法。   5. The method for producing hydrogen according to claim 2, wherein in the CO adsorbent regeneration step, a part of the reforming raw material in the reforming step is passed through the adsorption tower to regenerate the CO adsorbent. . 前記ＣＯ吸着剤再生ステップで前記ＣＯ吸着塔から排出されたＣＯ吸着塔オフガスを、前記改質工程における改質ガス製造のための加熱用燃料の一部として用いる請求項５〜７のいずれか１項に記載の水素製造方法。   8. The CO adsorption tower off-gas discharged from the CO adsorption tower in the CO adsorbent regeneration step is used as a part of heating fuel for producing reformed gas in the reforming process. The hydrogen production method according to item. 前記ＣＯ吸着剤再生ステップにおいて、前記ＣＯ吸着剤を再生するための熱量として、前記改質ガスの顕熱を用いる請求項５〜８のいずれか１項に記載の水素製造方法。   The method for producing hydrogen according to any one of claims 5 to 8, wherein, in the CO adsorbent regeneration step, sensible heat of the reformed gas is used as an amount of heat for regenerating the CO adsorbent. 前記ＣＯ吸着剤が、シリカ、アルミナ、活性炭、グラファイトおよびポリスチレン系樹脂よりなる群から選択される１種以上の担体に、ハロゲン化銅（Ｉ）および／もしくはハロゲン化銅（ＩＩ）を担持させた材料、またはこれを還元処理したものである請求項１〜９に記載の水素製造方法。   The CO adsorbent has copper (I) halide and / or copper (II) halide supported on one or more carriers selected from the group consisting of silica, alumina, activated carbon, graphite and polystyrene resin. The hydrogen production method according to claim 1, which is a material or a reduction treatment of the material.
JP2005280342A 2005-09-27 2005-09-27 Method of producing hydrogen Pending JP2007091498A (en)

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